JP2017111245A - Method of manufacturing touch panel substrate with cured film, cured film forming agent, photosensitive element, and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured film forming agent capable of forming, on a touch panel substrate, a cured film having sufficient adhesion to the substrate while having a sufficient optical adjustment function, and to provide a photosensitive element.SOLUTION: The photosensitive element includes a support film and a photosensitive layer provided on the support film and containing (A) a binder polymer, (B) a photopolymerizable compound having a (meth)acryloyl group, (C) a photopolymerization initiator, (F1) a compound having a triazine ring, and (F2) a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a substrate for a touch panel with a cured film, a cured film forming agent and a photosensitive element used therefor, and a touch panel.

  Liquid crystal display elements and touch panels (touch sensors) 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 electrode material. As the transparent electrode material, ITO (Indium-Tin-Oxide), indium oxide, and tin oxide are mainly used because of high visible light transmittance.

  Various types of touch panels have already been put to practical use. Since the projected capacitive touch panel can detect multiple fingertips, it has good operability such that a complicated instruction can be given. For this reason, in devices having a small display device such as a mobile phone or a portable music player, the use as an input device on a display surface is progressing.

  In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes form a two-layer structure pattern in order to express two-dimensional coordinates based on the X and Y axes. Forming. In recent years, the use of conductive fibers typified by Ag nanowires and carbon nanotubes has been studied as these electrodes, but ITO is still the mainstream.

  By the way, since the frame region of the touch panel is a region where the touch position cannot be detected, reducing the area of the frame region is an important element for improving the product value. In the frame area, 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.

  When the touch panel is brought into contact with the fingertip, corrosive components such as moisture and salt may enter the inside from the sensing area. When a corrosive component enters the inside of the touch panel, the metal wiring corrodes, and there is a risk of an increase in electrical resistance between the electrode and the driving circuit, or disconnection.

  In order to prevent corrosion of metal wiring, a projected capacitive touch panel in which an insulating layer is formed on metal is disclosed (for example, Patent Document 1). In this touch panel, 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. However, this method has problems such as requiring high temperature treatment, limiting the base material, and increasing the production cost.

  Accordingly, the present inventors provide a method for protecting a metal wiring on a transparent substrate by providing a photosensitive layer formed from a specific photosensitive resin composition on a transparent substrate, and exposing and developing the photosensitive layer. (For example, Patent Document 2).

  By the way, in the projected capacitive touch panel as described above, a plurality of X electrodes made of a transparent electrode material on a substrate and a plurality of Y electrodes orthogonal to the X electrodes are two-layer transparent electrodes. Although a pattern is formed, the color difference increases due to optical reflection between the part where the transparent electrode pattern is formed and the part where the transparent electrode pattern is not formed, and the transparent conductive pattern appears on the screen when modularized. There is a problem of so-called “bone appearance phenomenon”. Moreover, between a base material and a transparent electrode, or between a transparent electrode pattern and the visibility improvement film (OCA: Optical Clear Adhesive) which adhere | attaches the cover glass and transparent electrode pattern which are used when modularizing, a reflection There is also a problem that the light intensity increases and the transmittance of the screen decreases.

  In order to prevent the bone appearance phenomenon, a transfer film is disclosed in which an optical adjustment layer (IM layer) is formed on the transparent electrode pattern to prevent the bone appearance phenomenon (for example, Patent Document 3).

JP 2011-28594 A International Publication No. 2013/084873 International Publication No. 2014/084112

  However, when optical adjustment is performed with metal oxide particles as in the method described in Patent Document 3, the adhesion to the substrate is lowered, and it is difficult to sufficiently protect the metal wiring. Moreover, since the transfer film described in Patent Document 3 has a structure of three or more layers, there is a problem that it is not suitable for thinning the touch panel.

  The present invention provides a cured film forming agent and a photosensitive element capable of forming a cured film having sufficient optical adjustment function and sufficient adhesion with the substrate on the touch panel substrate, and It aims at providing the manufacturing method of the base material for touchscreens with a cured film provided with the cured film with sufficient adhesiveness with a base material, having sufficient optical adjustment function, and a touch panel.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in a photosensitive layer containing a binder polymer, a specific photopolymerizable compound, and a photopolymerization initiator, a compound having a specific skeleton is combined. It is found that a cured film having sufficient optical adjustment function and sufficient adhesion to the substrate can be formed by providing an optical adjustment portion, and the present invention is completed based on this finding. It came to.

  That is, the present invention comprises a support film, (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, and (C) a photopolymerization initiator provided on the support film. And (F1) a photosensitive element comprising a photosensitive layer containing a compound having a triazine ring and (F2) a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton.

  A part of the photosensitive layer is (B) a photopolymerizable compound having a (meth) acryloyl group, (F1) a compound having a triazine ring, and (F2) a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton. It is preferable that it consists of a part containing. Such a portion can function as an optical adjustment partial layer of the thin film. According to such a photosensitive layer, for example, when it is transferred onto a substrate for a touch panel having a transparent conductive pattern and cured, a decrease in the transmittance of the screen due to an increase in color difference is sufficiently suppressed, and bone appearance It is possible to form a cured film that can achieve a high level of both improved visibility of the touch screen by preventing the phenomenon and excellent adhesion to the transparent electrode and the metal wiring.

  The photosensitive layer preferably contains (B) a polyfunctional vinyl monomer having a polymerizable ethylenically unsaturated group or a compound having a polyester structure as a photopolymerizable compound having a (meth) acryloyl group. .

  The photosensitive layer preferably further contains at least one compound selected from the group consisting of (D) a triazole compound, a thiadiazole compound, and a tetrazole compound from the viewpoint of further improving the rust prevention property of the cured film.

  The photosensitive layer preferably contains an oxime ester compound or a phosphine oxide compound as a photopolymerization initiator (C) in that a cured film pattern can be formed with sufficient resolution even if it is a thin film.

  The photosensitive layer preferably has a thickness of 15 μm or less.

  The present invention also includes (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, (C) a photopolymerization initiator, (F1) a compound having a triazine ring, and (F2) A cured film forming agent used for forming a cured film of a substrate for a touch panel, comprising a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton.

  The cured film forming agent of the present invention includes (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, and (C) a first composition containing a photopolymerization initiator, and (B And a second composition containing a photopolymerizable compound having a (meth) acryloyl group, (F1) a compound having a triazine ring, and (F2) a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton, It may be a two-agent type composed of According to such a cured film forming agent, a photosensitive layer including a first layer formed by the first composition and a second layer formed by the second composition can be formed. Can be cured to form a cured film comprising a protective partial layer derived from the first layer and an optical adjustment partial layer of a thin film derived from the second layer.

  The cured film forming agent of the present invention further contains (D) at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound from the viewpoint of further improving the rust prevention property of the cured film. Can do.

  When the cured film forming agent of the present invention is the two-component type, the first composition further contains (D) at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound. be able to.

  The cured film forming agent of the present invention contains (B) a polyfunctional vinyl monomer having a polymerizable ethylenically unsaturated group or a compound having a polyester structure as a photopolymerizable compound having a (meth) acryloyl group. It is preferable to do.

  The cured film forming agent of the present invention preferably contains an oxime ester compound or a phosphine oxide compound as the (C) photopolymerization initiator in that a cured film pattern can be formed with sufficient resolution even if it is a thin film.

