JP6400289B2 - Base material for touch panel with cured film and method for producing the same, photosensitive element and touch panel - Google Patents

Description

  The present invention relates to a method for producing a base material for a touch panel with a cured film, a photosensitive resin composition, a photosensitive element and a touch panel used therefor.

  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, 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. As the transparent conductive electrode material, ITO (Indium-Tin-Oxide), indium oxide and tin oxide are known. Since these materials exhibit high visible light transmittance, transparent electrode materials such as substrates for liquid crystal display elements As mainstream.

  Various types of touch panels have already been put into practical use, but in recent years, the use of capacitive touch panels has progressed. In a 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.

  In particular, the projected capacitive touch panel can detect multiple fingertips, so it has a good operability to give complex instructions. Use as an input device on a display surface in a device having a small display device such as a music player is advancing.

  In general, in a projected capacitive touch panel, 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) is used as the electrode.

  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.

  However, when the touch panel as described above is brought into contact with a fingertip, corrosive components such as moisture and salt may enter the inside from the sensing region. When corrosive components enter 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, as a method of providing a resist film at a necessary location, a method of providing a photosensitive layer made of a photosensitive resin composition on a predetermined substrate and exposing and developing the photosensitive layer is known. (For example, Patent Documents 1 to 3).

International Publication No. 2013/084873

  However, in the method described in the above-mentioned patent document, both high transparency and rust prevention are realized by using a photopolymerizable compound having three or more ethylenically unsaturated groups. The composition using the polymerizable compound has room for improvement in achieving both rust prevention and moisture permeability.

  The present invention provides a method for producing a base material for a touch panel with a cured film, which has a desired shape, is excellent in transparency, and has sufficient low moisture permeability and rust prevention properties even if it is a thin film, and photosensitive used therein It aims at providing the touch panel obtained by the manufacturing method of the base material for touchscreen base materials with a photosensitive resin composition, a photosensitive element, and a cured film.

As a result of intensive studies by the present inventors to solve the above problems, a cured film formed using a photosensitive resin composition containing a specific photopolymerizable compound has sufficient low moisture permeability and sufficient rust prevention. As a result, the present invention has been completed.
The specific embodiment is as follows.
<1> A photosensitive resin composition layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is provided on a base material for a touch panel, and a predetermined portion of the photosensitive resin composition layer Of the base material for a touch panel with a cured film, which is cured by irradiation of actinic rays and then removes other than the predetermined portion, and forms a cured film of the photosensitive resin assembly covering a part or all of the base material Production method.

The present inventors consider the reason why the base material for a touch panel with a cured film of the present invention can achieve the above-described effects as follows. When the thickness of the cured film is reduced, the corrosive component easily enters the touch panel electrode. On the other hand, when the component (B) contains a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure, the cured state of the cured film after exposure can be made dense. Therefore, the present inventors speculate.
<2> The substrate for a touch panel with a cured film according to <1>, wherein the di (meth) acrylate compound having the dicyclopentanyl structure or the dicyclopentenyl structure is a compound represented by the following general formula (1): Manufacturing method.

［一般式（１）中、Ｘは、ジシクロペンタニル構造又はジシクロペンテニル構造を示す。Ｒは、それぞれ独立に炭素数１〜４のアルキレン基を示す。Ｒ^１、Ｒ^２は、水素原子又はメチル基を示す。ｎ、ｍは０〜２を示す。ｐ＋ｑ＝０〜１０を示す。］
＜３＞前記ジシクロペンタニル構造又はジシクロペンテニル構造を有するジ（メタ）アクリレート化合物が、ジメチロールトリシクロデカンジ（メタ）アクリレート又はトリシクロデカンジオールジ（メタ）アクリレートである＜１＞又は＜２＞に記載の硬化膜付きタッチパネル用基材の製造方法。
＜４＞前記感光性樹脂組成物が、トリアゾール化合物、チアジアゾール化合物、及びテトラゾール化合物からなる群より選択される少なくとも１種の化合物をさらに含有する、＜１＞〜＜３＞のいずれか一項に記載の硬化膜付きタッチパネル用基材の製造方法。
＜５＞前記感光性樹脂組成物がオキシムエステル化合物を含有する、＜１＞〜＜４＞のいずれか一項に記載の硬化膜付きタッチパネル用基材の製造方法。
＜６＞支持フィルムと、前記支持フィルム上に設けられた前記感光性樹脂組成物層と、を備える感光性エレメントを用意し、前記感光性エレメントの感光性樹脂組成物層を前記基材上に転写して前記感光性樹脂組成物層を設ける、＜１＞〜＜５＞のいずれか一項に記載の硬化膜付きタッチパネル用基材の製造方法。

[In General Formula (1), X shows a dicyclopentanyl structure or a dicyclopentenyl structure. R each independently represents an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. n and m represent 0-2. p + q = 0 to 10 is shown. ]
<3> The di (meth) acrylate compound having the dicyclopentanyl structure or dicyclopentenyl structure is dimethylol tricyclodecane di (meth) acrylate or tricyclodecanediol di (meth) acrylate <1> or The manufacturing method of the base material for touchscreens with a cured film as described in <2>.
<4> The photosensitive resin composition according to any one of <1> to <3>, further including at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound. The manufacturing method of the base material for touchscreens with a cured film of description.
<5> The manufacturing method of the base material for touchscreens with a cured film as described in any one of <1>-<4> in which the said photosensitive resin composition contains an oxime ester compound.
<6> A photosensitive element comprising a support film and the photosensitive resin composition layer provided on the support film is prepared, and the photosensitive resin composition layer of the photosensitive element is formed on the substrate. The manufacturing method of the base material for touchscreens with a cured film as described in any one of <1>-<5> which transfers and provides the said photosensitive resin composition layer.

<7> (A) component: binder polymer (B) component: photopolymerizable compound,
On the base material for touchscreens which contains (C) component: a photoinitiator and the said (B) component contains the di (meth) acrylate compound which has a dicyclopentanyl structure or a dicyclopentenyl structure. A photosensitive resin composition for forming a cured film.
<8> The photosensitive resin composition according to <7>, wherein the di (meth) acrylate compound having the dicyclopentanyl structure or the dicyclopentenyl structure is a compound represented by the following general formula (1).

