Touch panel sensor and method for manufacturing the touch panel sensor

Abstract

To provide a touch panel sensor configured to suppress the change in resistance value of a sensor electrode of the touch panel sensor after bending and prevent bright points from being generated when carried in a rolled state, and a manufacturing method of the touch panel sensor.SOLUTION: A touch panel sensor includes a conductive substrate including a substrate and a sensor electrode arranged on the substrate, and a protection film covering at least a part of the sensor electrode. A surface hardness of the protection film opposite the conductive substrate is equal to or greater than 185 mN / mm2. A diameter X to be obtained through a predetermined test is equal to or less than 3 mm.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a touch panel sensor and a method for manufacturing the touch panel sensor.

Background Art

[0002] In a display device provided with a touch panel such as a capacitance type input device (specifically, as the display device, an organic electroluminescence (EL) display device, a liquid crystal display device, etc.), a conductive pattern such as a sensor electrode pattern corresponding to the sensor of the visual recognition part, a peripheral wiring part, and wiring of a lead-out wiring part is provided inside the touch panel.

[0003] On this conductive pattern, usually, for the purpose of preventing problems such as corrosion of metal, increase in electrical resistance between the electrode and the driving circuit, and disconnection, a pattern made of resin may be arranged as a protective film (permanent film).

[0004] Generally, a photosensitive composition is used for forming a pattern. In particular, since the number of steps for obtaining a required pattern shape is small, a method using a transfer film having a temporary support and a photosensitive composition layer formed using a photosensitive composition is widely used. As a method for forming a pattern using a transfer film, a method of performing exposure and development on a photosensitive composition layer transferred from a transfer film onto an arbitrary base material through a mask having a predetermined pattern shape can be mentioned. For example, when the photosensitive composition layer is a negative type photosensitive composition layer, a dissolution contrast can occur between the exposed region and the unexposed region by curing the exposed region. As a result, a pattern can be formed by removing only the unexposed region during the development process.

[0005] As a photosensitive composition and a transfer film, for example, in Patent Document 1, "a photosensitive resin composition containing a binder polymer having a carboxy group with an acid value of 75 mgKOH / g or more, a photopolymerizable compound, and a photopolymerization initiator" and "a photosensitive element including a support film and a photosensitive layer made of the above photosensitive resin composition provided on the support film" are disclosed.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] The inventors of the present invention manufactured a touch panel sensor using the photosensitive element (transfer film) disclosed in Patent Document 1 and measured the resistance value of the sensor electrode after bending. As a result, it was found that the change in the resistance value was large before and after bending. Furthermore, when the touch panel sensor manufactured using the above transfer film was handled by roll conveyance or the like, bright spots sometimes occurred. In addition, as a result of the study by the inventors of the present invention, it was difficult to achieve both the reduction of the change in the resistance value and the suppression of the generation of bright spots. The change in the resistance value and the generation of bright spots were not desirable from the viewpoints of the change in the performance of the sensor and visibility, respectively.

[0008] Therefore, an object of the present invention is to provide a touch panel sensor in which the change in the resistance value of the sensor electrode of the touch panel sensor after bending is small and bright spots are less likely to occur during handling such as roll conveyance. Another object of the present invention is to provide a method for manufacturing a touch panel sensor.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventor has completed the present invention. That is, it has been found that the above problems can be solved by the following configuration.

[0010] 〔1〕 A touch panel sensor having a conductive substrate including a substrate and a sensor electrode disposed on the substrate, and a protective film covering at least a part of the sensor electrode, wherein the surface hardness of the protective film on the side opposite to the conductive substrate is 185 mN / mm 2 or more, and the diameter X obtained by performing the following mandrel test is 3 mm or less. Mandrel test: The operation of winding the touch panel sensor around a mandrel and returning it to its original state is repeated 10 times, and then the operation of observing the protective film of the touch panel sensor with an optical microscope at a magnification of 10 times to confirm the presence or absence of cracks in the protective film is repeated while reducing the diameter of the mandrel, and the diameter of the mandrel at which cracks occur in the protective film is defined as the diameter X. 〔2〕 The touch panel sensor according to 〔1〕, wherein the protective film is a film formed using a photosensitive composition, and the photosensitive composition contains a binder polymer having an ethylenically unsaturated group in a side chain. 〔3〕 The touch panel sensor according to 〔2〕, wherein the photosensitive composition further contains a first polymerizable compound having two ethylenically unsaturated groups and a second polymerizable compound having five or more ethylenically unsaturated groups. 〔4〕 The touch panel sensor according to 〔3〕, wherein the mass ratio of the content of the second polymerizable compound to the content of the first polymerizable compound is 0.4 to 1.3. 〔5〕 A preparation step of preparing a substrate with a photosensitive composition layer having a substrate and a conductive substrate including a sensor electrode disposed on the substrate, and a photosensitive composition layer disposed on the conductive substrate and containing a binder polymer, a compound having an ethylenically unsaturated group, and a photopolymerization initiator; an exposure step of pattern-exposing the photosensitive composition layer; Developing the exposed photosensitive composition layer to form a resin layer pattern; A method for manufacturing a touch panel sensor, comprising: a curing step of exposing the resin layer pattern at 50 to 120 °C to form a protective film covering at least a part of the sensor electrode. 〔6〕 The exposure amount in the curing step is 200 to 1500 mJ / cm 2 The method for manufacturing a touch panel sensor according to 〔5〕. 〔7〕 The exposure amount in the curing step is 200 mJ / cm 2 or more and less than 1000 mJ / cm 2 The method for manufacturing a touch panel sensor according to 〔5〕 or 〔6〕. 〔8〕 When the intensity of the infrared absorption peak derived from the ethylenically unsaturated group contained in the photosensitive composition layer is Y1, and the intensity of the infrared absorption peak derived from the ethylenically unsaturated group contained in the protective film is Y2, the reaction rate calculated by the following formula (1) is 70% or more. The method for manufacturing a touch panel sensor according to any one of 〔5〕 to 〔7〕. Formula (1) Reaction rate [%] = {1 - (Y2 / Y1)} × 100

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a touch panel sensor in which the change in the resistance value of the sensor electrode of the touch panel sensor after bending is small, and bright spots are less likely to occur during handling such as roll conveyance. Further, according to the present invention, a method for manufacturing a touch panel sensor can be provided.

Brief Description of the Drawings

[0012]

Figure 1

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0014] The following represents the meaning of each description in this specification. In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In this specification, in a numerically described stepwise range, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another stepwise numerical range. Also, in the numerical range described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

[0015] In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved.

[0016] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. In this specification, the transmittance is a value measured using a spectrophotometer. For example, it can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0017] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values converted using polystyrene of a standard substance measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all are trade names manufactured by Tosoh Corporation) as columns, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene of a standard substance. In this specification, unless otherwise specified, the ratio of the constitutional units of the polymer is a mass ratio. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of a metal element is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0018] In this specification, “(meth)acryl” is a concept encompassing both acrylic and methacrylic, and “(meth)acryloxy group” is a concept encompassing both acryloxy group and methacryloxy group.

[0019] In this specification, “alkali-soluble” means that the solubility in 100 g of a 1 mass% aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0020] In this specification, “water-soluble” means that the solubility in 100 g of water at pH 7.0 with a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, a water-soluble resin is intended to be a resin that satisfies the above solubility conditions.

[0021] In this specification, the “solid content” of a composition means the components that form the composition layer formed using the composition. When the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Also, any liquid component that forms the composition layer is regarded as a solid content.

[0022] <Touch panel sensor> The touch panel sensor of the present invention includes a conductive substrate including a base material and sensor electrodes disposed on the base material, and a protective film covering at least a part of the sensor electrodes. The characteristic point of the touch panel sensor of the present invention is that the surface hardness on the side opposite to the conductive substrate of the protective film is 185 mN / mm 2 or more, and the diameter X obtained by performing a mandrel test, which will be described in detail later, is 3 mm or less. The mechanism by which the touch panel sensor having the above characteristic points has little change in the resistance value of the sensor electrodes of the touch panel sensor after being bent and is less likely to generate bright spots is not necessarily clear in detail, but the present inventors presume as follows.

[0023] Since the diameter X obtained by the mandrel test of the touch panel sensor of the present invention is 3 mm or less, even if the touch panel sensor is bent during the manufacture of the touch panel sensor or the like, no crack occurs in the protective film, so that local stress acts on the sensor electrodes disposed below the protective film, and cracks or the like do not occur in the sensor electrodes. As a result, it is considered that the change in the resistance value of the sensor electrodes is small. Further, since the surface hardness on the side opposite to the conductive substrate of the protective film of the touch panel sensor of the present invention is 185 mN / mm 2 or more, even if another object contacts during the handling of the touch panel sensor (for example, during roll conveyance), no scratch or deformation occurs on the surface of the protective film, and as a result, it is considered that bright spots are less likely to occur in the manufactured touch panel sensor.

[0024] Hereinafter, the touch panel sensor of the present invention will be described. In addition, the manufacturing method of the touch panel sensor of the present invention will be described later. In addition, hereinafter, when at least one of the change in the resistance value of the sensor electrodes of the touch panel sensor after being bent is smaller and the bright spots are less likely to occur in the touch panel sensor is satisfied, it is also said that "the effect of the present invention is more excellent".

[0025] [Conductive Substrate] The touch panel sensor of the present invention has a conductive substrate including a substrate and sensor electrodes disposed on the substrate. Hereinafter, the substrate and the sensor electrodes will be described.

[0026] (Substrate) Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the substrate are described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, the content of which is incorporated herein. As the material of the resin substrate, a cycloolefin polymer or polyimide is preferred. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm. Further, the substrate may have a transparent layer. Examples of the transparent layer include a refractive index adjustment layer that the transfer film described later may have.

[0027] (Sensor electrodes) The sensor electrodes refer to patterned electrodes formed on the above-mentioned substrate. The sensor electrodes are electrodes that function as sensor portions when a touch panel including the touch panel sensor of the present invention is formed. The pattern shape of the sensor electrodes is not particularly limited and may be a known one. The sensor electrodes may be disposed on the entire surface of the substrate, may be disposed on a part of the substrate, or may be disposed on both surfaces of the substrate.

[0028] The sensor electrodes preferably include at least one conductive layer. As the conductive layer, from the viewpoints of fine wire formability and conductivity, it is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Also, only one conductive layer may be disposed as the sensor electrodes on the substrate, or two or more layers may be disposed. When two or more conductive layers are disposed, it is preferable to have conductive layers of different materials. As a preferred embodiment of the conductive layer, for example, it is described in paragraph

[0141] of WO 2018 / 155193, the content of which is incorporated herein.

[0029] The sensor electrode is preferably a transparent electrode. The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a fine metal wire such as a metal mesh and a metal nanowire. Examples of the fine metal wire include fine wires of silver, copper, etc. Among them, silver conductive materials such as a silver mesh and silver nanowires are preferable.

[0030] (Routing wiring) The conductive substrate may have routing wiring. The routing wiring is electrically connected to the above-described sensor electrode. When the conductive substrate has a transparent electrode and routing wiring, the conductive substrate can be preferably used as a substrate for a touch panel.

[0031] The material of the routing wiring is preferably a metal. Examples of the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements. The material of the routing wiring is preferably copper, molybdenum, aluminum, or titanium, and particularly preferably copper.

[0032] [Protective film] The protective film is disposed on the conductive substrate so as to cover at least a part of the sensor electrode. The protective film is not particularly limited as long as it has the above characteristics, but preferably contains the above resin, and more preferably is formed using a photosensitive composition. Further, the photosensitive composition more preferably contains a binder polymer having an ethylenically unsaturated group in the side chain. The protective film is preferably formed using a transfer film including a photosensitive composition layer, which will be described later. The preferred photosensitive composition layer is detailed in the part of the transfer film. Also, the preferred method for forming the protective film is detailed in the part of the method for manufacturing a touch panel sensor.

[0033] <Physical Properties of Touch Panel Sensor and Protective Film> The touch panel sensor of the present invention satisfies the physical properties shown in the above-described characteristic points. Hereinafter, each physical property will be described.

[0034] (Surface Hardness) The protective film of the touch panel sensor of the present invention has a surface hardness of 185 mN / mm or more on the surface opposite to the conductive base material of the protective film. 2 or more. The above surface hardness refers to the one measured by the following procedure in this specification.

[0035] First, prepare a touch panel sensor having a conductive base material including a base material and sensor electrodes disposed on the base material, and a protective film covering at least a part of at least the sensor electrodes. Cut the touch panel sensor into a 2 cm square to obtain a sample. Apply the instant adhesive Aron Alpha (registered trademark) 201 onto a slide glass (thickness: 0.7 mm) so that the diameter becomes 1 cm, and immediately bond the instant adhesive application surface of the slide glass and the surface of the sample opposite to the protective film. When bonding, hold the sample with a finger so that no gap is formed between the slide glass and the sample. After bonding, leave it to stand in an environment of 23°C and 50% humidity. Obtain a measurement sample by the above procedure. Using the obtained measurement sample, measure the surface hardness of the protective film using a microhardness tester under the following conditions. · Device name: Microhardness tester (model number: HM2000, manufactured by Fisher Instruments) · Indenter: Berkovich indenter · Maximum load: 1 mN · Loading time: 10 seconds (time from when the indenter detects the surface of the cured product until it reaches the maximum load) · Holding time: 5 seconds (time to hold the maximum load) · Unloading time: 10 seconds (time until the load becomes zero) Calculate the contact projection area of the indenter that has been pushed in from the depth of the push-in, divide the maximum load = 1 mN by that area, and obtain the surface hardness (N / mm 2 ). Change the measurement location to be more than 0.3 mm away from the measured location and measure 10 times. Arithmetically average the surface hardness obtained from the 10 measurements to obtain the surface hardness of the measurement sample.

[0036] The surface hardness of the protective film is 185 N / mm 2 or more, preferably 190 N / mm 2 or more, and more preferably 200 N / mm 2 or more. The upper limit is not particularly limited, but preferably 300 N / mm 2 or less, more preferably 250 N / mm 2 or less, and even more preferably 220 N / mm 2 or less. By setting the surface hardness of the protective film within the above-preferred range, it is possible to make it less likely for bright spots to occur on the touch panel sensor during handling such as roll conveyance. The above surface hardness can be adjusted by the type, content, and content ratio of the ethylenically unsaturated compound contained in the photosensitive composition layer described later, as well as the type of the binder polymer. Further, the surface hardness can also be adjusted by the manufacturing conditions of the manufacturing method of the touch panel sensor described later.