  The present invention also includes (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, (C) a photopolymerization initiator, and (F1) a triazine ring on a base material for a touch panel. And a photosensitive layer containing a compound having (F2) a fluorene skeleton or a compound having an isocyanuric acid skeleton, and a predetermined portion of the photosensitive layer after curing a predetermined portion of the photosensitive layer by irradiation with actinic rays. The manufacturing method of the base material for touchscreens with a cured film which forms the cured film which consists of the hardened | cured material of the photosensitive layer which removes other than that and coat | covers a part or all of a base material is provided.

  In the method for producing a substrate for a touch panel with a cured film of the present invention, a part of the photosensitive layer is (B) a photopolymerizable compound having a (meth) acryloyl group, (F1) a compound having a triazine ring, F2) It is preferable to provide the photosensitive layer so as to be a part containing a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton. In this case, an optical adjustment partial layer of a thin film can be formed from such a portion, and a decrease in the transmittance of the screen due to a large color difference is sufficiently suppressed, while improving the visibility of the touch screen by preventing the bone appearance phenomenon, A base material for a touch panel can be produced that includes a cured film that can achieve a high level of both excellent adhesion to a transparent electrode and metal wiring.

  The part is preferably formed as a layer having a thickness of 50 to 400 nm adjacent to the substrate.

  The photosensitive layer preferably contains (B) a polyfunctional vinyl monomer having a polymerizable ethylenically unsaturated group or a compound having a polyester structure as a photopolymerizable compound having a (meth) acryloyl group. .

  The photosensitive layer preferably further contains at least one compound selected from the group consisting of (D) a triazole compound, a thiadiazole compound, and a tetrazole compound from the viewpoint of further improving the rust prevention property of the cured film.

  The photosensitive layer preferably contains an oxime ester compound or a phosphine oxide compound as a photopolymerization initiator (C) in that a cured film pattern can be formed with sufficient resolution even if it is a thin film.

  This invention also provides a touch panel provided with the base material for touchscreens with a cured film obtained by the manufacturing method of the base material for touchscreens with a cured film which concerns on the said invention.

  According to the present invention, a cured film forming agent and a photosensitive element capable of forming a cured film having sufficient optical adjustment function and sufficient adhesion to the substrate on the touch panel substrate, And the manufacturing method of the base material for touchscreens with a cured film provided with the cured film with sufficient adhesiveness with a base material, having a sufficient optical adjustment function, and a touch panel can be provided.

  According to the cured film forming agent and the photosensitive element of the present invention, the decrease in the transmittance of the screen is small, the improvement of the visibility of the touch screen by preventing the bone appearance phenomenon of the transparent electrode pattern, and the protection of the sensor metal wiring It is possible to form a cured film that is compatible and has excellent adhesion to the transparent electrode and the sensor metal wiring.

It is a schematic cross section which shows the photosensitive element which concerns on one Embodiment of this invention. It is a schematic cross section which shows the base material for touchscreens with a cured film which concerns on one Embodiment of this invention. It is a model top view which shows the touchscreen which concerns on one Embodiment of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acrylate” means acrylate or a corresponding methacrylate. “(Poly) oxyethylene chain” means an oxyethylene group or a polyoxyethylene group. “A or B” only needs to include one of A and B, or may include both.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical value range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.

  In the present specification, the content of each component in the composition or agent is such that when there are a plurality of substances corresponding to each component in the composition or agent, the plural present in the composition or agent unless otherwise specified. Means the total amount of substances. In addition, the exemplary materials may be used alone or in combination of two or more unless otherwise specified.

  The cured film of the base material for touchscreens which concerns on this invention can be provided in the sensing area | region which has an electrode, the frame area | region which has metal wiring, or another area | region. The cured film of the touch panel base material may be provided only in one of the regions, or may be provided in a plurality of regions. Furthermore, the position and range where the cured film is provided, such as being provided on a part of the electrode formed in the sensing region, can be appropriately selected according to the purpose of use.

  FIG. 1 is a schematic cross-sectional view showing a photosensitive element according to an embodiment of the present invention. A photosensitive element 1 shown in FIG. 1 includes a support film 10, a photosensitive layer 20 provided on the support film, and a protective film 50 provided on the opposite side of the photosensitive layer 20 from the support film 10. The protective film 50 is not necessarily required, but is preferably provided as in the present embodiment.

  The photosensitive layer 20 includes (A) a binder polymer (hereinafter also referred to as the (A) component), (B) a photopolymerizable compound having a (meth) acryloyl group (hereinafter also referred to as the (B) component), and (C ) A photopolymerization initiator (hereinafter also referred to as (C) component), (F1) a compound having a triazine ring (hereinafter also referred to as (F1) component), and (F2) a compound having a fluorene skeleton or an isocyanuric acid skeleton. Having a compound (hereinafter also referred to as a component (F2)). The photosensitive layer 20 further contains at least one compound selected from the group consisting of (D) a triazole compound, a thiadiazole compound, and a tetrazole compound (hereinafter, also referred to as “component (D)”) as necessary. Can do. Furthermore, the photosensitive layer 20 can further contain (E) a phosphoric ester containing a photopolymerizable unsaturated bond (hereinafter also referred to as “component (E)”).

  According to the photosensitive element of the present embodiment, by transferring and curing on the base material for the touch panel, the decrease in the transmittance of the screen is small, and the visibility of the touch screen is improved by preventing the bone-visible phenomenon of the transparent electrode pattern. In addition, it is possible to form a cured film that achieves both the protection of the sensor metal wiring and the excellent adhesion to the transparent electrode and the sensor metal wiring. Moreover, according to the photosensitive element of this embodiment, the cured film which has said characteristic in a desired part can be formed by transferring on the base material for touchscreens, and performing exposure and image development.

  The photosensitive layer 20 of this embodiment contains, in order from the support film 10 side, (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, and (C) a photopolymerization initiator. A portion to be the protective partial layer 30, (B) a photopolymerizable compound having a (meth) acryloyl group, (F1) a compound having a triazine ring, and (F2) a compound having a fluorene skeleton or an isocyanuric acid skeleton And a portion to be an optical adjustment partial layer 40 containing a compound.

  As the support film 10, a polymer film can be used. Examples of the polymer film include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyether sulfone, and cycloolefin polymer.

  The thickness of the support film 10 is preferably 5 to 100 μm, preferably 10 to 70 μm, from the viewpoint of ensuring coverage and suppressing a reduction in resolution when irradiating actinic rays through the support film 10. More preferably, it is 15-40 micrometers, It is more preferable, It is especially preferable that it is 15-35 micrometers.

  As the component (A) contained in the protective partial layer 30, it is preferable to use a polymer having no hydroxyl group in the basic skeleton from the viewpoint of further improving the rust prevention property. Moreover, it is more preferable to use the polymer which has a carboxyl group from a viewpoint which enables patterning by alkali image development.

  Suitable (A) component includes a copolymer containing a structural unit derived from (meth) acrylic acid and a structural unit derived from (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, (meth) acrylic acid Examples thereof include hydroxyl ethyl ester.

  The said copolymer may further contain the structural unit derived from the (meth) acrylic acid and the other monomer which can be copolymerized with the (meth) acrylic-acid alkylester. Specific examples of the other monomer include (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, and styrene.

