WO2013084886A1 - 樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜 - Google Patents
樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜 Download PDFInfo
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- G—PHYSICS
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- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
Definitions
- the present invention relates to a method for forming a cured resin film pattern, a photosensitive resin composition, a photosensitive element, a touch panel manufacturing method, and a cured resin film.
- 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 inventors have found that when a photosensitive layer made of a photosensitive resin composition is formed on a substrate with a thickness of 10 ⁇ m or less and this photosensitive layer is patterned by exposure and development, the resolution tends to decrease. I found it. Moreover, in the photosensitive resin composition described in the said patent document 5 or 6, although it is possible to form a highly transparent protective film with a thin film, there was room for improvement in forming a pattern. .
- the present invention relates to a method for forming a cured resin film pattern capable of forming a cured resin film pattern with sufficient resolution even if it is a thin film, and a cured resin film having a good pattern shape even if it is a thin film on a substrate. It aims at providing the photosensitive resin composition which can be formed, the photosensitive element, the manufacturing method of a touch panel, and a resin cured film.
- a thickness of 10 ⁇ m or less is obtained by using a photosensitive resin composition containing a specific binder polymer, a photopolymerizable compound and a specific photopolymerization initiator.
- a photosensitive resin composition containing a specific binder polymer, a photopolymerizable compound and a specific photopolymerization initiator.
- the method for forming a cured resin film pattern of the present invention comprises a photosensitive material containing, on a substrate, a binder polymer having a carboxyl group with an acid value of 75 mgKOH / g or more, a photopolymerizable compound, and a photopolymerization initiator.
- a first step comprising a resin composition and providing a photosensitive layer having a thickness of 10 ⁇ m or less; a second step in which a predetermined portion of the photosensitive layer is cured by irradiation with actinic rays; and removing portions other than the predetermined portion of the photosensitive layer; A third step of forming a cured film pattern of a predetermined portion of the photosensitive layer, wherein the photosensitive resin composition includes an oxime ester compound and / or a phosphine oxide compound as the photopolymerization initiator. .
- a cured resin film pattern can be formed on a substrate with sufficient resolution even if it is a thin film having a thickness of 10 ⁇ m or less.
- the present inventors consider the reason why the above-described effect is achieved by the method of the present invention as follows.
- the cause of the decrease in sensitivity is that if the thickness of the photosensitive layer is reduced, it is easily affected by light scattering from the substrate and halation occurs.
- the oxime moiety contained in the oxime ester compound or the phosphine oxide moiety contained in the phosphine oxide compound has a relatively high photolysis efficiency, but has an appropriate threshold value that does not decompose with a slight amount of leaked light.
- the present inventors speculate that the influence of leakage light is suppressed, and as a result, sufficient resolution is obtained.
- the photosensitive resin composition further contains an ultraviolet absorber from the viewpoint of further improving the resolution.
- an ultraviolet absorber By containing an ultraviolet absorber, light leaked in the photosensitive layer can be absorbed.
- the ultraviolet absorber has a maximum absorption wavelength in a wavelength region of 360 nm or less.
- the absorbance at 365 nm of the photosensitive layer is 0.4 or less and the absorbance at 334 nm is 0.4 or more.
- the photosensitive layer has the above light absorption characteristics, it becomes easier to absorb leakage light, and it is possible to suppress decomposition of the oxime ester compound or phosphine oxide compound due to leakage light.
- the photosensitive layer preferably has a minimum visible light transmittance of 85% or more at 400 to 700 nm.
- the transparency of the cured resin film is preferably higher in consideration of the visibility and aesthetics of the touch panel.
- the conventional photosensitive resin composition mainly uses a photoreaction utilizing light in the ultraviolet region to the visible light region, a photoinitiator component whose absorption extends in the visible light region is often used. In many cases, pigments and dyes are necessary, and it is difficult to ensure transparency.
- the minimum value of the visible light transmittance of the photosensitive layer is 85% or more by providing the specific photosensitive layer and performing irradiation with actinic rays. Even in such a case, a sufficient resolution can be obtained.
- the photosensitive layer preferably has a b * in the CIELAB color system of ⁇ 0.2 to 1.0.
- the substrate includes an electrode for a touch panel, and the cured resin film pattern can be formed as a protective film for the electrode.
- a photosensitive element comprising a support film and a photosensitive layer made of the photosensitive resin composition provided on the support film is prepared, and the photosensitive element is prepared.
- the photosensitive layer of the photosensitive element can be transferred onto the substrate to provide a photosensitive layer.
- a protective film having a uniform film thickness can be easily formed by using the photosensitive element.