［一般式（１）中、Ｘは、ジシクロペンタニル構造又はジシクロペンテニル構造を示す。Ｒは、それぞれ独立に炭素数１〜４のアルキレン基を示す。Ｒ^１、Ｒ^２は、水素原子又はメチル基を示す。ｎ、ｍは０〜２を示す。ｐ＋ｑ＝０〜１０を示す。］
＜９＞前記ジシクロペンタニル構造又はジシクロペンテニル構造を有するジ（メタ）アクリレート化合物が、ジメチロールトリシクロデカンジ（メタ）アクリレート又はトリシクロデカンジオールジ（メタ）アクリレートである＜７＞又は＜８＞に記載の感光性樹脂組成物。
＜１０＞前記感光性樹脂組成物が、トリアゾール化合物、チアジアゾール化合物、及びテトラゾール化合物からなる群より選択される少なくとも１種の化合物をさらに含有する、＜７＞〜＜９＞のいずれか一項に記載の感光性樹脂組成物。
＜１１＞前記（Ｃ）成分がオキシムエステル化合物を含有する、＜７＞〜＜１０＞のいずれか一項に記載の感光性樹脂組成物。
＜１２＞支持フィルムと、該支持フィルム上に設けられた＜７＞〜＜１１＞のいずれか一項に記載の感光性樹脂組成物を含む感光性樹脂組成物層と、を備える、感光性エレメント。
＜１３＞前記感光性樹脂組成物層の厚みが１０μｍ以下である、＜１２＞に記載の感光性エレメント。
＜１４＞＜１＞〜＜６＞のいずれか一項に記載の硬化膜付きタッチパネル用基材の製造方法により得られる硬化膜付きタッチパネル用基材を備える、タッチパネル。

[In General Formula (1), X shows a dicyclopentanyl structure or a dicyclopentenyl structure. R each independently represents an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. n and m represent 0-2. p + q = 0 to 10 is shown. ]
<9> The di (meth) acrylate compound having the dicyclopentanyl structure or dicyclopentenyl structure is dimethylol tricyclodecane di (meth) acrylate or tricyclodecanediol di (meth) acrylate <7> or The photosensitive resin composition as described in <8>.
<10> The photosensitive resin composition according to any one of <7> to <9>, further containing at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound. The photosensitive resin composition as described.
<11> The photosensitive resin composition according to any one of <7> to <10>, wherein the component (C) contains an oxime ester compound.
<12> A support film and a photosensitive resin composition layer including the photosensitive resin composition according to any one of <7> to <11> provided on the support film, and a photosensitive property. element.
<13> The photosensitive element according to <12>, wherein the photosensitive resin composition layer has a thickness of 10 μm or less.
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 as described in any one of <14><1>-<6>.

  By the way, considering the visibility or aesthetics of the touch panel, it is desirable that the transparency of the cured film is higher. However, on the other hand, the present inventors have found that when patterning a thin photosensitive layer having high transparency, the resolution tends to decrease. The present inventors consider that the reason is that when the thickness of the photosensitive layer is reduced, it is easily affected by light scattering from the base material and halation occurs.

  On the other hand, in the present invention, the photopolymerization initiator contains an oxime ester compound, whereby a pattern can be formed with sufficient resolution.

  The reason why the above effect is obtained is that the oxime moiety contained in the oxime ester compound 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 this is a result of the influence being suppressed.

  According to the present invention, a method for producing a base material for a touch panel with a cured film having a cured film having sufficient low moisture permeability and high rust prevention properties even on a predetermined touch panel base material, such as A photosensitive resin composition and a photosensitive element that can form a cured film, and a touch panel provided with a substrate for a touch panel with a cured film can be provided.

It is a schematic cross section which shows one Embodiment of the photosensitive element of this invention. It is a schematic cross section for demonstrating one Embodiment of the manufacturing method of the base material for touchscreens with a cured film of this invention. It is a model top view which shows an example of an electrostatic capacitance type touch panel. It is a schematic top view which shows another example of an electrostatic capacitance type touch panel. (A) is the fragmentary sectional view in alignment with the VV line | wire of C part shown by FIG. 3, (b) is a fragmentary sectional view which shows another aspect. It is a top view which shows an example of the electrostatic capacitance type touch panel in which a transparent electrode exists in the same plane. It is a partially cutaway perspective view showing an example of a capacitive touch panel in which transparent electrodes are present on the same plane. It is a fragmentary sectional view in alignment with the VI-VI line in FIG. It is a figure for demonstrating an example of the manufacturing method of the capacitive touch panel in which a transparent electrode exists in the same plane, (a) is a partially notched perspective view which shows the board | substrate provided with a transparent electrode, (b) FIG. 3 is a partially cutaway perspective view showing the obtained capacitive touch panel. It is a figure for demonstrating an example of the manufacturing method of the electrostatic capacitance type touch panel in which a transparent electrode exists in the same plane, (a) is a fragmentary sectional view along the VIIIa-VIIIa line | wire in FIG. ) Is a partial cross-sectional view showing a step of providing an insulating film, and (c) is a partial cross-sectional view taken along line VIIIc-VIIIc in FIG. 9. It is a fragmentary sectional view showing an example of a touch panel in which an insulating film is provided on a transparent electrode wiring, a lead wiring is provided thereon, and the transparent electrode wiring and the lead wiring are connected by an opening.

  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 this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or the corresponding methacrylate, and (meth) acryloyl group means acryloyl. Means a group or a methacryloyl group. The (poly) oxyethylene chain means an oxyethylene group or a polyoxyethylene group, and the (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene group.

  In addition, in this specification, the term “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. In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.

  Further, in the present specification, the content of 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.

  In this specification, the cured film of the base material for touch panels 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 an embodiment of the photosensitive element of the present invention. A photosensitive element 1 shown in FIG. 1 includes a support film 10, a photosensitive resin composition layer (photosensitive layer) 20 including the photosensitive resin composition according to the present invention provided on the support film, and a photosensitive layer 20. It consists of a protective film 30 provided on the side opposite to the support film 10.

  The photosensitive element of this embodiment can be used suitably for formation of the cured film of the base material for touchscreens.

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

  The thickness of the support film 10 is preferably 5 to 100 μm, more preferably 10 to 70 μm, from the viewpoint of ensuring coverage and suppressing a decrease in resolution when exposed through the support film. More preferably, it is 15-40 micrometers, and it is especially preferable that it is 20-35 micrometers.

The photosensitive resin composition constituting the photosensitive layer 20 is composed of (A) component: binder polymer, (B) component: photopolymerizable containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure. Compound,
(C) component: It contains a photoinitiator.

  According to the photosensitive resin composition according to the present embodiment, a cured film having sufficient low moisture permeability and high antirust property can be formed even with a thickness of 10 μm or less.

  As the binder polymer of the component (A), for example, a polymer having a carboxyl group can be used. In this case, when the photosensitive layer other than the cured film portion after irradiation with actinic rays is removed, it can be removed by alkali development. Moreover, when removing other than the said predetermined part by stamping etc., without using image development processes, such as alkali image development, it does not need to have a carboxyl group.

  In the present embodiment, 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 hydroxyl ethyl ester.

