WO2013084875A1 - Protective film for touch panel electrode, and touch panel - Google Patents
Protective film for touch panel electrode, and touch panel Download PDFInfo
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- WO2013084875A1 WO2013084875A1 PCT/JP2012/081365 JP2012081365W WO2013084875A1 WO 2013084875 A1 WO2013084875 A1 WO 2013084875A1 JP 2012081365 W JP2012081365 W JP 2012081365W WO 2013084875 A1 WO2013084875 A1 WO 2013084875A1
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- protective film
- touch panel
- electrode
- film
- resin composition
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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
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- 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 protective film for an electrode for a touch panel, and a touch panel having the same.
- Liquid crystal display elements and touch panels are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA / FA devices.
- These liquid crystal display elements and touch panels are provided with electrodes made of a transparent conductive electrode material.
- ITO Indium-Tin-Oxide
- indium oxide and tin oxide are known, and these materials exhibit high visible light transmittance, so that they can be used as electrode materials for substrates for liquid crystal display elements. It has become mainstream.
- capacitive touch panel when a fingertip that is a conductor contacts the touch input surface, the fingertip and the conductive film are capacitively coupled to form a capacitor. For this reason, the capacitive touch panel detects the coordinates by capturing the change in charge at the contact position of the fingertip.
- the projected capacitive touch panel can detect multiple fingertips, so it has a good operability to give complex instructions.
- a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes.
- ITO Indium-Tin-Oxide
- the frame area of the touch panel is an area where the touch position cannot be detected, reducing the area of the frame area is an important factor for improving the product value.
- metal wiring is required to transmit a touch position detection signal, but in order to reduce the frame area, it is necessary to reduce the width of the metal wiring. Since the conductivity of ITO is not sufficiently high, the metal wiring is generally formed of copper.
- a capacitive projection type touch panel in which an insulating layer is formed on metal is disclosed (for example, Patent Document 1).
- a silicon dioxide layer is formed on a metal by a plasma chemical vapor deposition method (plasma CVD method) to prevent corrosion of the metal.
- plasma CVD method plasma chemical vapor deposition method
- this method uses a plasma CVD method, there is a problem that a high temperature treatment is required, a base material is limited, and a manufacturing cost is increased.
- Patent Documents 5 and 6 disclose forming a protective film for a touch panel by the above method.
- JP 2011-28594 A JP-A-7-253666 JP 2005-99647 A Japanese Patent Laid-Open No. 11-133617 JP 2010-27033 A Japanese Patent Application Laid-Open No. 2011-232585
- a protective film with a photosensitive resin composition can be expected to reduce costs compared to the plasma CVD method.
- the protective film is formed on the electrode for the touch panel, if the thickness of the resin film is large, a step may be conspicuous between the portion where the film is present and the portion where the film is not present. Therefore, it is preferable to make the protective film as thin as possible.
- the present invention provides a protective film for an electrode for a touch panel that has a desired shape, is excellent in transparency, and has sufficient anti-rust properties even if it is a thin film, and a touch panel having such a protective film. For the purpose.
- a cured resin film formed from a specific photosensitive resin composition and capable of detecting a specific compound by pyrolysis gas chromatography mass spectrometry has a desired shape. It was found that the film has excellent transparency and has sufficient rust prevention even at a thickness of 10 ⁇ m or less, and is suitable as a protective film for an electrode for a touch panel. It was.
- the present invention is a protective film for a touch panel electrode obtained by curing a predetermined portion of a photosensitive layer comprising a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.
- a protective film for an electrode for a touch panel in which heptanonitrile and benzoic acid are detected by pyrolysis gas chromatography mass spectrometry.
- the protective film for an electrode for a touch panel of the present invention can have a desired shape, is excellent in transparency, and has a sufficient antirust property even if it is a thin film having a thickness of 10 ⁇ m or less.
- the present inventors consider the reason why the protective film of the touch panel electrode of the present invention can achieve the above-described effects as follows.
- the photosensitive layer containing a component that is a detection source of heptanonitrile and benzoic acid has a sufficient transparency and pattern forming property and can form a dense cured state.
- the present invention achieves both a sufficient rust prevention property capable of suppressing the invasion of corrosive components, transparency and pattern formability. They guess.
- the detection peak area of benzoic acid in pyrolysis gas chromatography mass spectrometry is 1 to 10 relative to the detection peak area of heptanionitrile. % Is preferred.
- the protective film of the touch panel electrode of the present invention preferably has a minimum value of visible light transmittance of 90% or more at 400 to 700 nm.
- the binder polymer preferably has a carboxyl group and has an acid value of 75 mgKOH / g or more.
- the binder polymer preferably has a hydroxyl value of 50 mgKOH / g or less.
- the thickness of the protective film of the touch panel electrode of the present invention is preferably 10 ⁇ m or less.
- the present invention also provides a touch panel having the protective film according to the present invention.
- a protective film for a touch panel electrode having a desired shape, excellent in transparency, and having sufficient rust prevention even in a thin film, and a touch panel having such a protective film. Can be provided.
- FIG. 1 It is a schematic cross section which shows one Embodiment of the photosensitive element used in order to form the protective film of the electrode for touchscreens which concerns on this invention. It is a schematic cross section for demonstrating one Embodiment of the formation method of the protective film of the electrode for touchscreens which concerns on this invention. It is a model top view which shows an example of an electrostatic capacitance type touch panel. It is a schematic top view which shows another example of an electrostatic capacitance type touch panel. (A) is the fragmentary sectional view which followed the VV line
- (meth) acrylic acid means acrylic acid or methacrylic acid
- (meth) acrylate means acrylate or the corresponding methacrylate
- (meth) acryloyl group means acryloyl.
- the (poly) oxyethylene chain means an oxyethylene group or a polyoxyethylene group
- the (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene group.
- 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.
- the protective film of the electrode for touch panels of this invention is for touch panels obtained by hardening the predetermined part of the photosensitive layer which consists of a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a photoinitiator.
- An electrode protective film characterized in that heptanonitrile and benzoic acid are detected by pyrolysis gas chromatography mass spectrometry.
- pyrolysis gas chromatograph mass spectrometry of a protective film performs gas chromatograph mass spectrometry on a gas generated by heating a measurement sample at 140 ° C.
- the heating time of the measurement sample may be in the range of 1 to 60 minutes, but is preferably 30 minutes.
- the measurement conditions for pyrolysis gas chromatograph mass spectrometry are shown below.
- Measuring device GC / MS QP-2010 (manufactured by Shimadzu Corporation, product name) Column: HP-5MS (manufactured by Agilent Technologies, product name) Even Temp: heated at 40 ° C. for 5 minutes, then heated to 300 ° C. at a rate of 15 ° C./min.
