Method for manufacturing a cut product

Abstract

The present invention provides: a method for manufacturing a cut article, the method including a step in which a layered body having a photosensitive layer is clamped between an upper blade and a lower blade and cut, and the clearance between the edge of the upper blade and the edge of the lower blade is 5 μm or less; a layered body having a photosensitive layer, wherein the layered body has at least a surface that has been formed through cutting, and the cut surface has no more than three cracks per ten sites in cut surface portions that measure 50 μm in width; and a layered body having a photosensitive layer, wherein the layered body has at least a surface that has been formed through cutting, and the layered body has no more than 60 dent defects / m2.

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a cut product and a laminate.

Background Art

[0002] In a display device (such as an organic electroluminescence (EL) display device and a liquid crystal display device) provided with a touch panel such as a capacitive input device, a conductive layer pattern such as an electrode pattern corresponding to a sensor in a visual recognition unit, wiring in a peripheral wiring portion, and a wiring in a lead-out wiring portion is provided inside the touch panel. Generally, for forming a patterned layer, since the number of steps for obtaining a required pattern shape is small, a method of exposing a layer of a photosensitive composition provided on an arbitrary substrate through a mask having a desired pattern and then developing is widely used.

[0003] Further, as a conventional method for cutting a film, the one described in Patent Document 1 is known. Japanese Unexamined Patent Application Publication No. 2010-228023 describes a method for cutting a film in which a continuously running film is inserted between an upper blade and a lower blade that rotate so that one side surface of the blade tips thereof is in sliding contact with each other, and the film is cut so as to be divided along the running direction and in the width direction. As the upper blade, one having a blade tip angle in sliding contact with the lower blade of 80 to 90° is used, and as the lower blade, one having a blade tip angle in sliding contact with the upper blade of 80 to 90° is used.

Summary of the Invention

Problems to be Solved by the Invention

[0004] A problem to be solved by one embodiment of the present invention is to provide a method for manufacturing a cut product capable of suppressing a dent failure in the obtained cut product. Another problem to be solved by another embodiment of the present invention is to provide a laminate with few dent failures.

Means for Solving the Problems

[0005] Means for solving the above problems include the following aspects. <1> A method for manufacturing a cut product, which includes a step of sandwiching a laminate having a photosensitive layer between an upper blade and a lower blade and cutting it, and a clearance between the cutting edge of the upper blade and the cutting edge of the lower blade is 5 μm or less. <2> The method for manufacturing a cut product according to <1>, wherein, in a cross-section perpendicular to the feeding direction of the laminate of the upper blade, a chamfering angle θ1, which is an inclination angle on the lower blade side at the cutting edge of the upper blade, is 3° or less. <3> The method for manufacturing a cut product according to <1> or <2>, wherein, in a cross-section perpendicular to the feeding direction of the laminate of the upper blade, a cutting edge angle θ2 of the upper blade is 33° or less. <4> The method for manufacturing a cut product according to any one of <1> to <3>, wherein the thickness of the entire laminate is 50 μm or less. <5> The method for manufacturing a cut product according to any one of <1> to <4>, wherein the thickness of the photosensitive layer is 1 μm to 20 μm. <6> The method for manufacturing a cut product according to any one of <1> to <5>, wherein the laminate is a laminate having a support, the photosensitive layer, and a cover film. <7> The method for manufacturing a cut product according to <6>, wherein the thicknesses of the support and the cover film are each independently 10 μm to 20 μm. <8> The method for manufacturing a cut product according to <6> or <7>, wherein an arithmetic mean roughness Ra value of a surface of the support on the photosensitive layer side is 0.05 μm or less. <9> The method for manufacturing a cut product according to any one of <6> to <8>, wherein an arithmetic mean roughness Ra value of a surface of the cover film on the photosensitive layer side is 0.1 μm or less. <10> The method for manufacturing a cut product according to any one of <1> to <9>, which includes a step of winding at least a part of the cut product of the laminate obtained after the cutting step. <11> A laminate having a photosensitive layer, wherein the laminate has at least a cut surface, and the number of cracks per 10 cut surface portions having a cut surface width of 50 μm is 3 or less. <12> A laminate having a photosensitive layer, wherein the laminate has at least a cut surface formed by cutting, and the number of indentation failures in the laminate is 60 pieces / m 2 The following laminate.

Advantages of the Invention

[0006] According to one embodiment of the present invention, it is possible to provide a method for manufacturing a cut product that can suppress indentation failures in the obtained cut product. Moreover, according to another embodiment of the present invention, it is possible to provide a laminate with few indentation failures.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0008] Hereinafter, the content of the present disclosure will be described. Although the description will be made with reference to the accompanying drawings, reference numerals may be omitted in some cases. In addition, in this specification, the 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 addition, in this specification, "(meth)acryl" represents both acrylic and methacrylic, or either one, and "(meth)acrylate" represents both acrylate and methacrylate, or either one. Furthermore, in this specification, the amount of each component in the composition means the total amount of the plurality of substances corresponding to each component present in the composition, unless otherwise specified, when there are a plurality of substances corresponding to each component in the composition. In this specification, the term "step" includes not only an independent step but also cases where, even if it cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved. In the notation of groups (atomic groups) in this specification, notations that do not indicate substitution or non-substitution include both those having no substituents and those having substituents. For example, the term "alkyl group" includes not only an alkyl group having no substituents (unsubstituted alkyl group) but also an alkyl group having substituents (substituted alkyl group). In this specification, "exposure" includes, unless otherwise specified, not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Also, the light used for exposure generally includes actinic rays (active energy rays) such as the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams. Also, in this specification, chemical structural formulas may be described as abbreviated structural formulas in which hydrogen atoms are omitted. In the present disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Also, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. Also, in the present disclosure, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, unless otherwise specified, molecular weights converted using a gel permeation chromatography (GPC) analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all are product names manufactured by Tosoh Corporation), with the solvent THF (tetrahydrofuran) and detected by a differential refractometer, using polystyrene as a standard substance. In this specification, unless otherwise specified, the content of metal elements 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.). In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more. In this specification, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 at 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. In this specification, the "solid content" of a composition means the components that form a layer produced using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Also, any liquid component is regarded as a solid content as long as it is a component that forms the above layer. In this specification, the layer thickness of each layer provided in the photosensitive transfer member is measured by observing a cross-section in a direction perpendicular to the main surface of the photosensitive transfer member with a scanning electron microscope (SEM), measuring the thickness of each layer at any five or more points based on the obtained observation image, and calculating the average value thereof.

[0009] [Method for manufacturing a cut product] The method for manufacturing a cut product according to the present disclosure includes a step of sandwiching and cutting a laminate having a photosensitive layer with an upper blade and a lower blade, and the clearance between the upper blade and the lower blade is 5 μm or less.

[0010] For a resist material such as a photosensitive transfer member, it is theoretically advantageous to narrow the gap between the mask and the resist material in order to form a resist that is faithful to the patterning mask upon exposure. The smaller the gap, the shorter the optical path length, the less susceptible it is to the effects of diffraction and scattering, and a resist faithful to the mask can be realized. At high resolutions, the distance of the gap becomes prominent, and it is important to control these. In the case of a dry film, since exposure is performed through the support from the perspective of preventing mask contamination, it is necessary to reduce the thickness of the support, and accordingly, the total film thickness has been decreasing. Under conventional cutting conditions, it could not be cut well, and many pieces of chips were generated. The inventor has found that when these pieces of chips adhere to the laminate (cut product) having the above-described photosensitive layer that has been cut, a dent (depression) failure occurs. For example, when pieces of chips adhere to a laminate having a photosensitive layer, and then the cut products are stacked for storage, a dent (depression) failure occurs. Also, when a laminate having a photosensitive layer is wound into a roll, a dent failure occurs by winding in pieces of chips.