  The copolymer may further contain other monomers that can be copolymerized with the component (a) or the component (b) in the structural unit.

  Examples of the other monomer that can be copolymerized with the component (a) or the component (b) include, for example, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, Adamantyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, (Meth) acrylic acid adamantyloxyethyl, (meth) acrylic acid dicyclopentenyloxypropyloxyethyl, (meth) acrylic acid dicyclopentanyloxypropyloxyethyl, (meth) acrylic acid dicyclopentenyloxypropyloxyethyl, ( (Meth) acrylic acid ada Nthyloxypropyloxyethyl, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester Ester, (meth) acrylic acid phenoxy ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, Examples include diacetone (meth) acrylamide, styrene, and vinyltoluene. When synthesizing the binder polymer as component (A), the above monomers may be used alone or in combination of two or more.

  The weight average molecular weight of the binder polymer is preferably 10,000 to 200,000 from the viewpoint of resolution, more preferably 15,000 to 150,000, and 30,000 to 150,000. Is more preferable, 30,000 to 100,000 is particularly preferable, and 40,000 to 100,000 is very preferable. In addition, a weight average molecular weight can be measured on the same conditions as the Example of this-application specification.

The acid value of the binder polymer is preferably 75 mgKOH / g or more from the viewpoint of easily forming a cured film having a desired shape, and it is possible to achieve both the controllability of the cured film shape and the rust prevention of the cured film. From the viewpoint of aiming, it is more preferably 75 to 200 mgKOH / g, further preferably 75 to 150 mgKOH / g, and particularly preferably 75 to 120 mgKOH / g.

The acid value of the binder polymer as the component (A) can be measured as follows. That is, first, 1 g of the binder polymer that is the object of acid value measurement is precisely weighed. 30 g of acetone is added to the precisely weighed binder polymer and dissolved uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf indicates the titration amount (mL) of the KOH aqueous solution, Wp indicates the measured mass (g) of the solution containing the binder polymer, and I indicates the ratio (mass) of the non-volatile content in the measured solution containing the binder polymer. %). In addition, when blending the binder polymer in a state of being mixed with volatile components such as a synthetic solvent and a diluting solvent, the mixture is heated in advance for 1 to 4 hours at a temperature higher than the boiling point of the volatile components by 1 to 4 hours prior to precise weighing. The acid value is measured after removing the fraction.

  The hydroxyl value of the binder polymer as the component (A) is preferably 50 mgKOH / g or less, and more preferably 45 mgKOH / g or less, from the viewpoint of further improving rust prevention.

The hydroxyl value of the component (A) can be measured as follows.
First, 1 g of a binder polymer, which is a measurement target of the hydroxyl value, is precisely weighed. 10 mL of 10 mass% acetic anhydride pyridine solution is added to the precisely weighed binder polymer, and this is uniformly dissolved, and heated at 100 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine are added and heated at 100 ° C. for 10 minutes. Then, using an automatic titrator (“COM-1700” manufactured by Hiranuma Sangyo Co., Ltd.), measurement is performed by neutralization titration with an ethanol solution of 0.5 mol / L potassium hydroxide. The hydroxyl value can be calculated by the following formula.
Hydroxyl value = (A−B) × f × 28.05 / sample (g) + acid value
In the formula, A indicates the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test, and B indicates the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration. F represents a factor. In addition, when blending the binder polymer in a state of being mixed with a synthetic solvent or a diluting solvent, the solvent is removed in advance by heating at a temperature 10 ° C. or more higher than the boiling point of the synthetic solvent or diluting solvent. Then, the hydroxyl value is measured.

  (B) As a photopolymerizable compound which is a component, the di (meth) acrylate compound which has a dicyclopentanyl structure or a dicyclopentenyl structure is included. Specifically, it is preferable to include a compound represented by the following general formula (1) in order to prevent moisture from entering and further reduce moisture permeability.

［一般式（１）中、Ｘは、ジシクロペンタニル構造又はジシクロペンテニル構造を示す。Ｒは、それぞれ独立に炭素数１〜４のアルキレン基を示す。Ｒ^１、Ｒ^２は、水素原子又はメチル基を示す。ｎ、ｍは０〜２を示す。ｐ＋ｑ＝０〜１０を示す。］

[In General Formula (1), X shows a dicyclopentanyl structure or a dicyclopentenyl structure. R each independently represents an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. n and m represent 0-2. p + q = 0 to 10 is shown. ]

  The compound represented by the general formula (1) has a low-moisture permeability and high physical properties after photocuring because the dicyclopentanyl structure or dicyclopentenyl structure contained in X has a bulky structure. Both rust prevention properties can be achieved.

  In the general formula (1), R represents an alkylene group having 1 to 4 carbon atoms. R is preferably an ethylene group or a propylene group, and more preferably an ethylene group. The propylene group may be either an n-propylene group or an isopropylene group.

  In the said General formula (1), n and m show 0-2. Here, n and m indicate how much an alkylene group having 1 to 4 carbon atoms is added to the molecule. Therefore, an integer value is shown for a single molecule, but a rational number that is an average value is shown as an aggregate of a plurality of types of molecules.

  As the compound represented by the general formula (1), dimethylol tricyclodecane di (meth) acrylate or tricyclodecanediol di (meth) acrylate is preferable. These are commercially available as NK ester DCP and NK ester A-DCP (both manufactured by Shin-Nakamura Chemical Co., Ltd.).

  As the photopolymerizable compound as component (B), in addition to the compound represented by the general formula (1), a monofunctional vinyl monomer, a bifunctional vinyl monomer, a polyfunctional compound having three or more ethylenically unsaturated groups. A functional vinyl monomer may be mixed.

  As said monofunctional vinyl monomer, the monomer illustrated as a monomer used for the synthesis | combination of the copolymer which is a suitable example of the said (A) component is mentioned, for example.

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

  Examples of the polyfunctional vinyl monomer having three or more ethylenically unsaturated groups include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, and dipentaerythritol pentane. Compounds obtained by reacting α, β-unsaturated carboxylic acid with polyhydric alcohols such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin, pentaerythritol; trimethylolpropane triglycidyl ether triacrylate, etc. And a compound obtained by adding an α, β-unsaturated carboxylic acid to the glycidyl group-containing compound.

  Among these, it is preferable to contain a polyfunctional vinyl monomer having three or more ethylenically unsaturated groups.

  In the case of using a monomer having three or more ethylenically unsaturated groups and the above general formula (1) in combination, there is no particular limitation on the ratio to be used, but from the viewpoint of obtaining photocurability, low moisture permeability and rust prevention properties. The proportion of the monomer having three or more ethylenically unsaturated groups is preferably 10 parts by mass or more with respect to 100 parts by mass of the total amount of the photopolymerizable compound contained in the photosensitive resin composition, More preferably, it is at least part by mass.