- Carrier gas helium, 1.0 mL / min Interface temperature: 280 ° C
- Ion source temperature 250 ° C
- Sample injection volume 0.1 mL
- the detection peak area of benzoic acid in pyrolysis gas chromatography mass spectrometry of the protective film is preferably 1 to 10%, more preferably 1 to 9%, relative to the detection peak area of heptanonitrile, It is more preferably 1 to 7%, and particularly preferably 1 to 6%.
- the detection peak area of benzoic acid is 1 to 10%, the effect of the present invention is obtained more reliably with a desired shape, excellent transparency, and sufficient rust prevention even with a thin film. be able to.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive element used for forming a protective film for a touch panel electrode according to the present invention.
- the photosensitive element 1 shown in FIG. 1 includes a support film 10, a photosensitive layer 20 made of the photosensitive resin composition according to this embodiment provided on the support film 10, and the support film 10 of the photosensitive layer 20. It consists of a protective film 30 provided on the opposite side.
- the protective film for the touch panel electrode of the present invention can be formed.
- 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 film may be provided.
- a polymer film can be used as the support film 10.
- the polymer film include films made of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and the like.
- the thickness of the support film 10 is preferably 5 to 100 ⁇ m from the viewpoint of ensuring coverage and suppressing a decrease in resolution when irradiated with actinic rays through the support film 10. More preferably, it is more preferably 15 to 40 ⁇ m, and particularly preferably 20 to 35 ⁇ m.
- the photosensitive resin composition according to this embodiment 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), and photopolymerization. And an initiator (hereinafter also referred to as component (C)).
- the photosensitive resin composition can contain components that generate heptanionitrile and benzoic acid in the thermal decomposition of the cured product when the cured product is formed by irradiation with actinic rays.
- heptanonitrile and benzoic acid are detected by the pyrolysis gas chromatograph mass spectrometry mentioned above.
- 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.
- the copolymer may further contain other monomer that can be copolymerized with the component (a) and / or the component (b) as a constituent unit.
- Examples of the other monomer that can be copolymerized with the component (a) and / or the component (b) include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, and (meth) acrylic.
- Acid diethylaminoethyl ester (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate , (Meth) acrylamide, (meth) acrylonitrile, diacetone (meth) acrylamide, styrene, and vinyltoluene.
- the above monomers may be used alone or in combination of two or more.
- the weight average molecular weight of the binder polymer as component (A) is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and more preferably 30,000 to 200,000 from the viewpoint of resolution. 150,000 is more preferable, 30,000 to 100,000 is particularly preferable, and 40,000 to 100,000 is very preferable.
- 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 set to 75 mgKOH / g or more from the viewpoint of easily forming a protective film having a desired shape. From the viewpoint of achieving compatibility with rustability, it is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and still more preferably 75 to 120 mgKOH / g.
- the acid value of the binder polymer as the component (A) can be measured as follows. That is, first, 1 g of the binder polymer that is the object of acid value measurement is precisely weighed. 30 g of acetone is added to the precisely weighed binder polymer and dissolved uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by following Formula.
- Acid value 0.1 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I)
- Vf represents the titration amount (mL) of the KOH aqueous solution
- Wp represents the measured weight (g) of the solution containing the binder polymer
- I represents the ratio (mass) of the non-volatile content in the measured solution containing the binder polymer. %).
- the hydroxyl value of the binder polymer as the component (A) is preferably 50 mgKOH / g or less, more preferably 45 mgKOH / g or less, from the viewpoint of further improving rust prevention.
- the hydroxyl value of the component (A) can be measured as follows. First, 1 g of a binder polymer, which is a measurement target of the hydroxyl value, is precisely weighed. 10 mL of a 10% by mass acetic anhydride pyridine solution is added to the binder polymer under the above precision balance, and this is uniformly dissolved and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine are added and heated at 100 ° C. for 10 minutes. Then, it is measured by neutralization titration with an ethanol solution of 0.5 mol / L potassium hydroxide using an automatic titrator (“COM-1700” manufactured by Hiranuma Sangyo Co., Ltd.).
- A represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test
- B represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration
- f represents a factor.
- 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, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A polyoxyethylene polyoxypropylene di (meth) acrylate (2 , 2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane), bisphenol A diglycidyl ether di (meth) acrylate, etc., polyvalent carboxylic acids (phthalic anhydride, etc.), hydroxyl groups and ethylenically unsaturated Examples thereof include an esterified product with a substance having a group ( ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, etc.).
- 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 a polyhydric alcohol such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate with an ⁇ , ⁇ -unsaturated saturated carboxylic acid; such as trimethylolpropane triglycidyl ether triacrylate Examples thereof include compounds obtained by adding an ⁇ , ⁇ -unsaturated carboxylic acid to a glycidyl group-containing compound.
- a polyhydric alcohol such as dipentaerythritol penta (meth) acrylate and dipentaerythritol
- 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 From the viewpoint of obtaining an inhibitory power, 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. 30 parts by mass or more, preferably 50 parts by mass or more, and more preferably 75 parts by mass or more.
- the content of the component (A) and the component (B) in the photosensitive resin composition according to this embodiment is such that the component (A) is 35 with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferable that the component (B) is 15 to 65 parts by mass, the component (A) is 40 to 80 parts by mass, and the component (B) is 20 to 60 parts by mass. More preferably, the component A) is 50 to 70 parts by mass, the component (B) is 30 to 50 parts by mass, the component (A) is 55 to 65 parts by mass, and the component (B) is 35 to 45 parts by mass. It is particularly preferred.
- the content of the component (A) and the component (B) is (A) relative to 100 parts by mass of the total amount of the component (A) and the component (B).
- the component is preferably 35 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more.
- the photosensitive resin composition according to the present embodiment preferably contains an oxime ester compound as a photopolymerization initiator that is the component (C).
- an oxime ester compound as a photopolymerization initiator that is the component (C).
- Examples of the oxime ester compound include compounds represented by the following general formula (C-1).
- R 1 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.
- the aromatic ring in the general formula (C-1) may have a substituent.
- R 1 is preferably an alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 4 to 15 carbon atoms, and an alkyl group having 4 to 8 carbon atoms or a carbon number More preferably, it is a 4-10 cycloalkyl group.
- Examples of the compound represented by the general formula (C-1) include (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like.
- 2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is available as IRGACURE OXE 01 (trade name, manufactured by BASF Corporation).
- 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is particularly preferable.
- 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is a pyrolysis gas chromatograph mass for the protective film formed from the resin composition according to this embodiment. When analyzed, it is detected as heptanonitrile and benzoic acid.
- the detection peak area of benzoic acid in the pyrolysis gas chromatograph mass spectrometry of the protective film obtained in this case is preferably 1 to 10% with respect to the detection peak area of heptanonitrile.
- the detection peak area of benzoic acid is 1 to 10%, the effect of the present invention is obtained more reliably with a desired shape, excellent transparency, and sufficient rust prevention even with a thin film. be able to.