[0011] As a result of intensive studies, the inventor has found that by making the manufacturing method of the cut product having the above configuration, it is possible to suppress the depression failure in the obtained cut product. Although the detailed mechanism of manifestation of the above effects is unknown, it is presumed that by making the clearance between the cutting edge of the upper blade and the cutting edge of the lower blade 5 μm or less, generation of chips can be suppressed during cutting of the laminate having a photosensitive layer, and the depression failure caused by the chips adhering to the laminate can be suppressed.

[0012] The laminate having the above photosensitive layer is preferably a photosensitive transfer member. The photosensitive transfer member used in the present disclosure is preferably a negative photosensitive transfer member. Preferred embodiments of the laminate having the above photosensitive layer will be described later.

[0013] <Step of cutting> The manufacturing method of the cut product according to the present disclosure includes a step of sandwiching and cutting a laminate having a photosensitive layer with an upper blade and a lower blade, and the clearance between the cutting edge of the upper blade and the cutting edge of the lower blade is 5 μm or less. The cutting means having the upper blade and the lower blade used in the present disclosure is not particularly limited, and examples thereof include a cutting machine, a slitter, and the like. From the viewpoint of being capable of continuously cutting and being wound up in a roll shape, the cutting means is preferably a rotary slitter, and more preferably a disk-shaped rotary slitter.

[0014] FIG. 1 is a schematic cross-sectional view showing an example of the upper blade and the lower blade of the disk-shaped rotary slitter used in the present disclosure, and shows a cross-section in a direction perpendicular to the cutting surface of the laminate. The upper blade 102 is a blade having a chamfering angle θ1 and a cutting edge angle θ2, and has a chamfering length R1. The lower blade 104 is a blade having a chamfering angle θ3, and has a chamfering length R2. Further, the clearance CL between the cutting edge 102a of the upper blade 102 and the cutting edge 104a of the lower blade 104 shown in FIG. 1 is a value of R1 + R2. Furthermore, at the time of cutting, the laminate (not shown) having a photosensitive layer is sandwiched between the upper blade 102 and the lower blade 104 according to the penetration depth T of the upper blade 102 with respect to the lower blade 104, whereby the laminate having a photosensitive layer is cut. In FIG. 1, the laminate having a photosensitive layer is sandwiched between the upper blade 102 and the lower blade 104 and cut so as to be separated left and right.

[0015] The clearance CL between the cutting edge 102a of the upper blade 102 and the cutting edge 104a of the lower blade 104 is 5 μm or less, and from the viewpoint of suppressing dent defects, it is preferably 1 μm or more and 5 μm or less, more preferably 2 μm or more and 4.5 μm or less, still more preferably 2.5 μm or more and 4.0 μm or less, and particularly preferably 2.5 μm or more and 3.5 μm or less.

[0016] In the cross-section of the upper blade 102 in a plane perpendicular to the feeding direction of the laminate, from the viewpoint of suppressing indentation defects, the chamfer length R1 of the upper blade 102 is preferably 0.5 μm or more and 3 μm or less, more preferably 0.5 μm or more and 2.5 μm or less, still more preferably 0.8 μm or more and 2.0 μm or less, and particularly preferably 0.8 μm or more and 1.5 μm or less. Also, in the cross-section of the lower blade 104 in a plane perpendicular to the feeding direction of the laminate, from the viewpoint of suppressing indentation defects, the chamfer length R2 of the lower blade 104 is preferably 0.5 μm or more and 3 μm or less, more preferably 1.0 μm or more and 2.5 μm or less, and particularly preferably 1.5 μm or more and 2.5 μm or less.

[0017] In the cross-section of the upper blade 102 in a plane perpendicular to the feeding direction of the laminate, the chamfer angle θ1, which is the inclination angle on the lower blade side at the cutting edge 102a of the upper blade 102, is preferably 15° or less, more preferably 10° or less, still more preferably 3° or less, and particularly preferably 1° or more and 3° or less from the viewpoint of suppressing indentation defects. Also, from the viewpoint of suppressing indentation defects, the chamfer angle θ1 is preferably an angle exceeding 0°.

[0018] In the cross-section of the upper blade 102 in a plane perpendicular to the feeding direction of the laminate, the cutting edge angle θ2 of the upper blade 102 is preferably 45° or less, more preferably 40° or less, still more preferably 33° or less, and particularly preferably 20° or more and 33° or less from the viewpoint of suppressing indentation defects. Also, from the viewpoint of suppressing indentation defects, the cutting edge angle θ2 is preferably an angle of 2 times or more of the chamfer angle θ1, more preferably an angle of 5 times or more of the chamfer angle θ1, and particularly preferably an angle of 10 times or more of the chamfer angle θ1.

[0019] In the cross-section of the lower blade 104 in a plane perpendicular to the feeding direction of the laminate, the cutting edge angle θ3 of the lower blade 104, from the viewpoint of suppressing indentation defects , greater than 90° is preferably 120° or less 、1 more preferably 10° or less、1 More preferably, it is 5° or less. 、1 Particularly preferably, it is 0° or less.

[0020] There is no particular limitation on the materials of the upper blade 102 and the lower blade 104, and known materials can be used. For example, high-speed tool steel (SKH), alloy tool steel (e.g., SKD), cemented carbide, etc. are preferably used, and they are appropriately set according to the thickness of the above laminate, cutting conditions, etc. Also, regarding the shapes of the upper blade 102 and the lower blade 104 other than those described above, such as the thickness of the upper blade 102 and the thickness of the lower blade 104, they can be appropriately set respectively according to the thickness of the above laminate, etc. Also, in the above cutting step, the upper blade 102 is preferably located above the lower blade 104 in the direction of gravity.

[0021] The penetration depth T of the upper blade 102 into the lower blade 104 during cutting in the above cutting step is not particularly limited as long as cutting is possible. However, from the viewpoints of cutting speed and suppressing depression defects, in a rotary slitter, it is preferably 0.4 mm to 0.6 mm. Also, in a rotary slitter, the upper blade 102 and the lower blade 104 in the above cutting step are preferably in sliding contact at least partially.

[0022] In the above cutting step, the shape and size of the cut object obtained by cutting the above laminate are not particularly limited, and it may be cut into a desired shape and size. Also, regarding the materials and sizes of the above upper blade and the above lower blade, they can be appropriately selected according to the above laminate and the obtained cut object. Also, in the above cutting step, it is preferable to cut the above laminate in the thickness direction.

[0023] Also, the cutting speed in the above cutting step is not particularly limited and can be appropriately selected according to desire.

[0024] <Winding step> The manufacturing method of the cut product according to the present disclosure preferably includes a step of winding up at least a part of the cut product of the obtained laminate after the above-mentioned cutting step. When winding up the cut product, since a dent defect caused by the adhesion of chips is likely to occur, the effects according to the present disclosure can be more exerted. The winding method is not particularly limited, and a known method can be used. In the above-mentioned winding step, it is preferable to wind up the cut product in a roll shape.

[0025] <Other steps> The manufacturing method of the cut product according to the present disclosure may include any step (other steps) other than the above-mentioned steps. Examples of other steps include known steps.

[0026] The cutting device used in the present disclosure is not particularly limited, and in a known cutting device, the upper blade and the lower blade can be adjusted to the above range and used. A preferable cutting device is, for example, a cutting device including a disk-shaped rotary slitter, which has rotary shafts arranged in parallel with each other as the rotary shaft of the upper blade and the rotary shaft of the lower blade, and circular upper blades and lower blades are respectively fixed to each rotary shaft. At the time of cutting, the laminate is cut while one side surfaces of the blade tips of the upper blade and the lower blade are in sliding contact with each other. Further, each rotary shaft is configured to rotate in a predetermined direction by a drive mechanism, and the upper blade and the lower blade are respectively configured to rotate.

[0027] Hereinafter, the laminate having a photosensitive layer used in the present disclosure will be described in detail.