- the present invention also includes a binder polymer having a carboxyl group having an acid value of 75 mgKOH / g or more, a photopolymerizable compound, and a photopolymerization initiator, and the photopolymerization initiator is an oxime ester compound and / or phosphine oxide.
- a photosensitive resin composition for forming a cured resin film pattern having a thickness of 10 ⁇ m or less containing a compound is provided.
- a protective film having a good pattern shape can be formed on a predetermined touch panel electrode even if it is a thin film.
- the photosensitive resin composition of the present invention preferably further contains an ultraviolet absorber from the viewpoint of further improving the resolution.
- the ultraviolet absorber has a maximum absorption wavelength in a wavelength region of 360 nm or less.
- the absorbance at 365 nm is preferably 0.4 or less, and the absorbance at 334 nm is preferably 0.4 or more.
- the photosensitive resin composition of the present invention preferably has a minimum visible light transmittance of 85% or more at 400 to 700 nm.
- the photosensitive resin composition of the present invention preferably has a b * of ⁇ 0.2 to 1.0 in the CIELAB color system.
- the present invention also provides a photosensitive element comprising a support film and a photosensitive layer comprising the photosensitive resin composition according to the present invention provided on the support film.
- a protective film having a good pattern shape can be formed on a predetermined touch panel electrode even if it is a thin film.
- the thickness of the photosensitive layer can be 10 ⁇ m or less.
- the present invention also comprises a step of forming a cured resin film pattern as a protective film covering a part or all of the electrode on the substrate having a touch panel electrode by the method for forming a cured resin film pattern according to the present invention,
- a method of manufacturing a touch panel comprising:
- the present invention also provides a cured resin film comprising a cured product of the photosensitive resin composition of the present invention.
- the resin cured film pattern formation method which can form a resin cured film pattern with sufficient resolution, Resin which has a favorable pattern shape even if it is a thin film on the electrode for touchscreens
- the photosensitive resin composition which can form a cured film, a photosensitive element, the manufacturing method of a touch panel, and a resin cured film can be provided.
- the method for forming a cured resin film pattern according to the present invention is a protective film for an electronic component that requires protection by a thin film, such as a protective film for a touch panel electrode, in particular, protection of a metal electrode of a capacitive touch panel. It can be suitably used for forming a film.
- (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.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive element according to the present invention.
- the photosensitive element 1 shown in FIG. 1 is opposite to the support film 10, the photosensitive layer 20 made of the photosensitive resin composition according to the present invention provided on the support film 10, and the support film 10 of the photosensitive layer 20. And a protective film 30 provided on the side.
- the photosensitive element of the present embodiment can be suitably used for forming a protective film for a touch panel electrode.
- 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 the present invention constituting the photosensitive layer 20 includes a binder polymer having a carboxyl group with an acid value of 75 mgKOH / g or more (hereinafter also referred to as the component (A)), and a photopolymerizable compound (hereinafter referred to as “component”). (Also referred to as component (B)) and a photopolymerization initiator (hereinafter also referred to as component (C)), and the photopolymerization initiator includes an oxime ester compound and / or a phosphine oxide compound.
- 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) is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and 75 to 120 mgKOH / g in terms of excellent patternability. More preferably.
- 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. %).
- 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 of the present embodiment is such that the component (A) is 35 to 35 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 85 parts by mass, component (B) is preferably 15 to 65 parts by mass, component (A) is preferably 40 to 80 parts by mass, and component (B) is more preferably 20 to 60 parts by mass, More preferably, 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. 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 of this embodiment contains an oxime ester compound and / or a phosphine oxide compound as an essential component as a photopolymerization initiator which is the component (C).
- an oxime ester compound and / or a phosphine oxide compound as an essential component as a photopolymerization initiator which is the component (C).
- the present inventors infer the reason why the above effect is obtained as follows.
- the cause of the decrease in sensitivity is that if the thickness of the photosensitive layer is reduced, it is easily affected by light scattering from the substrate and halation occurs.
- the oxime moiety contained in the oxime ester compound or the phosphine oxide moiety contained in the phosphine oxide compound has a relatively high photolysis efficiency, but has an appropriate threshold value that does not decompose with a slight amount of light leakage.
- the present inventors speculate that the influence of leakage light is suppressed, and as a result, sufficient resolution is obtained.
- Examples of the oxime ester compound include compounds represented by the following general formula (C-1) and general formula (C-2). From the viewpoint of fast curability and transparency, a compound represented by the following general formula (C-1) is preferred.
- 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.