The weight average molecular weight of the component (A) is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and 30,000 to 150,000 from the viewpoint of resolution. More preferably, it is particularly preferably 30,000 to 100,000, and very preferably 40,000 to 100,000. In addition, the weight average molecular weight (Mw) of (A) component is derived | led-out by measuring on the following conditions by the gel permeation chromatography method (GPC), and converting using the calibration curve of a standard polystyrene.
<GPC conditions>
Pump: L-6000 (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: L-3300 (RI detector, manufactured by Hitachi, Ltd., product name)

The acid value of the component (A) is preferably 75 mgKOH / g or more from the viewpoint of easily forming a cured film having a desired shape by alkali development. Further, from the viewpoint of achieving both controllability of the cured film shape and rust prevention of the cured film, it is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and 75 to 120 mgKOH. More preferably, it is / g. In addition, an acid value is calculated | required in the following procedures.
After precisely weighing 1 g of the solid binder polymer, 30 g of acetone is added to the polymer, and this is uniformly dissolved. 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 / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I represents the proportion (mass%) of the non-volatile content in the measured resin solution.

The hydroxyl value of the component (A) is preferably 20 mgKOH / g or less, more preferably 10 mgKOH / g or less, from the viewpoint of further improving rust prevention. In addition, a hydroxyl value is calculated | required in the following procedures.
After precisely weighing 1 g of a solid binder polymer, the polymer is placed in an Erlenmeyer flask, 10 mL of 10 mass% acetic anhydride pyridine solution is added and dissolved uniformly, and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine were added and heated at 100 ° C. for 10 minutes. Then, using an automatic titrator (product name: COM-1700, manufactured by Hiranuma Sangyo Co., Ltd.), 0.5 mol / L of potassium hydroxide Perform neutralization titration with ethanol solution. Then, the hydroxyl value is calculated by the following formula.
Hydroxyl value = (A−B) × 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.

  Component (B) includes a monofunctional vinyl monomer having one (meth) acryloyl group, a bifunctional vinyl monomer having two (meth) acryloyl groups, or a polyfunctional compound having at least three polymerizable (meth) acryloyl groups. Functional vinyl monomers can be used.

  Examples of the monofunctional vinyl monomer include (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, and the like. As (meth) acrylic acid alkyl ester, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid hydroxyl group An ethyl ester etc. are mentioned.

  Examples of the bifunctional vinyl monomer include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, and 2,2-bis (4- (meth) acryloxypolyethoxypolypropoxy. Phenyl) propane, bisphenol A diglycidyl ether di (meth) acrylate, and the like.

  As said polyfunctional vinyl monomer, a conventionally well-known thing can be especially used without a restriction | limiting. (Meth) acrylate compounds having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri (meth) acrylate, from the viewpoint of corrosion prevention and developability of metal wiring and transparent electrodes; tetramethylolmethane tri (meth) acrylate, tetramethylol (Meth) acrylate compounds having a skeleton derived from tetramethylolmethane such as methanetetra (meth) acrylate; (meth) acrylates having a skeleton derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate Compound; (Meth) acrylate compound having a skeleton derived from dipentaerythritol such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate It is preferable to use or has a skeleton derived from diglycerol (meth) acrylate compound; which ditrimethylol having propane tetra (meth) ditrimethylolpropane derived skeleton such as acrylates (meth) acrylate compound.

  In this embodiment, as the component (B), the protective partial layer is a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, or a skeleton derived from trimethylolpropane. It is preferable to include a (meth) acrylate compound having a skeleton derived from (meth) acrylate having a skeleton derived from ditrimethylolpropane, and having a skeleton derived from a (meth) acrylate compound having a skeleton derived from dipentaerythritol, having a skeleton derived from trimethylolpropane ( It is more preferable to include a (meth) acrylate compound having a skeleton derived from a (meth) acrylate compound or ditrimethylolpropane, and further including a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane. Masui.

  Here, the “(meth) acrylate compound having a skeleton derived from” will be described by taking a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane as an example. (Meth) acrylate having a skeleton derived from ditrimethylolpropane means an esterified product of ditrimethylolpropane and (meth) acrylic acid, and the esterified product includes a compound modified with an alkyleneoxy group. The The esterified product preferably has a maximum number of 4 ester bonds in one molecule, but a compound having 1 to 3 ester bonds may be mixed.

  When the polyfunctional vinyl monomer is used in combination with the monofunctional vinyl monomer and / or the bifunctional vinyl monomer, the ratio of these monomers is not particularly limited, but from the viewpoint of preventing photocurability and electrode corrosion. The ratio of the polyfunctional vinyl monomer is preferably 30 parts by mass or more and more preferably 50 parts by mass or more with respect to 100 parts by mass of the total amount of the photopolymerizable compound contained in the protective partial layer. Preferably, it is 75 parts by mass or more.

  The content of the component (A) and the component (B) in the protective partial layer is based on 100 parts by mass of the total amount of the component (A) and the component (B) in that the pattern forming property and the transparency of the cured film are maintained. The component (A) is preferably 35 parts by mass or more, more preferably 40 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more. The content of the component (A) is preferably 35 to 85 parts by mass, more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). The amount is more preferably 50 to 70 parts by mass, and particularly preferably 55 to 65 parts by mass.

  As the component (C), any conventionally known photopolymerization initiator can be used without particular limitation as long as it is a highly transparent photopolymerization initiator. It is preferable to use an oxime ester compound in that a cured resin film pattern can be formed with sufficient resolution even on a thin film having a thickness of 10 μm or less on a substrate.

  The oxime ester compound is preferably a compound represented by the following formula (1), a compound represented by the following formula (2), or a compound represented by the following formula (3).

In formula (1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and R ¹³ represents —H, shown _{-OH, -COOH, -O (CH 2} ) OH, -O (CH 2) 2 OH, -COO (CH 2) OH or -COO _{(CH 2)} a 2 OH.

R ¹¹ and R ¹² are preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group, or a tolyl group, and an alkyl group having 1 to 4 carbon atoms, or 4 to 4 carbon atoms. 6 is more preferably a cycloalkyl group, a phenyl group or a tolyl group, and further preferably a methyl group, a cyclopentyl group, a phenyl group or a tolyl group. R ¹³ is preferably —H, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH, or —COO (CH ₂ ) ₂ OH, —H, — O (CH ₂ ) ₂ OH or —COO (CH ₂ ) ₂ OH is more preferable.

In formula (2), R ¹⁴ and R ¹⁵ each independently represents an alkyl group having 1 to 6 carbon atoms, R ¹⁶ represents NO ₂ or ArCO (wherein Ar represents an aryl group), R ¹⁷ and R ¹⁸ each independently represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group.

R ¹⁴ and R ¹⁵ are preferably propyl groups. As said Ar, a tolyl group is preferable. R ¹⁷ and R ¹⁸ are preferably a methyl group, a phenyl group, or a tolyl group.

In formula (3), R ¹⁹ represents an alkyl group having 1 to 6 carbon atoms, R ²⁰ is an organic group having an acetal bond, and R ²¹ and R ²² are each independently an alkyl group having 1 to 12 carbon atoms. A group, a phenyl group or a tolyl group;

R ¹⁹ is preferably an ethyl group. R ²⁰ is preferably a substituent corresponding to R ²⁰ in the compound represented by formula (3-1) described later. R ²¹ and R ²² are preferably a methyl group, a phenyl group, or a tolyl group, and more preferably a methyl group.

  Examples of the compound represented by the formula (1) include a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2). The compound represented by the following formula (1-1) is available as IRGACURE OXE-01 (product name) manufactured by BASF Corporation.