  The content of the component (A) and the component (B) in the photosensitive resin composition according to this embodiment is such that the component (A) is 35 with respect to 100 parts by mass of the total amount of the components (A) and (B). -85 parts by mass, (B) component is preferably 15-65 parts by mass, (A) component is preferably 40-80 parts by mass, and (B) component is more preferably 20-60 parts by mass, More preferably, the component (A) is 50 to 70 parts by mass, the component (B) is 30 to 50 parts by mass, the component (A) is 55 to 65 parts by mass, and the component (B) is 35 to 45 parts by mass. It is particularly preferred.

  By setting the content of the component (A) and the component (B) within the above range, sufficient sensitivity can be obtained while sufficiently ensuring the coating property or the film property in the photosensitive element, and the photocurability and development. , Low moisture permeability and rust prevention can be sufficiently secured.

  In this embodiment, it is preferable that an oxime ester compound is included as a photoinitiator which is (C) component. More preferably, the oxime ester compound includes a compound represented by the following general formula (2), a compound represented by the following general formula (3), or a compound represented by the following general formula (4). By using such a photosensitive resin composition, a cured film having a sufficient antirust property can be formed on a substrate even if it is a thin film. This cured film is sufficiently excellent in transparency.

In the general formula (2), R and R ¹ 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, but 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, preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group. More preferred is a methyl group, a cyclopentyl group, a phenyl group or a tolyl group.
R ² represents unsubstituted, OH, COOH, O (CH ₂ ) OH, O (CH ₂ ) ₂ OH, COO (CH ₂ ) OH or COO (CH ₂ ) ₂ OH. (CH ₂ ) OH, O (CH ₂ ) ₂ OH, COO (CH ₂ ) OH or COO (CH ₂ ) ₂ OH are preferred, unsubstituted, O (CH ₂ ) ₂ OH or COO (CH ₂ ) More preferably, it is ₂ OH.

In the general formula (3), R ³ represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group. R ⁴ represents NO ₂ or ArCO, Ar represents an aryl group, and Ar is preferably a tolyl group. R ⁵ and R ⁶ represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and are preferably a methyl group, a phenyl group, or a tolyl group.

In the general formula (4), R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group. Although R ⁸ is an organic group having an acetal bond, it is preferably a substituent group of the compound represented by the following formula (4-1). Furthermore, R ⁹ and R ¹⁰ is an alkyl group having 1 to 12 carbon atoms, but a phenyl group or a tolyl group, a methyl group is preferably a phenyl group or a tolyl group, and more preferably a methyl group.

  Examples of the compound represented by the general formula (2) include a compound represented by the following formula (2-1). This is available as Adeka Cruise NCI-930 (trade name, manufactured by ADEKA Corporation).

  Examples of the compound represented by the general formula (3) include compounds represented by the following formulas (3-1) and (3-2). These compounds are available as DFI-091 and DFI-020 (both manufactured by Daitokemix Co., Ltd., trade names).

  Examples of the compound represented by the general formula (4) include a compound represented by the following formula (4-1). It is available as Adekaoptomer N-1919 (manufactured by ADEKA, trade name).

  The photopolymerization initiator is a photopolymerization other than the compound represented by the general formula (2), the compound represented by the general formula (3), or the compound represented by the general formula (4) (oxime ester compound). An initiator can also be used in combination. Examples of such a photopolymerization initiator include benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- Aromatic ketones such as methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin and ethyl benzoin Benzoin compounds such as benzyl dimethyl ketal; benzyl derivatives such as benzyldimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane; N-phenylglycine and N-phenylglycine derivatives; Compound; 2 -Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; tertiary amine compounds; Examples include oxazole compounds. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.

  The content of the photopolymerization initiator that is the component (C) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), and 1 to 10 parts by mass. More preferably, it is 2-5 mass parts. The content of the component (C) is preferably 0.1 parts by mass or more in terms of excellent photosensitivity and resolution, and is preferably 20 parts by mass or less in terms of excellent visible light transmittance.

The photosensitive resin composition according to this embodiment preferably further contains at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound. Thereby, in addition to the fall of moisture permeability, rust prevention property improves by protecting metals, such as copper, and the cured film which has rust prevention property can be formed.
Contains a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group, a triazole compound having an amino group, or a tetrazole compound having an amino group from the viewpoint of further improving the rust prevention property of the cured film It is more preferable.

  Among these, it is preferable to contain a tetrazole compound having an amino group. Specific examples include compounds represented by the following general formula (D-1).

上記一般式（Ｄ−１）中のＲ^１１及びＲ^１２は、各々独立に、水素、炭素数１〜２０のアルキル基、アミノ基、メルカプト基、又はカルボキシメチル基を示し、Ｒ^１１及びＲ^１２の少なくともひとつは、アミノ基を有する。

R ¹¹ and R ¹² in the general formula (D-1) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an amino group, a mercapto group, or a carboxymethyl group, and R ¹¹ and R ¹² At least one of has an amino group.

  Among the tetrazole compounds represented by the general formula (D-1), 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, or 1- Carboxymethyl-5-amino-tetrazole is preferred.

  The tetrazole compound represented by the general formula (D-1) is suitable even if it is a water-soluble salt thereof. Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.

  Among these, 5-amino-1H-tetrazole and 1-methyl-5-mercapto-1H-tetrazole are particularly preferable from the viewpoints of adhesion to a metal electrode, ease of development, and transparency.

  These tetrazole compounds and water-soluble salts thereof may be used alone or in combination of two or more.

  Content of (D) component in the photosensitive resin composition which concerns on this embodiment shall be 0.05-10.0 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. Is preferably 0.1 to 2.0 parts by mass, and more preferably 0.2 to 1.0 part by mass.

  By the way, when providing a preservative film on a part of the ITO electrode of the touch panel, for example, a metal layer such as copper is formed on the ITO electrode in the frame region and the ITO electrode without forming the cured film in the sensing region. In the case where a cured film is provided on a portion, an unnecessary portion can be removed by performing exposure and development after providing a photosensitive layer on the whole. In this case, the photosensitive layer is required to have good developability so as not to cause development residue in unnecessary portions while having sufficient adhesion to the electrode to be protected. From the viewpoint of achieving both adhesion and developability in such a case, the photosensitive resin composition of the present invention contains a phosphoric ester containing a photopolymerizable unsaturated bond (hereinafter also referred to as component (E)). It is preferable to do.

  (E) As a phosphoric acid ester containing a photopolymerizable unsaturated bond as a component, it is possible to achieve a high level of both adhesion to an ITO electrode and developability while ensuring sufficient rust prevention of a cured film to be formed. Therefore, it is preferable to use a compound having the following structure as the phosphate ester. The compound is commercially available such as PM21 (manufactured by Nippon Kayaku Co., Ltd.).