- R 2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms
- R 3 represents an alkyl group having 1 to 12 carbon atoms or a cyclohexane having 3 to 20 carbon atoms.
- R 4 represents an alkyl group having 1 to 12 carbon atoms
- R 5 represents an alkyl group or an aryl group having 1 to 20 carbon atoms.
- p1 represents an integer of 0 to 3. When p1 is 2 or more, a plurality of R 4 may be the same or different. Note that carbazole may have a substituent as long as the effects of the present invention are not impaired.
- R 2 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferably.
- R 3 is preferably an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 4 to 15 carbon atoms, and an alkyl group having 1 to 4 carbon atoms or a carbon number A 4 to 10 cycloalkyl group is more preferable, and an ethyl group is particularly preferable.
- Examples of the compound represented by the general formula (C-1) include (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like.
- Examples of the compound represented by the formula (C-2) include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is available as IRGACURE OXE 01 (trade name, manufactured by BASF Corp.) Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is IRGACURE OXE 02 ( ASF (Ltd.) is commercially available as a trade name). These are used alone or in combination
- Examples of the phosphine oxide compound include compounds represented by the following general formula (C-3) and general formula (C-4). From the viewpoint of fast curability and transparency, a compound represented by the following general formula (C-3) is preferred.
- R 6 , R 7 and R 8 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
- R 9 , R 10 and R 11 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
- R 6 , R 7 or R 8 in the general formula (C-3) is an alkyl group having 1 to 20 carbon atoms
- R 9 , R 10 or R 11 in the general formula (C-4) are In the case of an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear, branched, or cyclic, and the alkyl group preferably has 5 to 10 carbon atoms. .
- R 6 , R 7 or R 8 in the general formula (C-3) is an aryl group
- R 9 , R 10 or R 11 in the general formula (C-4) is an aryl group
- the aryl The group may have a substituent.
- the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
- R 6 , R 7 , and R 8 are preferably aryl groups.
- R 9 , R 10 and R 11 are preferably aryl groups.
- 2,4,6-trimethylbenzoyl-diphenyl- is used because of the transparency of the protective film to be formed and the pattern forming ability when the film thickness is 10 ⁇ m or less.
- Phosphine oxide is preferred.
- 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide is commercially available, for example, as LUCIRIN TPO (trade name, manufactured by BASF Corporation).
- the component (C) can be used in combination with a photoinitiator other than the oxime ester compound and the phosphine oxide compound.
- a photoinitiator other than the oxime ester compound and the phosphine oxide compound examples include benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.
- benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin, Benzoin compounds such as methylbenzoin and ethylbenzoin; benzyl derivatives such as benzyldimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane; N-phenylglycine, N Phenylglycine derivatives; coumarin compounds; oxazole-based compounds.
- the 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 of the present embodiment can further contain an ultraviolet absorber (hereinafter also referred to as component (D)).
- an ultraviolet absorber (hereinafter also referred to as component (D)).
- the ultraviolet absorbent is preferably excellent in the ability to absorb ultraviolet light having a wavelength of 380 nm or less, and has little absorption of visible light having a wavelength of 400 nm or more from the viewpoint of transparency.
- an ultraviolet absorber having a maximum absorption wavelength of 360 nm or less corresponds to this.
- ultraviolet absorber examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, diphenylacrylate compounds, and nickel complex compounds.
- Particularly preferred ultraviolet absorbers are diphenyl acrylate compounds such as diphenyl cyanoacrylates.
- the content of the ultraviolet absorber as the component (D) is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferred is 2 to 10 parts by mass.
- the content of the component (D) is preferably 0.1 parts by mass or more from the viewpoint of excellent resolution, and absorption on the surface of the composition increases upon irradiation with actinic rays, thereby increasing the internal light.
- the amount is preferably 30 parts by mass or less.
- an adhesion imparting agent such as a silane coupling agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, an oxidation agent.
- An inhibitor, a fragrance, a thermal crosslinking agent, a polymerization inhibitor and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). These can be used alone or in combination of two or more.
- the minimum value of visible light transmittance at 400 to 700 nm is preferably 85% or more, more preferably 92% or more, and further preferably 95% or more. preferable.
- 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 light ray in the general visible light wavelength range, is 85% or more, for example, when protecting the transparent electrode in the sensing area of the touch panel (touch sensor) or touch panel (touch).
- the protective film is visible from the edge of the sensing area when the metal layer (for example, a layer in which the copper layer is formed on the ITO electrode) is protected, the image display quality, color tone in the sensing area, A decrease in luminance can be sufficiently suppressed.