  Examples of the compound represented by the above formula (2) include a compound represented by the following formula (2-1). The compound represented by the following formula (2-1) is available as DFI-091 (manufactured by Daito Chemix Co., Ltd., product name).

  Examples of the compound represented by the above formula (3) include a compound represented by the following formula (3-1). The compound represented by the following formula (3-1) is available as Adekaoptomer N-1919 (manufactured by ADEKA, product name).

  Examples of the oxime ester compound other than the above include a compound represented by the following formula (4) and a compound represented by the following formula (5).

  The content of the component (C) in the protective partial layer is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) in terms of excellent photosensitivity and resolution. Is preferably 1 to 5 parts by mass, more preferably 1 to 3 parts by mass, and particularly preferably 1 to 2 parts by mass.

  The protective partial layer according to the present embodiment further contains (D) at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound from the viewpoint of further improving the rust prevention property of the cured film. It is preferable. The triazole compound preferably has a mercapto group or an amino group. The thiadiazole compound preferably has a mercapto group. The tetrazole compound preferably has a mercapto group or an amino group.

  Examples of the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name: 3MT). Examples of the thiadiazole compound having a mercapto group include 2-amino-5-mercapto-1,3,4-thiadiazole (product name: ATT, manufactured by Wako Pure Chemical Industries, Ltd.).

  Examples of the triazole compound having an amino group include benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole and the like substituted with an amino group, Examples thereof include compounds in which an amino group is substituted for a triazole compound containing a mercapto group such as 3-mercaptotriazole and 5-mercaptotriazole.

  Examples of tetrazole compounds having an amino group include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole and the like. Is mentioned. These tetrazole compounds may be water-soluble salts thereof. Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.

  When the protective partial layer contains the component (D), the content thereof is preferably 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). 1-2.0 mass parts is more preferable, 0.2-1.0 mass part is further more preferable, and 0.3-0.8 mass part is especially preferable.

  The protective partial layer according to this embodiment preferably contains (E) a phosphate ester containing a photopolymerizable unsaturated bond from the viewpoint of adhesion to the ITO electrode and prevention of development residue.

  As a phosphoric acid ester containing a photopolymerizable unsaturated bond, Unichemical Co., Ltd. has a high level of both adhesion to an ITO electrode and developability while ensuring sufficient anticorrosion of the cured film to be formed. The Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP, etc.) manufactured by Nippon Kayaku Co., Ltd. (PM21, PM-2, etc.) is preferable.

  The optical adjustment partial layer 40 includes (B) a photopolymerizable compound having a (meth) acryloyl group, (F1) a compound having a triazine ring, (F2) a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton, Containing. This makes it possible to improve the refractive index at 633 nm.

  The component (B) contained in the optical adjustment partial layer 40 is preferably a dimer of a compound having a (meth) acryloyl group or a compound having a (meth) acryloyl group and a polyester structure.

  The compound having a triazine ring is preferably a hyperbranched polymer containing a triazine ring, and is commercially available, for example, as HYPERTECH UR-101 (product name, manufactured by Nissan Chemical Industries, Ltd.).

  As the compound having a fluorene skeleton, a compound having a 9,9-bis [4-2 (meth) acryloyloxyethoxy) phenyl] fluorene skeleton is preferable. The compound may be modified with (poly) oxyethylene or (poly) oxypropylene. These are commercially available, for example, as EA-200 (manufactured by Osaka Gas Chemical Co., Ltd., product name).

  As the compound having an isocyanuric acid skeleton, triallyl isocyanurate is preferable.

  The optical adjustment partial layer preferably has a refractive index at 633 nm of 1.50 to 1.90, more preferably 1.53 to 1.85, and further preferably 1.55 to 1.75. preferable. When the refractive index at 633 nm of the optical adjustment partial layer is 1.50 to 1.90, the photosensitive layer 20 is transferred onto the touch panel base material 60 provided with a transparent electrode pattern 60a such as ITO, and is shown in FIG. In the case of the substrate 100 for a touch panel with a cured film shown, the transparent electrode pattern 60a and various members provided on the photosensitive layer 20 (for example, an OCA that bonds a cover glass and a transparent electrode pattern used when modularized) ) And an intermediate value of the refractive index, and it is possible to reduce the color difference due to optical reflection between the portion where the transparent electrode pattern such as ITO is formed and the portion where the transparent electrode pattern is not formed. . Moreover, it becomes possible to reduce the reflected light intensity of the whole screen, and to prevent the transmittance | permeability fall on a screen.

  The refractive index of the optical adjustment partial layer is measured as follows. A coating solution for forming the optically adjusted partial layer is uniformly applied on a 0.7 mm thick glass substrate with a spin coater, and dried for 3 minutes with a hot air retention dryer at 100 ° C. to remove the solvent, An optical adjustment partial layer is formed and used as a sample for refractive index measurement. Next, the refractive index at 633 nm of the obtained refractive index measurement sample is measured by ETA-TCM (product name, manufactured by AudioDev GmbH).

  In the form of the photosensitive element, since it is difficult to measure the refractive index of only the optical adjustment partial layer, the refractive index of the outermost surface layer on the support film side of the optical adjustment partial layer is preferably in the above range.

  In the present embodiment, the refractive index of the transparent electrode such as ITO is preferably 1.80 to 2.10, more preferably 1.85 to 2.05, and 1.90 to 2.00. More preferably it is. Further, the refractive index of a member such as OCA is preferably 1.45 to 1.55, more preferably 1.47 to 1.53, and further preferably 1.48 to 1.51. .

  The thickness of the optical adjustment partial layer is preferably 50 to 400 nm, more preferably 60 to 350 nm, still more preferably 70 to 300 nm, and most preferably 80 to 250 nm. When the film thickness is 50 to 400 nm, the reflected light intensity of the entire screen can be further reduced.

  The content of the component (F1) and the component (F2) in the optical adjustment partial layer is preferably in the following range in order to adjust the refractive index at 633 nm of the optical adjustment partial layer to a range of 1.5 to 1.9.

  Content of the compound which has a triazine ring in an optical adjustment partial layer can be 10-100 mass parts with respect to a total of 100 mass parts of all the components which comprise an optical adjustment partial layer, and is 10-90 mass parts. It is preferably 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, and particularly preferably 30 to 70 parts by mass.

  When the optical adjustment partial layer contains a compound having a fluorene skeleton, the content thereof can be 10 to 100 parts by mass with respect to a total of 100 parts by mass of all components constituting the optical adjustment partial layer. The mass is preferably 20 parts by mass, more preferably 20 to 90 parts by mass, still more preferably 30 to 80 parts by mass, and particularly preferably 30 to 60 parts by mass.

  When the optical adjustment partial layer contains a compound having an isocyanuric acid skeleton, the content is preferably 10 to 90 parts by mass with respect to 100 parts by mass in total of all components constituting the optical adjustment partial layer. More preferably, it is 80 mass parts, and it is still more preferable that it is 30-70 mass parts.

  When the optical adjustment partial layer includes a dimer of a compound having a (meth) acryloyl group or a compound having a (meth) acryloyl group and a polyester structure, these contents are all components constituting the optical adjustment partial layer. It is preferable that it is 1-20 mass parts with respect to a total of 100 mass parts, It is more preferable that it is 3-15 mass parts, It is further more preferable that it is 5-15 mass parts.