  In addition to the photosensitive resin composition according to the present embodiment, if necessary, an adhesion imparting agent such as a silane coupling agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, An antioxidant, a fragrance, a thermal crosslinking agent, a polymerization inhibitor and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). These can be used alone or in combination of two or more.

  Here, the visible light transmittance of the photosensitive resin composition is determined 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 μm 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.

  In addition, the suitable transmittance | permeability mentioned above means the minimum value of the transmittance | permeability in the said wavelength range.

  If the transmittance in the wavelength range of 400 to 700 nm, which is a light ray in the general visible light wavelength range, is 90% or more, the transparent electrode in the sensing area of the touch panel (touch sensor) is protected, or the touch panel (touch sensor) When the protective film is visible from the edge of the sensing area when the metal layer (for example, a layer in which a copper layer is formed on the ITO electrode) is protected, the image display quality, color, and brightness in the sensing area are It can suppress sufficiently that it falls.

  The photosensitive resin composition according to this embodiment can be used for forming a photosensitive layer on a substrate. For example, a coating solution that can be obtained by uniformly dissolving or dispersing the photosensitive resin composition in a solvent (solvent) is prepared, and a coating film is formed by coating on a substrate, and the solvent is removed by drying. Thus, a photosensitive layer can be formed. A conventionally well-known thing can be used suitably as a solvent.

  The photosensitive resin composition according to the present embodiment is preferably used after being formed on a photosensitive film like the photosensitive element 1. Laminating the photosensitive film on the touch panel substrate can easily realize a roll-to-roll process, shorten the solvent (solvent) drying process, and greatly contribute to shortening the manufacturing process and reducing costs. it can.

  The photosensitive layer 20 of the photosensitive element 1 can be formed by preparing a coating solution containing the photosensitive resin composition according to the present embodiment, and applying and drying the coating solution on the support film 10. The coating liquid can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition according to the present embodiment described above in a solvent. There is no restriction | limiting in particular as a solvent, A well-known thing can be used.

  The thickness of the photosensitive layer is preferably 1 μm or more and 9 μm or less, and preferably 1 μm or more and 8 μm or less, in terms of the thickness after drying so that the level difference on the surface of the touch panel (touch sensor) generated by the cured film formation is minimized. More preferably, it is 2 μm or more and 8 μm or less, and particularly preferably 3 μm or more and 8 μm or less.

  In the present embodiment, the photosensitive layer 20 preferably has a minimum visible light transmittance of 90% or more, more preferably 92% or more, and even more preferably 95% or more.

  When the photosensitive element 20 is cut, 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 fragments of the photosensitive resin composition 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. It 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 (cover film) include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, and a laminated film of polyethylene-vinyl acetate copolymer and polyethylene.

  The thickness of the protective film 30 is preferably about 5 to 100 μm, but from the viewpoint of storing it in a roll shape, it is preferably 70 μm or less, more preferably 60 μm or less, and further preferably 50 μm or less. It is preferably 40 μm or less.

  In this embodiment, the photosensitive layer 20 which consists of a photosensitive resin composition which apply | coats the coating liquid containing the photosensitive resin composition and solvent which concern on this embodiment mentioned above on the base material for touchscreens, dries. May be provided. Even in this application, the photosensitive layer preferably satisfies the above-described film thickness and visible light transmittance.

  Next, a method for forming a cured film on the touch panel substrate will be described. FIG. 2 is a schematic cross-sectional view for explaining an embodiment of the method for producing a base material for a touch panel with a cured film of the present invention.

  The manufacturing method of the base material for touchscreens with a cured film of this embodiment provides the photosensitive layer 20 containing the photosensitive resin composition which concerns on this embodiment on the base material 100 which has the electrodes 110 and 120 for touchscreens. 1 step (FIG. 2 (a)), a second step (FIG. 2 (b)) in which a predetermined portion of the photosensitive layer 20 is cured by irradiation with actinic rays, and a photosensitive layer other than the predetermined portion after irradiation with actinic rays. And a third step (FIG. 2C) of forming a protective film 22 made of a cured film pattern of a photosensitive resin composition that is removed and covers a part or all of the electrode. In this way, a touch panel (touch sensor) 200 with a protective film, which is a touch input sheet, 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). On this board | 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.

  Moreover, the base material in which transparency is requested | required other than the base material for touchscreens can be used. Specifically, substrates for optical adjustment films for invisible electrode wiring such as ITO, substrates for plasma display panels (PDP), substrates for liquid crystal display (LCD) modules, for flat panel displays (FPD) A base material is mentioned.

  The base material 100 which has the electrodes 110 and 120 for touch panels shown by FIG. 2 can be obtained in the following procedures, for example. 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.

  Conventionally known conditions can be used in the first to third steps. Thereby, the base material for touchscreens with a cured film which concerns on this invention can be manufactured.

  Next, an example of the place where the cured film of the present invention is used will be described with reference to FIGS. 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.

  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. The photosensitive resin composition according to the present invention can be suitably used for forming the protective film 122 for the lead-out wiring 105, the connection electrode 106, and the connection terminal 107. At this time, the electrodes in the sensing region can be protected at the same time. In FIG. 3, 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, but the location where the protective film is provided may be changed as appropriate. For example, as shown in FIG. 4, a protective film 123 may be provided so as to protect the entire touch screen 102.

  With reference to FIG. 5, the cross-sectional structure of the connection portion between the transparent electrode and the lead-out wiring in the touch panel shown in FIG. 3 will be described. 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. As shown in FIG. 5A, the transparent electrode 104 and the lead wiring 105 are electrically connected via the connection electrode 106. As shown in FIG. 5A, a part of the transparent electrode 104 and all of the lead-out wiring 105 and the connection electrode 106 are covered with a protective film 122. Similarly, 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 above-described photosensitive resin composition and photosensitive element according to the present embodiment are suitable for use for forming a cured resin film pattern as a protective film for the structural portion.

  The manufacturing method of the touch panel in this embodiment is demonstrated. First, the transparent electrode (X position coordinate) 103 is formed on the transparent electrode 101 provided on the substrate 100. Subsequently, 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.

  Next, on the surface of the transparent substrate 101, 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 transparent electrode 103 and the transparent electrode 104 are formed, or may be formed at the same time as each transparent electrode is formed. 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. Next, a connection terminal 107 for connecting the lead wiring 105 and an external circuit is formed.

  The photosensitive element 1 according to this embodiment 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. Next, the actinic ray L is irradiated to the transferred photosensitive layer 20 in a desired shape through a photomask. After irradiating the actinic ray L, 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.