- b * in the CIELAB color system is preferably ⁇ 0.2 to 1.0, more preferably 0.0 to 0.7, A more preferred range is 0.1 to 0.4.
- b * may be ⁇ 0.2 or more and 0.8 or less from the viewpoint of image display quality in the sensing area and prevention of deterioration in hue. preferable.
- the measurement of b * in the CIELAB color system 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 preferably has an absorbance at 365 nm of 0.4 or less. Moreover, it is preferable that the light absorbency in 334 nm is 0.4 or more.
- the photosensitive layer has the above light absorption characteristics, it becomes easier to absorb leakage light, and it is possible to suppress decomposition of the oxime ester compound or phosphine oxide compound due to leakage light.
- the absorbance can be measured using a UV spectrophotometer (manufactured by Hitachi, Ltd., spectrophotometer U-3310).
- a photosensitive element in which a photosensitive layer made of a photosensitive resin composition is formed on a support film is placed on the measurement side, and a support film is placed on the reference side. This is done by measuring and reading the values at 334 nm and 365 nm.
- Examples of the method for adjusting the absorbance within the above range include blending an oxime ester compound and / or phosphine oxide compound and an ultraviolet absorber, and controlling the film thickness of the photosensitive layer.
- the photosensitive resin composition of the present 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 of the present invention is preferably used by forming a film on a photosensitive film like a photosensitive element.
- the roll-to-roll process can be easily realized, and the solvent drying process can be shortened. it can.
- the photosensitive layer 20 of the photosensitive element 1 can be formed by preparing a coating solution containing the photosensitive resin composition of the present embodiment, and applying and drying the coating solution on the support film 10.
- the coating 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, 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 85% or more, more preferably 92% or more, and still more preferably 95% or more.
- the photosensitive layer 20 preferably has a b * in the CIELAB color system of ⁇ 0.2 to 1.0, more preferably 0.0 to 0.7, and more preferably 0.1 to 0.00. More preferably, it is 4.
- the absorbance at 365 nm of the photosensitive layer 20 is preferably 0.4 or less. Moreover, it is preferable that the light absorbency in 334 nm is 0.4 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 above-mentioned photosensitive resin composition of the present embodiment and a coating solution containing a solvent are applied onto a substrate having a touch panel electrode, dried, and then a photosensitive layer comprising the photosensitive resin composition. 20 may be provided.
- the photosensitive layer preferably satisfies the above-mentioned conditions of film thickness, visible light transmittance, b * in the CIELAB color system, and absorbance.
- FIG. 2 is a schematic cross-sectional view for explaining an example of a method for forming a cured resin film pattern according to the present invention.
- the method for forming a protective film for a touch panel electrode according to the present embodiment is made of the photosensitive resin composition according to the present embodiment on the base material 100 having the touch panel electrodes 110 and 120, and has a thickness of 10 ⁇ m or less.
- a third step of forming a protective film 22 made of a cured film pattern of a photosensitive resin composition that covers a part or all of the electrode is obtained.
- Examples of the base material 100 used in the present embodiment include substrates such as glass plates, plastic plates, and ceramic plates that are generally used for touch panels (touch sensors).
- 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 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 transferred to the substrate by pressure bonding and laminated (see FIG. 2A).
- Crimping means includes a crimping roll.
- the pressure roll may be provided with a heating means so that it can be heat-pressure bonded.
- the heating temperature for thermocompression bonding is such that the constituent components of the photosensitive layer 20 are sufficient to ensure the adhesion between the photosensitive layer 20 and the substrate 100 and the adhesion between the photosensitive layer 20 and the touch panel electrodes 110 and 120.
- the temperature is preferably 10 to 180 ° C., more preferably 20 to 160 ° C., and still more preferably 30 to 150 ° C. so that it is not easily cured or thermally decomposed.
- the pressure at the time of thermocompression bonding is 50 to 1 ⁇ 10 5 N / m in terms of linear pressure from the viewpoint of suppressing deformation of the substrate 100 while ensuring sufficient adhesion between the photosensitive layer 20 and the substrate 100.
- it is 2.5 ⁇ 10 2 to 5 ⁇ 10 4 N / m, more preferably 5 ⁇ 10 2 to 4 ⁇ 10 4 N / m.
- the preheating temperature at this time is preferably 30 to 180 ° C.
- the photosensitive layer 20 can be formed by coating and drying.
- the photosensitive layer 20 preferably satisfies the above-described conditions of film thickness, visible light transmittance, b * in the CIELAB color system, and absorbance.