  The thickness of the photosensitive layer is preferably 5 to 15 μm, more preferably 5 to 12 μm, and still more preferably 5 to 10 μm, from the viewpoint of improving the followability during lamination.

  The photosensitive layer preferably has a minimum visible light transmittance at 400 to 700 nm after curing of 90.00% or more, more preferably 90.50% or more, and 90.70% or more. Is more preferable. If the transmittance in a general visible light wavelength region of 400 to 700 nm is 90.00% or more, the image display quality in the sensing region when protecting the transparent electrode in the sensing region of the touch panel (touch sensor), It can suppress sufficiently that a hue and a brightness | luminance fall.

The visible light transmittance and haze of the photosensitive layer after curing can be measured by the following procedure. While peeling off the protective film of the photosensitive element, using a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type) so that the optical adjustment partial layer is in contact with a glass substrate having a thickness of 0.7 mm, 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, and the linear pressure at this time was 9. (8 × 10 ³ N / m) is laminated to produce a laminate in which a photosensitive layer having an optical adjustment partial layer and a protective partial layer and a support film are laminated on a glass substrate. Next, using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.), an exposure amount of 5 × 10 ² J / m ² (measured value at a wavelength of 365 nm) from above the protective partial layer side is used for the obtained laminate. Then, after irradiating with ultraviolet rays, the support film was removed, and left in a box-type dryer (Mitsubishi Electric Co., Ltd., model number: NV50-CA) heated to 140 ° C. for 30 minutes. obtain. Subsequently, the visible light transmittance and haze are measured in the measurement wavelength region of 400 to 700 nm using the obtained transmittance measurement sample using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NDH 7000). .

  The viscosity of the photosensitive layer is determined from the viewpoint of preventing the components constituting the photosensitive layer from oozing out from the end face of the photosensitive element when the photosensitive element is stored in a roll shape and when the photosensitive element is cut. From the viewpoint of preventing debris from adhering to the substrate, it is preferably 15 to 100 mPa · s, more preferably 20 to 90 mPa · s at 30 ° C., and preferably 25 to 80 mPa · s. Further preferred.

  In this embodiment, it is preferable that the photosensitive layer does not substantially contain metal oxide particles.

  Examples of the protective film 50 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, a laminated film of polyethylene-vinyl acetate copolymer and polyethylene, and the like.

  The thickness of the protective film 50 is preferably 5 to 100 μm, but is preferably 70 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less from the viewpoint of storing in a roll. 40 μm or less is particularly preferable.

  The photosensitive element which concerns on this embodiment can be manufactured with the following method, for example. The protective partial layer forming coating solution containing the components constituting the protective partial layer is applied onto the support film 10 and dried to form the protective partial layer. On the other hand, the optical adjustment partial layer is formed by applying an optical adjustment partial layer forming coating liquid containing the components constituting the optical adjustment partial layer described above onto the protective film 50 and drying. And these are bonded together so that a protection partial layer and an optical adjustment partial layer may touch.

  The coating liquid can be obtained by dissolving each component constituting the protective partial layer and the optical adjustment partial layer according to the present embodiment described above with a solvent.

  There is no restriction | limiting in particular as a solvent used for a coating liquid, A well-known thing can be used. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform, methylene chloride and the like.

  Application methods include doctor blade coating method, Mayer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, and die coating method. Etc.

  Although there is no restriction | limiting in particular in drying conditions, It is preferable that drying temperature shall be 60-130 degreeC, and it is preferable that drying time shall be 0.5-30 minutes.

  In this embodiment, (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, (C) a photopolymerization initiator, (F1) a compound having a triazine ring, and (F2 ) A cured film forming agent used for forming a cured film of a substrate for a touch panel, comprising a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton.

  In the present embodiment, the cured film forming agent includes (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, and (C) a first composition containing a photopolymerization initiator, (B) A second composition comprising a photopolymerizable compound having a (meth) acryloyl group, (F1) a compound having a triazine ring, and (F2) a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton. And may be a two-agent type composed of According to such a cured film forming agent, a photosensitive layer including a first layer formed by the first composition and a second layer formed by the second composition can be formed. Can be cured to form a cured film comprising a protective partial layer derived from the first layer and an optical adjustment partial layer of a thin film derived from the second layer.

  FIG. 2 is a schematic cross-sectional view showing a base material for a touch panel with a cured film according to an embodiment of the present invention. 2 includes a touch panel substrate 60 having a transparent conductive pattern 60a and a cured film 20 provided on the transparent conductive pattern 60a of the touch panel substrate 60. The cured film 20 is formed of a photosensitive layer according to this embodiment having a protective partial layer 30 and an optical adjustment partial layer 40. One Embodiment of the manufacturing method of this base material for touchscreens with a cured film is described.

  The manufacturing method of the base material for touchscreens with a cured film which concerns on this embodiment is the photopolymerizable compound which has (A) binder polymer, (B) (meth) acryloyl group, and (C) on the base material for touchscreens. A photosensitive layer containing a photopolymerization initiator, (F1) a compound having a triazine ring, and (F2) a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton is provided, and a predetermined portion of the photosensitive layer is actinic rays. After curing by irradiating, a portion other than a predetermined portion of the photosensitive layer is removed, and a cured film made of a cured product of the photosensitive layer covering a part or all of the substrate is formed.

  In this embodiment, a part of the photosensitive layer is (B) a photopolymerizable compound having a (meth) acryloyl group, (F1) a compound having a triazine ring, and (F2) a compound having a fluorene skeleton or isocyanuric. The photosensitive layer is preferably provided so as to be a portion containing a compound having an acid skeleton. In this case, the other part of the photosensitive layer can be a part that does not contain the component (F1) and the component (F2).

  As a base material for touch panels, base materials, such as a glass plate, a plastic plate, a ceramic plate, used for a touch panel (touch sensor), for example are mentioned. On this base material, an electrode to be a target for forming a cured film is provided. Examples of the electrode include electrodes such as ITO, Cu, Al, and Mo. In addition, an insulating layer may be provided on the base material between the base material and the electrode. In the touch panel substrate 60 shown in FIG. 2, a transparent conductive pattern 60a made of ITO or the like is provided.

  Said photosensitive layer can be provided using the photosensitive element of this embodiment mentioned above. For example, the protective film 50 is removed from the photosensitive element 1 and laminated (transferred) by pressure bonding so that the optical adjustment partial layer 40 is in contact with the surface of the touch panel substrate 60. Examples of the pressing means include a pressing roll. The pressure roll may be provided with a heating means so that it can be heat-pressure bonded.

  The heating temperature in the case of thermocompression bonding is from the viewpoint of making the adhesiveness between the optical adjustment partial layer 40 and the touch panel substrate 60 and the components of the protective partial layer and the optical adjustment partial layer difficult to be thermally cured or pyrolyzed. 10 to 160 ° C, more preferably 20 to 150 ° C, and further preferably 30 to 150 ° C.

In addition, the pressure at the time of thermocompression bonding is 50 to 1 in terms of linear pressure from the viewpoint of suppressing deformation of the touch panel substrate 60 while sufficiently securing the adhesion between the optical adjustment partial layer 40 and the touch panel substrate 60. X10 ⁵ N / m is preferable, 2.5 × 10 ^{2 to} 5 × 10 ⁴ N / m is more preferable, and 5 × 10 ² to 4 × 10 ⁴ N / m is further preferable. preferable.