[0028] <Laminate having a photosensitive layer> The laminate having a photosensitive layer used in the present disclosure is not particularly limited as long as it is a laminate having two or more layers having a photosensitive layer, but it is preferably a laminate having at least a support and a photosensitive layer, and more preferably a laminate having a support, a photosensitive layer, and a cover film. Further, the laminate having the photosensitive layer is preferably a photosensitive transfer member. The photosensitive transfer member may have the support and the photosensitive layer directly laminated without an intervening layer, or may be laminated via another layer. Further, another layer may be laminated on the surface of the photosensitive layer opposite to the surface facing the support. Examples of the other layers other than the support and the photosensitive layer include a thermoplastic resin layer, an intermediate layer, a refractive index adjustment layer, and a cover film. Also, each layer may be a single layer or a multi-layer of two or more layers.

[0029] From the viewpoint of more effectively exhibiting the effects in the present disclosure, the thickness of the entire laminate is preferably 50 μm or less, more preferably 42 μm or less, and particularly preferably 20 μm or more and 42 μm or less.

[0030] An example of the aspect of the laminate having the photosensitive layer used in the present disclosure is shown below, but it is not limited thereto. (1) "Support / Photosensitive layer / Refractive index adjustment layer / Cover film" (2) "Support / Photosensitive layer / Cover film" (3) "Support / Intermediate layer / Photosensitive layer / Cover film" (4) "Support / Thermoplastic resin layer / Intermediate layer / Photosensitive layer / Cover film" In each of the above configurations, the photosensitive layer is preferably a negative photosensitive layer. Also, it is preferable that the photosensitive layer is a colored resin layer. The laminate having the photosensitive layer used in the present disclosure may be used as a photosensitive transfer member for a wiring protection film or as a photosensitive transfer member for an etching resist as described later. When used as a photosensitive transfer member for a wiring protection film, the configuration of the laminate is preferably, for example, the configuration of (1) or (2) described above. When used as a photosensitive transfer member for an etching resist, the configuration of the laminate is preferably, for example, the configuration of (2) to (4) described above.

[0031] In the laminate having a photosensitive layer used in the present disclosure, in the case of a configuration having another layer on the side opposite to the support side of the photosensitive layer, the total thickness of the other layers disposed on the side opposite to the support side of the photosensitive layer is preferably 0.1% to 30% with respect to the layer thickness of the photosensitive layer, and more preferably 0.1% to 20%.

[0032] From the viewpoint of suppressing the generation of bubbles during bonding, the maximum width of the undulation of the laminate having a photosensitive layer used in the present disclosure is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 60 μm or less. In addition, the lower limit value of the maximum width of the undulation of the photosensitive transfer member 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 laminate having a photosensitive layer used in the present disclosure is a value measured by the following procedure. First, the laminate is cut in a direction perpendicular to the main surface so as to have a size of 20 cm in length × 20 cm in width to prepare a test sample. When the laminate has a cover film, the cover film is peeled off. Next, the test sample is placed on a smooth and horizontal stage so that the surface of the support faces the stage. After standing, for the range of a 10 cm square at the center of the test sample, the surface of the test sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) to obtain a three-dimensional surface image, and the minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. The above operation is performed on 10 test samples, and the arithmetic mean value is taken as the "maximum undulation width of the photosensitive transfer member".

[0033] Hereinafter, the laminate having a photosensitive layer used in the present disclosure will be described. The laminate of Embodiment A below is a configuration that can be suitably used for a photosensitive transfer member for an etching resist, and the laminate of Embodiment B below is a configuration that can be suitably used for a photosensitive transfer member for a wiring protection film.

[0034] 〔〔Laminate of Embodiment A〕〕 Hereinafter, the laminate of Embodiment A will be described.

[0035] [Support] The laminate used in the present disclosure preferably has a support. The photosensitive transfer member used in the present disclosure has a support. The support supports a photosensitive layer or a laminate including a photosensitive layer, and is a peelable support.

[0036] From the viewpoint that the photosensitive layer can be exposed through the support when the photosensitive layer is pattern-exposed, the support preferably has light transmissivity. In the present specification, "having light transmissivity" means that the transmittance of light having a wavelength used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive layer, the transmittance of light having a wavelength (more preferably a wavelength of 365 nm) used for pattern exposure is preferably 60% or more, and more preferably 70% or more. The transmittance of the layer provided in the photosensitive transfer member is the ratio of the intensity of the emitted light that has passed through the layer to the intensity of the incident light when light is incident in the direction perpendicular to the main surface of the layer (thickness direction), and is measured using the MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0037] The support may have a single-layer structure or a multilayer structure. Examples of the material constituting the support include a glass substrate, a resin film, and paper, and a resin film is preferred from the viewpoints of strength, flexibility, and light transmissivity. Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a PET film is preferred, and a biaxially stretched PET film is more preferred.

[0038] The thickness of the support (layer thickness) is not particularly limited and may be selected according to the material from the viewpoints of the strength as a support, the flexibility required for bonding to the substrate for forming circuit wiring, and the light transmittance required in the first exposure process. The thickness of the support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 20 μm, and particularly preferably in the range of 10 μm to 16 μm, from the viewpoints of ease of handling and versatility. Further, the average thickness of the support is preferably 50 μm or less, more preferably 25 μm or less, from the viewpoints of resolution and linearity when exposing through the support.

[0039] Examples of the support include a biaxially stretched polyethylene terephthalate film with a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a film thickness of 9 μm.

[0040] Also, the film used as the support preferably has no deformations such as wrinkles, scratches, defects, etc. From the viewpoints of pattern formability during pattern exposure through the support and the transparency of the support, the number of fine particles, foreign substances, defects, precipitates, etc. contained in the support is preferably small. The number of fine particles, foreign substances, and defects with a diameter of 1 μm or more is preferably 2 50 pieces / 10 mm or less, 2 more preferably 10 pieces / 10 mm or less, 2 still more preferably 3 pieces / 10 mm or less, 2 and particularly preferably 0 pieces / 10 mm.

[0041] Preferable embodiments of the support include, for example, those described in paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019 to 0026 of JP-A-2016-27363, paragraphs 0041 to 0057 of WO 2012 / 081680, paragraphs 0029 to 0040 of WO 2018 / 179370, and paragraphs 0012 to 0032 of JP-A-2019-101405. The contents of these publications are incorporated herein.

[0042] From the viewpoint of further exerting the effects in the present disclosure, the arithmetic mean roughness Ra value of the surface of the support on the photosensitive layer side is preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. The lower limit of the Ra value of the surface of the support in contact with the photosensitive layer is not particularly limited, but is preferably 0.001 μm or more.

[0043] The Ra values of the surfaces of the support and the cover film are measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), measure the surface of the support or the cover film under the following conditions to obtain the surface profile of the optical film. As the measurement / analysis software, use the Microscope Application of MetroPro ver8.3.2. Next, display the Surface Map screen with the above analysis software, and obtain the histogram data in the Surface Map screen. Calculate the arithmetic mean roughness from the obtained histogram data to obtain the Ra value of the surface of the support or the cover film. When the support or the cover film is adhered to a photosensitive layer or the like, the support or the cover film may be peeled off from the photosensitive layer, and the Ra value of the surface on the peeled side may be measured.

[0044] From the viewpoint of imparting handleability, a layer containing fine particles (also referred to as a "lubricant layer") may be provided on the surface of the support. The lubricant layer may be provided on one side or both sides of the support. The diameter of the particles contained in the lubricant layer is preferably 0.05 μm to 0.8 μm. Further, the thickness of the lubricant layer is preferably 0.05 μm to 1.0 μm.

[0045] 〔Photosensitive layer〕 The laminate used in the present disclosure has a photosensitive layer. The photosensitive transfer member used in the present disclosure has a photosensitive layer.

[0046] The photosensitive layer is preferably a negative photosensitive layer in which the solubility of the exposed portion in the developer decreases upon exposure and the unexposed portion is removed by development. However, the photosensitive layer is not limited to a negative photosensitive layer, and may be a positive photosensitive layer in which the solubility of the exposed portion in the developer improves upon exposure and the exposed portion is removed by development.