- 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 20 has an absorbance at 365 nm of 0.4 or less, an absorbance at 334 nm of 0.4 or more, and an actinic ray light source that oscillates at an ultrahigh pressure mercury lamp, 355 nm, 364 nm, or the like. Combinations such as UV lasers with a
- 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 of the electrode Or the protective film 22 which consists of the cured film pattern of the photosensitive resin composition of this embodiment whose thickness which covers all is 10 micrometers or less is formed (refer (c) of FIG. 2).
- 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 of the present embodiment.
- a surfactant an antifoaming agent, a small amount of an organic solvent for promoting development, and the like can be mixed in the alkaline aqueous solution.
- the base of the alkaline aqueous solution remaining in the photosensitive layer 20 after development and photocuring is used by known methods such as spraying, rocking immersion, brushing, and scraping using an organic acid, an inorganic acid, or an acid aqueous solution thereof.
- Acid treatment neutralization treatment
- the cured 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 of the present embodiment exhibits excellent adhesion to a metal without a heating step after development, but if necessary, instead of irradiation with actinic light after development or an active A heat treatment (80 to 250 ° C.) may be performed in combination with the irradiation of light.
- the photosensitive resin composition and photosensitive element of the present embodiment are suitable for use for forming a cured resin film pattern.
- the photosensitive resin composition and photosensitive element of this embodiment are suitable for use (use as a resin cured film pattern formation material) for forming the resin cured film pattern as a protective film of the electrode for touch panels.
- a protective film can be formed using the coating liquid mixed with the solvent.
- the present invention can provide a cured resin film pattern forming material containing the photosensitive resin composition according to the present invention.
- This cured resin film pattern forming material can contain the photosensitive resin composition of the present embodiment described above, and is preferably a coating solution containing the solvent described above.
- 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.
- the lead-out wiring 105 is connected to the transparent electrode 103 and the transparent electrode 104 by a connection electrode 106 provided on the transparent electrode 103 and the transparent electrode 104.
- a connection terminal 107 for connecting to an external circuit is provided at the end of the lead-out wiring 105 opposite to the connection portion between the transparent electrode 103 and the transparent electrode 104.
- the photosensitive resin composition of the present invention can be suitably used for forming a cured resin film pattern as the protective film 122 of the lead-out wiring 105, the connection electrode 106, and the connection terminal 107.
- 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 cured resin film pattern as the protective film 122.
- the transparent electrode 103 and the lead wiring 105 are electrically connected via the connection electrode 106. As shown in FIG. 5B, the transparent electrode 104 and the lead-out wiring 105 may be directly electrically connected.
- the photosensitive resin composition and photosensitive element of the present invention 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.
- 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 dropping (2), stirring was continued at 80 ° C. ⁇ 2 ° C. for 6 hours to obtain a binder polymer solution (solid content 45 mass%) (A1) having a weight average molecular weight of about 80,000.
- 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.
- Example 1 [Preparation of Coating Solution (V-1) Containing Photosensitive Resin Composition]
- the materials shown in Table 2 were mixed for 15 minutes using a stirrer to prepare a coating solution (V-1) containing a photosensitive resin composition for forming a protective film.
- photosensitive element (E-1) A polyethylene terephthalate film having a thickness of 50 ⁇ m was used as the support film, and the coating liquid (V-1) containing the photosensitive resin composition prepared above was uniformly applied onto the support film using a comma coater, and 100 ° C. The solvent was removed by drying with a hot air convection dryer for 3 minutes to form a photosensitive layer (photosensitive resin composition layer) made of the photosensitive resin composition. The resulting photosensitive layer had a thickness of 2.5 ⁇ 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.
- the photosensitive layer of the obtained laminate is exposed at an exposure amount of 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 cured film pattern of a photosensitive layer having a thickness of 2.5 ⁇ 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 High-Technologies Corporation.
- the transmittance of the obtained cured film was 97% at a wavelength of 700 nm, 96% at a wavelength of 550 nm, and 94% at a wavelength of 400 nm.
- the minimum value of the transmittance at 400 to 700 nm was 94%, and good transmittance was obtained. It was secured.
- the obtained photosensitive layer was subjected to an exposure amount of 5 ⁇ 10 2 J / m 2 from the upper side of the photosensitive layer (i-line (wavelength 365 nm) 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 b * measurement sample having a cured film pattern of a photosensitive layer having a thickness of 2.5 ⁇ m was obtained.
- CM-5 spectrocolorimeter
- the b * of the cured film was 0.45, and it was confirmed that the cured film had a good b * .