  Next, the use location of the cured film which concerns on this invention is demonstrated using FIGS. The cured film of the present invention can be suitably used as, for example, the protective film (insulating film) 124 shown in FIGS.

  FIG. 6 is a plan view showing an example of a capacitive touch panel in which the transparent electrode (X position coordinates) 103 and the transparent electrode (Y position coordinates) 104 exist on the same plane, and FIG. FIG. FIG. 8 is a partial cross-sectional view taken along line VI-VI in FIG. The capacitive touch panel includes a transparent electrode 103 that detects a change in capacitance and uses X position coordinates, and a transparent electrode 104 uses Y position coordinates on a transparent substrate 101. Each of the transparent electrodes 103 and 104 having the X and Y position coordinates has lead-out wirings 105a and 105b for connecting to a control circuit of a driver element circuit (not shown) that controls an electrical signal as a touch panel. .

  An insulating film 124 is provided at a portion where the transparent electrode (X position coordinate) 103 and the transparent electrode (Y position coordinate) 104 intersect.

  A method of manufacturing a capacitive touch panel in which the transparent electrode (X position coordinates) 103 and the transparent electrode (Y position coordinates) 104 are present on the same plane will be described.

  A method for manufacturing a capacitive touch panel is, for example, a known method using a transparent conductive material, and a part of a transparent electrode that becomes a transparent electrode (X position coordinate) 103 and a transparent electrode 104 that later detects a Y position coordinate. Alternatively, a substrate formed in advance on the transparent substrate 101 may be used. FIG. 9 is a diagram for explaining an example of a method for manufacturing a capacitive touch panel in which transparent electrodes are present on the same plane, and (a) is a partially cutaway perspective view showing a substrate provided with transparent electrodes. (B) is a partially cutaway perspective view showing the obtained capacitive touch panel. FIG. 10 is a diagram for explaining an example of a method for manufacturing a capacitive touch panel in which transparent electrodes exist on the same plane.

  First, as shown in FIG. 9A and FIG. 10A, a substrate on which a transparent electrode (X position coordinate) 103 and a part 104a of the transparent electrode are formed in advance is prepared. An insulating film 124 is provided on a part (a part sandwiched between part 104a of the transparent electrode) ((b) in FIG. 10). Thereafter, a conductive pattern is formed by a known method. With this conductive pattern, the bridge portion 104b of the transparent electrode can be formed (FIG. 10C). By this transparent electrode bridge portion 104 b, a part of the transparent electrodes 104 a formed in advance can be connected to each other, and a transparent electrode (Y position coordinate) 104 is formed.

  The previously formed transparent electrode may be formed by a known method using ITO or the like, for example. The lead-out wirings 105a and 105b can be formed by a known method using a metal such as Cu or Ag in addition to the transparent conductive material. Alternatively, a substrate on which the lead wirings 105a and 105b are formed in advance may be used.

  FIG. 11 is a partial plan view showing an example of another capacitive touch panel. The configuration described in FIG. 11 is intended to narrow the frame of the touch panel. In FIG. 11, the transparent insulating film 125 is provided on the transparent electrode wiring 104 c extending from the transparent electrode 104 on the transparent substrate 101, and the lead-out wiring 105 is further provided on the transparent insulating film 125. Openings 108 are provided above and below the necessary portion of the transparent insulating film 125, and the transparent electrode 104 and the lead-out wiring 105 are connected and conducted. The photosensitive resin composition and photosensitive element of this invention can be used suitably as a resin cured film pattern as a partial insulation film of the said structure.

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

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: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name)
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)

[Measurement method of acid value]
Moreover, the acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content. Then, after precisely weighing 1 g of the polymer whose acid value is to be measured, 30 g of acetone was added to this polymer and dissolved uniformly. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 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 hydroxyl value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content. Then, after precisely weighing 1 g of the polymer whose hydroxyl value is to be measured, the accurately weighed photosensitive resin composition is put in an Erlenmeyer flask, and 10 mL of 10% by mass acetic anhydride pyridine solution is added and uniformly dissolved. Heated at 0 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine were added and heated at 100 ° C. for 10 minutes, and then using an automatic titrator (“COM-1700” manufactured by Hiranuma Sangyo Co., Ltd.), an ethanol solution of 0.5 mol / L potassium hydroxide. Neutralization titration. And the hydroxyl value was computed by following Formula.
Hydroxyl value = (A−B) × f × 28.05 / sample (g) + acid value
In the formula, A indicates the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test, and B indicates the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration. F represents a factor.

(Examples 1-8, Comparative Examples 1-5)
[Preparation of coating solution containing photosensitive resin composition]
The materials shown in Tables 2 and 3 were mixed for 15 minutes using a stirrer to prepare a coating solution containing the photosensitive resin composition.

[Production of photosensitive element]
A polyethylene terephthalate film having a thickness of 50 μm is used as the support film, and the coating solution containing the photosensitive resin composition prepared above is uniformly applied on the support film using a comma coater, followed by hot air convection drying at 100 ° C. The solvent was removed by drying with a machine 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 5 μm.

  Next, a polyethylene film having a thickness of 25 μm was further laminated as a cover film on the obtained photosensitive layer to produce a photosensitive element.

[Moisture permeability measurement]
The obtained photosensitive resin composition solution (V-1) was uniformly applied onto a polyethylene terephthalate film having a thickness of 50 μm using an applicator to produce a photosensitive element (E-2) having a thickness of 40 μm. The obtained photosensitive element (E-2) was No. Lamination was performed under conditions of a roll temperature of 80 ° C., a substrate feed rate of 0.6 m / min, and a pressure bonding pressure (cylinder pressure) of 0.5 MPa so that the photosensitive layer was in contact with 5C filter paper (manufactured by Advantech). A laminate in which a photosensitive layer and a polyethylene terephthalate film were laminated on 5C filter paper was produced.

After producing the laminate obtained above, using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) with an exposure amount of 5 × 10 ² J / m ² from the vertically upper side of the polyethylene terephthalate film surface (line i (Measurement value at a wavelength of 365 nm)) was irradiated with ultraviolet rays.

Next, the support film laminated on the photosensitive layer is peeled off and removed, and further irradiated with ultraviolet rays at an exposure amount of 1 × 10 ⁴ J / m ² (measured value at i-line (wavelength 365 nm)) from above the photosensitive layer side. Thus, a moisture permeability measurement sample in which a cured product of the photosensitive layer having a thickness of 40 μm was formed was obtained.