- the component (C) can be used in combination with a photopolymerization initiator other than the oxime ester compound.
- photopolymerization initiators other than oxime ester compounds include benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2 Aromatic ketones such as methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin, methyl benzoin, ethyl Benzoin compounds such as benzoin; benzyl derivatives such as benzyldimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) hept
- the content of the photopolymerization initiator as component (C) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B), and 1 to 10 parts by mass. More preferably, the amount is 2 to 5 parts by mass.
- the content of the component (C) is preferably 0.1 parts by mass or more in terms of excellent light sensitivity and resolution, and is preferably 20 parts by mass or less in terms of excellent visible light transmittance.
- the photosensitive resin composition according to the present embodiment has a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group, and an amino group from the viewpoint of further improving the rust prevention property of the protective film. It is preferable to further contain a triazole compound or a tetrazole compound having an amino group (hereinafter also referred to as component (D)).
- the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 3MT).
- Examples of the thiadiazole compound having a mercapto group include 2-amino-5-mercapto-1,3,4-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd., trade name: ATT).
- 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.
- a compound in which an amino group is substituted for a triazole compound containing a mercapto group examples include 3-amino-5-mercaptotriazole (BASF Corporation, trade name: AMT).
- 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) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an amino group, a mercapto group, or a carboxymethyl group, and R 11 and R 12 At least one of has an amino group.
- alkyl group examples include a methyl group, an ethyl group, and a propyl group.
- tetrazole compounds represented by the general formula (D-1) 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, or 1- Carboxymethyl-5-amino-tetrazole is 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 having an amino group. It is preferable to further contain a compound in which an amino group is substituted for a triazole compound containing a group. 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 according to 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). It is preferably 0.1 to 2.0 parts by mass, more preferably 0.2 to 1.0 part by mass.
- a protective film on a part of the ITO electrode of the touch panel for example, a part where a protective layer is not formed in the sensing area, and a metal layer such as copper is formed on the ITO electrode in the frame area and the ITO electrode.
- a protective film 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 invention contains a phosphoric ester containing a photopolymerizable unsaturated bond (hereinafter also referred to as component (E)). It is preferable to do.
- an adhesion imparting agent such as a silane coupling agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, An antioxidant, a fragrance, a thermal crosslinking agent, a polymerization inhibitor, and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). These can be used alone or in combination of two or more.
- the visible light transmittance of the photosensitive resin composition is obtained as follows. First, a photosensitive resin composition layer (photosensitive layer) is coated by applying a coating solution containing the photosensitive resin composition on a support film so that the thickness after drying is 10 ⁇ m or less, and drying it. Form. Next, it laminates on a glass substrate using a laminator so that the photosensitive resin composition layer (photosensitive layer) is in contact. 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 general visible light wavelength range, is 90% or more
- the transparent electrode in the sensing area of the touch panel (touch sensor) is protected, or the touch panel (touch sensor)
- the protective film is visible from the edge of the sensing area when the metal layer (for example, a layer in which a copper layer is formed on the ITO electrode) is protected, the image display quality, color, and brightness in the sensing area are It can suppress sufficiently that it falls.
- the photosensitive resin composition according to this embodiment can be used for forming a photosensitive layer on a substrate.
- a coating solution that can be obtained by uniformly dissolving or dispersing a photosensitive resin composition in a solvent is prepared, and a coating film is formed by coating on a substrate, and then the solvent is removed by drying.
- a layer can be formed.
- solvent ketone, aromatic hydrocarbon, alcohol, glycol ether, glycol alkyl ether, glycol alkyl ether acetate, ester, or diethylene glycol is used from the viewpoint of solubility of each component, ease of film formation, etc. Can do.
- solvents may be used alone or as a mixed solvent composed of two or more solvents.
- ethylene glycol monobutyl ether acetate diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or the like.
- the photosensitive resin composition according to the present embodiment is preferably used after being formed on a photosensitive film like the photosensitive element 1.
- a photosensitive film like the photosensitive element 1.
- the photosensitive layer 20 of the photosensitive element 1 can be formed by preparing a coating solution containing the photosensitive resin composition according to the present embodiment, and applying and drying the coating solution on the support film 10.
- the coating liquid can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition according to the present embodiment described above in a solvent.
- the solvent is not particularly limited and known ones can be used.
- Examples include ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform, and methylene chloride.
- These solvents may be used alone or as a mixed solvent composed of two or more solvents.
- Application methods include, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating A coating method is mentioned.
- 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 not less than 1 ⁇ m and not more than 9 ⁇ m in thickness after drying so that the step on the surface of the touch panel (touch sensor) generated by the partial electrode protection film formation becomes as small as possible, while exhibiting a sufficient effect for electrode protection. It is preferably 1 ⁇ m or more and 8 ⁇ m or less, more preferably 2 ⁇ m or more and 8 ⁇ m or less, and particularly preferably 3 ⁇ m or more and 8 ⁇ m or less.
- the photosensitive layer 20 preferably has a minimum visible light transmittance of 90% or more, more preferably 92% or more, and still more preferably 95% or more.
- the viscosity of the photosensitive layer 20 prevents the photosensitive resin composition from exuding from the end face of the photosensitive element 1 for more than one month. From the point of preventing exposure failure and residual development when irradiated with actinic rays caused by the photosensitive resin composition fragments adhering to the substrate, it is preferably 15 to 100 mPa ⁇ s at 30 ° C., It is more preferably 20 to 90 mPa ⁇ s, and further preferably 25 to 80 mPa ⁇ s.
- the viscosity is 1.96 ⁇ at 30 ° C. and 80 ° C. in the thickness direction of this sample using a circular film of 7 mm in diameter and 2 mm in thickness formed from the photosensitive resin composition as a measurement sample. This is a value obtained by measuring the rate of change of thickness when a load of 10 ⁇ 2 N is applied, and converting it to viscosity from the rate of change assuming a Newtonian fluid.
- Examples of the protective film 30 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, and a film made of a laminated film of polyethylene-vinyl acetate copolymer and polyethylene.
- the thickness of the protective film 30 is preferably about 5 to 100 ⁇ m, but it is preferably 70 ⁇ m or less, more preferably 60 ⁇ m or less, and further preferably 50 ⁇ m or less from the viewpoint of being wound and stored in a roll shape. It is preferably 40 ⁇ m or less.
- Photosensitive element 1 can be stored in a roll or stored.
- the coating liquid containing the photosensitive resin composition and the solvent according to the present embodiment described above is coated on a substrate having a touch panel electrode, dried, and then formed of the photosensitive resin composition.
- a photosensitive layer 20 may be provided. Even in this application, the photosensitive layer preferably satisfies the above-described film thickness and visible light transmittance.
- FIG. 2 is a schematic cross-sectional view for explaining an example of a method for forming a protective film for a touch panel electrode 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.