[0047] The photosensitive layer preferably contains a polymerizable compound and a binder polymer, more preferably contains a polymerizable compound, a binder polymer, and a photopolymerization initiator, and particularly preferably contains Polymer A, a polymerizable compound, and a photopolymerization initiator. Based on the total mass of the photosensitive layer, the photosensitive layer preferably contains: binder polymer: 10% by mass to 90% by mass; polymerizable compound: 5% by mass to 70% by mass; and photopolymerization initiator: 0.01% by mass to 20% by mass. Hereinafter, each component will be described in order.

[0048] (Binder polymer) The photosensitive layer preferably contains a binder polymer. There is no particular limitation on the binder polymer, and for example, known binder polymers used in etching resists are preferably used. Further, examples of the binder polymer include alkali-soluble polymers. The alkali-soluble polymer is preferably an alkali-soluble polymer having an acid group. Among them, Polymer A described later is preferable as the binder polymer.

[0049] -Polymer A- As the binder polymer, it is preferable to contain polymer A. Polymer A is preferably an alkali-soluble polymer. The alkali-soluble polymer includes polymers that are easily soluble in alkali substances.

[0050] The acid value of polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g, from the viewpoint of more excellent resolution by suppressing the swelling of the photosensitive layer by the developer. The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of more excellent developability, it is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more.

[0051] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. In this specification, the unit is described as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of polymer A may be adjusted according to the types of constitutional units constituting polymer A and the content of constitutional units containing acid groups.

[0052] The weight average molecular weight of polymer A is preferably from 5,000 to 500,000. Setting the weight average molecular weight to 500,000 or less is preferable from the viewpoint of improving resolution and developability. It is more preferable to set the weight average molecular weight to 100,000 or less, still more preferable to set it to 60,000 or less, and particularly preferable to set it to 50,000 or less. On the other hand, setting the weight average molecular weight to 5,000 or more is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge fusion property and chip cut property. It is more preferable to set the weight average molecular weight to 10,000 or more, still more preferable to set it to 20,000 or more, and particularly preferable to set it to 30,000 or more. The edge fusion property refers to the degree of ease of the photosensitive layer protruding from the end face of the roll when the photosensitive transfer member is wound into a roll shape. The chip cut property refers to the degree of ease of the chips flying off when the unexposed film is cut with a cutter. When these chips adhere to the upper surface of the photosensitive transfer member or the like, they are transferred to the mask in a subsequent exposure process or the like, causing defective products. The dispersity of polymer A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and still more preferably from 1.0 to 3.0. In the present disclosure, the molecular weight is a value measured using gel permeation chromatography. The dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

[0053] From the viewpoint of suppressing line width thickening and resolution deterioration when the focus position during exposure is shifted, the polymer A preferably has an aromatic hydrocarbon group, and more preferably has a structural unit having an aromatic hydrocarbon group. Examples of such an aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content ratio of the structural unit having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of the polymer A. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. In the case where a plurality of types of the polymer A are contained, the content ratio of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.

[0054] Examples of the monomer that forms the structural unit having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferable. In one aspect, when the monomer that forms the structural unit having an aromatic hydrocarbon group in the polymer A is styrene, the content ratio of the structural unit derived from styrene is preferably 20% by mass to 50% by mass, more preferably 25% by mass to 45% by mass, still more preferably 30% by mass to 40% by mass, and particularly preferably 30% by mass to 35% by mass, based on the total mass of the polymer A. In the case where the photosensitive layer contains a plurality of types of the polymer A, the content ratio of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.

[0055] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group, etc., and a substituted or unsubstituted benzyl group is preferable.

[0056] Examples of the monomer having a phenylethyl group other than a substituted or unsubstituted benzyl group include phenylethyl (meth)acrylate and the like.

[0057] Examples of the monomer having a substituted or unsubstituted benzyl group include (meth)acrylate having a substituted or unsubstituted benzyl group (for example, benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.); vinyl monomers having a benzyl group (for example, vinyl benzyl chloride, vinyl benzyl alcohol, etc.). Among them, benzyl (meth)acrylate is preferable. In one aspect, when the monomer forming the structural unit having an aromatic hydrocarbon group in Polymer A is benzyl (meth)acrylate, the content ratio of the structural unit derived from benzyl (meth)acrylate is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, still more preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass based on the total mass of Polymer A.

[0058] Polymer A having a structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one monomer having an aromatic hydrocarbon group and at least one of the first monomer described below and / or at least one of the second monomer described below.

[0059] Polymer A having no structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, and more preferably obtained by copolymerizing at least one of the first monomers described below and at least one of the second monomers described below.

[0060] The first monomer is a monomer having a carboxy group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid semiester, and the like. Among these, (meth)acrylic acid is preferable. The content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 15% by mass to 30% by mass based on the total mass of the polymer A.

[0061] The content ratio of the structural unit derived from the first monomer is preferably 10% by mass to 50% by mass based on the total mass of the polymer A. Setting the above copolymerization ratio to 10% by mass or more is preferable from the viewpoints of developing good developability and controlling edge fusion properties, etc., more preferably 15% by mass or more, and still more preferably 20% by mass or more. Setting the above content ratio to 50% by mass or less is preferable from the viewpoints of high resolution of the resist pattern and the SUSO shape, and further from the viewpoint of the chemical resistance of the resist pattern. In these viewpoints, 35% by mass or less is more preferable, 30% by mass or less is still more preferable, and 27% by mass or less is particularly preferable.

[0062] The second monomer is a non-acidic monomer having at least one ethylenically unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile and the like. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferable, and methyl (meth)acrylate is particularly preferable. The content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and still more preferably 20% by mass to 45% by mass based on the total mass of the polymer A.

[0063] In addition, from the viewpoint of suppressing line width thickening and resolution deterioration when the focus position during exposure is deviated, it is preferable that the polymer A contains at least one kind of structural unit selected from the group consisting of a structural unit having an aralkyl group and a structural unit derived from styrene. As the polymer A, for example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, etc. are preferable. In one aspect, it is preferable that the polymer A is a polymer containing 25% by mass to 40% by mass of a structural unit having an aromatic hydrocarbon group, 20% by mass to 35% by mass of a structural unit derived from a first monomer, and 30% by mass to 45% by mass of a structural unit derived from a second monomer. Further, in another aspect, it is preferable that the polymer is a polymer containing 70% by mass to 90% by mass of a structural unit having an aromatic hydrocarbon group and 10% by mass to 25% by mass of a structural unit derived from a first monomer.

[0064] The polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. The alicyclic structure may be a monocyclic structure or a polycyclic structure. Specific examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate is preferable, and i-propyl methacrylate or t-butyl methacrylate is more preferable. Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Also, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms (number of carbon atoms) can be mentioned. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2-methyl-2-adamantyl, (meth)acrylic acid 2-ethyl-2-adamantyl, (meth)acrylic acid 3-hydroxy-1-adamantyl, (meth)acrylic acid octahydro-4,7-menthanoylinden-5-yl, (meth)acrylic acid octahydro-4,7-menthanoylinden-1-ylmethyl, (meth)acrylic acid-1-menthyl, (meth)acrylic acid tricyclodecane, (meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl, (meth)acrylic acid (nor)bornyl, (meth)acrylic acid isobornyl, (meth)acrylic acid fenchyl, (meth)acrylic acid-2,2,5-trimethylcyclohexyl, and (meth)acrylic acid cyclohexyl, etc. Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, phentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecanyl (meth)acrylate is preferable, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecanyl (meth)acrylate is more preferable.

[0065] The photosensitive layer may contain the polymer A alone or in combination of two or more. When containing two or more, it is preferable to mix and use two kinds of the polymer A having an aromatic hydrocarbon group, or to mix and use the polymer A having an aromatic hydrocarbon group and the polymer A having no aromatic hydrocarbon group. In the latter case, the content ratio of the polymer A having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more based on the total mass of the polymer A.