[0037] (Mandrel test) The diameter X obtained by performing the mandrel test on the touch panel sensor of the present invention is 3 mm or less. The diameter X obtained by performing the mandrel test refers to the one measured by the following procedure in this specification.

[0038] Evaluate the bendability using a Type 2 test apparatus in accordance with the method specified in JIS K-5600-5-1 (1999), i.e., by the cylindrical mandrel method. In the above method, use mandrels with diameters of 1 mm, 2 mm, 3 mm, 4 mm, and 5 mm, and set the number of bending times to 10. After bending, observe the surface of the protective film of the touch panel sensor under an optical microscope at a magnification of 10 times to confirm the presence or absence of cracks in the protective film. If no cracks can be confirmed in the protective film, conduct the same test using a mandrel with a smaller diameter than the one used. Repeat the above test, and define the diameter of the mandrel at which cracks first occur in the protective film as diameter X. If no cracks occur even with a 1-mm mandrel, diameter X is 1 mm.

[0039] The above diameter X is 3 mm or less, preferably 2 mm or less, and more preferably 1 mm. By setting diameter X within the above preferred range, changes in the resistance value of the sensor electrode can be reduced more effectively. The above diameter X can be adjusted according to the type, content, and content ratio of the ethylenically unsaturated compound contained in the photosensitive composition layer described below, as well as the type of binder polymer, etc. Also, the surface hardness can be adjusted according to the manufacturing conditions of the manufacturing method of the touch panel sensor described below.

[0040] <Transfer film> The transfer film preferably used for forming the protective film of the touch panel sensor of the present invention will be described. The transfer film has a temporary support and a composition layer disposed on the temporary support, and the above composition layer includes a photosensitive composition layer. The above composition layer is not particularly limited as long as it includes a photosensitive composition layer. The above photosensitive composition layer is preferably a negative photosensitive composition layer. Also, the above composition layer may have a single-layer structure or a structure of two or more layers. When the above composition layer includes other composition layers in addition to the photosensitive composition layer, examples of the other composition layers include a thermoplastic resin layer, an intermediate layer, a refractive index adjustment layer, etc. Further, the transfer film may have a protective film on the composition layer.

[0041] An example of the mode of the transfer film is shown below, but it is not limited thereto. (1) "Temporary support / photosensitive composition layer / refractive index adjustment layer / protective film" (2) "Temporary support / photosensitive composition layer / protective film" (3) "Temporary support / intermediate layer / photosensitive composition layer / protective film" (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film" In each of the above configurations, the photosensitive composition layer is preferably a negative photosensitive composition layer. Also, it is preferable that the photosensitive composition layer is a colored resin layer. As the configuration of the transfer film, for example, the configuration of (1) or (2) described above is preferable.

[0042] In the composition layer of the transfer film, in the case of a configuration having another composition layer on the side opposite to the temporary support side of the photosensitive composition layer, the total thickness of the other layers arranged on the side opposite to the temporary support side of the photosensitive composition layer is preferably 0.1 to 30% with respect to the thickness of the photosensitive composition layer, and more preferably 0.1 to 20%.

[0043] From the viewpoint of suppressing the generation of bubbles in the bonding step described later, the maximum width of the undulation of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. Note that the lower limit value of the maximum width of the undulation is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the undulation of the transfer film is a value measured by the following procedure. First, cut the transfer film in a direction perpendicular to the main surface so that it has a size of 20 cm in length and 20 cm in width to prepare a test sample. When the transfer film has a protective film, the protective film is peeled off. Next, place the test sample on a smooth and horizontal stage so that the surface of the temporary support faces the stage. After standing, scan the surface of the test sample within a range of 10 cm square at the center of the test sample with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) to obtain a three-dimensional surface image, and subtract the lowest concave height from the maximum convex height observed in the obtained three-dimensional surface image. Perform the above operation on 10 test samples, and take the arithmetic mean value as the "maximum undulation width of the transfer film".

[0044] Hereinafter, an example of a specific embodiment will be given to explain the transfer film.

[0045] [Temporary support] The transfer film has a temporary support. The temporary support is a member that supports the composition layer and is finally removed by a peeling process.

[0046] The temporary support may have a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film that has flexibility and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat is preferred. Examples of the film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a triacetate cellulose film, a polystyrene film, a polyimide film, and a polycarbonate film. Among them, a polyethylene terephthalate film is preferred as the temporary support. In addition, the film used as the temporary support preferably has no deformations such as wrinkles and no scratches.

[0047] The temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support. The transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign matters, and defects contained in the temporary support is preferably small. The number of fine particles, foreign matters, and defects having a diameter of 1 μm or more in the temporary support is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, still more preferably 3 pieces / 10 mm 2 or less, and particularly preferably 0 pieces / 10 mm. 2

[0048] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and most preferably 5 to 25 μm from the viewpoints of ease of handling and versatility. The thickness of the temporary support is calculated as the average value of any five points measured by cross-sectional observation using SEM (Scanning Electron Microscope).

[0049] In addition, in order to improve the adhesion between the temporary support and the composition layer, the side of the temporary support in contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like. When surface-modified by UV irradiation, the exposure amount is preferably 10 to 2000 mJ / cm 2 and more preferably 50 to 1000 mJ / cm. 2 Examples of the light source for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, light-emitting diodes (LEDs), etc. that emit light in the wavelength band of 150 to 450 nm. As long as the light irradiation amount can be within this range, the lamp output and illuminance are not particularly limited.

[0050] Examples of the temporary support include, for example, a biaxially stretched polyethylene terephthalate film with a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 μm.

[0051] Preferred forms of the temporary support include, for example, the paragraphs

[0017] to

[0018] of JP-A-2014-085643, the paragraphs

[0019] to

[0026] of JP-A-2016-027363, the paragraphs

[0041] to

[0057] of WO 2012 / 081680, and the paragraphs

[0029] to

[0040] of WO 2018 / 179370, and the contents of these publications are incorporated herein.

[0052] In terms of imparting handleability, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. Also, the film thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Examples of commercially available products of the temporary support include Lumirror 16KS40, Lumirror 16FB40 (both manufactured by Toray Industries, Inc.), Cosmo Shine A4100, Cosmo Shine A4300, Cosmo Shine A8300 (all manufactured by Toyobo Co., Ltd.).

[0053] [Photosensitive Composition Layer] The transfer film has a photosensitive composition layer. After transferring the photosensitive composition layer onto the object to be transferred and performing exposure and development, a pattern can be formed on the object to be transferred. As the photosensitive composition layer, a negative type is preferred. The negative type photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer decreases upon exposure. When the photosensitive composition layer is a negative type photosensitive composition layer, the formed pattern corresponds to a cured layer.

[0054] Hereinafter, the components that can be contained in the photosensitive composition layer will be described in detail.

[0055] (Binder polymer) The photosensitive composition layer may contain a binder polymer. Examples of the binder polymer include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, epoxy acrylate resins obtained by the reaction of epoxy resins and (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of epoxy acrylate resins and acid anhydrides.

[0056] As one of the preferred embodiments of the binder polymer, a (meth)acrylic resin is mentioned in terms of excellent alkali developability and film-forming properties. In this specification, the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more based on all the structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of structural units derived from the (meth)acrylic compound, or may have structural units derived from polymerizable monomers other than the (meth)acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth)acrylic compound is 100% by mass or less based on all the structural units of the (meth)acrylic resin.

[0057] (Meth)acrylic compounds include, for example, (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, (meth)acrylic acid glycidyl esters, (meth)acrylic acid benzyl esters, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl esters are preferred. Examples of (meth)acrylamides include acrylamides such as diacetoneacrylamide.

[0058] The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include (meth)acrylic acid alkyl esters having an alkyl group with 1 to 12 carbon atoms such as (meth)acrylic acid methyl, (meth)acrylic acid ethyl, (meth)acrylic acid propyl, (meth)acrylic acid butyl, (meth)acrylic acid pentyl, (meth)acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid octyl, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid nonyl, (meth)acrylic acid decyl, (meth)acrylic acid undecyl, and (meth)acrylic acid dodecyl. As the (meth)acrylic acid ester, (meth)acrylic acid alkyl esters having an alkyl group with 1 to 4 carbon atoms are preferred, and (meth)acrylic acid methyl or (meth)acrylic acid ethyl is more preferred.

[0059] (Meth)acrylic resins may have structural units other than the structural units derived from (meth)acrylic compounds. The polymerizable monomer forming the above-mentioned structural unit is not particularly limited as long as it is a compound other than (meth)acrylic compounds copolymerizable with (meth)acrylic compounds. For example, styrene compounds which may have a substituent at the α-position or on the aromatic ring such as styrene, vinyltoluene, and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0060] In addition, from the viewpoint of making the alkali developability better, the (meth)acrylic resin preferably has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Among them, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0061] The content of the structural unit having an acid group (preferably the structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more based on the total mass of the (meth)acrylic resin in terms of excellent developability. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less in terms of excellent alkali resistance.

[0062] Moreover, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester. When having a structural unit derived from an (meth)acrylic acid alkyl ester, the content of the structural unit derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 1 to 90% by mass, more preferably 1 to 50% by mass, and still more preferably 1 to 30% by mass with respect to all the structural units of the (meth)acrylic resin.

[0063] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from an (meth)acrylic acid alkyl ester is preferable, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from an (meth)acrylic acid alkyl ester is more preferable. Further, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

[0064] Further, from the viewpoint of more excellent effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester. The total content of the structural unit derived from methacrylic acid and the structural unit derived from a methacrylic acid alkyl ester in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more with respect to all the structural units of the (meth)acrylic resin from the viewpoint of more excellent effects of the present invention. The upper limit is not particularly limited and may be 100% by mass or less, and preferably 80% by mass or less.

[0065] Further, from the viewpoint of more excellent effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylate, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from alkyl acrylate. From the viewpoint of more excellent effects of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is preferably 60 / 40 to 80 / 20 by mass ratio with respect to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.

[0066] The (meth)acrylic resin preferably has an ester group at the terminal in terms of excellent developability of the photosensitive composition layer after transfer. Note that the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. The (meth)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0067] Further, another preferred embodiment of the binder polymer includes an alkali-soluble resin. The binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more, for example, from the viewpoint of developability. Further, the binder polymer is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint of easily forming a strong film by thermally crosslinking with a crosslinking component by heating, and even more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth)acrylic resin). When the binder polymer is a resin having a carboxy group, for example, by adding a thermally crosslinkable compound such as a blocked isocyanate compound and performing thermal crosslinking, the three-dimensional crosslinking density can be increased. Further, when the carboxy group of the resin having a carboxy group is anhydrified and hydrophobized, the wet heat resistance can be improved.

[0068] The carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph

[0025] of JP-A-2011-095716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs

[0033] to

[0052] of JP-A-2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.

[0069] Another preferred embodiment of the binder polymer includes a styrene-acrylic copolymer. In the present specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer. Further, the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 5 to 80% by mass, based on all the structural units of the copolymer. Further, the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20 to 95% by mass, based on all the structural units of the copolymer.

[0070] The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint of more excellent effects of the present invention. Examples of the monomer that forms a structural unit having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferable. Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl group), and a substituted or unsubstituted benzyl group, etc., and a substituted or unsubstituted benzyl group is preferable.

[0071] Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate, etc.

[0072] Examples of the monomer having a benzyl group include (meth)acrylate having a benzyl group, for example, benzyl (meth)acrylate, and chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, for example, vinylbenzyl chloride, and vinylbenzyl alcohol, etc. Among them, benzyl (meth)acrylate is preferable.

[0073] Furthermore, the binder polymer more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene), from the viewpoint of more excellent effects of the present invention.

[0074]

Chemical formula

[0075] When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass with respect to all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention. In addition, from the viewpoint of more excellent effects of the present invention, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 60 mol% based on all the structural units of the binder polymer. Furthermore, from the viewpoint of more excellent effects of the present invention, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 60 mol%, particularly preferably 20 to 50 mol% based on all the structural units of the binder polymer. In the present specification, when the content of the "structural unit" is defined by a molar ratio, the above "structural unit" shall be synonymous with the "monomer unit". Also, in the present specification, the above "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0076] From the viewpoint of more excellent effects of the present invention, the binder polymer preferably has an aliphatic hydrocarbon ring structure. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be a monocyclic or polycyclic ring. Among them, the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

[0077] Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isobornyl ring. Among them, from the viewpoint of more excellent effects of the present invention, a ring in which two or more aliphatic hydrocarbon rings are fused is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 decane ring) is more preferable. Examples of the monomer forming the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Further, from the viewpoint of more excellent effects of the present invention, the binder polymer more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0078]

Chemical formula

[0079] In formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0080] R M in formula (Cy) is preferably a methyl group. R Cy in formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms, from the viewpoint of more excellent effects of the present invention. Further, the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure, from the viewpoint of more excellent effects of the present invention. Furthermore, the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, and more preferably a ring in which 2 to 4 aliphatic hydrocarbon rings are fused, from the viewpoint of more excellent effects of the present invention. Furthermore, R CyFrom the viewpoint of more excellent effects of the present invention, it is preferable that the oxygen atom of -C(=O)O- in the formula (Cy) and the aliphatic hydrocarbon ring structure are directly bonded, that is, it is an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and still more preferably a dicyclopentanyl group.