- Examples of the base material 100 used in the present embodiment include substrates such as glass plates, plastic plates, and ceramic plates that are generally used for touch panels (touch sensors).
- substrate the electrode for touchscreens used as the object which forms the resin cured film used as a protective film is provided.
- Examples of the electrode include electrodes such as ITO, Cu, Al, and Mo, and TFT.
- An insulating layer may be provided on the substrate between the substrate and the electrode.
- the substrate 100 having the touch panel electrodes 110 and 120 shown in FIG. 2 can be obtained, for example, by the following procedure. After forming a metal film by sputtering in the order of ITO and Cu on a substrate 100 such as a PET film, an etching photosensitive film is pasted on the metal film to form a desired resist pattern, and unnecessary Cu is chlorinated. After removing with an etching solution such as an iron aqueous solution, the resist pattern is peeled off.
- an etching solution such as an iron aqueous solution
- the protective film 30 of the photosensitive element 1 which concerns on this embodiment, it heat-sensitive the photosensitive element on the surface in which the electrodes 110 and 120 for touchscreens of the base material 100 are provided.
- the layer 20 is transferred by pressure bonding and laminated (see FIG. 2A).
- Crimping means includes a crimping roll.
- the pressure roll may be provided with a heating means so that it can be heat-pressure bonded.
- the heating temperature for thermocompression bonding is such that the constituent components of the photosensitive layer 20 are sufficient to ensure the adhesion between the photosensitive layer 20 and the substrate 100 and the adhesion between the photosensitive layer 20 and the touch panel electrodes 110 and 120.
- the temperature is preferably 10 to 160 ° C., more preferably 20 to 150 ° C., and still more preferably 30 to 150 ° C. so that it is not easily cured or thermally decomposed.
- the pressure at the time of thermocompression bonding is 50 to 1 ⁇ 10 5 N / m in terms of linear pressure from the viewpoint of suppressing deformation of the substrate 100 while ensuring sufficient adhesion between the photosensitive layer 20 and the substrate 100.
- it is 2.5 ⁇ 10 2 to 5 ⁇ 10 4 N / m, more preferably 5 ⁇ 10 2 to 4 ⁇ 10 4 N / m.
- the preheating temperature at this time is preferably 30 to 150 ° C.
- the coating liquid containing the photosensitive resin composition and the solvent according to this embodiment is prepared, and the touch panel electrodes 110 and 120 of the substrate 100 are provided.
- the photosensitive layer 20 can be formed by applying to the surface and drying.
- the photosensitive layer 20 preferably satisfies the above-described conditions of film thickness and visible light transmittance.
- a predetermined portion of the photosensitive layer 20 is irradiated with an actinic ray L in a pattern via a photomask 130 (see FIG. 2B).
- the actinic light When irradiating actinic light, if the support film 10 on the photosensitive layer 20 is transparent, the actinic light can be irradiated as it is, and if it is opaque, the actinic light is irradiated after removal. From the viewpoint of protecting the photosensitive layer 20, it is preferable to use a transparent polymer film as the support film 10 and to irradiate actinic rays through the polymer film with the polymer film remaining.
- a known actinic light source can be used, for example, a carbon arc lamp, an ultra high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, etc. If it is, it will not be restrict
- the irradiation amount of the actinic ray L is usually 1 ⁇ 10 2 to 1 ⁇ 10 4 J / m 2 , and heating can be accompanied at the time of irradiation. If the irradiation amount of actinic rays is less than 1 ⁇ 10 2 J / m 2 , the effect of photocuring tends to be insufficient, and if it exceeds 1 ⁇ 10 4 J / m 2 , the photosensitive layer 20 tends to discolor. There is.
- the photosensitive layer after irradiation with actinic rays is developed with a developer to remove a portion not irradiated with actinic rays (that is, other than a predetermined portion of the photosensitive layer), and a part or all of the electrode is removed.
- a protective film 22 made of a cured film pattern of the photosensitive resin composition according to this embodiment having a thickness of 10 ⁇ m or less is formed (see FIG. 2C).
- the formed protective film 22 can have a predetermined pattern.
- the support film 10 is laminated on the photosensitive layer 20 after irradiation with actinic rays, the support film 10 is removed, and then development is performed to remove a portion not irradiated with actinic rays by the developer.
- 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 mass 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 according to the present embodiment.
- a surfactant an antifoaming agent, a small amount of an organic solvent for promoting development, and the like can be mixed in the alkaline aqueous solution.
- the base of the alkaline aqueous solution remaining in the photosensitive layer 20 after development and photocuring is used by known methods such as spraying, rocking immersion, brushing, and scraping using an organic acid, an inorganic acid, or an acid aqueous solution thereof.
- Acid treatment neutralization treatment
- the cured film pattern may be further cured by irradiation with actinic rays (for example, 5 ⁇ 10 3 to 2 ⁇ 10 4 J / m 2 ) as necessary.
- actinic rays for example, 5 ⁇ 10 3 to 2 ⁇ 10 4 J / m 2
- the photosensitive resin composition according to the present embodiment exhibits excellent adhesion to a metal even without a heating step after development, but if necessary, instead of irradiation with actinic rays after development, or A heat treatment (80 to 160 ° C.) may be applied in combination with the irradiation with actinic rays.
- the protective film for the touch panel electrode according to the present invention can be formed.
- the photosensitive resin composition constituting the photosensitive layer has 1, 2 as component (C). And -octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)].
- FIG. 3 is a schematic top view illustrating an example of a capacitive touch panel.
- the touch panel shown in FIG. 3 has a touch screen 102 for detecting touch position coordinates on one surface of the transparent substrate 101, and the transparent electrode 103 and the transparent electrode 104 for detecting a change in capacitance in this region are the substrate 101. It is provided above.
- the transparent electrode 103 and the transparent electrode 104 detect the X coordinate and the Y coordinate of the touch position, respectively.
- a lead-out wiring 105 for transmitting a touch position detection signal from the transparent electrode 103 and the transparent electrode 104 to an external circuit is provided on the transparent substrate 101.
- the lead-out wiring 105 is connected to the transparent electrode 103 and the transparent electrode 104 by a connection electrode 106 provided on the transparent electrode 103 and the transparent electrode 104.
- a connection terminal 107 for connecting to an external circuit is provided at the end of the lead-out wiring 105 opposite to the connection portion between the transparent electrode 103 and the transparent electrode 104.
- the photosensitive resin composition according to the present invention can be suitably used to form the protective film 122 for the lead-out wiring 105, the connection electrode 106, and the connection terminal 107. At this time, the electrodes in the sensing region can be protected at the same time.
- the lead-out wiring 105, the connection electrode 106, a part of the sensing region electrode, and a part of the connection terminal 107 are protected by the protective film 122.
- a protective film 123 may be provided so as to protect the entire touch screen 102.