[0066] The synthesis of the polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting the above-described single or plural monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring. In some cases, synthesis may be carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, the solvent may be further added to adjust to a desired concentration. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0067] The glass transition temperature Tg of the polymer A is preferably 30°C or higher and 135°C or lower. By using the polymer A having a Tg of 135°C or lower in the photosensitive layer, it is possible to suppress the line width thickening and the deterioration of resolution when the focus position during exposure is shifted. From this viewpoint, the Tg of the polymer A is more preferably 130°C or lower, still more preferably 120°C or lower, and particularly preferably 110°C or lower. Also, using the polymer A having a Tg of 30°C or higher is preferable from the viewpoint of improving the edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0068] The photosensitive layer may contain a resin other than the polymer A. Examples of the resin other than the polymer A include acrylic resins, styrene-acrylic copolymers (provided that the styrene content is 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0069] Further, the content of the structural unit formed from methacrylic acid in the binder polymer is preferably 40% by mass or less, more preferably 5% by mass or more and 40% by mass or less, still more preferably 10% by mass or more and 35% by mass or less, and particularly preferably 15% by mass or more and 30% by mass or less with respect to the total mass of the binder polymer, from the viewpoints of the resolution of the obtained etching pattern and the residue suppression property during development. Furthermore, the acid value of the binder polymer is preferably 100 mgKOH / g to 200 mgKOH / g from the viewpoints of the resolution of the obtained etching pattern and the residue suppression property during development.

[0070] The binder polymer can be used alone or in combination of two or more kinds. The proportion of the binder polymer in the total mass of the photosensitive layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and still more preferably 40% by mass to 60% by mass. Setting the proportion of the binder polymer in the photosensitive layer to 90% by mass or less is preferable from the viewpoint of controlling the development time. On the other hand, setting the proportion of the binder polymer in the photosensitive layer to 10% by mass or more is preferable from the viewpoint of improving the edge fuse resistance.

[0071] (Polymerizable compound) The photosensitive layer preferably contains a polymerizable compound. In this specification, the "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator described later and is different from the binder polymer described above.

[0072] As the polymerizable compound, an ethylenically unsaturated compound is preferable. The ethylenically unsaturated compound is a component that contributes to the photosensitivity (i.e., photocurability) of the negative photosensitive layer and the strength of the cured film. Also, the ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups. The photosensitive layer preferably contains a polyfunctional or higher ethylenically unsaturated compound as the ethylenically unsaturated compound. Here, the polyfunctional or higher ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, a (meth)acryloyl group is more preferable. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferable.

[0073] The photosensitive layer preferably contains a polymerizable compound having a polymerizable group. The polymerizable groups possessed by the polymerizable compound are not particularly limited as long as they are groups involved in the polymerization reaction. For example, groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group such as an epoxy group and an oxetane group can be mentioned. As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

[0074] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferable in terms of the photosensitivity of the photosensitive layer being more excellent, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferable. Also, in terms of more excellent resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0075] The photosensitive layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule in terms of a better balance between the photosensitivity, resolution, and peelability of the photosensitive layer, and more preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. Regarding the content of the bifunctional ethylenically unsaturated compound with respect to the content of the polymerizable compound in the photosensitive layer, from the viewpoint of excellent peelability, it is preferably 60% by mass or more, more preferably more than 70% by mass, and even more preferably 90% by mass or more. The upper limit is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds contained in the photosensitive layer may be bifunctional ethylenically unsaturated compounds. Also, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as the polymerizable group is preferable.

[0076] -Polymerizable Compound B1- The photosensitive layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-described polymerizable compounds.

[0077] In the photosensitive layer, the mass ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0078] Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof. An aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred. The above aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring or two or more aromatic rings.

[0079] The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive layer by the developer. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). The bisphenol A structure is preferred.

[0080] Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable. The number of added alkyleneoxy groups to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, and more preferably 6 to 14. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated herein.

[0081] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0082] As the polymerizable compound B1, the following general formula (I):

[0083] [Chemical formula]

[0084] {In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1 and n3 each independently are integers from 1 to 39, and n1 + n3 is an integer from 2 to 40, n2 and n4 each independently are integers from 0 to 29, and n2 + n4 is an integer from 0 to 30. The arrangement of the repeating units of -(A-O)- and -(B-O)- may be random or block. And in the case of block, either -(A-O)- or -(B-O)- may be on the bisphenol group side.} The compound represented by the formula can be used. In one embodiment, n1 + n2 + n3 + n4 is preferably from 2 to 20, more preferably from 2 to 16, and still more preferably from 4 to 12. Also, n2 + n4 is preferably from 0 to 10, more preferably from 0 to 4, still more preferably from 0 to 2, and particularly preferably 0.

[0085] The polymerizable compound B1 may be used alone or in combination of two or more. The content of the polymerizable compound B1 in the photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoints of transferability and edge fusion (the phenomenon that components in the photosensitive layer, particularly binder polymers, etc. ooze out from the edge of the transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0086] The photosensitive layer may contain a polymerizable compound other than the above-described polymerizable compound B1. The polymerizable compounds other than the polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds having no aromatic ring, and ethylenically unsaturated compounds having three or more functional groups can be mentioned.

[0087] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0088] Examples of the difunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of the urethane di(meth)acrylate include propylene oxide-modified urethane di(meth)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0089] 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, trimethylolethane tri(meth)acrylate, tris(meth)acrylate isocyanurate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof. Here, “(tri / tetra / penta / hexa)(meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra)(meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate. In one aspect, the photosensitive layer preferably contains the above-described polymerizable compound B1 and an ethylenically unsaturated compound having three or more functional groups, and more preferably contains the above-described polymerizable compound B1 and two or more ethylenically unsaturated compounds having three or more functional groups. In this case, the mass ratio of the polymerizable compound B1 to the ethylenically unsaturated compound having three or more functional groups is preferably (total mass of the polymerizable compound B1):(total mass of the ethylenically unsaturated compound having three or more functional groups)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and still more preferably 1.5:1 to 3:1. In another aspect, the photosensitive layer preferably contains the above-described polymerizable compound B1 and two or more ethylenically unsaturated compounds having three functional groups.

[0090] Examples of alkylene oxide-modified products of ethylenically unsaturated compounds having three or more functional groups include caprolactone-modified (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 (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., etc.), ethoxylated glycerin triacrylate (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), and Aronix M-510 (manufactured by Toagosei Co., Ltd.).

[0091] In addition, as the polymerizable compound other than the polymerizable compound B1, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.

[0092] From the viewpoints of the resolution of the obtained etching pattern and the residue suppression property during development, the value of the ratio Mm / Mb of the content Mm of the polymerizable compound to the content Mb of the binder polymer in the photosensitive layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. In addition, from the viewpoints of curability and the resolution of the obtained etching pattern, the polymerizable compound in the photosensitive layer preferably contains a (meth)acrylic compound. Furthermore, from the viewpoints of curability, the resolution of the obtained etching pattern, and the residue suppression property during development, the polymerizable compound in the photosensitive layer contains a (meth)acrylic compound, and the content of the acrylic compound with respect to the total mass of the (meth)acrylic compound contained in the photosensitive layer is more preferably 60% by mass or less.

[0093] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound in the photosensitive layer is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and still more preferably 20% to 50% by mass with respect to the total mass of the photosensitive layer.

[0094] As the weight average molecular weight (Mw) of the polymerizable compound containing the polymerizable compound B1, 200 to 3,000 is preferable, 280 to 2,200 is more preferable, and 300 to 2,200 is still more preferable.

[0095] (Other components) The photosensitive layer may contain components other than the binder polymer and the polymerizable compound.

[0096] -Photoinitiator- The photosensitive layer preferably contains a photoinitiator. The photoinitiator is a compound that initiates the polymerization of the polymerizable compound upon receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photoinitiator is not particularly limited, and known photoinitiators can be used. Examples of the photoinitiator include a photo radical polymerization initiator and a photo cationic polymerization initiator, and a photo radical polymerization initiator is preferable.