[0081] The binder polymer may have one kind or two or more kinds of structural units having an aliphatic hydrocarbon ring structure. When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects of the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass based on all the structural units of the binder polymer. Further, from the viewpoint of more excellent effects of the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer. Furthermore, from the viewpoint of more excellent effects of the present invention, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

[0082] When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects of the present invention, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass based on all the structural units of the binder polymer. In addition, from the viewpoint of more excellent effects of the present invention, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% based on all the structural units of the binder polymer. Furthermore, from the viewpoint of more excellent effects of the present invention, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% based on all the structural units of the binder polymer. In addition, from the viewpoint of more excellent effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and still more preferably satisfy the following formula (SCy-2). 0.2 ≦ nS / (nS + nCy) ≦ 0.8 Formula (SCy) 0.30 ≦ nS / (nS + nCy) ≦ 0.75 Formula (SCy-1) 0.40 ≦ nS / (nS + nCy) ≦ 0.70 Formula (SCy-2)

[0083] From the viewpoint of more excellent effects of the present invention, the binder polymer preferably has a structural unit having an acid group. Examples of the above acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferred. As the structural unit having the above acid group, the structural unit derived from (meth)acrylic acid shown below is preferred, and the structural unit derived from methacrylic acid is more preferred.

[0084]

Chemical formula

[0085] The binder polymer may have one kind of the structural unit having an acid group alone or two or more kinds thereof. When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention. Further, the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% with respect to all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention. Furthermore, the content of the structural unit derived from (meth)acrylic acid in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% with respect to all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention.

[0086] The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint of more excellent effects of the present invention. As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain. That is, as the binder polymer, a binder polymer having an ethylenically unsaturated group in the side chain is preferable. In the present specification, the "main chain" represents the relatively longest bond chain in the molecule of the high molecular compound constituting the resin, and the "side chain" represents an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable. Examples of the structural unit having a reactive group include, but are not limited to, those shown below.

[0087]

Chemical formula

[0088] The binder polymer may have one or more than two kinds of structural units having reactive groups. When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass based on all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention. Also, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention.

[0089] Examples of means for introducing a reactive group into the binder polymer include methods of reacting functional groups such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group with compounds such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride. A preferred example of the means for introducing a reactive group into the binder polymer is a method in which a polymer having a carboxy group is synthesized by a polymerization reaction, and then glycidyl (meth) acrylate is reacted with a part of the carboxy groups of the obtained polymer by a polymer reaction to introduce a (meth) acryloxy group into the polymer. By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained. The above polymerization reaction is preferably carried out under temperature conditions of 70 to 100 ° C, more preferably 80 to 90 ° C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fuji Film Wako Pure Chemical Corporation is more preferable. The above polymer reaction is preferably carried out under temperature conditions of 80 to 110 ° C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0090] The binder polymer may be the polymers shown below. The content ratios (a to d) and weight average molecular weight Mw, etc. of each constitutional unit shown below can be appropriately changed according to the purpose.

[0091]

Chemical formula

[0092] In the above binder polymer, a to d are preferably a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%, respectively.

[0093]

Chemical formula

[0094] In the above binder polymer, a to d are preferably a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%, respectively.

[0095]

Chemical formula

[0096] In the above binder polymer, a to d are preferably a: 30 to 65 wt%, b: 1.0 to 20 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%, respectively.

[0097]

Chemical formula

[0098] In the above binder polymer, a to d are preferably a: 1.0 to 20 wt%, b: 20 to 60 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%, respectively.

[0099] Further, the binder polymer may contain a polymer having a structural unit with a carboxylic anhydride structure (hereinafter also referred to as "polymer X"). The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure. As the ring of the cyclic carboxylic anhydride structure, a 5- to 7-membered ring is preferred, a 5- or 6-membered ring is more preferred, and a 5-membered ring is even more preferred.

[0100] The structural unit having a carboxylic anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from the compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0101] [Chemical formula]

[0102] In formula P-1, R A1a represents a substituent, and n 1a R's A1a may be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-O-C(=O)-, and n 1a represents an integer of 0 or more.

[0103] Examples of the substituent represented by R A1a include, for example, an alkyl group. As Z 1a , an alkylene group having 2 to 4 carbon atoms is preferred, an alkylene group having 2 or 3 carbon atoms is more preferred, and an alkylene group having 2 carbon atoms is even more preferred. n 1a represents an integer of 0 or more. When Z 1a represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. n 1a When n represents an integer of 2 or more, a plurality of R's A1a may be the same or different. Also, a plurality of R's A1a may combine with each other to form a ring, but it is preferably that they do not combine with each other to form a ring.

[0104] As the structural unit having a carboxylic anhydride structure, a structural unit derived from an unsaturated carboxylic anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic anhydride is more preferable, a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride is still more preferable, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.

[0105] Hereinafter, specific examples of the structural unit having a carboxylic anhydride structure will be given, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0106]

Chemical formula

[0107]

Chemical formula

[0108] The structural unit having a carboxylic anhydride structure in polymer X may be a single type or two or more types.

[0109] The total content of the structural unit having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 35 mol% with respect to all the structural units of polymer X.

[0110] The photosensitive composition layer may contain only one type of polymer X or two or more types. When the photosensitive composition layer contains polymer X, from the viewpoint of more excellent effects of the present invention, the content of polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 20% by mass, and still more preferably 1 to 20% by mass based on the total mass of the photosensitive composition layer.

[0111] From the viewpoint of more excellent effects of the present invention, the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and particularly preferably 15,000 to 30,000.

[0112] The acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 mg to 200 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 70 to 130 mgKOH / g. Note that the acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992. From the viewpoint of developability, the dispersity of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0113] The photosensitive composition layer may contain only one kind of binder polymer or two or more kinds of binder polymers. From the viewpoint of more excellent effects of the present invention, the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass based on the total mass of the photosensitive composition layer.

[0114] (Compound having an ethylenically unsaturated group) The photosensitive composition layer may contain a compound having an ethylenically unsaturated group (hereinafter, also simply referred to as "ethylenically unsaturated compound"). As the ethylenically unsaturated group, a (meth)acryloxy group is preferable. In addition, the ethylenically unsaturated compound in this specification is a compound other than the above binder polymer, and preferably has a molecular weight of less than 5,000.

[0115] As one of the preferred embodiments of the ethylenically unsaturated compound, a compound represented by the following formula (M) (simply referred to as "compound M") can be mentioned. Q 2 -R 1 -Q 1 Formula (M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.

[0116] Q in formula (M) 1 and Q 2 are preferably the same group from the viewpoint of ease of synthesis. 1 and Q 2 are preferably the same group. Also, Q in formula (M) 1 and Q 2 are preferably acryloyloxy groups from the viewpoint of reactivity. As R in formula (M) 1 , from the viewpoint that the effects of the present invention are more excellent, an alkylene group, an alkyleneoxyalkylene group (-L 1 -O-L 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferable, a hydrocarbon group having 2 to 20 carbon atoms, or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is still more preferable, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferable. The hydrocarbon group only needs to have a chain structure at least in part, and there are no particular restrictions on the part other than the chain structure. For example, it may be any of a branched-chain structure, a cyclic structure, or a linear alkylene group, an arylene group, an ether bond, and combinations thereof having 1 to 5 carbon atoms. A group combining an alkylene group or two or more alkylene groups and one or more arylene groups is preferable, an alkylene group is more preferable, and a linear alkylene group is even more preferable. In addition, the above L 1 each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

[0117] Also, the shortest number of atoms in the connecting chain connecting Q 1 and Q 2 in compound M is preferably 3 to 50, more preferably 4 to 40, even more preferably 6 to 20, and particularly preferably 8 to 12, from the viewpoint of more excellent effects of the present invention. In this specification, the "shortest number of atoms in the connecting chain connecting Q 1 and Q 2 " means the shortest number of atoms connecting from the atom in R 1 connected to Q 1 to the atom in R 2 connected to Q 1 ".

[0118] Specific examples of Compound M include 1,3 - butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, 1,7 - heptanediol di(meth)acrylate, 1,8 - octanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, from the viewpoint of more excellent effects of the present invention, it is preferably at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; more preferably at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, and 1,10 - decanediol di(meth)acrylate; and even more preferably at least one compound selected from the group consisting of 1,9 - nonanediol di(meth)acrylate and 1,10 - decanediol di(meth)acrylate.

[0119] Also, as one of the preferred embodiments of the ethylenically unsaturated compound, a polyfunctional ethylenically unsaturated compound having two or more functional groups is exemplified. In this specification, the "polyfunctional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0120] There is no particular limitation on the difunctional ethylenically unsaturated compound, and it can be appropriately selected from known compounds. Examples of the difunctional ethylenically unsaturated compound other than the above compound M include tricyclodecane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, and 1,4-cyclohexanediol di(meth)acrylate.

[0121] Examples of commercially available difunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and dioxane glycol diacrylate (KAYARAD R-604 manufactured by Nippon Kayaku Co., Ltd.).

[0122] There is no particular limitation on the ethylenically unsaturated compound having three or more functional groups, and it can be appropriately selected from known compounds. Examples of the ethylenically unsaturated compound having three or more functional groups include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0123] Here, “(tri / tetra / penta / hexa)(meth)acrylate” is a concept encompassing tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra)(meth)acrylate” is a concept encompassing tri(meth)acrylate and tetra(meth)acrylate.

[0124] Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), and ethoxylated glycerol triacrylate (such as NK ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0125] Examples of the ethylenically unsaturated compound also include urethane (meth)acrylate compounds. Examples of urethane (meth)acrylate include urethane di(meth)acrylate, for example, propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. In addition, examples of urethane (meth)acrylate include those having three or more functional groups. As the lower limit of the number of functional groups, six or more functional groups are more preferable, and eight or more functional groups are even more preferable. As the upper limit of the number of functional groups, 20 or less functional groups are preferable. Examples of urethane (meth)acrylate having three or more functional groups include 8UX-015A (manufactured by Dainippon Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0126] As one of the preferred embodiments of the ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group can be mentioned. Examples of the acid group include a phosphoric acid group, a sulfo group, and a carboxy group. Among these, as the acid group, a carboxy group is preferable. Examples of the ethylenically unsaturated compound having an acid group include ethylenically unsaturated compounds having 3 to 4 functional groups having an acid group (compounds in which a carboxy group is introduced into a pentaerythritol tri- and tetraacrylate (PETA) skeleton (acid value: 80 to 120 mgKOH / g)), ethylenically unsaturated compounds having 5 to 6 functional groups having an acid group (compounds in which a carboxy group is introduced into a dipentaerythritol penta- and hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mgKOH / g)), and the like. These ethylenically unsaturated compounds having three or more functional groups having an acid group may be used in combination with an ethylenically unsaturated compound having two functional groups having an acid group, if necessary.

[0127] As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of ethylenically unsaturated compounds having two or more functional groups having a carboxy group and carboxylic anhydrides thereof is preferable. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a polyfunctional ethylenically unsaturated compound having a carboxy group and its carboxylic anhydride, the developability and film strength are further enhanced. The polyfunctional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of the polyfunctional ethylenically unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0128] As the ethylenically unsaturated compound having an acid group, the ethylenically unsaturated compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 is preferable, and the content described in this publication is incorporated herein.

[0129] Examples of the ethylenically unsaturated compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid-based compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters. These are used alone or in combination of two or more.

[0130] Examples of the compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; trimethylolpropane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane ethoxytri(meth)acrylate; trimethylolpropane diethoxytri(meth)acrylate; trimethylolpropane triethoxytri(meth)acrylate; trimethylolpropane tetraethoxytri(meth)acrylate; trimethylolpropane pentaethoxytri(meth)acrylate; di(trimethylolpropane) tetraacrylate; tetramethylolmethane tri(meth)acrylate; tetramethylolmethane tetra(meth)acrylate; dipentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate; and dipentaerythritol hexa(meth)acrylate. Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable.

[0131] Examples of ethylenically unsaturated compounds include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), ethoxylated glycerol triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

[0132] As the ethylenically unsaturated compound, those containing an ester bond are particularly preferable in terms of excellent developability of the photosensitive composition layer after transcription. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable in terms of excellent effects of the present invention, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable. From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure. Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0133] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). As the ethylenically unsaturated compound, an ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferable, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecane dimethanol di(meth)acrylate is even more preferable. As the aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects of the present invention, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure is preferable.

[0134] The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and particularly preferably 300 to 2,200. Among the ethylenically unsaturated compounds contained in the photosensitive composition layer, the proportion of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less with respect to the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0135] As one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains an ethylenically unsaturated compound having two or more functional groups, more preferably contains an ethylenically unsaturated compound having three or more functional groups, and even more preferably contains an ethylenically unsaturated compound having three or four functional groups.

[0136] Also, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring.

[0137] Further, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0138] Further, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0139] Further, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoints of development residue suppression and rust prevention, the photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a polyfunctional ethylenically unsaturated compound having three or more functional groups (preferably a polyfunctional (meth)acrylate compound having three or more functional groups). The mass ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polyfunctional ethylenically unsaturated compound having three or more functional groups is preferably 10:90 to 90:10, and more preferably 30:70 to 70:30. The content of the bifunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. The content of the bifunctional ethylenically unsaturated compound in the photosensitive composition layer is preferably 10 to 60% by mass, and more preferably 15 to 40% by mass.

[0140] Further, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoint of rust prevention, the photosensitive composition layer preferably contains Compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure. Also, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention properties, the photosensitive composition layer preferably contains Compound M and an ethylenically unsaturated compound having an acid group, more preferably contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, still more preferably contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having three or more functional groups, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having three or more functional groups, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound. Also, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention properties, the photosensitive composition layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0141] The photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the ethylenically unsaturated compound having two or more functional groups in the above ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass based on the total content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0142] The ethylenically unsaturated compound may be used alone or in combination of two or more. Among them, in terms of more excellent effects of the present invention, the photosensitive composition layer preferably contains a first polymerizable compound having two ethylenically unsaturated groups and a second polymerizable compound having five or more ethylenically unsaturated groups. The content of the ethylenically unsaturated compound in the photosensitive composition layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, still more preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass with respect to the total mass of the photosensitive composition layer. When the photosensitive composition layer contains the first polymerizable compound and the second polymerizable compound, in terms of more excellent effects of the present invention, the mass ratio of the content of the second polymerizable compound to the content of the first polymerizable compound is preferably 0.2 to 1.8, more preferably 0.4 to 1.3, and still more preferably 0.5 to 1.3.