- FIG. 5 is a partial cross-sectional view taken along the line VV of the portion C shown in FIG. 3 and is a view for explaining a connection portion between the transparent electrode 104 and the lead-out wiring 105.
- the transparent electrode 104 and the lead wiring 105 are electrically connected via the connection electrode 106.
- a part of the transparent electrode 104 and all of the lead-out wiring 105 and the connection electrode 106 are covered with a protective film 122.
- the transparent electrode 103 and the lead wiring 105 are electrically connected via the connection electrode 106.
- the transparent electrode 104 and the lead-out wiring 105 may be directly electrically connected.
- the above-described photosensitive resin composition and photosensitive element according to the present embodiment are suitable for use for forming a cured resin film pattern as a protective film for the structural portion.
- the transparent electrode (X position coordinate) 103 is formed on the transparent electrode 101 provided on the substrate 100.
- a transparent electrode (Y position coordinate) 104 is formed.
- the transparent electrode 103 and the transparent electrode 104 can be formed by a method of etching the transparent electrode layer formed on the transparent substrate 100.
- a lead-out wiring 105 for connecting to an external circuit and a connection electrode 106 for connecting the lead-out wiring with the transparent electrode 103 and the transparent electrode 104 are formed.
- the lead-out wiring 105 and the connection electrode 106 may be formed after the formation of the transparent electrode 103 and the transparent electrode 104, or may be formed simultaneously with the formation of each transparent electrode.
- the lead-out wiring 105 and the connection electrode 106 can be formed by etching after metal sputtering.
- the lead-out wiring 105 can be formed at the same time as the connection electrode 106 is formed by screen printing using a conductive paste material containing flaky silver, for example.
- a connection terminal 107 for connecting the lead wiring 105 and an external circuit is formed.
- the photosensitive element 1 is pressure-bonded so as to cover the transparent electrode 103 and the transparent electrode 104, the lead-out wiring 105, the connection electrode 106, and the connection terminal 107 formed by the above-described process, and the photosensitive element 1 is exposed on the electrode.
- Layer 20 is provided.
- the actinic ray L is irradiated to the transferred photosensitive layer 20 in a desired shape through a photomask.
- development is performed to remove portions other than the predetermined portion of the photosensitive layer 20, thereby forming a protective film 122 made of a cured product of the predetermined portion of the photosensitive layer 20. In this manner, a touch panel including the protective film 122 can be manufactured.
- 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 0.1 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I)
- Vf represents the titration amount (mL) of the KOH aqueous solution
- Wp represents the weight (g) of the measured resin solution
- I represents the ratio (mass%) of the non-volatile content in the measured resin solution.
- the hydroxyl 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 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.
- A represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test
- B represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration
- f represents a factor.
- Examples 1 to 8, Comparative Examples 1 to 8 [Preparation of coating solution containing photosensitive resin composition]
- the materials shown in Table 2 were mixed for 15 minutes using a stirrer to prepare a coating solution containing a photosensitive resin composition for forming a protective film.
- a polyethylene terephthalate film having a thickness of 50 ⁇ m is used as the support film, and the coating solution containing the photosensitive resin composition prepared above is uniformly applied onto the support film using a comma coater, and is heated at 100 ° C. with hot air convection. The solvent was removed by drying for 3 minutes in a machine 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 for forming a protective film.
- a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) is used for the photosensitive layer of the obtained laminate, and the exposure amount is 5 ⁇ 10 2 J / m 2 from the upper side of the photosensitive layer (i line).
- the support film was removed and left in a box dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) heated to 140 ° C. for 30 minutes.
- a transmittance measurement sample having a protective film having a thickness of 5 ⁇ m was obtained.
- the obtained sample was measured for visible light transmittance in a measurement wavelength range of 400 to 700 nm using a UV-visible spectrophotometer (U-3310) manufactured by Hitachi High-Technologies Corporation, and the minimum value was calculated. . Tables 4 and 5 show the measurement results.
- 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)).
- the sample was allowed to stand for 30 minutes in a box dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) that was irradiated and heated to 140 ° C.
- a sample for evaluating artificial sweat resistance with a protective film having a thickness of 5.0 ⁇ m was obtained.
- Laminator Hitachi Chemical Industry Co., Ltd.
- the photosensitive layer is in contact with the polytetrafluoroethylene sheet (manufactured by Nitto Denko Corporation, product name: Nitoflon Film No. 900U) while peeling the polyethylene film of the obtained photosensitive element (Product name: HLM-3000 type) was used for lamination under conditions of a roll temperature of 120 ° C., a substrate feed rate of 1 m / min, and a pressure (cylinder pressure) of 4 ⁇ 10 5 Pa.
- a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) was used for the photosensitive layer of the obtained laminate, and the exposure amount was 5 ⁇ 10 2 J / m 2 (i-line ( Measured value at a wavelength of 365 nm), after irradiating with ultraviolet rays, the support film is removed, and further the ultraviolet ray is irradiated at an exposure amount of 1 ⁇ 10 4 J / m 2 from above the photosensitive layer side (measured value at i-line (wavelength 365 nm)). Irradiated to obtain a measurement sample for pyrolysis gas chromatograph mass spectrometry.
- the measurement sample was heated to 140 ° C. for 30 min using a Tekmar 7000HT headspace sampler, and the generated gas was GC / MS (manufactured by Shimadzu Corporation, model number: GC / MS QP-2010, carrier gas: helium, 1.0 mL / min.
- FIG. 6 shows a gas chromatogram when pyrolysis gas chromatograph mass spectrometry was performed on the protective film obtained in Example 6.
- A shows the detection peak of benzoic acid
- B shows the detection peak of heptanonitrile.
- IRGACURE OXE 01 1,2-octanedione, 1-[(4-phenylthio)-, 2- (O-benzoyloxime)] (manufactured by BASF Corporation)
- IRGACURE 184 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Corporation)
- IRGACURE 651 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF Corporation)
- IRGACURE 369 2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butanone-1 (manufactured by BASF Corp.)
- IRGACURE 907 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF Corporation)
- IRGACURE 2959 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1
- HAT 5-amino-1H-tetrazole (Toyobo Co., Ltd.)
- AMT 3-amino-5-mercaptotriazole (manufactured by Wako Pure Chemical Industries, Ltd.)
- ATT 2-amino-5-mercapto-1,3,4-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
- Antage W-500 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd.)
- PM-21 Phosphate ester containing photopolymerizable unsaturated bond (Nippon Kayaku Co., Ltd.)
- SH-30 Octamethylcyclotetrasiloxane (manufactured by Dow Corning Toray) Methyl ethyl ketone: manufactured by Tonen Chemical Co., Ltd.