[0097] Examples of the photo radical polymerization initiator include a photo polymerization initiator having an oxime ester structure, a photo polymerization initiator having an α-aminoalkylphenone structure, a photo polymerization initiator having an α-hydroxyalkylphenone structure, a photo polymerization initiator having an acylphosphine oxide structure, and a photo polymerization initiator having an N-phenylglycine structure.

[0098] Further, from the viewpoints of photosensitivity, visibility of the exposed portion and the non-exposed portion, and resolution, the photosensitive layer preferably contains at least one selected from the group consisting of 2,4,5-triaryl imidazole dimers and their derivatives as the photo radical polymerization initiator. Note that the two 2,4,5-triaryl imidazole structures in the 2,4,5-triaryl imidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer.

[0099] As the photo radical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783 may be used.

[0100] Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0101] Examples of commercially available photo radical polymerization initiators include 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-acet yloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (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-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.Examples include oxime ester-based photoinitiators (trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0102] A photo cationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving actinic radiation. As the photo cationic polymerization initiator, a compound that is sensitive to actinic radiation with a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm, and generates an acid is preferred, but its chemical structure is not limited. Also, for a photo cationic polymerization initiator that is not directly sensitive to actinic radiation with a wavelength of 300 nm or more, if it can be made sensitive to actinic radiation with a wavelength of 300 nm or more and generate an acid by being used in combination with a sensitizer, it can be preferably used in combination with the sensitizer. As the photo cationic polymerization initiator, a photo cationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photo cationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photo cationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. The lower limit value of the pKa is not particularly defined, but for example, -10.0 or more is preferred.

[0103] Examples of the photo cationic polymerization initiator include ionic photo cationic polymerization initiators and non-ionic photo cationic polymerization initiators. Examples of the ionic photo cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As the ionic photo cationic polymerization initiator, the ionic photo cationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.

[0104] Examples of the nonionic photo cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, the compounds described in paragraphs 0083 to 0088 of JP-A No. 2011-221494 may be used. As the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 may be used.

[0105] The photosensitive layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof.

[0106] The photosensitive layer may contain a photo polymerization initiator alone or in combination of two or more. The content of the photo polymerization initiator in the photosensitive layer is not particularly limited, but 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 layer. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less with respect to the total mass of the photosensitive layer.

[0107] - Dye - From the viewpoints of visibility of the exposed portion and non-exposed portion, pattern visibility after development, and resolution, the photosensitive layer preferably contains a dye (also simply referred to as "dye N") having a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development of 450 nm or more, and the maximum absorption wavelength is changed by an acid, a base, or a radical. When the dye N is contained, although the detailed mechanism is unknown, the adhesion to an adjacent layer (for example, a support and an intermediate layer) is improved, and the resolution is more excellent.

[0108] In this specification, the statement that the maximum absorption wavelength of a dye "changes due to an acid, a base, or a radical" may mean any of the following modes: a mode in which a dye in a colored state is decolorized by an acid, a base, or a radical; a mode in which a dye in a decolorized state is colored by an acid, a base, or a radical; and a mode in which a dye in a colored state changes to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In this case, it may be a dye in which an acid, a base, or a radical is generated and acts in the photosensitive layer upon exposure, thereby changing the colored or decolorized state, or a dye in which the state (e.g., pH) in the photosensitive layer changes due to an acid, a base, or a radical, thereby changing the colored or decolorized state. Further, it may be a dye that directly receives an acid, a base, or a radical as a stimulus without exposure and changes its colored or decolorized state.

[0109] Among them, from the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the dye N is preferably a dye whose maximum absorption wavelength changes due to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes due to a radical. From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the photosensitive layer preferably contains both a dye whose maximum absorption wavelength changes due to a radical as the dye N and a photo radical polymerization initiator. Also, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that is colored by an acid, a base, or a radical.

[0110] Examples of the coloring mechanism of the dye N in the present disclosure include a mode in which a photo radical polymerization initiator, a photo cationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive layer, and a radical, an acid, or a base generated from the photo radical polymerization initiator, the photo cationic polymerization initiator, or the photobase generator after exposure causes a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) to be colored.

[0111] From the perspective of the visibility of the exposed and non-exposed areas, the maximum absorption wavelength of Pigment N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or more, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm. In addition, Pigment N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or may have two or more. When Pigment N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0112] The maximum absorption wavelength of Pigment N is obtained by measuring the transmission spectrum of a solution containing Pigment N (solution temperature 25 °C) in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) under an air atmosphere, and detecting the wavelength at which the light intensity becomes minimum (maximum absorption wavelength).

[0113] Examples of the pigment that develops color or fades by exposure include leuco compounds. Examples of the pigment that fades by exposure include leuco compounds, diarylmethane-based pigments, oxazine-based pigments, xanthene-based pigments, iminonaphthoquinone-based pigments, azomethine-based pigments, and anthraquinone-based pigments. From the perspective of the visibility of the exposed and non-exposed areas, leuco compounds are preferred as Pigment N.

[0114] Examples of the leuco compound include leuco compounds having a triarylmethane skeleton (triarylmethane-based pigments), leuco compounds having a spiropyran skeleton (spiropyran-based pigments), leuco compounds having a fluoran skeleton (fluoran-based pigments), leuco compounds having a diarylmethane skeleton (diarylmethane-based pigments), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based pigments), leuco compounds having an indolyl phthalide skeleton (indolyl phthalide-based pigments), and leuco compounds having a leuco auramine skeleton (leuco auramine-based pigments). Among them, triarylmethane-based dyes or fluoran-based dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triarylmethane-based dyes) or fluoran-based dyes are more preferred.

[0115] As the leuco compound, from the viewpoint of visibility of the exposed portion and the non-exposed portion, it preferably has a lactone ring, a sultine ring or a sultone ring. Thereby, the lactone ring, the sultine ring or the sultone ring of the leuco compound is reacted with a radical generated from a photo radical polymerization initiator or an acid generated from a photo cationic polymerization initiator to change the leuco compound to a closed ring state for decolorization, or the leuco compound can be changed to an open ring state for color development. As the leuco compound, a compound having a lactone ring, a sultine ring or a sultone ring and in which the lactone ring, the sultine ring or the sultone ring is opened by a radical or an acid to develop color is preferred, and a compound having a lactone ring and in which the lactone ring is opened by a radical or an acid to develop color is more preferred.

[0116] Examples of the dye N include the following dyes and leuco compounds. Specific examples of the dyes among the coloring matters N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinoline red, rose bengal, metanil yellow, thymol sulfophthalein, xylenol blue, methyl orange, para methyl red, congo red, benzopurpurin 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, para fuchsin, victoria pure blue-naphthalene sulfonate, victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by Orient Chemical Industries, Ltd.), oil pink #312 (manufactured by Orient Chemical Industries, Ltd.), oil red 5B (manufactured by Orient Chemical Industries, Ltd.), oil scarlet #308 (manufactured by Orient Chemical Industries, Ltd.), oil red OG (manufactured by Orient Chemical Industries, Ltd.), oil red RR (manufactured by Orient Chemical Industries, Ltd.), oil green #502 (manufactured by Orient Chemical Industries, Ltd.), spiron red BEH special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonated rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0117] Specific examples of the leuco compound among the pigments N include p,p’,p”-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chloro-fluorane, 3-(N,N-diethylamino)-6-methoxy-7-amino-fluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chloro-fluorane, 3-(N,N-diethylamino)-7-benzylamino-fluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-xanthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3’,6’-bis(diphenylamino)spiroisobenzofuran-1(3H),9’-[9H]xanthen-3-one.

[0118] From the viewpoints of the visibility of the exposed and unexposed areas, the pattern visibility after development, and the resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue - naphthalene sulfonate is preferable.

[0119] The dye N may be used alone or in combination of two or more. From the viewpoints of the visibility of the exposed and unexposed areas, the pattern visibility after development, and the resolution, the content of the dye N is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, still more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass based on the total mass of the photosensitive layer.