- the obtained absorbance value was 0.44 at 334 nm and 0.14 at 365 nm.
- Irradiation with actinic rays was carried out by placing on an exposure machine (manufactured by Oak Co., Ltd.) EXM-1201 Mylar PET having a high-pressure mercury lamp lamp and irradiating a predetermined amount of actinic rays through the filter. After standing for 10 minutes at room temperature after irradiation with actinic rays, the polyethylene terephthalate was removed, and the photosensitive resin composition in a portion not irradiated with actinic rays with a 30% 1% aqueous sodium carbonate solution was spray-developed for 60 seconds. After spray development, ultraviolet irradiation of 1 J / cm 2 was performed using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd.
- the sensitivity in the evaluation was the exposure amount necessary for obtaining 6/21 steps with a 41-step tablet manufactured by Hitachi Chemical Co., Ltd.
- a PET photomask having a wiring pattern with a line width / space width of 6/6 to 47/47 (unit: ⁇ m) is closely attached, and the pattern at the exposure amount obtained 6/21 steps is observed with an optical microscope.
- the resolution ( ⁇ m) was determined from the line width ( ⁇ m) remaining as line and space.
- Examples 2 to 5 Comparative Examples 1 to 6
- a photosensitive element was prepared in the same manner as in Example 1 except that the coating solution containing the photosensitive resin composition shown in Tables 2 and 3 was used, and transmittance measurement, b * , absorbance, and photosensitive properties were evaluated. did.
- the numerical value in Table 2 and Table 3 has shown the mass part.
- IRGACURE OXE 01 1,2-octanedione, 1-[(4-phenylthio)-, 2- (O-benzoyloxime)] (manufactured by BASF Corporation)
- IRGACURE OXE 02 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF Corp.)
- LUCIRIN TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF Corporation)
- Other photopolymerization initiator 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
- Examples 6 to 10 and Comparative Examples 5 to 12 Further, in the case where the film thicknesses of the photosensitive layers in Examples 1 to 5 and Comparative Examples 1 to 6 were set to 5 ⁇ m (Examples 6 to 10 and Comparative Examples 5 to 12), evaluation was performed in the same manner as described above. However, the necessary exposure amount in the above [photosensitive characteristics of the photosensitive layer] was the exposure amount for obtaining 10/41 steps with a 41-step tablet manufactured by Hitachi Chemical Co., Ltd. The results are shown in Table 5 and Table 7 below.
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Abstract
Description
すなわち、まず、酸価の測定対象であるバインダーポリマー1gを精秤する。上記精秤したバインダーポリマーにアセトンを30g添加し、これを均一に溶解する。次いで、指示薬であるフェノールフタレインをその溶液に適量添加して、0.1NのKOH水溶液を用いて滴定を行う。そして、次式により酸価を算出する。
酸価=0.1×Vf×56.1/(Wp×I)
式中、VfはKOH水溶液の滴定量(mL)を示し、Wpは測定したバインダーポリマー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。
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80,000のバインダーポリマーの溶液(固形分45質量%)(A1)を得た。
GPC条件
ポンプ:日立 L-6000型((株)日立製作所製、製品名)
カラム:Gelpack GL-R420、Gelpack GL-R430、Gelpack GL-R440(以上、日立化成工業(株)製、製品名)