  If the photosensitive element is thermocompression-bonded as described above, a pre-heat treatment of the base material is not necessarily required. However, from the viewpoint of further improving the adhesion between the optical adjustment partial layer 40 and the touch panel base material 60, The material 60 may be preheated. It is preferable that the processing temperature at this time shall be 30-150 degreeC.

  Next, a predetermined portion of the photosensitive layer after transfer is irradiated with actinic rays in a pattern through a photomask. When irradiating actinic light, if the support film 10 on the photosensitive layer 20 is transparent, it can be irradiated with actinic light as it is. A known active light source can be used as the active light source.

The irradiation amount of actinic rays is 1 * 10 < ² > -1 * 10 < ⁴ > J / m < ² >, and it can also be accompanied with heating in the case of irradiation. If the irradiation amount of this actinic ray is 1 × 10 ² J / m ² or more, photocuring can proceed sufficiently, and if it is 1 × 10 ⁴ J / m ² or less, the photosensitive layer is discolored. There is a tendency to be able to suppress this.

  Subsequently, the unexposed portion of the photosensitive layer after irradiation with actinic rays is removed with a developer to form a cured film (protective pattern) that covers part or all of the transparent electrode. When the support film 10 is laminated on the photosensitive layer after irradiation with actinic rays, the developing step is performed after removing the support film 10.

  The development step can be performed by a known method such as spraying, showering, rocking dipping, brushing, scraping, or the like using a known developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Of these, spray development is preferably performed using an alkaline aqueous solution from the viewpoint of environment and safety. The development temperature and time can be adjusted within a conventionally known range.

  In this embodiment, although the cured film (protective pattern) is formed on the base material for touch panels with the photosensitive element of this embodiment, the photosensitive layer 20 is formed using the cured film forming agent described above, and By performing the exposure and development, a cured film (protective pattern) can be formed on the touch panel substrate.

  FIG. 3 is a schematic top view showing a touch panel according to an embodiment of the present invention. The touch panel shown in FIG. 3 is a capacitive touch panel, and has a touch screen 102 for detecting touch position coordinates on one side of the transparent base material 101, and for detecting a change in capacitance in this region. A transparent electrode 103 and a transparent electrode 104 are provided on the substrate 101.

  The transparent electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.

  On the transparent substrate 101, 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.

  In the touch panel according to the embodiment, using the photosensitive element or the cured film forming agent of the present embodiment, a cured film (protective pattern) 123 is formed across the portion where the transparent electrode pattern is formed and the portion where the transparent electrode pattern is not formed. Is formed. According to this cured film, the transparent electrode 103, the transparent electrode 104, the lead-out wiring 105, the connection electrode 106, and the connection terminal 107 are protected, and the bone-visible phenomenon of the sensing region (touch screen 102) formed from the transparent electrode pattern. The prevention function can be performed at the same time.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Preparation of Binder Polymer Solution A1]
Into a flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer, the component (1) shown in Table 1 was charged, heated to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature was set to 80 ° C. While maintaining the temperature at ± 2 ° C., the component (2) shown in Table 1 was uniformly added dropwise over 4 hours. After dropwise addition of the component (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and a binder polymer solution A1 having a weight average molecular weight of 65,000, an acid value of 78 mgKOH / g, and a hydroxyl value of 2 mgKOH / g (solid) 45% by mass).

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 conditions>
Pump: L-6000 (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: L-3300 (RI detector, manufactured by Hitachi, Ltd., product name)

  The acid value and hydroxyl value of the binder polymer were measured by the following methods.

[Measurement method of acid value]
The binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components, thereby obtaining a solid content. And after precisely weighing 1 g of the polymer of the solid content, 30 g of acetone was added to the polymer, and this was uniformly dissolved. 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 / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I represents the proportion (mass%) of the non-volatile content in the measured resin solution.

[Measurement method of hydroxyl value]
The binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components, thereby obtaining a solid content. Then, after accurately weighing 1 g of the polymer having the above solid content, the polymer was put into an Erlenmeyer flask, 10 mL of 10% by mass acetic anhydride pyridine solution was added and dissolved uniformly, and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine were added and heated at 100 ° C. for 10 minutes. Then, using an automatic titrator (product name: COM-1700, manufactured by Hiranuma Sangyo Co., Ltd.), 0.5 mol / L of potassium hydroxide Neutralization titration was performed with an ethanol solution. And the hydroxyl value was computed by following Formula.
Hydroxyl value = (A−B) × 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.

(Examples 1 to 11)
[Preparation of coating solution for forming a protective partial layer]
Each component and solvent of the compounding quantity (mass%) shown in Table 2 were mixed for 15 minutes using the stirrer, and the coating liquid A and the coating liquid B for forming a protective partial layer were produced.

The symbol of the component in Table 2 has the following meaning.
(A) Component A1: A solution A1 of the binder polymer obtained as described above, and having a monomer blending ratio (methacrylic acid / methyl methacrylate / ethyl acrylate = 12/58/30 (mass ratio)) Propylene glycol monomethyl ether / toluene solution, weight average molecular weight 65,000, acid value 78 mgKOH / g, hydroxyl value 2 mgKOH / g, T _g 60 ° C.

(B) Component T-1420 (T): Ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., product name)

Component (C) IRGACURE OXE 01: 1,2-octanedione, 1-[(4-phenylthio) phenyl-, 2- (O-benzoyloxime)] (manufactured by BASF Corporation, product name)

(D) Component HAT: 5-amino-1H-tetrazole (manufactured by Toyobo Co., Ltd., product name)

(E) Component PM-21: Phosphate ester containing a photopolymerizable unsaturated bond (product name, manufactured by Nippon Kayaku Co., Ltd.)

(Others) Component W-500: 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd., product name)
SH-30: Octamethylcyclotetrasiloxane (made by Toray Dow Corning Co., Ltd., product name)
Methyl ethyl ketone: manufactured by Tonen Chemical Corporation

[Preparation of coating liquid for forming optical adjustment partial layer]
Each component of the blending amount (% by mass) shown in “Optical Adjustment Partial Layer” in Table 3 was mixed for 15 minutes using a stirrer to prepare a coating solution for forming the optical adjustment partial layer.

The symbols of the components in Table 3 have the following meanings.
(F1) Component UR101: a polymer having a triazine skeleton (manufactured by Nissan Chemical Industries, Ltd., product name: HYPERTECH (trade name))

(F2) Component EA-200: polyoxyethylene-modified 9,9-bis (4-hydroxyphenyl) full orange acrylate (manufactured by Osaka Gas Chemical Co., Ltd., product name)
EA-F5503: Polyoxyethylene-modified 9,9-bis (4-hydroxyphenyl) fluorene acrylate / benzyl acrylate / 9,9-bis (4-hydroxyphenyl) fluorene skeleton compound mixture (manufactured by Osaka Gas Chemical Co., Ltd., product name)
EA-HC931: Mixture containing polyoxyethylene-modified 9,9-bis (4-hydroxyphenyl) fluorene acrylate (product name, manufactured by Osaka Gas Chemical Co., Ltd.)

(B) Component T-1420 (T): Ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., product name)
PE9079: Bis-A-epichlorohydrin polyester acrylate (BASF Corporation, product name)

(Others) Component L-7001: Octamethylcyclotetrasiloxane (product name, manufactured by Toray Dow Corning Co., Ltd.)