[0120] The content of the dye N means the content of the dye when all the dye N contained in the photosensitive layer is in the developed state. Hereinafter, taking the dye that develops color due to radicals as an example, the method for quantifying the content of the dye N will be described. Prepare two kinds of solutions by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone. To each of the obtained solutions, add the photo radical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.), and generate radicals by irradiating with light of 365 nm to make all the dyes in the developed state. Then, in an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25 °C, and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are developed in the same manner as above except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. Calculate the content of the dye contained in the photosensitive layer based on the calibration curve from the absorbance of the solution containing the obtained photosensitive layer.

[0121] -Thermally crosslinkable compound- From the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, the photosensitive layer preferably contains a thermally crosslinkable compound. In the present specification, a thermally crosslinkable compound having a polymerizable group described later is not treated as a polymerizable compound but is treated as a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound. Among them, from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, a blocked isocyanate compound is preferable. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a binder polymer and / or a polymerizable compound or the like has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film decreases, and the function when the film obtained by curing the photosensitive layer is used as a protective film tends to be 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".

[0122] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, and more preferably 130°C 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.

[0123] Examples of the blocking agent having a dissociation temperature of 100°C 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 [compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime]. Among these, as the blocking agent having a dissociation temperature of 100°C to 160°C, for example, from the viewpoint of storage stability, it is preferable to contain an oxime compound.

[0124] 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 body. 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 a blocking agent is preferable from the viewpoints that it is easier to make the dissociation temperature in a preferable range than the compound having no oxime structure and that it is easier to reduce the development residue.

[0125] The blocked isocyanate compound may have a polymerizable group. There is no particular limitation on the polymerizable group, and known polymerizable groups can be used, with radical polymerizable groups being preferable. 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 preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is even more preferable.

[0126] Commercially available products can be used as the blocked isocyanate compound. Examples of commercially available blocked isocyanate compounds 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 (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Also, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0127]

Chemical formula

[0128] The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive layer.

[0129] - Surfactant - From the viewpoint of thickness uniformity, the photosensitive layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, and nonionic surfactants are preferred.

[0130] Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based nonionic surfactants, and fluorine-based nonionic surfactants. From the viewpoint of better resolution, the photosensitive layer preferably contains a fluorine-based nonionic surfactant. It is considered that when the photosensitive layer contains a fluorine-based nonionic surfactant, the penetration of the etching solution into the photosensitive layer is suppressed to reduce side etching. Examples of commercially available fluorine-based nonionic surfactants include Megafac F-551-A, F-552, and F-554 (all manufactured by DIC Corporation).

[0131] As the surfactant, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784, and the surfactants described in paragraphs 0060 to 0071 of Japanese Unexamined Patent Application Publication No. 2009-237362 can also be used. Moreover, as the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable.

[0132] Examples of commercially available fluorosurfactants include, for example, Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, 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, MFS-578, MFS-579, MFS-586, 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 (all of the above are manufactured by DIC Corporation), Fluorad (trade name) FC430, FC431, FC171 (all of the above are manufactured by Sumitomo 3M Limited), Surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all of the above are manufactured by AGC Inc.), PolyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (all of the above are manufactured by OMNOVA Solutions Inc.), Ftergent (trade name) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all of the above are 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 and capable of volatilizing fluorine atoms when heated by cleavage of the portion of the functional group containing a fluorine atom can also be preferably used. Examples of such fluorosurfactants include the Megafac (trade name) DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial Newspaper (February 23, 2016)), for example, Megafac (trade name) DS-21.

[0133] 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. As the fluorosurfactant, a block polymer can also be used. 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. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Examples thereof include Megafac (trade name) RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation, etc.). As the fluorosurfactant, for example, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental suitability, it is preferable to use an alternative material to perfluorooctanoic acid (PFOA) or perfluorooctane sulfonic acid (PFOS) as the fluorosurfactant.

[0134] 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 octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse (trade name) 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Corporation), Pyonin (trade name) 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.

[0135] 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. Specific examples of silicone surfactants include DOWSIL (trade name) 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 Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie), etc.

[0136] The photosensitive layer may contain a surfactant alone or in combination of two or more. The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive layer.

[0137] - Additive - The photosensitive layer may contain known additives as necessary in addition to the above components. Examples of the additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, resins other than Polymer A, and solvents. The photosensitive layer may contain each additive alone or in combination of two or more.

[0138] The photosensitive layer may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, and the like. In order not to impair the sensitivity of the photosensitive layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0139] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole, and the like.

[0140] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole, and the like. As the carboxybenzotriazoles, commercially available products such as CBT-1 (Shiroki Chemical Industry Co., Ltd., trade name) can be used.

[0141] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, based on 100% by mass of the total mass of the photosensitive layer. Setting the above content to 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive layer. On the other hand, setting the above content to 3% by mass or less is preferable from the viewpoints of maintaining sensitivity and suppressing decolorization of the dye.

[0142] The photosensitive layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0143] The photosensitive layer may contain one kind of sensitizer alone or two or more kinds of sensitizers. When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. From the viewpoints of improving the sensitivity to the light source and improving the curing rate by the balance between the polymerization rate and the chain transfer, 0.01% by mass to 5% by mass is preferable, and 0.05% by mass to 1% by mass is more preferable, based on the total mass of the photosensitive layer.

[0144] The photosensitive layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound. Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0145] The photosensitive layer may contain a solvent. When the photosensitive layer is formed from a photosensitive composition containing a solvent, the solvent may remain in the photosensitive layer.

[0146] In addition, the photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid generators, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-precipitation agents. The additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated herein.

[0147] (Physical properties, etc.) The thickness (layer thickness) of the photosensitive layer is preferably from 0.1 μm to 300 μm, more preferably from 0.2 μm to 100 μm, still more preferably from 0.5 μm to 50 μm, even more preferably from 0.5 μm to 30 μm, particularly preferably from 1 μm to 20 μm, and most preferably from 2 μm to 10 μm. Thereby, the developability of the photosensitive layer is improved and the resolution can be improved. The layer thickness of each layer provided in the photosensitive transfer member is measured by observing a cross section in a direction perpendicular to the main surface of the laminate or the photosensitive transfer member with a scanning electron microscope (SEM: Scanning Electron Microscope), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value thereof.

[0148] Also, from the viewpoint of excellent adhesion, the transmittance of light with a wavelength of 365 nm of the photosensitive layer is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

[0149] (Impurities, etc.) The photosensitive layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so it is preferable to set the content as follows.

[0150] The content of impurities in the photosensitive 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 layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.

[0151] As a method for setting the impurities within the above range, those with a low content of impurities are selected as raw materials for the photosensitive layer. Examples include selecting, preventing the mixing of impurities during the formation of the photosensitive layer, and washing and removing them. By such methods, the amount of impurities can be set within the above range.

[0152] Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0153] 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 layer is preferably low. The content of these compounds in the photosensitive 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 100 ppb or more on a mass basis. The content of these compounds can be suppressed by the same method as the above metal impurities. Also, they can be quantified by known measurement methods.

[0154] ​The water content in the photosensitive layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and laminability.

[0155] (Residual monomer) The photosensitive layer may contain a residual monomer corresponding to each structural unit of the binder polymer described above. The content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, still more preferably 500 ppm by mass or less, based on the total mass of the binder polymer, from the viewpoints of patterning property and reliability. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more. The residual monomer of each structural unit of the binder polymer is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, still more preferably 100 ppm by mass or less, based on the total mass of the photosensitive layer, from the viewpoints of patterning property and reliability. The lower limit is not particularly limited, but is preferably 0.1 ppm by mass or more, more preferably 1 ppm by mass or more.

[0156] The amount of the residual monomer in the synthesis of the binder polymer by a polymer reaction is also preferably in the above range. For example, when synthesizing a binder polymer by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably in the above range. The amount of the residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0157] (Forming method) The forming method of the photosensitive layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. Examples of the forming method of the photosensitive layer include a method of preparing a photosensitive composition containing a binder polymer, a polymerizable compound, and a solvent, applying the photosensitive composition to the surface of a support or the like, and drying the coating film of the photosensitive composition.