[0143] (Photoinitiator) The photosensitive composition layer may contain a photoinitiator. There is no particular limitation on the photoinitiator, and known photoinitiators can be used. Examples of the photoinitiator include a photoinitiator having an oxime ester structure (hereinafter also referred to as an "oxime-based photoinitiator"), a photoinitiator having an α-aminoalkylphenone structure (hereinafter also referred to as an "α-aminoalkylphenone-based photoinitiator"), a photoinitiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), a photoinitiator having an acylphosphine oxide structure (hereinafter also referred to as an "acylphosphine oxide-based photoinitiator"), and a photoinitiator having an N-phenylglycine structure (hereinafter also referred to as an "N-phenylglycine-based photoinitiator").

[0144] The photoinitiator preferably contains at least one selected from the group consisting of an oxime-based photoinitiator, an α-aminoalkylphenone-based photoinitiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photoinitiator, and more preferably contains at least one selected from the group consisting of an oxime-based photoinitiator, an α-aminoalkylphenone-based photoinitiator, and an N-phenylglycine-based photoinitiator.

[0145] Further, as the photoinitiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A No. 2011-95716 and paragraphs

[0064] to

[0081] of JP-A No. 2015-014783 may be used.

[0146] As commercially available photoinitiators, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetoxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, manufactured by IGM Resins B.V.], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad® 907, manufactured by IGM Resins B.V.], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad® 127, manufactured by IGM Resins B.V.], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad® 369, manufactured by IGM Resins B.V.], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad® 1173, manufactured by IGM Resins B.V.], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad® 184, manufactured by IGM Resins B.V.], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: Omnirad® 651, manufactured by IGM Resins B.Those such as [manufactured by Valve Corporation], oxime ester-based [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-, 2-(O-acet yloxime) (trade name: TR-PBG-326, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.) and the like can be mentioned.

[0147] The photoinitiator may be used alone or in combination of two or more. When two or more are used, it is preferable to use an oxime-based photoinitiator and at least one selected from an α-aminoalkylphenone-based photoinitiator and an α-hydroxyalkylphenone-based polymerization initiator. When the photosensitive composition layer contains a photoinitiator, the content of the photoinitiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more with respect to the total mass of the photosensitive composition layer. Further, as the upper limit value, it is preferably 10% by mass or less, more preferably 5% by mass or less with respect to the total mass of the photosensitive composition layer.

[0148] (Heterocyclic compound) The photosensitive composition layer may contain a heterocyclic compound. The heterocyclic ring of the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of the heteroatom in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0149] Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound. Among them, as the heterocyclic compound, at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound, and a benzoxazole compound is preferable, and at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, and a benzoxazole compound is more preferable.

[0150] Preferable specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

[0151]

Chemical formula

[0152]

Chemical formula

[0153] Examples of the tetrazole compound include the following compounds.

[0154]

Chemical formula

[0155]

Chem.

[0156] Examples of the thiadiazole compound include the following compounds.

[0157]

Chem.

[0158] Examples of the triazine compound include the following compounds.

[0159]

Chem.

[0160] Examples of the rhodanine compound include the following compounds.

[0161]

Chem.

[0162] Examples of the thiazole compound include the following compounds.

[0163]

Chem.

[0164] Examples of the benzothiazole compound include the following compounds.

[0165]

Chem.

[0166] Examples of the benzimidazole compound include the following compounds.

[0167] [Chemistry]

[0168] [Chemistry]

[0169] Examples of the benzoxazole compound include the following compounds.

[0170] [Chemistry]

[0171] The heterocyclic compound may be used alone or in combination of two or more. When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, still more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass with respect to the total mass of the photosensitive composition layer.

[0172] (Aliphatic thiol compound) The photosensitive composition layer may contain an aliphatic thiol compound. When the photosensitive composition layer contains an aliphatic thiol compound, the hardening shrinkage of the formed film is suppressed and the stress is relaxed by the en-thiol reaction between the aliphatic thiol compound and a radically polymerizable compound having an ethylenically unsaturated group.

[0173] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, an aliphatic thiol compound having two or more functional groups) is preferable.

[0174] Among these, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is preferable from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure).

[0175] In the present specification, the "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0176] As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0177] As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, from the viewpoint of the adhesion of the formed pattern, 2 to 10 functional groups are preferable, 2 to 8 functional groups are more preferable, and 2 to 6 functional groups are even more preferable.

[0178] Examples of the polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.

[0179] Among these, as the polyfunctional aliphatic thiol compound, at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferable.

[0180] Examples of the monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, and stearyl 3-mercaptopropionate.

[0181] The photosensitive composition layer may contain a single aliphatic thiol compound or may contain two or more aliphatic thiol compounds.

[0182] When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, still more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass based on the total mass of the photosensitive composition layer.

[0183] (Thermally crosslinkable compound) From the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, the photosensitive composition layer preferably contains a thermally crosslinkable compound. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is treated as a thermally crosslinkable compound and not as an ethylenically unsaturated compound. Examples of the thermally crosslinkable compound include an epoxy compound, an oxetane compound, a methylol compound, and a blocked isocyanate compound. Among them, a blocked isocyanate compound is preferable from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of a binder polymer and a radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease and the function as a protective film is enhanced. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent.

[0184] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 90 to 160°C, more preferably 100 to 150°C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter". As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

[0185] Examples of the blocking agent having a dissociation temperature of 100 to 160 °C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and compounds having a structure represented by -C(=N-OH)- in the molecule such as cyclohexanone oxime). Among these, as the blocking agent having a dissociation temperature of 90 to 160 °C, for example, from the viewpoint of storage stability, at least one selected from oxime compounds and pyrazole compounds is preferable.

[0186] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoints of improving the brittleness of the film and enhancing the adhesion to the transfer target. The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among the blocked isocyanate compounds having an isocyanurate structure, the compound having an oxime structure using an oxime compound as the blocking agent is preferable because it is easier to make the dissociation temperature in a preferable range and to reduce the development residue compared to the compound not having an oxime structure.

[0187] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, with a radically polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as glycidyl group. Among them, as the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloxy group is more preferred, and an acryloxy group is even more preferred.

[0188] Commercially available products can be used as the blocked isocyanate compound. Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI - BM, Karenz (registered trademark) MOI - BM, Karenz (registered trademark) MOI - BP, etc. (manufactured by Showa Denko K.K.), and the blocked Duranate series (for example, Duranate (registered trademark) TPA - B80E, Duranate (registered trademark) SBN - 70D, Duranate (registered trademark) WT32 - B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). As the blocked isocyanate compound, it is preferable to contain a blocked isocyanate compound having an NCO value of 4.5 mmol / g or more (hereinafter sometimes referred to as the first blocked isocyanate compound) from the viewpoint of more excellent effects of the present invention. The NCO value of the first blocked isocyanate compound is preferably 5.0 mmol / g or more, and more preferably 5.3 mmol / g or more. The upper limit value of the NCO value of the first blocked isocyanate compound is preferably 8.0 mmol / g or less, more preferably 6.0 mmol / g or less, still more preferably less than 5.8 mmol / g, and particularly preferably 5.7 mmol / g or less from the viewpoint of more excellent effects of the present invention. The NCO value of the blocked isocyanate compound in the present invention means the number of moles of isocyanate groups contained per 1 g of the blocked isocyanate compound, and is a value calculated from the structural formula of the blocked isocyanate compound. The first-block isocyanate compound preferably has a ring structure in terms of more excellent effects of the present invention. Examples of the ring structure include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring. In terms of more excellent effects of the present invention, an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring are preferable, and an aliphatic hydrocarbon ring is more preferable. Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring. Among them, a cyclohexane ring is preferable. Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring. Among them, a benzene ring is preferable. Specific examples of the heterocyclic ring include an isocyanurate ring. When the first-block isocyanate compound has a ring structure, the number of rings is preferably 1 to 2, and more preferably 1, in terms of more excellent effects of the present invention. When the first-block isocyanate compound contains a condensed ring, the number of rings constituting the condensed ring is counted. For example, the number of rings in a naphthalene ring is counted as 2.

[0189] The number of block isocyanate groups in the first-block isocyanate compound is preferably 2 to 5, more preferably 2 to 3, and still more preferably 2, in terms of excellent strength of the formed pattern and more excellent effects of the present invention.

[0190] The first-block isocyanate compound is preferably a block isocyanate compound represented by formula Q in terms of more excellent effects of the present invention. B 1 -A 1 -L 1 -A 2 -B 2 Formula Q

[0191] In formula Q, B 1 and B 2 each independently represents a block isocyanate group. The blocked isocyanate group is not particularly limited, but from the viewpoint of more excellent effects of the present invention, a group in which the isocyanate group is blocked with an oxime compound is preferable, and a group in which the isocyanate group is blocked with methyl ethyl ketoxime (specifically, a group represented by *-NH-C(=O)-O-N=C(CH3)-C2H5. * represents the bonding position to A 1 or A 2 is more preferable.) B 1 and B 2 are preferably the same group.

[0192] In formula Q, A 1 and A 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 10 carbon atoms is preferable. The alkylene group may be linear, branched or cyclic, but is preferably linear. The number of carbon atoms of the alkylene group is 1 to 10, but from the viewpoint of more excellent effects of the present invention, 1 to 5 is preferable, 1 to 3 is more preferable, and 1 is still more preferable. A 1 and A 2 are preferably the same group.

[0193] In formula Q, L 1 represents a divalent linking group. Specific examples of the divalent linking group include divalent hydrocarbon groups. Specific examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by linking two or more of these groups. The divalent saturated hydrocarbon group may be linear, branched or cyclic, and from the viewpoint of more excellent effects of the present invention, it is preferably cyclic. The number of carbon atoms of the divalent saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 10, and still more preferably 5 to 8 from the viewpoint of more excellent effects of the present invention. The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. The divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group). Among them, as the divalent linking group, a linear, branched or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a group in which a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms is linked to a linear alkylene group having 1 to 3 carbon atoms, a divalent aromatic hydrocarbon group which may have a substituent, or a group in which a divalent aromatic hydrocarbon group is linked to a linear alkylene group having 1 to 3 carbon atoms is preferable, a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, or a phenylene group which may have a substituent is more preferable, a cyclohexylene group or a phenylene group which may have a substituent is still more preferable, and a cyclohexylene group is particularly preferable.

[0194] The blocked isocyanate compound represented by formula Q is particularly preferably a blocked isocyanate compound represented by formula QA from the viewpoint of more excellent effects of the present invention. B 1a -A 1a -L 1a -A 2a -B 2a Formula QA

[0195] In formula QA, B 1a and B 2a each independently represent a blocked isocyanate group. The preferred embodiments of B 1a and B 2a are the same as those of B 1 and B 2 in formula Q.

[0196] In formula QA, A 1a and A 2a each independently represent a divalent linking group. The preferred embodiments of the divalent linking group in A 1a and A 2a are the same as those of A 1 and A 2 in formula Q.

[0197] In formula QA, L 1arepresents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group. L 1a The number of carbon atoms of the cyclic divalent saturated hydrocarbon group in 1a is preferably 5 to 10, more preferably 5 to 8, still more preferably 5 to 6, and particularly preferably 6. L 1a The preferred embodiment of the divalent aromatic hydrocarbon group in 1a is the same as L in formula Q. 1 The same applies. Among them, L 1a is preferably a cyclic divalent saturated hydrocarbon group, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, still more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, particularly preferably a cyclic divalent saturated hydrocarbon group having 5 to 6 carbon atoms, and most preferably a cyclohexylene group. L 1a When L is a cyclohexylene group, the blocked isocyanate compound represented by formula QA may be a mixture of isomers of the cis form and the trans form (hereinafter, also referred to as "cis-trans isomer mixture"). The mass ratio of the cis form to the trans form is preferably cis form / trans form = 10 / 90 to 90 / 10, and more preferably cis form / trans form = 40 / 60 to 60 / 40.

[0198] Specific examples of the first blocked isocyanate compound are shown below, but the first blocked isocyanate compound is not limited thereto.

[0199]

Chemical formula

[0200] The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0201] (Surfactant) The photosensitive composition layer may contain a surfactant. Examples of the surfactant include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of JP-A-2009-237362.

[0202] As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, EXP.MFS-578, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation); Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc.); PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by NEOS Co., Ltd.), etc. In addition, as the fluorosurfactant, an acrylic compound having a molecular structure with a functional group containing a fluorine atom, in which the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heated, can also be preferably used. As such a fluorosurfactant, the MegaFac DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial Newspaper (February 23, 2016)), for example, MegaFac DS-21 can be mentioned. In addition, as the fluorosurfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. In addition, a block polymer can also be used as the fluorosurfactant. In addition, as the fluorosurfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably an ethyleneoxy group or a propyleneoxy group) can also be preferably used. In addition, as the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Examples include MegaFac RS-101, RS-102, RS-718K, RS-72-K (all of the above are manufactured by DIC Corporation), etc.

[0203] From the viewpoint of improving environmental suitability, the fluorosurfactant is preferably a surfactant derived from a substitute material for compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Corporation), Pyonin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0204] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified silicone polymers with organic groups introduced into the side chains or terminals.

[0205] Specific examples of silicone surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie GmbH), etc.

[0206] The surfactant may be used alone or in combination of two or more. When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 0.80% by mass based on the total mass of the photosensitive composition layer.

[0207] (Polymerization inhibitor) The photosensitive composition layer may contain a polymerization inhibitor. The polymerization inhibitor means a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0208] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; hindered phenol compounds such as bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among them, from the viewpoint of more excellent effects of the present invention, at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound is preferable as the polymerization inhibitor, and phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, and aluminum salt of N-nitrosophenylhydroxylamine are more preferable.

[0209] The polymerization inhibitor may be used alone or in combination of two or more kinds. When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.02 to 2.0% by mass based on the total mass of the photosensitive composition layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.01 to 1.0% by mass based on the total mass of the ethylenically unsaturated compound.

[0210] <Hydrogen donating compound> The photosensitive composition layer may contain a hydrogen donating compound. The hydrogen donating compound has effects such as further improving the sensitivity of the photoinitiator to actinic rays and suppressing the polymerization inhibition of the ethylenically unsaturated compound by oxygen.

[0211] Examples of the hydrogen donating compound include amines and amino acid compounds.