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Abstract
Description
測定装置:GC/MS QP-2010(島津製作所製、製品名)
カラム:HP-5MS(アジレント・テクノロジー株式会社製、製品名)
Oven Temp:40℃で5分間加熱後、15℃/minの割合で300℃まで昇温
キャリアーガス:ヘリウム、1.0mL/min
インターフェイス温度:280℃
イオンソース温度:250℃
サンプル注入量:0.1mL (Measurement conditions for pyrolysis gas chromatograph mass spectrometry)
Measuring device: GC / MS QP-2010 (manufactured by Shimadzu Corporation, product name)
Column: HP-5MS (manufactured by Agilent Technologies, product name)
Even Temp: heated at 40 ° C. for 5 minutes, then heated to 300 ° C. at a rate of 15 ° C./min. Carrier gas: helium, 1.0 mL / min
Interface temperature: 280 ° C
Ion source temperature: 250 ° C
Sample injection volume: 0.1 mL
酸価=0.1×Vf×56.1/(Wp×I)
式中、VfはKOH水溶液の滴定量(mL)を示し、Wpは測定したバインダーポリマー含有する溶液の重量(g)を示し、Iは測定したバインダーポリマー含有する溶液中の不揮発分の割合(質量%)を示す。
なお、バインダーポリマーを合成溶媒や希釈溶媒などの揮発分と混合した状態で配合する場合は、精秤前に予め、揮発分の沸点よりも10℃以上高い温度で1~4時間加熱し、揮発分を除去してから酸価を測定する。 The acid value of the binder polymer as the component (A) can be measured as follows. That is, first, 1 g of the binder polymer that is the object of acid value measurement is precisely weighed. 30 g of acetone is added to the precisely weighed binder polymer and dissolved uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the measured weight (g) of the solution containing the binder polymer, and I represents the ratio (mass) of the non-volatile content in the measured solution containing the binder polymer. %).
When blending the binder polymer in a state mixed with volatile components such as a synthetic solvent or a diluting solvent, the mixture is volatilized by heating for 1 to 4 hours at a
まず、水酸基価の測定対象であるバインダーポリマー1gを精秤する。上記精秤下バインダーポリマーに、10質量%の無水酢酸ピリジン溶液を10mL加えてこれを均一に溶解し、100℃で1時間加熱する。加熱後、水10mLとピリジン10mLを加えて100℃で10分間加熱する。その後、自動滴定機(平沼産業(株)製「COM-1700」)を用いて、0.5mol/Lの水酸化カリウムのエタノール溶液により中和滴定することにより測定する。
なお、水酸基価は次式により算出できる。
水酸基価=(A-B)×f×28.05/試料(g)+酸価
式中、Aは空試験に用いた0.5mol/L水酸化カリウムエタノール溶液の量(mL)を示し、Bは滴定に用いた0.5mol/L水酸化カリウムエタノール溶液の量(mL)を示し、fはファクターを示す。
なお、バインダーポリマーを合成溶媒や希釈溶媒と混合した状態で配合する場合は、予め、係る合成溶媒や希釈溶媒の沸点よりも10℃以上高い温度で1~4時間加熱し、上記溶媒を除去してから水酸基価を測定する。 The hydroxyl value of the component (A) can be measured as follows.
First, 1 g of a binder polymer, which is a measurement target of the hydroxyl value, is precisely weighed. 10 mL of a 10% by mass acetic anhydride pyridine solution is added to the binder polymer under the above precision balance, and this is uniformly dissolved and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine are added and heated at 100 ° C. for 10 minutes. Then, it is measured by neutralization titration with an ethanol solution of 0.5 mol / L potassium hydroxide using an automatic titrator (“COM-1700” manufactured by Hiranuma Sangyo Co., Ltd.).
The hydroxyl value can be calculated by the following formula.
Hydroxyl value = (AB) × f × 28.05 / sample (g) + acid value In the formula, A represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test, B represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration, and f represents a factor.
When the binder polymer is blended with a synthetic solvent or a diluting solvent, it is heated in advance at a
撹拌機、還流冷却機、不活性ガス導入口及び温度計を備えたフラスコに、表1に示す(1)を仕込み、窒素ガス雰囲気下で80℃に昇温し、反応温度を80℃±2℃に保ちながら、表1に示す(2)を4時間かけて均一に滴下した。(2)の滴下後、80℃±2℃で6時間撹拌を続け、重量平均分子量が約65,000、酸価が78mgKOH/g、水酸基価が2mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A1)を得た。 [Preparation of binder polymer solution (A1)]
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with (1) shown in Table 1, heated to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature was 80 ° C. ± 2 While maintaining the temperature, (2) shown in Table 1 was added dropwise uniformly over 4 hours. After the dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and a binder polymer solution having a weight average molecular weight of about 65,000, an acid value of 78 mgKOH / g, and a hydroxyl value of 2 mgKOH / g (solid content 45 % By mass) (A1) was obtained.
GPC条件
ポンプ:日立 L-6000型((株)日立製作所製、製品名)
カラム:Gelpack GL-R420、Gelpack GL-R430、Gelpack GL-R440(以上、日立化成工業(株)製、製品名)
溶離液:テトラヒドロフラン
測定温度:40℃
流量:2.05mL/分
検出器:日立 L-3300型RI((株)日立製作所製、製品名) The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
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)
また、酸価は、次のようにして測定した。まず、バインダーポリマーの溶液を、130℃で1時間加熱し、揮発分を除去して、固形分を得た。そして、酸価を測定すべきポリマー1gを精秤した後、このポリマーにアセトンを30g添加し、これを均一に溶解した。次いで、指示薬であるフェノールフタレインをその溶液に適量添加して、0.1NのKOH水溶液を用いて滴定を行った。そして、次式により酸価を算出した。
酸価=0.1×Vf×56.1/(Wp×I)
式中、VfはKOH水溶液の滴定量(mL)を示し、Wpは測定した樹脂溶液の重量(g)を示し、Iは測定した樹脂溶液中の不揮発分の割合(質量%)を示す。 [Measurement method of acid value]
Moreover, 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 = 0.1 × Vf × 56.1 / (Wp × I)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the weight (g) of the measured resin solution, and I represents the ratio (mass%) of the non-volatile content in the measured resin solution.
水酸基価は、次のようにして測定した。まず、バインダーポリマーの溶液を、130℃で1時間加熱し、揮発分を除去して、固形分を得た。そして、水酸基価を測定すべきポリマー1gを精秤した後、精秤した感光性樹脂組成物を三角フラスコに入れ、10質量%の無水酢酸ピリジン溶液を10mL加えてこれを均一に溶解し、100℃で1時間加熱した。加熱後、水10mLとピリジン10mLを加えて100℃で10分間加熱後、自動滴定機(平沼産業(株)製「COM-1700」)を用いて、0.5mol/Lの水酸化カリウムのエタノール溶液により中和滴定を行った。そして、次式により水酸基価を算出した。
水酸基価=(A-B)×f×28.05/試料(g)+酸価
式中、Aは空試験に用いた0.5mol/L水酸化カリウムエタノール溶液の量(mL)を示し、Bは滴定に用いた0.5mol/L水酸化カリウムエタノール溶液の量(mL)を示し、fはファクターを示す。 [Measurement method of hydroxyl value]
The hydroxyl 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 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, 0.5 mol / L of potassium hydroxide ethanol was used using an automatic titrator (“COM-1700” manufactured by Hiranuma Sangyo Co., Ltd.). Neutralization titration was performed with the solution. And the hydroxyl value was computed by following Formula.