溶離液:テトラヒドロフラン
測定温度:40℃
流量:2.05mL/分
検出器:日立 L-3300型RI((株)日立製作所製、製品名)
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。
[感光性樹脂組成物を含有する塗布液(V-1)の作製]
表2に示す材料を、攪拌機を用いて15分間混合し、保護膜を形成するための感光性樹脂組成物を含有する塗布液(V-1)を作製した。
支持フィルムとして厚さ50μmのポリエチレンテレフタレートフィルムを使用し、上記で作製した感光性樹脂組成物を含有する塗布液(V-1)を支持フィルム上にコンマコーターを用いて均一に塗布し、100℃の熱風対流式乾燥機で3分間乾燥して溶剤を除去し、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2.5μmであった。
得られた感光性エレメント(E-1)のカバーフィルムであるポリエチレンフィルムをはがしながら、厚さ1mmのガラス基板上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、このときの線圧は9.8×103N/m)の条件でラミネートして、ガラス基板上に、感光層及び支持フィルムが積層された積層体を作製した。
得られた感光性エレメント(E-1)のポリエチレンフィルムをはがしながら、厚さ0.7mmのガラス基板上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、この時の線圧は9.8×103N/m)の条件でラミネートして、ガラス基板上に、感光層及び支持体フィルムが積層された基板を作製した。
UV分光光度計((株)日立ハイテクノロジーズ製、分光光度計U-3310)を用いて測定した。測定は、測定側に感光性エレメントを置き、リファレンス側に支持フィルムを置き、吸光度モードにより300~700nmまでを連続測定し、334nm、365nmにおける値を読みとることにより行った。
PETフィルム[厚さ125μm、東洋紡績製、商品名A4300]に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、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。活性光線の照射は、高圧水銀灯ランプを有する露光機(オーク(株)製)EXM―1201のマイラーPET上に設置し、そのフィルターを介して所定量の活性光線を照射することにより行った。活性光線の照射後から室温で10分間放置した後、ポリエチレンテレフタレートを除去し、30℃の1%炭酸ナトリウム水溶液で活性光線が照射されていない部分の感光性樹脂組成物を60秒間スプレー現像した。スプレー現像後、(株)オーク製作所製紫外線照射装置を使用して1J/cm2の紫外線照射を行った。評価における感度は、日立化成工業(株)製、41段ステップタブレットにて6/21段を得るための必要量の露光量とした。また、ライン幅/スペース幅が6/6~47/47(単位:μm)の配線パターンを有するPET製のフォトマスクを密着させ、6/21段得られる露光量におけるパターンを光学顕微鏡により観察し、ライン・アンド・スペースとして残ったライン幅(μm)から解像度(μm)を求めた。
表2及び表3に示す感光性樹脂組成物を含有する塗布液を用いた以外は、実施例1と同様に感光性エレメントを作製し、透過率の測定、b*、吸光度、感光特性について評価した。なお、表2及び表3中の数値は質量部を示している。
(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
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)
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 OXE 02:エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)(BASF(株)製)
LUCIRIN TPO:2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド(BASF(株)製)
他の光重合開始剤
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-(モルホリノフェニル)-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-モルホリノプロパン-1-オン(BASF(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)
SB501:エチル-2-シアノ-3,3-ジフェニルアクリレート(シプロ化成(株)製)
SB502:2’-エチルヘキシル-2-シアノ-3,3-ジフェニルアクリレート(シプロ化成(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)
SH30: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
また、上記実施例1~5及び比較例1~6の感光層の膜厚を5μmとした場合(実施例6~10、及び比較例5~12)について上記と同様に評価した。但し、上記[感光層の感光特性]における必要量の露光量は、日立化成工業(株)製、41段ステップタブレットにて10/41段を得るための露光量とした。結果を下記表5及び表7に示す。
Claims (18)
- 基材上に、酸価が75mgKOH/g以上のカルボキシル基を有する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り、厚みが10μm以下である感光層を設ける第1工程と、
前記感光層の所定部分を活性光線の照射により硬化させる第2工程と、
前記感光層の前記所定部分以外を除去し、前記感光層の前記所定部分の硬化膜パターンを形成する第3工程と、
を備え、
前記感光性樹脂組成物が前記光重合開始剤としてオキシムエステル化合物及び/又はホスフィンオキサイド化合物を含む、樹脂硬化膜パターンの形成方法。 - 前記感光性樹脂組成物が紫外線吸収剤を更に含む、請求項1に記載の樹脂硬化膜パターンの形成方法。
- 前記紫外線吸収剤が360nm以下の波長域に最大吸収波長を有するものである、請求項2に記載の樹脂硬化膜パターンの形成方法。
- 前記感光層の365nmにおける吸光度が、0.4以下であり、334nmにおける吸光度が、0.4以上である、請求項1~3のいずれか一項に記載の樹脂硬化膜パターンの形成方法。
- 前記感光層は400~700nmにおける可視光透過率の最小値が85%以上である、請求項1~4のいずれか一項に記載の樹脂硬化膜パターンの形成方法。
- 前記感光層はCIELAB表色系でのb*が-0.2~1.0である、請求項1~5のいずれか一項に記載の樹脂硬化膜パターンの形成方法。
- 前記基材がタッチパネル用電極を備え、当該電極の保護膜として前記樹脂硬化膜パターンを形成する、請求項1~6のいずれか一項に記載の樹脂硬化膜パターンの形成方法。