[0212] Examples of the amines include the compounds described in "Journal of Polymer Society", Vol. 10, p. 3173 (1972) by M.R. Sander et al., Japanese Patent Publication No. 44-020189, Japanese Patent Laid-Open No. 51-082102, Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-084305, Japanese Patent Laid-Open No. 62-018537, Japanese Patent Laid-Open No. 64-033104, and Research Disclosure No. 33825, etc. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline are included. Among these, in terms of more excellent effects of the present invention, as the amines, at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferable.

[0213] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, in terms of more excellent effects of the present invention, as the amino acid compound, N-phenylglycine is preferable.

[0214] Examples of the hydrogen-donating compound also include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. Sho 48-042965, hydrogen donors described in Japanese Patent Publication No. Sho 55-034414, and sulfur compounds (such as trithiane) described in Japanese Unexamined Patent Application Publication No. Hei 6-308727.

[0215] The hydrogen-donating compound may be used alone or in combination of two or more. When the photosensitive composition layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and still more preferably 0.03 to 5.0% by mass with respect to the total mass of the photosensitive composition layer from the viewpoint of improving the curing rate based on the balance between the polymerization growth rate and chain transfer.

[0216] (Impurities, etc.) The photosensitive composition layer may contain a predetermined amount of impurities. Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among these, halide ions (chloride ions, bromide ions, iodide ions), sodium ions, and potassium ions are likely to be mixed as impurities, so it is preferable to have the following contents.

[0217] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and still more preferably 2 ppm or less on a mass basis. The content of impurities in the photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more on a mass basis. Specific examples of the content of impurities in the photosensitive composition layer include the aspect where all of the above impurities are 0.6 ppm on a mass basis.

[0218] As methods for bringing the impurities within the above range, there may be mentioned selecting a raw material for the photosensitive composition layer having a low content of impurities, preventing the mixing of impurities during the formation of the photosensitive composition layer, and washing and removing them. By such methods, the amount of impurities can be brought within the above range.

[0219] Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0220] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably low. The content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and still more preferably 4 ppm or less on a mass basis. The lower limit can be 10 ppb or more and can be 100 ppb or more on a mass basis. The content of these compounds can be suppressed by the same methods as the above metal impurities. Also, they can be quantified by known measurement methods.

[0221] The water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminability.

[0222] (Residual monomer) The photosensitive composition layer may contain residual monomers of each structural unit of the above-described alkali-soluble resin. From the viewpoints of patterning properties and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and still more preferably 500 ppm by mass or less, based on the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning properties and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and still more preferably 100 ppm by mass or less, based on the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0223] It is also preferable that the amount of the residual monomer in the synthesis of the alkali-soluble resin by the polymer reaction is within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the content of glycidyl acrylate is within the above range. The amount of the residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0224] (Other components) The photosensitive composition layer may contain components other than the above-described components (hereinafter also referred to as "other components"). Examples of the other components include colorants, antioxidants, and particles (for example, metal oxide particles). In addition, as the other components, other additives described in paragraphs

[0058] to

[0071] of JP-A No. 2000-310706 are also included.

[0225] -Particles- As the particles, metal oxide particles are preferable. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, for example, from the viewpoint of the transparency of the protective film. The average primary particle diameter of the particles is calculated by measuring the particle diameters of any 200 particles using an electron microscope and calculating the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0226] When the photosensitive composition layer contains particles, it may contain only one kind of particles different in metal species, size, etc., or may contain two or more kinds. The photosensitive composition layer does not contain particles, or when the photosensitive composition layer contains particles, the content of the particles is preferably more than 0% by mass and 35% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably more than 0% by mass and 5% by mass or less, still more preferably more than 0% by mass and 1% by mass or less, and particularly preferably does not contain particles, based on the total mass of the photosensitive composition layer.

[0227] -Colorant- The photosensitive composition layer may contain a small amount of a colorant (such as a pigment or a dye), but preferably does not substantially contain a colorant, for example, from the viewpoint of transparency. When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive composition layer.

[0228] -Antioxidant- Examples of the antioxidant include 3 - pyrazolidones such as 1 - phenyl - 3 - pyrazolidone (alias: phenidone), 1 - phenyl - 4,4 - dimethyl - 3 - pyrazolidone, and 1 - phenyl - 4 - methyl - 4 - hydroxymethyl - 3 - pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, para - aminophenol, para - hydroxyphenylglycine, and paraphenylenediamine. Among them, in terms of more excellent effects of the present invention, 3 - pyrazolidones are preferable as the antioxidant, and 1 - phenyl - 3 - pyrazolidone is more preferable.

[0229] When the photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more with respect to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but preferably 1% by mass or less.

[0230] (Thickness of the photosensitive composition layer) The thickness of the photosensitive composition layer is not particularly limited, but is often 30 μm or less. In terms of more excellent effects of the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5.0 μm or less. As the lower limit, in terms of excellent strength of the film obtained by curing the photosensitive composition layer, it is preferably 0.60 μm or more, and more preferably 1.5 μm or more. The thickness of the photosensitive composition layer can be calculated as the average value of any five points measured by cross - sectional observation using a scanning electron microscope (SEM), for example.

[0231] (Refractive index of the photosensitive composition layer) The refractive index of the photosensitive composition layer is preferably from 1.41 to 1.59, and more preferably from 1.47 to 1.56.

[0232] (Color of the photosensitive composition layer) The photosensitive composition layer is preferably achromatic. Specifically, for total reflection (incident angle: 8°, light source: D-65 (2° field of view)), in the CIE1976 (L*, a*, b*) color space, the L * value is preferably from 10 to 90, and the a * value is preferably from -1.0 to 1.0, and the b * value is preferably from -1.0 to 1.0.

[0233] Note that the pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) is preferably achromatic. Specifically, for total reflection (incident angle: 8°, light source: D-65 (2° field of view)), in the CIE1976 (L*, a*, b*) color space, the L of the pattern * value is preferably from 10 to 90, the a of the pattern * value is preferably from -1.0 to 1.0, and the b of the pattern * value is preferably from -1.0 to 1.0.

[0234] (Transmittance of the photosensitive composition layer) The visible light transmittance per 1.0 μm film thickness of the photosensitive composition layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more. As the visible light transmittance, the average transmittance of wavelengths from 400 nm to 800 nm, the minimum value of the transmittance of wavelengths from 400 nm to 800 nm, and the transmittance at a wavelength of 400 nm are all preferably satisfied. Preferred values of the transmittance include, for example, 87%, 92%, 98%, etc. The transmittance per 1 μm film thickness of the cured film of the photosensitive composition layer is the same.

[0235] (Moisture permeability of the photosensitive composition layer) The moisture permeability at a film thickness of 40 μm of the pattern (cured film of the photosensitive composition layer) obtained by curing the photosensitive composition layer is preferably 500 g / m 2 / 24 h or less, more preferably 300 g / m 2 / 24 h or less, and most preferably 100 g / m 2More preferably, it is below 24 hr. The moisture permeability is measured using a cured film obtained by curing the photosensitive composition layer by performing post-baking at 145°C for 30 minutes after exposing the photosensitive composition layer to an exposure amount of 300 mJ / cm 2 with i-line. The measurement of the moisture permeability is carried out in accordance with the cup method of JIS Z0208. It is preferable that the moisture permeability is as described above under any of the test conditions of temperature 40°C / humidity 90%, temperature 65°C / humidity 90%, and temperature 80°C / humidity 95%. Specific preferable numerical values include, for example, 80 g / m 2 / 24 hr, 150 g / m 2 / 24 hr, 220 g / m 2 / 24 hr, etc.

[0236] (Dissolution rate of the photosensitive composition layer) From the viewpoint of suppressing residues during development, the dissolution rate of the photosensitive composition layer in a 1.0% aqueous solution of sodium carbonate is preferably 0.01 μm / sec or more, more preferably 0.10 μm / sec or more, and still more preferably 0.20 μm / sec or more. From the viewpoint of the edge shape of the pattern, it is preferably 5.0 μm / sec or less, more preferably 4.0 μm / sec or less, and still more preferably 3.0 μm / sec or less. Specific preferable numerical values include, for example, 1.8 μm / sec, 1.0 μm / sec, 0.7 μm / sec, etc. The dissolution rate per unit time of the photosensitive composition layer in a 1.0 mass% aqueous solution of sodium carbonate shall be measured as follows. For a photosensitive composition layer (with a film thickness in the range of 1.0 to 10 μm) formed on a glass substrate and from which the solvent has been sufficiently removed, shower development is carried out at 25°C using a 1.0 mass% aqueous solution of sodium carbonate until the photosensitive composition layer completely dissolves (however, the maximum time is 2 minutes). The film thickness of the photosensitive composition layer is obtained by dividing it by the time required for the photosensitive composition layer to completely dissolve. In the case where it does not completely dissolve within 2 minutes, it is calculated in the same manner from the film thickness change amount up to that point. The dissolution rate of the cured film of the photosensitive composition layer (in the range of 1.0 to 10 μm in film thickness) in a 1.0% aqueous solution of sodium carbonate is preferably 3.0 μm / second or less, more preferably 2.0 μm / second or less, still more preferably 1.0 μm / second or less, and most preferably 0.2 μm / second or less. The cured film of the photosensitive composition layer is a film obtained by exposing the photosensitive composition layer with i-line at an exposure amount of 300 mJ / cm 2 and is the film obtained by exposure. Specific preferable numerical values include, for example, 0.8 μm / second, 0.2 μm / second, 0.001 μm / second, etc. Development is carried out using a shower nozzle of 1 / 4MINJJX030PP manufactured by Ikeuchi Co., Ltd., and the spray pressure of the shower is 0.08 MPa. At the above conditions, the shower flow rate per unit time is 1,800 mL / min.

[0237] (Swelling ratio of the photosensitive composition layer) From the viewpoint of improving pattern formability, the swelling ratio of the photosensitive composition layer after exposure in a 1.0 mass% aqueous solution of sodium carbonate is preferably 100% or less, more preferably 50% or less, and still more preferably 30% or less. The swelling ratio of the photosensitive resin layer after exposure in a 1.0 mass% aqueous solution of sodium carbonate is measured as follows. The photosensitive resin layer (in the range of 1.0 to 10 μm in film thickness) formed on a glass substrate with the solvent sufficiently removed is exposed with an ultra-high pressure mercury lamp at 500 mj / cm2 (i-line measurement). The entire glass substrate is immersed in a 1.0 mass% aqueous solution of sodium carbonate at 25°C, and the film thickness at the time when 30 seconds have elapsed is measured. Then, the ratio of the increase in the film thickness after immersion to the film thickness before immersion is calculated. Specific preferable numerical values include, for example, 4%, 13%, 25%, etc.

[0238] (Foreign matters in the photosensitive composition layer) From the viewpoint of pattern formability, the number of foreign matters with a diameter of 1.0 μm or more in the photosensitive composition layer is preferably 10 pieces / mm 2 or less, and more preferably 5 pieces / mm 2It is more preferable that the following conditions are met. The number of foreign substances shall be measured as follows. Five arbitrary regions (1 mm × 1 mm) on the surface of the photosensitive composition layer are visually observed using an optical microscope from the normal direction of the surface of the photosensitive composition layer, and the number of foreign substances with a diameter of 1.0 μm or more in each region is measured, and they are arithmetically averaged to calculate the number of foreign substances. Specific preferable numerical values include, for example, 0 pieces / mm 2 , 1 piece / mm 2 , 4 pieces / mm 2 , 8 pieces / mm 2 and the like can be mentioned.

[0239] (Haze of the dissolved matter in the photosensitive composition layer) From the viewpoint of suppressing the generation of aggregates during development, the haze of the solution obtained by dissolving 1.0 cm3 of the photosensitive resin layer in 1.0 liter of a 30°C aqueous solution of 1.0 mass% sodium carbonate is preferably 60% or less, more preferably 30% or less, still more preferably 10% or less, and most preferably 1% or less. The haze shall be measured as follows. First, prepare a 1.0 mass% aqueous solution of sodium carbonate and adjust the liquid temperature to 30°C. Put 1.0 cm3 of the photosensitive resin layer into 1.0 L of the aqueous sodium carbonate solution. Stir at 30°C for 4 hours while taking care not to mix in air bubbles. After stirring, measure the haze of the solution in which the photosensitive resin layer has dissolved. The haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) and a liquid measurement unit and a dedicated cell for liquid measurement with an optical path length of 20 mm. Specific preferable numerical values include, for example, 0.4%, 1.0%, 9%, 24% and the like.

[0240] [Protective film] The transfer film may have a protective film. As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. Alternatively, a resin film made of the same material as the above-mentioned temporary support may be used as the protective film. Among them, as the protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is even more preferable.

[0241] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and preferably 100 μm or less in terms of relatively low cost.

[0242] In addition, in the protective film, the number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5 pieces / m 2 or less. Note that "fish eye" refers to a material obtained by melting, kneading, extruding, and producing a film by methods such as biaxial stretching and casting method, and foreign substances, undissolved substances, and oxidation degradation products of the material are taken into the film.

[0243] The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 pieces / mm 2 or less, more preferably 10 pieces / mm 2 or less, and even more preferably 5 pieces / mm 2 or less. Thereby, defects caused by the transfer of unevenness caused by the particles contained in the protective film to the photosensitive composition layer or the conductive layer can be suppressed.

[0244] From the viewpoint of imparting winding property, the arithmetic mean roughness Ra of the surface on the side opposite to the surface in contact with the composition layer of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably less than 0.40 μm, and even more preferably less than 0.30 μm. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

[0245] [Relationship between the temporary support, the photosensitive composition layer, and the protective film] The elongation at break of the cured film obtained by curing the photosensitive composition layer at 120 °C is 15% or more, The arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive composition layer side is 50 nm or less, The arithmetic mean roughness Ra of the surface of the protective film on the photosensitive composition layer side is preferably 150 nm or less.

[0246] It is preferable to satisfy the following formula (1). X × Y < 1500 Formula (1) Here, in Formula (1), X represents the value (%) of the elongation at break of the cured film obtained by curing the photosensitive composition layer at 120 °C, and Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive composition layer side. The above X × Y is more preferably 750 or less. Specific numerical values of the above X can include 18%, 25%, 30%, 35%, etc. Specific numerical values of the above X × Y can include 4 nm, 8 nm, 15 nm, 30 nm, etc. Specific numerical values of the above X × Y can include 150, 200, 300, 360, 900, etc.