Hydroxyl value = (AB) × f × 28.05 / sample (g) + acid value In the formula, A represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test, B represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration, and f represents a factor.
[感光性樹脂組成物を含有する塗布液の作製]
表2に示す材料を、攪拌機を用いて15分間混合し、保護膜を形成するための感光性樹脂組成物を含有する塗布液を作製した。 (Examples 1 to 8, Comparative Examples 1 to 8)
[Preparation of coating solution containing photosensitive resin composition]
The materials shown in Table 2 were mixed for 15 minutes using a stirrer to prepare a coating solution containing a photosensitive resin composition for forming a protective film.
支持フィルムとして厚さ50μmのポリエチレンテレフタレートフィルムを使用し、上記で作製した感光性樹脂組成物を含有する塗布液を支持フィルム上にコンマコーターを用いて均一に塗布し、100℃の熱風対流式乾燥機で3分間乾燥して溶剤を除去し、感光性樹脂組成物からなる感光層(感光性樹脂組成物層)を形成した。得られた感光層の厚さは5μmであった。 [Production of photosensitive element]
A polyethylene terephthalate film having a thickness of 50 μm is used as the support film, and the coating solution containing the photosensitive resin composition prepared above is uniformly applied onto the support film using a comma coater, and is heated at 100 ° C. with hot air convection. The solvent was removed by drying for 3 minutes in a machine to form a photosensitive layer (photosensitive resin composition layer) made of the photosensitive resin composition. The resulting photosensitive layer had a thickness of 5 μm.
得られた感光性エレメントのカバーフィルムであるポリエチレンフィルムをはがしながら、厚さ1mmのガラス基板上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、このときの線圧は9.8×103N/m)の条件でラミネートして、ガラス基板上に、感光層及び支持フィルムが積層された積層体を作製した。 [Measurement of transmittance of protective film]
Laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-3000) so that the photosensitive layer is in contact with the glass substrate having a thickness of 1 mm while peeling the polyethylene film as the cover film of the obtained photosensitive element. Using a roll temperature of 120 ° C., a substrate feed speed of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 10 5 Pa (thickness of 1 mm, length of 10 cm × width of 10 cm, the linear pressure at this time was 9 .8 × 10 3 N / m) to obtain a laminate in which a photosensitive layer and a support film are laminated on a glass substrate.
得られた感光性エレメントのポリエチレンフィルムをはがしながら、スパッタ銅付きポリイミドフィルム(東レフィルム加工(株)製)上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、この時の線圧は9.8×103N/m)の条件でラミネートして、スパッタ銅上に、感光層及び支持フィルムが積層された積層体を作製した。 [Salt spray test of protective film (artificial sweat resistance evaluation test)]
While peeling the polyethylene film of the obtained photosensitive element, a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name HLM-) is applied so that the photosensitive layer is in contact with the polyimide film with sputter copper (manufactured by Toray Film Processing Co., Ltd.) 3000 type), a roll temperature of 120 ° C., a substrate feed speed of 1 m / min, a pressure bonding pressure (cylinder pressure) of 4 × 10 5 Pa (thickness of 1 mm, length of 10 cm × width of 10 cm) was used. The laminate was laminated under the condition of a linear pressure of 9.8 × 10 3 N / m), and a laminate in which a photosensitive layer and a support film were laminated on sputtered copper.
A : 保護膜表面に全く変化なし。
B : 保護膜表面にごくわずかな痕跡が見えるが、銅は変化なし。
C : 保護膜表面に痕跡が見えるが、銅は変化なし。
D : 保護膜表面に痕跡があり、かつ銅が変色する。 Next, referring to the JIS standard (Z 2371), using the salt spray tester (STP-90V2 manufactured by Suga Test Instruments Co., Ltd.), the above-mentioned sample was placed in the test tank, and the salt water having a concentration of 50 g / L. (PH = 6.7) was sprayed for 48 hours at a test bath temperature of 35 ° C. and a spray amount of 1.5 mL / h. After spraying, the salt water was wiped off, the surface state of the sample for evaluation was observed, and evaluation was performed according to the following scores. Tables 4 and 5 show the measurement results.
A: No change on the surface of the protective film.
B: Slight traces are visible on the surface of the protective film, but copper remains unchanged.
C: Traces are visible on the surface of the protective film, but copper is unchanged.
D: There is a trace on the surface of the protective film, and copper is discolored.
得られた感光性エレメントのポリエチレンフィルムをはがしながら、ポリ四フッ化エチレンシート(日東電工株式会社製、製品名:ニトフロンフィルムNo.900U)感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Paの条件でラミネートした。 [Measurement of evolved gas after heating at 140 ° C. for 30 minutes (pyrolysis gas chromatography mass spectrometry)]
Laminator (Hitachi Chemical Industry Co., Ltd.) so that the photosensitive layer is in contact with the polytetrafluoroethylene sheet (manufactured by Nitto Denko Corporation, product name: Nitoflon Film No. 900U) while peeling the polyethylene film of the obtained photosensitive element (Product name: HLM-3000 type) was used for lamination under conditions of a roll temperature of 120 ° C., a substrate feed rate of 1 m / min, and a pressure (cylinder pressure) of 4 × 10 5 Pa.
(A)成分
(A1):モノマー配合比(メタクリル酸/メタクリル酸メチル/アクリル酸エチル=12/58/30(質量比))である共重合体のプロピレングリコールモノメチルエーテル/トルエン溶液、重量平均分子量65,000、酸価78mgKOH/g、水酸基価2mgKOH/g、Tg60℃ The symbols of the components in Table 2 and Table 3 have the following meanings.
(A) Component (A1): Propylene glycol monomethyl ether / toluene solution of copolymer having a monomer blending ratio (methacrylic acid / methyl methacrylate / ethyl acrylate = 12/58/30 (mass ratio)), weight average molecular weight 65,000, acid value 78 mgKOH / g, hydroxyl value 2 mgKOH / g, Tg 60 ° C.
A-TMMT:ペンタエリスリトールテトラアクリレート(新中村化学工業(株)製)
DPHA:ジペンタエリスリトールヘキサアクリレート(日本化薬(株)製)
TMPTA:トリメチロールプロパントリアクリレート(日本化薬(株)製)
UX-3204:ヒドロキシエチルアクリレートとポリエステルジオールとヘキサメチレンジイソシアネートを原料成分に含むウレタンアクリレート(日本化薬(株)製)
PET-30:ペンタエリスリトールトリアクリレート(日本化薬(株)製) (B) Component A-TMMT: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
DPHA: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
TMPTA: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.)