[Measurement of refractive index]
The optical adjustment partial layer forming coating solution prepared above is uniformly coated on a 0.7 mm thick glass substrate with a spin coater, and dried for 3 minutes with a 100 ° C. hot-air drier to remove the solvent. An optical adjustment partial layer was formed.

  Next, the refractive index at 633 nm of the obtained sample for refractive index measurement was measured with ETA-TCM (manufactured by AudioDev GmbH, product name).

[Production of photosensitive element]
Using a 30 μm-thick polypropylene film (manufactured by Oji F-Tex Co., Ltd., product name: E-201F) as the protective film, the coating liquid for forming an optical adjustment partial layer prepared above was used on the protective film using a die coater. It apply | coated uniformly, it dried for 3 minutes with a 100 degreeC hot-air residence type dryer, the solvent was removed, and the optical adjustment partial layer was formed.

  Using a 16 μm thick polyethylene terephthalate film (product name: FB40, manufactured by Toray Industries, Inc.) as the support film, uniformly apply the coating solution for forming the protective partial layer prepared above onto the support film using a comma coater. The solvent was removed by drying for 3 minutes with a hot air convection dryer at 100 ° C. to form a protective partial layer having a thickness of 8 μm.

  Next, the obtained protective film having the optical adjustment partial layer and the support film having the protective partial layer are bonded to each other at 23 ° C. using a laminator (manufactured by Hitachi Chemical Co., Ltd., product name HLM-3000 type). A sex element was produced.

[Measurement of film thickness of optical adjustment partial layer and protective partial layer]
The film thickness of the optical adjustment partial layer was measured by measuring the optical adjustment partial layer formed on the 30 μm polypropylene produced above with F20 (product name, manufactured by FILMETRICS Co., Ltd.). Moreover, the film thickness of the protective partial layer is measured by measuring the protective partial layer formed on the 16 μm polyethylene terephthalate film prepared above with a digital thickness gauge (manufactured by Nikon Corporation, product name: DIGIMICROSTAND MS-5C). did. In the table, the total film thickness of the optical adjustment partial layer and the protective partial layer is shown as the film thickness of the photosensitive layer.

[Measurement of transmittance and haze of cured film]
Laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type) so that the optical adjustment partial layer is in contact with the 0.7 mm thick glass substrate while peeling off the protective film of the photosensitive element produced above. , Roll temperature of 120 ° C., substrate feed rate of 1 m / min, pressure bonding pressure (cylinder pressure) of 4 × 105 Pa (thickness of 1 mm, length of 10 cm × width of 10 cm, the linear pressure at this time is (9.8 × 10 3 N / m) was laminated to prepare a laminate in which an optical adjustment partial layer, a protective partial layer, and a support film were laminated on a glass substrate.

Next, using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.), an exposure amount of 5 × 10 ² J / m ² (measured value at a wavelength of 365 nm) from above the protective partial layer side is used for the obtained laminate. Then, after irradiating with ultraviolet rays, the support film was removed, and left in a box-type dryer (Mitsubishi Electric Co., Ltd., model number: NV50-CA) heated to 140 ° C. for 30 minutes. Obtained.

  Next, using the haze meter (product name: NDH 7000, manufactured by Nippon Denshoku Industries Co., Ltd.), the visible light transmittance and haze were measured in the measurement wavelength range of 400 to 700 nm.

[Salt spray test of cured film]
Laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-) so that the optical adjustment partial layer is in contact with a polyimide film with sputter copper (manufactured by Toray Film Processing Co., Ltd.) while peeling off the protective film of the obtained photosensitive element. 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 with the optical adjustment partial layer, the protective partial layer, and the support film on the sputtered copper by laminating under the condition that the linear pressure was 9.8 × 10 ³ N / m).

Next, using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., product name: EXM1201), an exposure amount of 5 × 10 ² J / m ² (at a wavelength of 365 nm) from above the protective partial layer side was used for the obtained laminate. (Measurement value), after irradiating with ultraviolet rays, the support film is removed, and further irradiated with ultraviolet rays with an exposure amount of 1 × 10 ⁴ J / m ² (measurement value at a wavelength of 365 nm) from above the protective partial layer side to 140 ° C. It left still for 30 minutes in the heated box-type dryer (Mitsubishi Electric Corporation make, model number: NV50-CA). This obtained the sample for salt spray test evaluation.

Next, referring to the JIS standard (Z 2371), using the salt spray tester (manufactured by Suga Test Instruments Co., Ltd., product name: STP-90V2), the aforementioned sample was placed in the test tank, and the concentration was 50 g / L salt water (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.
A: No change on the surface.
B: A very slight trace can be seen on the surface, but copper does not change.
C: Traces are visible on the surface, but copper is unchanged.
D: There are traces on the surface, and copper discolors.

[Measurement of hue (reflection R)]
While peeling off the protective film of the obtained photosensitive element, a laminator (manufactured by Hitachi Chemical Co., Ltd., product name HLM) is placed on the transparent conductive film (manufactured by Toyobo Co., Ltd., product name: 300R) so that the optical adjustment partial layer is in contact therewith. -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, At this time, the linear pressure was laminated under the condition of 9.8 × 10 ³ N / m) to prepare a laminate in which the optical adjustment partial layer, the protective partial layer, and the support film were laminated on the glass substrate.

Next, using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., product name: EXM1201), an exposure amount of 5 × 10 ² J / m ² (measurement at a wavelength of 365 nm) was applied to the obtained laminate from the upper side of the protective partial layer. Value), the support film was removed, and a hue (reflection R) measurement sample having a cured film was obtained.

  Subsequently, Y value (this is set as reflectance R) was measured for the obtained sample for measuring hue (reflection R) using a spectrocolorimeter (manufactured by Konica Minolta, product name CM-5).

[Cross-cut adhesion test of cured film for touch panel electrode protection]
While peeling off the protective film of the obtained photosensitive element, the optical adjustment partial layer is in contact with the polyimide film with sputtered copper (manufactured by Toray Film Processing Co., Ltd.) and the PET film with sputtered ITO (manufactured by Toyobo). Using a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name HLM-3000 type), roll temperature 120 ° C., substrate feed rate 1 m / min, pressure bonding pressure (cylinder pressure) 4 × 10 ⁵ Pa (thickness 1 mm, Since a substrate of 10 cm in length × 10 cm in width was used, the linear pressure at this time was laminated under the condition of 9.8 × 10 ³ N / m), and the optical adjustment partial layer, protection on the sputtered copper and sputtered ITO A substrate on which the partial layer and the support film were laminated was produced.

Next, the obtained laminate was subjected to (i-line (wavelength) with an exposure amount of 5 × 10 ² J / m ² from above the protective partial layer side using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.). Measured value at 365 nm), after irradiating with ultraviolet rays, the support film is removed, and further, the ultraviolet rays are irradiated at an exposure amount of 1 × 10 ⁴ J / m ² from above the protective partial layer side (measured value at i-line (wavelength 365 nm)). Irradiated to obtain a sample for cross-cut adhesion test.