[0247] It is preferable that the elongation at break at 120 °C is at least twice as large as the elongation at break at 23 °C of the cured film obtained by curing the photosensitive composition layer.

[0248] The elongation at break is measured by a tensile test on a cured film obtained by exposing a photosensitive composition layer with a thickness of 20 μm to light with an ultra-high pressure mercury lamp at 120 mJ / cm 2 for curing, then further exposing with a high pressure mercury lamp at 400 mJ / cm 2 and heating at 145 °C for 30 minutes.

[0249] It is preferable to satisfy the following formula (2). Y ≦ Z Formula (2) Here, in Formula (2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the temporary support, and Z represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the protective film.

[0250] [Refractive Index Adjusting Layer] The transfer film preferably has a refractive index adjusting layer. As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the materials contained in the refractive index adjusting layer include a binder polymer, an ethylenically unsaturated compound, a metal salt, and particles. The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin.

[0251] Examples of the binder polymer and the ethylenically unsaturated compound include the binder polymer and the ethylenically unsaturated compound described in the section of the above "photosensitive composition layer".

[0252] Examples of the particles include metal oxide particles and metal particles. The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be mentioned. The metals in the metal oxide particles also include semi-metals such as B, Si, Ge, As, Sb, and Te.

[0253] The average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and taking the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0254] Specifically, as the metal oxide particles, at least one selected from the group consisting of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof is preferable. Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable from the viewpoint of easy adjustment of the refractive index.

[0255] Examples of commercially available metal oxide particles include fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nano Use OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nano Use OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0256] The particles may be used alone or in combination of two or more. The content of the particles in the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 85% by mass based on the total mass of the refractive index adjustment layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 85% by mass based on the total mass of the refractive index adjustment layer.

[0257] The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive composition layer. The refractive index of the refractive index adjustment layer is preferably 1.50 or more, more preferably 1.55 or more, still more preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjustment layer is preferably 2.10 or less, more preferably 1.85 or less, and still more preferably 1.78 or less.

[0258] The thickness of the refractive index adjustment layer is preferably 50 to 500 nm, more preferably 55 to 110 nm, and still more preferably 60 to 100 nm. The thickness of the refractive index adjustment layer is calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0259] <Method for manufacturing a transfer film> The method for manufacturing the transfer film of the first embodiment is not particularly limited, and known methods can be used. Examples of the method for manufacturing the transfer film described above include a step of applying a photosensitive composition on the surface of a temporary support to form a coating film, and further drying the coating film to form a photosensitive composition layer; and a step of applying a composition for forming a refractive index adjustment layer on the surface of the photosensitive composition layer to form a coating film, and further drying the coating film to form a refractive index adjustment layer.

[0260] As the method for manufacturing the transfer film of the first embodiment, it is preferable to manufacture a transfer film including a temporary support, a photosensitive composition layer, a refractive index adjustment layer, and a protective film by including a step of providing a protective film so as to contact the surface of the transfer film on the side opposite to the side having the temporary support of the refractive index adjustment layer. After manufacturing the transfer film by the above manufacturing method, the transfer film may be wound up to produce and store the transfer film in a roll form. The transfer film in a roll form can be provided in the same form for the bonding step with the base material in the roll-to-roll method described later.

[0261] Further, as the method for manufacturing the transfer film described above, a method may be used in which a refractive index adjustment layer is formed on a protective film, and then a photosensitive resin layer is formed on the surface of the refractive index adjustment layer. Further, as the method for manufacturing the above transfer film, a method may be adopted in which a photosensitive composition layer is formed on a temporary support, and separately, a refractive index adjustment layer is formed on a protective film, and the photosensitive composition layer and the refractive index adjustment layer are laminated together.

[0262] [Photosensitive Composition and Method for Forming Photosensitive Composition Layer] In terms of excellent productivity, the photosensitive composition layer in the transfer film is preferably formed by a coating method using a photosensitive composition containing the components constituting the above-described photosensitive composition layer (for example, a binder polymer, an ethylenically unsaturated compound, a photopolymerization initiator, etc.) and a solvent. Specifically, as the method for manufacturing the transfer film of the first embodiment, it is preferable that a photosensitive composition is applied on a temporary support to form a coating film, and this coating film is subjected to a drying treatment at a predetermined temperature to form a photosensitive composition layer.

[0263] As the solvent that can be contained in the photosensitive composition, an organic solvent is preferable. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0264] Further, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 to 250°C can be used as necessary.

[0265] The solvent may be used alone or in combination of two or more. The total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and still more preferably 5 to 30% by mass with respect to the total mass of the photosensitive composition. That is, the content of the solvent in the photosensitive composition is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and still more preferably 70 to 95% by mass with respect to the total mass of the photosensitive composition.

[0266] The viscosity of the photosensitive composition at 25°C is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s from the viewpoint of coatability, for example. The viscosity is measured using a viscometer. As the viscometer, for example, a viscometer (trade name: VISCOMETER TV-22) manufactured by Toki Sangyo Co., Ltd. can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

[0267] The surface tension of the photosensitive composition at 25°C is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m from the viewpoint of coatability, for example. The surface tension is measured using a surface tensiometer. As the surface tensiometer, for example, a surface tensiometer (trade name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. can be preferably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0268] Examples of the coating method of the photosensitive composition include a printing method, a spraying method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (i.e., a slit coating method).

[0269] As the drying method of the coating film of the photosensitive composition, heat drying and vacuum drying are preferable. In this specification, "drying" means removing at least a part of the solvent contained in the composition. Examples of the drying method include natural drying, heat drying, and vacuum drying. The above-mentioned methods can be applied alone or in combination of a plurality. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. Also, the upper limit value is preferably 130°C or lower, more preferably 120°C or lower. It is also possible to dry by continuously changing the temperature. Also, the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. Also, the upper limit value is not particularly limited, but is preferably 600 seconds or shorter, more preferably 300 seconds or shorter.

[0270] [Composition for Forming Refractive Index Adjustment Layer and Method for Forming Refractive Index Adjustment Layer] The composition for forming the refractive index adjustment layer preferably contains various components for forming the above-described refractive index adjustment layer and a solvent. In the composition for forming the refractive index adjustment layer, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the above-described refractive index adjustment layer. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjustment layer. At least one selected from the group consisting of water and water-miscible organic solvents is preferred, and a mixed solvent of water or water and a water-miscible organic solvent is more preferred. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and still more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.

[0271] The method for forming the refractive index adjustment layer is not particularly limited as long as it can form a layer containing the above components. Examples thereof include known coating methods (such as slit coating, spin coating, curtain coating, and inkjet coating).

[0272] Also, the transfer film of the first embodiment can be manufactured by bonding a protective film to the refractive index adjustment layer. The method for bonding the protective film to the refractive index adjustment layer is not particularly limited, and examples thereof include known methods. Examples of the apparatus for bonding the protective film to the refractive index adjustment layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0273] <Method for manufacturing a touch panel sensor> The method for manufacturing a touch panel sensor of the present invention is not particularly limited as long as it can manufacture a touch panel sensor having the above characteristics. However, in terms of ease of manufacturing a touch panel sensor having the above characteristics, it is preferable to manufacture it using the above transfer film. Among them, a preparation step of preparing a base material with a photosensitive composition layer having a touch panel sensor base material and a conductive base material including sensor electrodes disposed on the base material, and a photosensitive composition layer disposed on the conductive base material and including a binder polymer, a compound having an ethylenically unsaturated group, and a photopolymerization initiator; An exposure step of pattern-exposing the photosensitive composition layer; A development step of developing the pattern-exposed photosensitive composition layer to form a resin layer pattern; A method for manufacturing a touch panel sensor is more preferable, which includes a curing step of exposing the resin layer pattern at 50 to 120 °C to form a protective film covering at least a part of the sensor electrodes. According to the above manufacturing method, a touch panel sensor can be manufactured in which the change in the resistance value of the sensor electrodes of the touch panel sensor after bending is small, and bright spots are less likely to occur in the touch panel sensor during handling such as roll conveyance. In particular, by performing the above curing step, it is easy to manufacture a touch panel sensor having the above characteristics. Hereinafter, the procedure of the above more preferable steps will be described in detail.

[0274] [Preparation step] In the preparation step, a base material with a photosensitive composition layer having a touch panel sensor base material and a conductive base material including sensor electrodes disposed on the base material, and a photosensitive composition layer disposed on the conductive base material and including a binder polymer, a compound having an ethylenically unsaturated group, and a photopolymerization initiator is prepared. The conductive base material is as described above including preferred embodiments. The photosensitive composition layer is preferably disposed on the conductive substrate using the transfer film, and more preferably disposed by a laminating step of laminating the conductive substrate and the transfer film to form the photosensitive composition layer.

[0275] The laminating step is a step of bringing the surface of the transfer film opposite to the temporary support into contact with the conductive substrate and laminating them to obtain a substrate with a composition layer having the conductive substrate, the sensor electrode, the photosensitive composition layer, and the temporary support in this order. In the case where the transfer film has a protective film, the laminating step is performed after peeling off the protective film.

[0276] In the above lamination, pressure bonding is performed so that the sensor electrode is in contact with the surface of the composition layer. The method of the pressure bonding is not particularly limited, and known transfer methods and laminating methods can be used. Among them, it is preferable that the surface of the composition layer is overlapped with the conductive substrate having the sensor electrode, and pressure and heat are applied by a roll or the like. For the lamination, known laminators such as a vacuum laminator and an auto cut laminator can be used. The lamination temperature is not particularly limited, but for example, it is preferably 70 to 130°C.

[0277] The protective film formed using the photosensitive composition layer in the transfer film of the present invention is preferably provided so as to cover at least a part of the sensor electrode directly or through another layer for the purpose of protecting the sensor electrode.

[0278] [Exposure step] The exposure step is a step of pattern-exposing the photosensitive composition layer. Here, "pattern exposure" refers to a form of exposure in a pattern shape, that is, exposure in a form in which an exposed portion and a non-exposed portion exist. The positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited and is adjusted as appropriate. During exposure, exposure may be performed from the side opposite to the base material of the photosensitive composition layer, or from the base material side of the composition layer.

[0279] As the light source for pattern exposure, any light source that can irradiate light in a wavelength range capable of curing at least the photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used. Among them, the main wavelength of the exposure light for pattern exposure is preferably 365 nm. The main wavelength is the wavelength with the highest intensity.

[0280] Examples of the light source include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 to 200 mJ / cm 2 and more preferably 10 to 200 mJ / cm 2 is more preferable.

[0281] Preferred embodiments of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and the contents thereof are incorporated herein.

[0282] By performing the exposure step and the development step described below, a resin layer pattern covering at least the sensor electrode is formed on the sensor electrode on the conductive substrate.

[0283] [Peeling step] The above manufacturing method preferably has a peeling step of peeling the temporary support from the substrate with the photosensitive composition layer between the preparation step and the exposure step, or between the exposure step and the development step described below. The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A No. 2010-072589 can be used.

[0284] [Development step] The development step is a step of developing the exposed photosensitive composition layer to form a resin layer pattern. The development of the photosensitive composition layer can be carried out using a developer solution. As the developer solution, an alkaline aqueous solution is preferred. Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0285] Examples of the development method include methods such as paddle development, shower development, spin development, and dip development.

[0286] Examples of the developer solution preferably used in this specification include the developer solution described in paragraph

[0194] of WO 2015 / 093271. Examples of the development method preferably used include the development method described in paragraph

[0195] of WO 2015 / 093271.

[0287] [Curing step] The curing step is a step of forming a protective film that covers at least a part of the sensor electrode by exposing the resin layer pattern under the condition that the resin layer pattern is at 50 to 120 °C. That is, in the curing step, exposure is performed while heating the resin layer pattern. The temperature of the curing step refers to the temperature of the surface of the resin layer pattern measured with a radiation thermometer (manufactured by HORIBA, IT-540). Here, "exposing the resin layer pattern under the condition of 50 to 120°C" means that among the surfaces of the resin layer pattern exposed in the curing process, the temperature at at least one measurement location is 50 to 120°C. Among the surfaces of the resin layer pattern to be exposed, the ratio of the area where the resin layer pattern is at 50 to 120°C is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more, and particularly preferably 70% or more with respect to the total area of the resin layer pattern. The upper limit is 100% or less. The ratio of the area where the resin layer pattern is at 50 to 120°C can be calculated by measuring the temperature of the resin layer pattern while changing the measurement location. The temperature of the resin layer pattern in the curing process is 50 to 120°C as described above, but 70 to 100°C is preferable, 80 to 95°C is more preferable, and 85 to 90°C is still more preferable. Further, it is also preferable that the ratio of the area within the above preferable temperature range among the surfaces of the resin layer pattern to be exposed is within the above preferable ratio range with respect to the total area of the resin layer pattern.

[0288] The exposure dose in the curing process is preferably 200 to 1500 mJ / cm 2 and more preferably 200 mJ / cm 2 or more and less than 1000 mJ / cm 2 . By setting the exposure dose in the curing process within the above range, it is easy to manufacture a touch panel sensor having the above characteristics.

[0289] [Post-baking process] The above manufacturing method may have a step of heating the protective film obtained in the above curing process (post-baking process). The temperature of the post-baking is preferably 80°C to 250°C, and more preferably 90°C to 160°C. The time of the post-baking is preferably 1 minute to 180 minutes, and more preferably 10 minutes to 60 minutes.

[0290] [Reaction rate] In the above manufacturing method, when the intensity of the infrared absorption peak derived from the ethylenically unsaturated group contained in the photosensitive composition layer is Y1, and the intensity of the infrared absorption peak derived from the ethylenically unsaturated group contained in the protective film is Y2, it is also preferable that the reaction rate calculated by the following formula (1) is 70% or more. The upper limit is not particularly limited, but examples include 100% or less, preferably 90% or less, and more preferably 85% or less. Formula (1) Reaction rate [%] = {1 - Y2 / Y1)} × 100 By setting the above reaction rate within the above range, it is easy to manufacture the touch panel sensor having the above characteristics.