- 支持フィルムと、該支持フィルム上に設けられた前記感光性樹脂組成物からなる感光層と、を備える感光性エレメントを用意し、当該感光性エレメントの感光層を前記基材上に転写して前記感光層を設ける、請求項1~7のいずれか一項に記載の樹脂硬化膜パターンの形成方法。
- 酸価が75mgKOH/g以上のカルボキシル基を有する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、を含有し、
前記光重合開始剤がオキシムエステル化合物及び/又はホスフィンオキサイド化合物を含み、
10μm以下の厚みの樹脂硬化膜パターンを形成するために用いられる、感光性樹脂組成物。 - 紫外線吸収剤を更に含む、請求項9に記載の感光性樹脂組成物。
- 前記紫外線吸収剤が360nm以下の波長域に最大吸収波長を有するものである、請求項10に記載の感光性樹脂組成物。
- 365nmにおける吸光度が、0.4以下であり、334nmにおける吸光度が、0.4以上である、請求項9~11のいずれか一項に記載の感光性樹脂組成物。
- 400~700nmにおける可視光透過率の最小値が85%以上である、請求項9~12のいずれか一項に記載の感光性樹脂組成物。
- CIELAB表色系でのb*が-0.2~1.0である、請求項9~13のいずれか一項に記載の感光性樹脂組成物。
- 支持フィルムと、該支持フィルム上に設けられた請求項9~14のいずれか一項に記載の感光性樹脂組成物からなる感光層と、を備える、感光性エレメント。
- 前記感光層の厚みが10μm以下である、請求項15に記載の感光性エレメント。
- タッチパネル用電極を有する基材上に、請求項1~7のいずれか一項に記載の方法により前記電極の一部又は全部を被覆する保護膜として樹脂硬化膜パターンを形成する工程、を備える、タッチパネルの製造方法。
- 請求項9~14のいずれか一項に記載の感光性樹脂組成物の硬化物からなる樹脂硬化膜。
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JP2013516811A JP5304968B1 (ja) | 2011-12-05 | 2012-12-04 | 樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜 |
CN201280059872.4A CN103988154B (zh) | 2011-12-05 | 2012-12-04 | 树脂固化膜图案的形成方法、感光性树脂组合物、感光性元件、触摸面板的制造方法及树脂固化膜 |
KR1020187018655A KR102174783B1 (ko) | 2011-12-05 | 2012-12-04 | 수지 경화막 패턴의 형성 방법, 감광성 수지 조성물, 감광성 엘리먼트, 터치패널의 제조 방법 및 수지 경화막 |
US14/362,726 US9348223B2 (en) | 2011-12-05 | 2012-12-04 | Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film |
KR1020147016026A KR20140101783A (ko) | 2011-12-05 | 2012-12-04 | 수지 경화막 패턴의 형성 방법, 감광성 수지 조성물, 감광성 엘리먼트, 터치패널의 제조 방법 및 수지 경화막 |
US15/062,996 US10386719B2 (en) | 2011-12-05 | 2016-03-07 | Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film |
US15/459,959 US9964849B2 (en) | 2011-12-05 | 2017-03-15 | Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film |
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KR20220143718A (ko) | 2020-03-19 | 2022-10-25 | 후지필름 가부시키가이샤 | 감광성 재료, 전사 필름, 회로 배선의 제조 방법, 터치 패널의 제조 방법, 패턴 형성 방법 |
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JP7036094B2 (ja) | 2022-03-15 |
CN103988154A (zh) | 2014-08-13 |
US10663861B2 (en) | 2020-05-26 |
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WO2013084282A1 (ja) | 2013-06-13 |
TWI509355B (zh) | 2015-11-21 |
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US20140363767A1 (en) | 2014-12-11 |
CN103999023A (zh) | 2014-08-20 |
US20180321587A1 (en) | 2018-11-08 |
KR102174783B1 (ko) | 2020-11-05 |
US20160223906A1 (en) | 2016-08-04 |
US10386719B2 (en) | 2019-08-20 |
US20170184965A1 (en) | 2017-06-29 |
CN107256105A (zh) | 2017-10-17 |
TW201329631A (zh) | 2013-07-16 |
JPWO2013084886A1 (ja) | 2015-04-27 |
KR20140101783A (ko) | 2014-08-20 |
KR20170104644A (ko) | 2017-09-15 |
JP2020073957A (ja) | 2020-05-14 |
JP2017223994A (ja) | 2017-12-21 |
JP5304968B1 (ja) | 2013-10-02 |
JP6589953B2 (ja) | 2019-10-16 |
TW201602728A (zh) | 2016-01-16 |
CN103988154B (zh) | 2017-07-11 |
TWI550349B (zh) | 2016-09-21 |
TW201327041A (zh) | 2013-07-01 |
CN107272349A (zh) | 2017-10-20 |
US9964849B2 (en) | 2018-05-08 |
KR20180077336A (ko) | 2018-07-06 |
US9348223B2 (en) | 2016-05-24 |
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