Next, a cross cut test of 100 squares was performed with reference to JIS standard (K5400). Using a cutter knife on the test surface, make a 1 x 1 mm square cut on the grid, and firmly press Mending Tape # 810 (manufactured by 3M Co., Ltd.) on the grid, so that the end of the tape is approximately 0 °. After slowly peeling off at an angle, the cross-cut state was observed, and cross-cut adhesion was evaluated according to the following score.
A: Almost 100% of the entire area is in close contact.
○: 95% or more of the total area remains adhered.
○ to Δ: 85% or more and less than 95% of the total area remains adhered.
Δ: 65% or more and less than 85% of the total area remains adhered.
Δ to X: 35% or more and less than 65% of the total area remains adhered.
X: 0% or more and less than 35% of the total area remains adhered.

  The results are summarized in Table 5.

(Comparative Examples 1-8)
The components (mass%) shown in “Photosensitive layer” in Table 4 were mixed for 15 minutes using a stirrer to prepare a coating solution for forming a photosensitive layer.

The symbols of the components in Table 4 have the same meanings as above and the following meanings.
(D) Component 3MT: 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name)

Metal oxide OZ-S40K-AC: Zirconia dispersion (manufactured by Nissan Chemical Industries, Ltd., product name: Nanouse OZ-S40K-AC)
OZ-S30K: Zirconia dispersion (manufactured by Nissan Chemical Industries, Ltd., product name: Nanouse OZ-S30K)

[Measurement of refractive index]
The coating solution prepared above is evenly coated on a 0.7 mm thick glass substrate with a spin coater, dried for 3 minutes with a 100 ° C. hot air drier, and the solvent is removed to form a photosensitive layer. did.

  Next, the refractive index at 633 nm of the obtained sample for refractive index measurement was measured with ETA-TCM (manufactured by AudioDev GmbH, product name).

[Production of photosensitive element]
Using a polyethylene terephthalate film (product name: FB40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm as the support film, the coating solution prepared above was uniformly applied on the support film using a comma coater, and hot air at 100 ° C. The solvent was removed by drying with a convection dryer for 3 minutes to form a photosensitive layer having a thickness of 8 μm.

  Next, a 30 μm-thick polypropylene film (manufactured by Oji F-Tex Corporation, product name: E-201F) is used as a protective film on the photosensitive layer, and a laminator (manufactured by Hitachi Chemical Co., Ltd., product name HLM-3000 type) is used. Then, the photosensitive element was prepared by bonding at 23 ° C.

  About the produced photosensitive element, the transmittance | permeability of a cured film, the measurement of a haze, the salt spray test of a cured film, the measurement of a hue (reflection R), and the crosscut adhesiveness test of the cured film for touchscreen electrode protection are carried out similarly to the above. Went. The results are shown in Table 6.

  As shown in Table 5, in Examples 1 to 11 using the photosensitive element having the photosensitive layer according to the present invention having the optical adjustment partial layer, the adhesion was good and the resistance to the salt spray test was sufficient. It was. On the other hand, as shown in Table 6, the adhesiveness is not sufficiently obtained in Comparative Examples 1 to 8 using a photosensitive element that does not have an optical adjustment partial layer and includes a photosensitive layer containing a metal oxide, The resistance to the salt spray test was also poor.

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support film, 20 ... Photosensitive layer, 30 ... Protection partial layer, 40 ... Optical adjustment partial layer, 50 ... Protection film, 60 ... Base material for touch panels, 60a ... Transparent conductive pattern, 100 ... Curing 10. Touch panel substrate with film, 101... Transparent substrate, 102... Sensing region, 103, 104 .. transparent electrode, 105 .. lead wire, 106 .. connection electrode, 107.

Claims (19)

  A support film, (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, (C) a photopolymerization initiator, and (F1) a triazine ring provided on the support film. And a photosensitive layer comprising (F2) a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton.   A part of the photosensitive layer comprises the photopolymerizable compound (B) having a (meth) acryloyl group, the compound (F1) having a triazine ring, the compound (F2) having a fluorene skeleton, or an isocyanuric acid skeleton. The photosensitive element of Claim 1 which consists of a part containing the compound which has.   The photosensitive layer contains a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups or a compound having a polyester structure as the photopolymerizable compound having (B) (meth) acryloyl group. Item 3. The photosensitive element according to Item 1 or 2.   4. The photosensitive element according to claim 1, wherein the photosensitive layer further contains at least one compound selected from the group consisting of (D) a triazole compound, a thiadiazole compound, and a tetrazole compound.   The photosensitive element as described in any one of Claims 1-4 in which the said photosensitive layer contains an oxime ester compound or a phosphine oxide compound as said (C) photoinitiator.   The photosensitive element as described in any one of Claims 1-5 whose thickness of the said photosensitive layer is 15 micrometers or less.   (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, (C) a photopolymerization initiator, (F1) a compound having a triazine ring, and (F2) a compound having a fluorene skeleton. Or the compound which has an isocyanuric acid frame | skeleton, The cured film formation agent used for cured film formation of the base material for touchscreens. A first composition comprising (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, and (C) a photopolymerization initiator;
(B) a second photopolymerizable compound having a (meth) acryloyl group, the (F1) compound having a triazine ring, and the (F2) compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton. The cured film forming agent of Claim 7 which is a 2 agent type | mold comprised from a composition.   (D) The cured film forming agent of Claim 7 which further contains the at least 1 sort (s) of compound selected from the group which consists of a triazole compound, a thiadiazole compound, and a tetrazole compound.   The cured film forming agent according to claim 8, wherein the first composition further contains (D) at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound.   The photopolymerizable compound having the (B) (meth) acryloyl group contains a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups or a compound having a polyester structure. The cured film formation agent as described in any one.   The cured film formation agent as described in any one of Claims 7-11 containing an oxime ester compound or a phosphine oxide compound as said (C) photoinitiator.   On the touch panel substrate, (A) a binder polymer, (B) a photopolymerizable compound having a (meth) acryloyl group, (C) a photopolymerization initiator, (F1) a compound having a triazine ring, ( F2) A photosensitive layer containing a compound having a fluorene skeleton or a compound having an isocyanuric acid skeleton is provided, and a predetermined portion of the photosensitive layer is cured by irradiation with actinic rays and then the portions other than the predetermined portion of the photosensitive layer are removed. And the manufacturing method of the base material for touchscreens with a cured film which forms the cured film which consists of the hardened | cured material of the said photosensitive layer which coat | covers a part or all of the said base material.   A part of the photosensitive layer comprises the photopolymerizable compound (B) having a (meth) acryloyl group, the compound (F1) having a triazine ring, the compound (F2) having a fluorene skeleton, or an isocyanuric acid skeleton. The manufacturing method of the base material for touchscreens with a cured film of Claim 13 which provides the said photosensitive layer so that it may become a part containing the compound which has.   The manufacturing method of the base material for touchscreens with a cured film of Claim 14 which forms the said part as a 50-400 nm-thick layer adjacent to the said base material.   The photosensitive layer contains a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups or a compound having a polyester structure as the photopolymerizable compound having (B) (meth) acryloyl group. The manufacturing method of the base material for touchscreens with a cured film as described in any one of claim | item 13-15.   The touch panel with a cured film according to any one of claims 13 to 16, wherein the photosensitive layer further contains at least one compound selected from the group consisting of (D) a triazole compound, a thiadiazole compound, and a tetrazole compound. Method for manufacturing a substrate.   The manufacturing method of the base material for touchscreens with a cured film as described in any one of Claims 13-17 in which the said photosensitive layer contains an oxime ester compound or a phosphine oxide compound as said (C) photoinitiator. A touch panel provided with the base material for touchscreens with a cured film obtained by the method as described in any one of Claims 13-18.

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