[0291] Note that the above Y1 refers to the value measured by the following procedure. Peel off the temporary support on the surface of the substrate with the photosensitive composition layer obtained in the above preparation step, and expose the surface of the photosensitive composition layer. Regarding the surface of the photosensitive composition layer, using a full-auto microscope FT-IR system LUMOS (manufactured by Bruker Optics), perform ATR-IR (detector: MCT, crystal: Ge, wavenumber resolution: 4 cm -1 , integration: 32 times) to obtain an infrared absorption spectrum. From the obtained infrared absorption spectrum, calculate the peak area of 810 cm corresponding to the peak of the double bond corresponding to the ethylenically unsaturated group, and set the area value as Y1. -1 Also, for the above Y2, regarding the protective film obtained in the above curing step, obtain Y2 in the same manner as the measurement of Y1.

[0292] <Use of the touch panel sensor> The touch panel sensor of the present invention can be applied to various devices. Examples of the device equipped with the above touch panel sensor include, for example, a display device, a semiconductor package input device, etc., preferably a touch panel, and more preferably a capacitive touch panel. More specifically, the touch panel sensor of the present invention can be suitably used for the manufacture of a touch panel module. Note that a touch panel module has a touch panel sensor, a cover glass, and peripheral wirings. In addition, the touch panel sensor of the present invention can be suitably used for manufacturing a touch panel. The touch panel has a touch panel module and a display device. As the above display device, it can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device.

Example

[0293] The present invention will be described in more detail based on the following examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the examples shown below.

[0294] <Preparation of Materials Used for Transfer Film> [Binder Polymer] (Synthesis of Polymer P-1) A solution P-1 containing polymer P-1 represented by the following chemical formula was prepared. The composition ratio of the constituent units in the following chemical formula is a molar ratio. The P-1 solution was prepared by the following method.

[0295]

Chemical Formula

[0296] Propylene glycol monomethyl ether (82.4 g) was charged into a flask and heated to 90 °C under a nitrogen stream. A solution in which styrene (38.4 g), dicyclopentanyl methacrylate (30.1 g), and methacrylic acid (34.0 g) were dissolved in 20 g of propylene glycol monomethyl ether, and a solution in which a polymerization initiator V-601 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 5.4 g) was dissolved in propylene glycol monomethyl ether acetate (43.6 g) were simultaneously dropped into the flask over 3 hours. After the dropping was completed, V-601 (0.75 g) was added 3 times at 1-hour intervals, and the reaction was further continued for 3 hours. The reaction solution was diluted with propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). Under a stream of air, the reaction solution was heated to 100 °C, and tetraethylammonium bromide (0.53 g) and p-methoxyphenol (0.26 g) were added. To the resulting mixture, glycidyl methacrylate (Blemmer GH manufactured by NOF Corporation, 25.5 g) was added dropwise over 20 minutes. The resulting mixture was reacted at 100 °C for 7 hours to obtain a solution P-1 containing polymer P-1. The solid content concentration of the solution containing solution P-1 was 36.5 mass%. The amount of residual monomer measured by gas chromatography was less than 0.1 mass% with respect to the solid content of polymer P-1 for any monomer.

[0297] The properties of polymer P-1 were as follows. The weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights in terms of standard polystyrene measured by gel permeation chromatography (GPC). · Weight average molecular weight (Mw): 17,000 · Number average molecular weight (Mn): 7,400 · Dispersity: 2.3 · Acid value: 95 mgKOH / g

[0298] (Synthesis of polymer P-2) A solution P-2 containing polymer P-2 represented by the following chemical formula was produced. Note that the composition ratio of the constituent units in the following chemical formula is a molar ratio. The P-2 solution was produced by the following method.

[0299]

Chemical formula

[0300] Propylene glycol monomethyl ether (113.5 g) was charged into a flask and heated to 90 °C under a nitrogen stream. A solution prepared by dissolving styrene (172 g), methyl methacrylate (4.7 g) and methacrylic acid (112.1 g) in propylene glycol monomethyl ether (30 g), and a solution prepared by dissolving polymerization initiator V-601 (manufactured by Fuji Film Wako Pure Chemical Corporation, 27.6 g) in propylene glycol monomethyl ether (57.7 g) were simultaneously added dropwise over 3 hours. After completion of the addition, V-601 (2.5 g) was added three times at 1-hour intervals. Thereafter, the reaction was further carried out for 3 hours. The reaction solution was diluted with propylene glycol monomethyl ether acetate (160.7 g) and propylene glycol monomethyl ether (233.3 g). Under an air stream, the temperature of the reaction solution was raised to 100 °C, tetraethylammonium bromide (1.8 g) and p-methoxyphenol (0.86 g) were added, and then glycidyl methacrylate (Blemmer G manufactured by NOF Corporation, 71.9 g) was added dropwise over 20 minutes. The resulting mixture was reacted at 100 °C for 7 hours to obtain a solution P-2 containing polymer P-2. The solid content concentration of solution P-2 was 36.2% by mass. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass with respect to the polymer solid content for any monomer.

[0301] The properties of polymer P-2 were as follows. The weight average molecular weight (Mw) and number average molecular weight (Mn) are the molecular weights in terms of standard polystyrene measured by gel permeation chromatography (GPC). · Weight average molecular weight (Mw): 18,000 · Number average molecular weight (Mn): 7,800 · Dispersity: 2.3 · Acid value: 124 mgKOH / g

[0302] (Synthesis of polymer P-3) Polymer P-3 was synthesized in the same manner as the synthesis of polymer P-1, except that the step of adding glycidyl methacrylate dropwise was not performed, and solution P-3 was obtained. The solid content concentration of Solution P-3 was 36.5% by mass. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass with respect to the solid content of Polymer P-3 for any monomer.

[0303] The properties of Polymer P-3 were as follows. The weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights in terms of standard polystyrene measured by gel permeation chromatography (GPC). · Weight average molecular weight (Mw): 18,000 · Number average molecular weight (Mn): 7,800 · Dispersity: 2.3 · Acid value: 174 mgKOH / g

[0304] (Synthesis of Polymer P-4) A solution P-4 containing Polymer P-4 represented by the following chemical formula was produced. Note that the composition ratio of the constitutional units in the following chemical formula is a molar ratio. The P-4 solution was produced by the following method.

[0305]

Chemical formula

[0306] 60 g of propylene glycol monomethyl ether acetate (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM-Ac) and 240 g of propylene glycol monomethyl ether (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM) were introduced into a 2000 mL flask. The resulting liquid was heated to 90°C while stirring. As the preparation of the dropping solution (1), 107.1 g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd., trade name Acryester M), 5.46 g of methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name MMA), and 231.42 g of cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name CHMA) were mixed and diluted with 60 g of PGM-Ac to obtain the dropping solution (1). As the preparation of the dropping solution (2), 9.637 g of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601) was dissolved in 136.56 g of PGM-Ac to obtain the dropping solution (2). The dropping solution (1) and the dropping solution (2) were simultaneously dropped into the above-mentioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90°C) over 3 hours. Next, the container of the dropping solution (1) was washed with 12 g of PGM-Ac, and the washing solution was dropped into the above 2000 mL flask. Next, the container of the dropping solution (2) was washed with 6 g of PGM-Ac, and the washing solution was dropped into the above 2000 mL flask. During these droppings, the reaction solution in the above 2000 mL flask was maintained at 90°C and stirred. Further, as a post-reaction, the reaction solution was stirred at 90°C for 1 hour. To the reaction solution after the post-reaction, 2.401 g of V-601 was added as the first additional addition of the initiator. Further, the container of V-601 was washed with 6 g of PGM-Ac, and the washing solution was introduced into the reaction solution. Then, it was stirred at 90°C for 1 hour. Next, as the second additional addition of the initiator, 2.401 g of V-601 was added to the reaction solution. Further, the container of V-601 was washed with 6 g of PGM-Ac, and the washing solution was introduced into the reaction solution. Then, it was stirred at 90°C for 1 hour. Next, as the third additional addition of the initiator, 2.401 g of V-601 was added to the reaction solution. Further, the container of V-601 was washed with 6 g of PGM-Ac, and the washing solution was introduced into the reaction solution. Then, it was stirred at 90°C for 3 hours.

[0307] After the obtained reaction solution was stirred at 90°C for 3 hours, 178.66 g of PGM-Ac was introduced into the reaction solution. Next, 1.8 g of tetraethylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.8 g of hydroquinone monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the reaction solution. Further, each container was washed with 6 g of PGM-Ac, and the washing solution was introduced into the reaction solution. Then, the temperature of the reaction solution was raised to 100°C. Next, glycidyl methacrylate (manufactured by NOF Corporation, trade name: Blemmer G) (76.03 g) was added dropwise to the reaction solution over 1 hour. The container of Blemmer G was washed with PGM-Ac (6 g), and the washing solution was introduced into the reaction solution. Thereafter, as an addition reaction, the mixture was stirred at 100°C for 6 hours to obtain a solution P-4 containing polymer P-4. The solid content concentration of solution P-4 was 36.3 mass%. The amount of residual monomer measured by gas chromatography was less than 0.1 mass% with respect to the polymer solid content for any monomer.

[0308] The properties of polymer P-4 were as follows. The weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights in terms of standard polystyrene measured by gel permeation chromatography (GPC). · Weight average molecular weight (Mw): 27,000 · Number average molecular weight (Mn): 15,000 · Dispersity: 1.8 · Acid value: 95 mgKOH / g

[0309] [Thermal crosslinking agent] (Synthesis of block isocyanate compound Q-1) Under a nitrogen stream, 453 g of butanone oxime (manufactured by Idemitsu Kosan Co., Ltd.) was dissolved in 700 g of methyl ethyl ketone. To the resulting mixture, 500 g of 1,3-bis(isocyanatomethyl)cyclohexane (a mixture of cis-trans isomers, manufactured by Mitsui Chemicals, Inc., Takenate 600) was added dropwise over 1 hour under ice cooling, and then the mixture was reacted for another 1 hour. Thereafter, the temperature was raised to 40°C and the mixture was reacted for 1 hour. 1 It was confirmed by 1H-NMR (nuclear magnetic resonance) and HPLC (high performance liquid chromatography) that the reaction was completed, and a methyl ethyl ketone solution of block isocyanate compound Q-1 was obtained. Block isocyanate compound Q-1 is represented by the following chemical formula.

[0310]

Chemical formula

[0311] (Preparation of Block Isocyanate Compound Q-2) As the block isocyanate compound Q-2, "Duranate TPA-B80E" (manufactured by Asahi Kasei Corporation) was prepared.

[0312] <Example 1> Hereinafter, the procedure of Example 1 will be described.

[0313] [Preparation of Photosensitive Composition A-1] The following components (1) to (5), methyl ethyl ketone, and 1-methoxy-2-propyl acetate were mixed to prepare Photosensitive Composition A-1. The unit of the content of the following components (1) to (5) is parts by mass in terms of solid content. The addition amounts of methyl ethyl ketone and 1-methoxy-2-propyl acetate were adjusted so that the solid content concentration of Photosensitive Composition A-1 would be 25% by mass. The addition amount of methyl ethyl ketone was adjusted so that the ratio of methyl ethyl ketone in the solvent in Photosensitive Composition A-1 would be 60% by mass.

[0314] (1) Binder Polymer · P-1 solution: an amount such that the solid content of the polymer is 52.67 parts by mass

[0315] (2) Polymerizable Compound (2-1) Monomer having two ethylenically unsaturated bonds: · Tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.): 17.90 parts by mass · Acrylic monomer (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.): 2.73 parts by mass (2-2) Monomer having five or more ethylenically unsaturated bonds · Monomer having a carboxy group (Aronix TO2349, manufactured by Toagosei Co., Ltd.): 2.98 parts by mass · Acrylic monomer (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.): 7.99 parts by mass

[0316] (3) Thermally Crosslinkable Compound · Block isocyanate compound Q-2: 12.50 parts by mass

[0317] (4) Polymerization initiator · 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxyoxime) (OXE-02, manufactured by BASF): 0.36 parts by mass · 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (APi-307, manufactured by Shenzhen UV-ChemTech): 0.73 parts by mass

[0318] (5) Additive · N-Phenylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.10 parts by mass · Benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.52 parts by mass · Isonicotinamide (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.13 parts by mass · XIRAN EF-40 (manufactured by Kawasaki Kasei Co., Ltd.): 1.20 parts by mass · Megafac F551A (manufactured by DIC Corporation): 0.19 parts by mass

[0319] [Preparation of transfer film] As a temporary support, a 16-μm-thick polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was prepared. Onto the temporary support, the photosensitive composition A-1 was applied using a slit nozzle, and the solvent was volatilized in a drying zone at 100 °C to form a photosensitive composition layer with a film thickness of 5.5 μm. A protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded to the photosensitive composition layer to prepare a transfer film.

[0320] [Preparation of touch panel sensor] A touch panel sensor was prepared by the following steps. Each of the steps shown below was carried out in a roll-to-roll process.

[0321] (Preparation step) - Preparation of conductive substrate - A substrate including a base material, a transparent film, and a transparent electrode pattern (electrode sensor) in this order was obtained by the following procedure.

[0322] As the base material, a cycloolefin polymer film (thickness: 38 μm, refractive index: 1.53) was prepared. Corona discharge treatment was performed on the base material using a high-frequency oscillator under the following conditions. Output voltage: 100% Output: 250 W Electrode: A wire electrode with a diameter of 1.2 mm Electrode length: 240 mm Distance between work electrodes: 1.5 mm Treatment time: 3 seconds

[0323] Next, a composition containing the components shown in Table 1 (the numerical values of each component in Table 1 are the contents (parts by mass)) was applied onto the base material using a slit nozzle, and then irradiated with ultraviolet light (integrated light quantity: 300 mJ / cm 2 ) and dried at about 110°C to form a transparent film (refractive index: 1.60, thickness: 80 nm).