Next, with reference to JIS standard (Z0208), a cup method was performed as a moisture permeability measurement. Put 20 g of dried calcium chloride into the measuring cup, cover with a circular sample cut from the above test sample with a scissors of 70 mm in diameter, and cover in a constant temperature and humidity chamber at 60 ° C. and 90% RH. The condition was left for 24 hours. The moisture permeability was calculated from the change in mass before and after standing, and the moisture permeability was evaluated according to the following ratings. Tables 4 and 5 show the measurement results.
A: Moisture permeability ≦ 350 (g / m ² · 24 h).
B: 350 <moisture permeability ≦ 450 (g / m ² · 24 h).
C: Moisture permeability> 450 (g / m ² · 24 h).

[Measurement of transmittance of cured film]
Using a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name HLM-3000) so that the photosensitive layer is in contact with a 1 mm-thick glass substrate while peeling the polyethylene film that is the cover film of the obtained photosensitive element. , A roll temperature of 120 ° C., a substrate feed rate 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 is used, and the linear pressure at this time is 9.8 × 10 ³ N / m) was laminated to prepare a laminate in which a photosensitive layer and a support film were laminated on a glass substrate.

Next, a parallel light exposure machine (EXM1201, manufactured by Oak Manufacturing Co., Ltd.) was used for the photosensitive layer of the obtained laminate, and an exposure amount of 5 × 10 ² J / m ² (i-line ( Measured value at a wavelength of 365 nm), after irradiating with ultraviolet rays, the support film was removed and left in a box dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) heated to 140 ° C. for 30 minutes, A transmittance measurement sample having a cured film having a thickness of 5 μm was obtained.

  Subsequently, the visible light transmittance | permeability was measured in the measurement wavelength range 400-700 nm using Hitachi High-Technologies Co., Ltd. make and ultraviolet-visible spectrophotometer (U-3310), and the minimum value was computed. Tables 4 and 5 show the measurement results.

[Salt spray test of cured film (artificial sweat resistance evaluation test)]
Laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-3000) so that the photosensitive layer is in contact with the polyimide film with sputter copper (manufactured by Toray Film Processing Co., Ltd.) while peeling off the polyethylene film of the obtained photosensitive element. , A roll temperature of 120 ° C., a substrate feed rate of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa (thickness of 1 mm, length of 10 cm × width of 10 cm, a linear pressure at this time is 9.8 × 10 ³ N / m) was laminated to prepare a laminate in which the photosensitive layer and the support film were laminated on the sputtered copper.

Next, a parallel light exposure machine (EXM1201, manufactured by Oak Manufacturing Co., Ltd.) was used for the photosensitive layer of the obtained laminate, and an exposure amount of 5 × 10 ² J / m ² (i-line ( Measured value at a wavelength of 365 nm), after irradiating with ultraviolet rays, the support film is peeled off and removed, and further from the upper side of the photosensitive layer at an exposure amount of 1 × 10 ⁴ J / m ² (measured value at i-line (wavelength 365 nm)) ) It was allowed to stand for 30 minutes in a box-type dryer (Mitsubishi Electric Corporation, model number: NV50-CA) irradiated with ultraviolet rays and heated to 140 ° C. A sample for evaluating artificial sweat resistance with a cured film having a thickness of 5.0 μm was obtained.

Next, referring to the JIS standard (Z 2371), using a salt spray tester (STP-90V2 manufactured by Suga Test Instruments Co., Ltd.), the above-mentioned sample was placed in the test tank, and the salt water (concentration 50 g / L) ( pH = 6.7) was sprayed for 48 hours at a test bath temperature of 35 ° C. and a spraying amount of 1.5 mL / h. After spraying, the salt water was wiped off, the surface state of the sample for evaluation was observed, and evaluation was performed according to the following scores. Tables 4 and 5 show the measurement results.
A: No change on the surface of the cured film.
B: Slight traces are visible on the cured film surface, but copper remains unchanged.
C: Traces are visible on the surface of the cured film, but copper is unchanged.
D: There is a trace on the surface of the cured film, and copper is discolored.

表２の成分の記号は以下の意味を示す。
（Ａ）成分（Ａ１）：モノマー配合比（メタクリル酸／メタクリル酸メチル／アクリル酸エチル＝１２／５８／３０（質量比））である共重合体のプロピレングリコールモノメチルエーテル／トルエン溶液、重量平均分子量６５，０００、酸価７８ｍｇＫＯＨ／ｇ、水酸基価２ｍｇＫＯＨ／ｇ、Ｔｇ６０℃。

The symbols of the components in Table 2 have the following meanings.
(A) Component (A1): Propylene glycol monomethyl ether / toluene solution of copolymer having a monomer blending ratio (methacrylic acid / methyl methacrylate / ethyl acrylate = 12/58/30 (mass ratio)), weight average molecular weight 65,000, acid value 78 mgKOH / g, hydroxyl value 2 mgKOH / g, Tg 60 ° C.

(B) Component A-DCP (made by Shin-Nakamura Chemical Co., Ltd., product name)

（一般式（１）で、ｐ＝ｑ＝０、ｎ＝ｍ＝１、Ｘ＝ジシクロペンタニル基）
Ｔ−１４２０（Ｔ）：ジトリメチロールプロパンテトラアクリレート（日本化薬株式会社製）
Ａ−ＤＯＧ：ジオキサングリコールジアクリレート（新中村化学工業株式会社製）
ＢＰＥ−１００：エトキシ化ビスフェノールＡメタクリレート、ＥＯ２．６ｍｏｌ（新中村化学工業株式会社製）
ＢＰＥ−２００：エトキシ化ビスフェノールＡメタクリレート、ＥＯ４．０ｍｏｌ（新中村化学工業株式会社製）
ＦＡ−３２１Ｍ：ＥＯ変性ビスフェノールＡジメタクリレート、ＥＯ１０ｍｏｌ（日立化成株式会社製）

(In general formula (1), p = q = 0, n = m = 1, X = dicyclopentanyl group)
T-1420 (T): Ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd.)
A-DOG: Dioxane glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
BPE-100: Ethoxylated bisphenol A methacrylate, EO 2.6 mol (manufactured by Shin-Nakamura Chemical Co., Ltd.)
BPE-200: Ethoxylated bisphenol A methacrylate, EO 4.0 mol (manufactured by Shin-Nakamura Chemical Co., Ltd.)
FA-321M: EO-modified bisphenol A dimethacrylate, EO 10 mol (manufactured by Hitachi Chemical Co., Ltd.)