UX-3204: Urethane acrylate containing hydroxyethyl acrylate, polyester diol and hexamethylene diisocyanate as raw material components (manufactured by Nippon Kayaku Co., Ltd.)
PET-30: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd.)
IRGACURE OXE 01:1,2-オクタンジオン,1-[(4-フェニルチオ)-,2-(O-ベンゾイルオキシム)](BASF(株)製)
IRGACURE 184:1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF(株)製)
IRGACURE 651:2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(BASF(株)製)
IRGACURE 369:2-ベンジル-2-ジメチルアミノ-1-(モルフォリノフェニル)-ブタノン-1(BASF(株)製)
IRGACURE 907:2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン(BASF(株)製)
IRGACURE 2959:1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン(BASF(株)製)
DETX:2,4-ジエチルチオキサントン(日本化薬(株)製)
N-1717:1,7-ビス(9-アクリジニル)ヘプタン((株)ADEKA製)
EAB:4,4’-ビス(ジエチルアミノ)ベンゾフェノン(保土ヶ谷化学(株)製) (C) Component IRGACURE OXE 01: 1,2-octanedione, 1-[(4-phenylthio)-, 2- (O-benzoyloxime)] (manufactured by BASF Corporation)
IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Corporation)
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF Corporation)
IRGACURE 369: 2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butanone-1 (manufactured by BASF Corp.)
IRGACURE 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF Corporation)
IRGACURE 2959: 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by BASF Corporation)
DETX: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)
N-1717: 1,7-bis (9-acridinyl) heptane (manufactured by ADEKA Corporation)
EAB: 4,4′-bis (diethylamino) benzophenone (Hodogaya Chemical Co., Ltd.)
HAT:5-アミノ-1H-テトラゾール(東洋紡績(株)製)
AMT:3-アミノ-5-メルカプトトリアゾール(和光純薬(株)製)
ATT:2-アミノ-5-メルカプト-1,3,4-チアジアゾール(和光純薬(株)製)
その他の成分
Antage W-500:2,2’-メチレン-ビス(4-エチル-6-tert-ブチルフェノール)(川口化学(株)製)
PM-21:光重合性不飽和結合を含むリン酸エステル(日本化薬株式会社製)
SH-30:オクタメチルシクロテトラシロキサン(東レ・ダウコーニング(株)製)
メチルエチルケトン:東燃化学(株)製 Component (D) HAT: 5-amino-1H-tetrazole (Toyobo Co., Ltd.)
AMT: 3-amino-5-mercaptotriazole (manufactured by Wako Pure Chemical Industries, Ltd.)
ATT: 2-amino-5-mercapto-1,3,4-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
Other components Antage W-500: 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd.)
PM-21: Phosphate ester containing photopolymerizable unsaturated bond (Nippon Kayaku Co., Ltd.)
SH-30: Octamethylcyclotetrasiloxane (manufactured by Dow Corning Toray)
Methyl ethyl ketone: manufactured by Tonen Chemical Co., Ltd.
Claims (7)
- バインダーポリマーと、光重合性化合物と、光重合開始剤と、を含有する感光性樹脂組成物からなる感光層の所定部分を硬化させて得られるタッチパネル用電極の保護膜であって、
熱分解ガスクロマトグラフ質量分析によりヘプタノニトリル及び安息香酸が検出される、タッチパネル用電極の保護膜。 A protective film for a touch panel electrode obtained by curing a predetermined portion of a photosensitive layer comprising a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator,
The protective film of the electrode for touchscreens in which heptanonitrile and benzoic acid are detected by pyrolysis gas chromatography mass spectrometry. - 前記分析における前記安息香酸の検出ピーク面積が、前記ヘプタノニトリルの検出ピーク面積に対して、1~10%である、請求項1に記載のタッチパネル用電極の保護膜。 2. The protective film for a touch panel electrode according to claim 1, wherein a detection peak area of the benzoic acid in the analysis is 1 to 10% with respect to a detection peak area of the heptanonitrile.
- 400~700nmにおける可視光透過率の最小値が90%以上である、請求項1又は2に記載のタッチパネル用電極の保護膜。 3. The protective film for a touch panel electrode according to claim 1, wherein the minimum value of visible light transmittance at 400 to 700 nm is 90% or more.
- 前記バインダーポリマーは、カルボキシル基を有し、酸価が75mgKOH/g以上である、請求項1~3のいずれか一項に記載のタッチパネル用電極の保護膜。 The touch-electrode protective film according to any one of claims 1 to 3, wherein the binder polymer has a carboxyl group and has an acid value of 75 mgKOH / g or more.
- 前記バインダーポリマーは、水酸基価が50mgKOH/g以下である、請求項1~4のいずれか一項に記載のタッチパネル用電極の保護膜。 The protective film for a touch panel electrode according to any one of claims 1 to 4, wherein the binder polymer has a hydroxyl value of 50 mgKOH / g or less.
- 厚みが10μm以下である、請求項1~5のいずれか一項に記載のタッチパネル用電極の保護膜。 6. The protective film for a touch panel electrode according to claim 1, wherein the thickness is 10 μm or less.
- 請求項1~6のいずれか一項に記載の保護膜を有する、タッチパネル。 A touch panel having the protective film according to any one of claims 1 to 6.
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- 2012-12-04 CN CN201810052144.XA patent/CN108108072A/en active Pending
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- 2012-12-04 KR KR1020147016028A patent/KR101592803B1/en active IP Right Grant
- 2012-12-05 TW TW101145694A patent/TWI512399B/en active
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JP2015129992A (en) * | 2014-01-06 | 2015-07-16 | 大日本印刷株式会社 | Touch panel sensor and method for manufacturing touch panel sensor |
KR20210009714A (en) | 2019-07-17 | 2021-01-27 | 제이에스알 가부시끼가이샤 | Curable resin composition, protective film for organic el device using same and process for forming the protective film |
Also Published As
Publication number | Publication date |
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TW201610026A (en) | 2016-03-16 |
JP2018049616A (en) | 2018-03-29 |
CN104054042B (en) | 2018-02-13 |
TWI621671B (en) | 2018-04-21 |
TW201331709A (en) | 2013-08-01 |
CN104054042A (en) | 2014-09-17 |
KR20140097355A (en) | 2014-08-06 |
JP6540766B2 (en) | 2019-07-10 |
TWI512399B (en) | 2015-12-11 |
KR101592803B1 (en) | 2016-02-18 |
WO2013084284A1 (en) | 2013-06-13 |
CN108108072A (en) | 2018-06-01 |
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