[0324]

Table 1

[0325]

Chemical formula

[0326] An ITO (Indium Tin Oxide) film with a thickness of 40 nm and a refractive index of 1.82 was formed on the transparent film by DC magnetron sputtering, and the formed ITO film was patterned by photolithography to form a transparent electrode pattern (electrode sensor) on the transparent film. The formation of the ITO film and the patterning of the ITO film were performed by the method described in paragraphs

[0119] to

[0122] of JP-A-2014-10814.

[0327] -Laminating process- After peeling off the protective film of the transfer film, the transfer film was laminated onto the substrate such that the photosensitive composition layer covered the transparent film and the electrode sensor. The lamination was carried out using a vacuum laminator manufactured by MCK under the conditions that the temperature of the base material (i.e., cycloolefin polymer film) was 40 °C, the temperature of the rubber roller was 100 °C, the linear pressure was 3 N / cm, and the conveyance speed was 4 m / min. By the above procedure, a base material with a photosensitive composition layer was obtained.

[0328] (Exposure step) Next, using a proximity type exposure machine having an ultra-high pressure mercury lamp (manufactured by Hitachi High-Technologies Corporation), the exposure mask (quartz exposure mask having a pattern for overcoat formation) and the temporary support were brought into close contact, and through the temporary support, the photosensitive composition layer was pattern-exposed at an exposure dose of 150 mJ / cm 2 . The above exposure dose was measured with i-line.

[0329] (Development step) The exposed resin layer was left standing for 24 hours in an environment of 23 °C and 55% RH relative humidity, then the temporary support was peeled off, and development treatment was performed for 25 seconds using a 1.0 mass% aqueous sodium carbonate solution (liquid temperature: 25 °C). For the sample after the development treatment, pure water at 21 °C was sprayed from an ultra-high pressure cleaning nozzle for 25 seconds for water washing treatment, and air was blown to remove the moisture adhering to the sample. By the above procedure, a resin layer pattern was formed on the conductive base material.

[0330] (Curing step) While heating the resin layer pattern obtained in the above step, using a post-exposure machine having an ultra-high pressure mercury lamp (manufactured by Ushio Inc.), the resin layer pattern was exposed at an exposure dose of 500 mJ / cm 2 . More specifically, a hot plate was installed directly under the lamp of the post-exposure machine, and the temperature of the hot plate was adjusted such that the surface temperature of the resin layer pattern became 90 °C. The surface temperature of the resin layer pattern was measured with a radiation thermometer (manufactured by HORIBA, IT-540). Also, the exposure dose was 2 confirmed in advance as the irradiation time that would result in an exposure dose of 500 mJ / cm, and exposure was performed for that irradiation time. The above exposure dose was measured with i-line. By the above process, a protective film covering at least a part of the sensor electrode was formed.

[0331] (Post-baking process) Heat treatment was performed at 145°C for 30 minutes to obtain a touch panel sensor used in Example 1 having a substrate, a transparent film, an electrode sensor, and a protective film in this order. The protective film is a cured product of the photosensitive composition A-1.

[0332] <Examples 2 to 9, 12 to 14, and 17 to 19> Touch panel sensors used in Examples 2 to 9, 12 to 14, and 17 to 19 were obtained in the same manner as the procedure of Example 1, except that the photosensitive composition was changed as shown in Table 4 in the subsequent stage, and the exposure conditions in the curing process were changed as shown in Table 4. In the photosensitive composition used in each example, the additives and their amounts used in the preparation of the photosensitive composition A-1 of Example 1 were the same as those of A-1.

[0333] <Examples 10 and 11> Touch panel sensors used in Examples 10 and 11 were obtained according to the procedure of Example 1, except that in the production of the transfer film of Example 1, a refractive index adjustment layer was provided on the surface of the photosensitive composition layer opposite to the temporary support, the photosensitive composition layer was changed as shown in Table 4 in the subsequent stage, and the exposure conditions in the curing process were changed as shown in Table 4. In the photosensitive composition used in each example, the additives and their amounts used in the preparation of the photosensitive composition A-1 of Example 1 were the same as those of A-1. Hereinafter, a method for producing the refractive index adjustment layer will be described.

[0334] [Formation of refractive index adjustment layer] As a temporary support, a 16-μm-thick polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was prepared. On the temporary support, photosensitive composition A-1 was applied using a slit nozzle, and the solvent was volatilized in a drying zone at 100 °C to form a photosensitive composition layer with a film thickness of 5.5 μm. Thereafter, a composition containing the components shown in Table 2 (the numerical values of each component in Table 2 are the contents (parts by mass)) was applied onto the photosensitive composition layer using a slit nozzle, and then the solvent was volatilized in a drying zone at 110 °C to form a refractive index adjustment layer (refractive index: 1.68, thickness: 73 nm). A protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded to the refractive index adjustment layer to produce a transfer film.

[0335]

Table 2

[0336] <Examples 15 and 16> Touch panel sensors used in Examples 15 and 16 were obtained in the same manner as in the procedure of Example 1, except that the photosensitive composition was changed as shown in Table 3 below, and the exposure conditions in the curing step were changed as shown in Table 4.

[0337]

Table 3

[0338] In Table 3 above, each notation of the compound is as follows.

[0339] (1) Binder polymer · P-2: The above P-2 solution · P-4: The above P-4 solution Note that the parts by mass in the table represent the solid content of each solution.

[0340] (2) Polymerizable compound (2-1) Monomer having two ethylenically unsaturated bonds: ·KAYARAD R-604: Acrylic monomer, manufactured by Nippon Kayaku Co., Ltd. ·A-NOD-N: Acrylic monomer, manufactured by Shin-Nakamura Chemical Co., Ltd. (2-2) Monomer having five or more ethylenically unsaturated bonds ·TO2349: Monomer having a carboxy group, Aronix TO2349, manufactured by Toagosei Co., Ltd. ·A-DPH: Acrylic monomer, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0341] (3) Thermally crosslinkable compound ·SBN-70D: Duranate SBN-70D, manufactured by Asahi Kasei Corporation

[0342] (4) Polymerization initiator ·APi-307: 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech ·Irgacure379EG: 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, manufactured by BASF

[0343] (5) Additive ·Benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) ·Isonicotinamide (manufactured by Tokyo Chemical Industry Co., Ltd.) ·EXP.MFS-578: Megafac EXP.MFS-578, manufactured by DIC Corporation

[0344] <Comparative Examples 1 and 2> Touch panel sensors used in Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that the temperature of the surface of the protective film in the curing process was changed to 30 °C and the exposure amount in the curing process was changed as shown in Table 4 below.

[0345] <Measurement> [Surface hardness] The surface hardness of the touch panel sensors of each example and each comparative example was measured by the method described above. The obtained surface hardness is shown in Table 4 below.

[0346] [Mandrel Test] The mandrel test of the touch panel sensors of each example and each comparative example was conducted by the method described above. The obtained diameter X is shown in Table 4 below.

[0347] [Reaction Rate] The reaction rate in the manufacturing process of the touch panel sensors of each example and each comparative example was measured by the method described above. The obtained reaction rate is shown in Table 4 below.

[0348] [Evaluation] [Bright Spot Evaluation] Regarding the web sample of the touch panel sensor fabricated above, it was conveyed using a web handling device equipped with a conveyance roll. Regarding the conveyed touch panel sensor, the surface of the protective film was observed visually and with an optical microscope (binocular stereomicroscope, magnification: 10 times). The visual observation was performed from the side of the protective film under fluorescent lamp illumination. Also, the observation with the optical microscope was performed from the side of the protective film. During the observation, based on the following evaluation criteria, a bright spot evaluation was performed according to the situation of bright spots where the reflected light was strongly visible. Note that evaluations of A to C are evaluations with no practical problems.

[0349] (Evaluation Criteria) A: No bright spots are visible in both microscopic observation and visual observation. B: Slight bright spots are visible in microscopic observation. No bright spots are visible in visual observation. C: Slight bright spots are visible in visual observation. D: Bright spots are visible in visual observation.

[0350] [Resistance Change Evaluation] The touch panel sensor was left stationary in a state where it was deformed in an S shape, and the change in the resistance value of the sensor electrode before and after standing was measured. More specifically, as shown in the cross-sectional view (Figure 1) showing the deformed state 10 of the touch panel sensor, the touch panel sensor 12 was deformed in an S shape along a rod 14 of a cylinder with a diameter of 3 mm, and a load 16 was applied so as to be 10 g / cm. In this state, the touch panel sensor was left stationary in an environment of 60°C and 90% for 500 hours. Thereafter, based on the following evaluation criteria, a resistance change evaluation was performed from the change in the resistance value of the sensor electrode (ITO electrode) before and after standing. The change in the resistance value (%) was calculated by {(resistance value after standing - resistance value before standing) / resistance value before standing}×100. Note that A to C represent resistance changes without practical problems.

[0351] (Evaluation criteria) A: Resistance value change is less than 0.1% B: Resistance value change is 0.1% or more and less than 1.0% C: Resistance value change is 1.0% or more and less than 5.0% D: Resistance value change is 5.0% or more

[0352] <Results> Table 4 shows the above evaluation results for each example and each comparative example. Note that in Table 4, the notations of the respective compounds of the transfer film are as follows.

[0353] (1) Binder polymer · P-1: The above P-1 solution · P-2: The above P-2 solution · P-3: The above P-3 solution Note that the parts by mass in the table represent the solid content of each solution.

[0354] (2) Polymerizable compound (2-1) Monomer having two ethylenically unsaturated bonds: · A-DCP: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. · A-NOD-N: Acrylic monomer, manufactured by Shin-Nakamura Chemical Co., Ltd. (2-2) Monomer having five or more ethylenically unsaturated bonds ·TO2349: Monomer having a carboxy group, Aronix TO2349, manufactured by Toagosei Co., Ltd. ·A-DPH: Acrylic monomer, manufactured by Shin-Nakamura Chemical Co., Ltd. ·8UX-015A: Urethane acrylate monomer, manufactured by Dainippon Fine Chemical Co., Ltd.

[0355] (3) Thermally crosslinkable compound ·Q-1: The above block isocyanate compound Q-1 ·Q-2: The above block isocyanate compound Q-2

[0356] (4) Polymerization initiator ·OXE-02: 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxime), manufactured by BASF ·Irgacure907: 2-Methyl-4'-methylthio-2-morpholinopropiophenone, manufactured by BASF ·APi-307: 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech

[0357]

Table 4

[0358] From the results in Table 4, it was confirmed that the touch panel sensor of the present invention exhibits the desired effects. From the comparison between Example 7 and other examples, it was confirmed that when the photosensitive composition contains a binder polymer having an ethylenically unsaturated group in the side chain, the effects of the present invention are more excellent. From the comparison between Examples 8 and 9 and other examples, it was confirmed that when the photosensitive composition contains a first polymerizable compound having two ethylenically unsaturated groups and a second polymerizable compound having five or more ethylenically unsaturated groups, the effects of the present invention are more excellent. From the comparison between Example 3 and Example 18 and other examples, it was confirmed that when the photosensitive composition contains a first polymerizable compound and a second polymerizable compound, and the mass ratio of the content of the second polymerizable compound to the content of the first polymerizable compound is 0.4 to 1.3, the effects of the present invention are more excellent. From the comparison between each comparative example and each example, it was confirmed that according to the above more preferable method for manufacturing a touch panel sensor, the touch panel sensor of the present invention can be manufactured. From the comparison between Example 6 and other examples, when the exposure amount in the curing step is 200 mJ / cm 2 or more and less than 1000 mJ / cm 2 it was confirmed that a touch panel sensor with more excellent effects of the present invention is manufactured.

Explanation of Reference Signs

[0359] 10 Deformed state of the touch panel sensor 12 Touch panel sensor 14 Cylindrical rod 16 Load

Claims

1. A touch panel sensor comprising a base material and a conductive base material having a sensor electrode disposed on the base material, and a protective film covering at least a part of the sensor electrode, wherein the protective film is a film formed using a photosensitive composition, the photosensitive composition contains a binder polymer having an ethylenically unsaturated group in a side chain, the surface hardness of the surface of the protective film opposite to the conductive base material is 185 mN / mm ２ or more, A touch panel sensor having a diameter X of 3 mm or less obtained by performing the following mandrel test. Mandrel test: After repeating the operation of winding the touch panel sensor around a mandrel and returning it to its original state 10 times, the operation of observing the presence or absence of cracks in the protective film of the touch panel sensor with an optical microscope at a magnification of 10 times is repeated while reducing the diameter of the mandrel, and the diameter of the mandrel at which cracks occur in the protective film is defined as diameter X.

2. The touch panel sensor according to claim 1, wherein the photosensitive composition contains an ethylenically unsaturated compound having an acid group, and the molecular weight of the ethylenically unsaturated compound having an acid group is less than 5000.

3. A touch panel sensor comprising a base material and a conductive base material having a sensor electrode disposed on the base material, and a protective film covering at least a part of the sensor electrode, wherein the protective film is a film formed using a photosensitive composition, the photosensitive composition contains an ethylenically unsaturated compound having an acid group, the molecular weight of the ethylenically unsaturated compound having an acid group is less than 5000, the surface hardness of the surface of the protective film opposite to the conductive base material is 185 mN / mm 2 or more, and a touch panel sensor having a diameter X of 3 mm or less obtained by performing the following mandrel test. Mandrel test: After repeating the operation of winding the touch panel sensor around a mandrel and then unwinding it 10 times, the operation of observing the protective film of the touch panel sensor under an optical microscope at a magnification of 10 times to check for cracks in the protective film is repeated while reducing the diameter of the mandrel, and the diameter of the mandrel at which cracks occur in the protective film is defined as diameter X. Claim 4 The touch panel sensor according to any one of claims 1 to 3, wherein the photosensitive composition further contains a first polymerizable compound having two ethylenically unsaturated groups and a second polymerizable compound having five or more ethylenically unsaturated groups. Claim 5 The touch panel sensor according to claim 4, wherein the mass ratio of the content of the second polymerizable compound to the content of the first polymerizable compound is 0.4 to 1.

3. Claim 6: The touch panel sensor according to any one of claims 1 to 5, wherein the photosensitive composition contains a 5- to 6-functional ethylenically unsaturated compound having an acid group, and the acid value of the 5- to 6-functional ethylenically unsaturated compound having an acid group is 25 to 70 mgKOH / g.

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