(C) Component IRGACURE OXE01: 1,2-octanedione, 1-[(4-phenylthio) phenyl-, 2- (O-benzoyloxime)] (manufactured by BASF)
NCI-930: Adeka Cruise NCI-930 (formula (2-1), manufactured by ADEKA Corporation)
N-1919: Adekaoptomer N-1919 (formula (4-1), manufactured by ADEKA Corporation)
DFI-091: manufactured by Daito Chemix Co., Ltd. (formula (3-1), other photopolymerization initiator)

(D) Component B-6030: 5-amino-1H-tetrazole (manufactured by Chiyoda Chemical Co., Ltd., trade name: Thioale B-6030)
(E) Component PM21: Phosphate ester containing a photopolymerizable unsaturated bond (ethylene oxide-modified phosphate dimethacrylate, manufactured by Nippon Kayaku Co., Ltd.)
Other AW500: Antage W-500, 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd.)
ADDITIVE 8032: Silicone leveling agent (manufactured by Dow Corning Toray)
Methyl ethyl ketone: manufactured by Tonen Chemical Corporation

In Examples 1 to 8 using a di (meth) acrylate compound having the dicyclopentanyl structure (the above general formula (5)) as the component (B) shown in Table 3, high transparency at a film thickness of 5 μm It was possible to achieve both low moisture permeability and high rust prevention (salt spray test).
On the other hand, in Comparative Example 1, a relatively high rust prevention property (salt spray test) could be obtained, but the moisture permeability was relatively high and could not be achieved at the same time. Moreover, in Comparative Examples 2-5, low moisture permeability and high rust prevention property (salt water spray test) were not able to be made compatible.

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support film, 20 ... Photosensitive layer, 22 ... Protective film, 30 ... Protective film, 100 ... Base material for touch panels, 101 ... Transparent substrate, 102 ... Touch screen, 103 ... Transparent electrode (X position) (Coordinates), 104 ... transparent electrode (Y position coordinates), 104a ... part of the transparent electrode, 104b ... bridge portion of the transparent electrode, 104c ... transparent electrode wiring, 105, 105a, 105b ... extraction wiring, 106 ... connection electrode, 107 DESCRIPTION OF SYMBOLS ... Connection terminal, 108 ... Opening part, 110, 120 ... Electrode for touch panels, 122, 123, 124 ... Protective film, 125 ... Transparent insulating film, 130 ... Photomask, 200 ... Base material for touch panels with cured film.

Claims (18)

A method for manufacturing a base material for a touch panel with a cured film comprising a base material for a touch panel and a cured film,
The touch panel substrate includes a sensing region having an electrode, and a region having a metal wiring electrically connected to the electrode while being located outside the sensing region,
The said manufacturing method provides the photosensitive resin composition layer containing the photosensitive resin composition containing (A) component: Binder polymer and (B) component: Photopolymerizable compound on the base material for touchscreens. A step of curing a predetermined portion of the photosensitive resin composition layer by irradiation with actinic rays and then removing the portion other than the predetermined portion to form a cured film of the photosensitive resin composition on at least the metal wiring. ,
The (A) component includes a copolymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester,
The component (B) includes a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure,
The content of the component (A) is 35 to 85 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B),
(B) the content of the component, the (A) component and the (B) Ru 15 to 65 parts by mass der weight per 100 parts by weight of the component, method for producing a cured film with a touch panel for substrates. The dicyclopentenyl structure, or di (meth) acrylate compound having a dicyclopentenyl structure is a compound represented by the following general formula (1), production of a cured film with a touch panel for substrate according to claim 1 Method.

[In General Formula (1), X shows a dicyclopentanyl structure or a dicyclopentenyl structure. R each independently represents an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. n and m represent 0-2. p + q = 0 to 10 is shown. ] The dicyclopentenyl structure, or di (meth) acrylate compound having a dicyclopentenyl structure, dimethylol tricyclodecane di (meth) acrylate or tricyclodecane di (meth) acrylate, to claim 1 or 2 The manufacturing method of the base material for touchscreens with a cured film of description. When the acid value of component (A) is 75 mgKOH / g or more, the production method of the cured film with a touch panel for substrate according to any one of claims 1-3. The cured resin film according to any one of claims 1 to 4 , wherein the photosensitive resin composition further contains at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound. Manufacturing method of base material for touch panels. The manufacturing method of the base material for touchscreens with a cured film as described in any one of Claims 1-5 in which the said photosensitive resin composition contains an oxime ester compound. The manufacturing method of the base material for touchscreens with a cured film as described in any one of Claims 1-6 whose thickness of the said photosensitive resin composition layer is 10 micrometers or less. The manufacturing method of the base material for touchscreens with a cured film as described in any one of Claims 1-6 whose thickness of the said photosensitive resin composition layer is 9 micrometers or less. A photosensitive element for transfer comprising a support film and a photosensitive resin composition layer provided on the support film,
In the base material for touch panels, wherein the photosensitive resin composition layer includes a sensing region having an electrode, and a region located outside the sensing region and having a metal wiring electrically connected to the electrode. comprises a photosensitive resin composition for forming a cured film on at least said metal wire,
The photosensitive resin composition, (A) component: a binder polymer, (B) component: contains a photopolymerization initiator,: a photopolymerizable compound, (C) component
The (A) component includes a copolymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester,
The component (B), see contains di (meth) acrylate compound having a dicyclopentanyl structure or dicyclopentenyl structure,
The content of the component (A) is 35 to 85 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B),
(B) the content of the component, Ru 15 to 65 parts by mass der respect to the (A) component and the (B) total 100 parts by mass of the component, the photosensitive element. The dicyclopentenyl structure, or di (meth) acrylate compound having a dicyclopentenyl structure is a compound represented by the following general formula (1), photosensitive element of claim 9.

[In General Formula (1), X shows a dicyclopentanyl structure or a dicyclopentenyl structure. R each independently represents an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. n and m represent 0-2. p + q = 0 to 10 is shown. ] The dicyclopentenyl structure, or di (meth) acrylate compound having a dicyclopentenyl structure, dimethylol tricyclodecane di (meth) acrylate or tricyclodecane di (meth) acrylate, to claim 9 or 10 The photosensitive element as described. When the acid value of component (A) is 75 mgKOH / g or more, photosensitive element according to any one of claims 9-11. The photosensitive element according to any one of claims 9 to 12 , wherein the photosensitive resin composition further contains at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound. . The component (C) contains an oxime ester compound, a photosensitive element according to any one of claims 9-13. The photosensitive element as described in any one of Claims 9-14 whose thickness of the said photosensitive resin composition layer is 10 micrometers or less. The photosensitive element as described in any one of Claims 9-14 whose thickness of the said photosensitive resin composition layer is 9 micrometers or less. A base material for a touch panel;
Comprising a cured film of the photosensitive resin composition of the photosensitive element according to any one of 請 Motomeko 9-16, a,
The touch panel substrate includes a sensing region having an electrode, and a region having a metal wiring electrically connected to the electrode while being located outside the sensing region,
A substrate for a touch panel with a cured film, wherein the cured film is disposed on at least the metal wiring. A touch panel provided with the base material for touch panels with a cured film of Claim 17 .

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