[0158] Examples of the photosensitive composition used for forming the photosensitive layer include compositions containing a binder polymer, a polymerizable compound, the above optional components, and a solvent. The photosensitive composition preferably contains a solvent in order to adjust the viscosity of the photosensitive composition and facilitate the formation of the photosensitive layer.

[0159] - Solvent - The solvent contained in the photosensitive composition is not particularly limited as long as it can dissolve or disperse the binder polymer, the polymerizable compound, and the above optional components, and known solvents can be used. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N - dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these. When producing a photosensitive transfer member including a support, a thermoplastic resin layer, an intermediate layer, and a photosensitive layer, the photosensitive composition preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable, and a mixed solvent containing at least three kinds, namely at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent, is even more preferable.

[0160] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of JP-A-2018-177889 may be used, and the contents thereof are incorporated herein.

[0161] The photosensitive composition may contain one kind of solvent alone or two or more kinds of solvents. When applying the photosensitive composition, the content of the solvent is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive composition.

[0162] The method for preparing the photosensitive composition is not particularly limited. For example, a method of preparing a photosensitive composition by previously preparing a solution in which each component is dissolved in the above solvent and mixing the obtained solutions at a predetermined ratio can be mentioned. Before forming the photosensitive layer, the photosensitive composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm.

[0163] The method for applying the photosensitive composition is not particularly limited, and it may be applied by a known method. Examples of the application method include slit coating, spin coating, curtain coating, and inkjet coating. Alternatively, the photosensitive layer may be formed by applying a photosensitive composition onto a cover film described below and drying it.

[0164] [Thermoplastic resin layer] The above laminate may have a thermoplastic resin layer. The photosensitive transfer member may have a thermoplastic resin layer. The photosensitive transfer member preferably includes a thermoplastic resin layer between the support and the photosensitive layer. By providing a thermoplastic resin layer between the photosensitive transfer member and the support, the followability to the substrate during bonding to the substrate is improved, the mixing of air bubbles between the substrate and the photosensitive transfer member is suppressed, and the adhesion to an adjacent layer (for example, the support) is improved.

[0165] (Alkali-soluble resin) The thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin. In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more. Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0166] From the viewpoints of developability and adhesion to an adjacent layer, acrylic resin is preferred as the alkali-soluble resin. Here, the acrylic resin means a resin having at least one structural unit selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylic acid ester, and a structural unit derived from (meth)acrylamide. As the acrylic resin, it is preferable that the total content of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylic acid ester, and the structural units derived from (meth)acrylamide is 50% by mass or more based on the total mass of the acrylic resin. Among them, it is preferable that the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester is 30% by mass to 100% by mass based on the total mass of the acrylic resin, and more preferably 50% by mass to 100% by mass.

[0167] Also, the alkali-soluble resin is preferably a polymer 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, and a carboxy group is preferable. From the viewpoint of developability, an alkali-soluble resin having an acid value of 60 mgKOH / g or more is more preferable as the alkali-soluble resin, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is even more preferable. The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

[0168] The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited and can be appropriately selected from known resins and used. For example, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162 can be mentioned. The copolymerization ratio of the structural unit having a carboxy group in the above carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 12% by mass to 30% by mass based on the total mass of the acrylic resin. As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoints of developability and adhesion to an adjacent layer.

[0169] The alkali-soluble resin may have a reactive group. The reactive group may be any addition-polymerizable group, and examples thereof include ethylenically unsaturated groups; polycondensable groups such as hydroxy groups and carboxy groups; and polyaddition-reactive groups such as epoxy groups and (block) isocyanate groups.

[0170] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and still more preferably 20,000 to 50,000.

[0171] The thermoplastic resin layer may contain one kind of the alkali-soluble resin alone or two or more kinds thereof. From the viewpoints of developability and adhesion to an adjacent layer, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, still more preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass based on the total mass of the thermoplastic resin layer.

[0172] (Dye) The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development and whose maximum absorption wavelength changes due to an acid, a base, or a radical. The preferred embodiment of dye B is the same as the preferred embodiment of dye N except for the points described below.

[0173] Dye B is preferably a dye whose maximum absorption wavelength changes due to an acid or a radical from the viewpoints of visibility and resolution of the exposed and unexposed portions, and more preferably a dye whose maximum absorption wavelength changes due to an acid. From the viewpoints of visibility and resolution of the exposed and unexposed portions, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes due to an acid as Dye B and a compound that generates an acid upon irradiation with light described later.

[0174] Dye B may be used alone or in combination of two or more. From the viewpoint of visibility of the exposed and unexposed portions, the content of Dye B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, still more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass based on the total mass of the thermoplastic resin layer.

[0175] Here, the content of Dye B means the content of the dye when all of the Dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content of Dye B will be described using a dye that is colored by a radical as an example. Prepare solutions by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone. Add the photoinitiator Irgacure OXE01 (trade name, BASF Japan Ltd.) to each of the obtained solutions and irradiate with light at 365 nm to generate radicals, thereby bringing all the dyes into a colored state. Then, in an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25°C and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are colored in the same manner as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. Calculate the amount of the dye contained in the thermoplastic resin layer based on the calibration curve from the absorbance of the solution containing the obtained thermoplastic resin layer.

[0176] (Compound that generates an acid, a base, or a radical upon irradiation with light) The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical upon exposure to light (simply referred to as "Compound C"). As Compound C, a compound that generates an acid, a base, or a radical upon exposure to actinic rays such as ultraviolet rays and visible light is preferable. As Compound C, known photoacid generators, photobase generators, and photo radical polymerization initiators (photo radical generators) can be used. Among them, photoacid generators are preferable.

[0177] - Photoacid generator - From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the photo cationic polymerization initiators that the above-described photosensitive layer may contain, and the preferred embodiments are the same except for the points described later.

[0178] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably contains an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. In addition, as the photoacid generator, a photoacid generator having the following structure is also preferable.

[0179]

Chemical formula

[0180] - Photo radical polymerization initiator - The thermoplastic resin layer may contain a photo radical polymerization initiator (photo radical polymerization initiator). Examples of the photo radical polymerization initiator include the photo radical polymerization initiators that the above-described photosensitive layer may contain, and the preferred embodiments are the same.

[0181] - Photobase generator - The thermoplastic resin layer may contain a photobase generator. The photo-base generator is not particularly limited as long as it is a known photo-base generator. For example, 2-nitrobenzyl cyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamine, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethyl borate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine may be mentioned.

[0182] The thermoplastic resin layer may contain Compound C alone or in combination of two or more. From the viewpoints of visibility and resolution of the exposed part and the unexposed part, the content of Compound C is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, based on the total mass of the thermoplastic resin layer.

[0183] (Plasticizer) From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the thermoplastic resin layer preferably contains a plasticizer. The plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin. The molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. However, from the perspective of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and a polyalkylene glycol compound is more preferable. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0184] Also, from the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to an adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described as the polymerizable compounds contained in the photosensitive layer described above. In the photosensitive transfer member, when the thermoplastic resin layer and the photosensitive layer are directly contacted and laminated, it is preferable that both the thermoplastic resin layer and the photosensitive layer contain the same (meth)acrylate compound. This is because when the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound, component diffusion between the layers is suppressed and storage stability is improved.

[0185] When the thermoplastic resin layer contains a (meth)acrylate compound as the plasticizer, from the viewpoint of adhesion to an adjacent layer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed portion after exposure. Also, from the viewpoints of resolution, adhesion to an adjacent layer, and developability, the (meth)acrylate compound used as the plasticizer is preferably a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule. Furthermore, as the (meth)acrylate compound used as the plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferable.

[0186] The thermoplastic resin layer may contain a plasticizer alone or in combination of two or more. From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass based on the total mass of the thermoplastic resin layer.

[0187] (Surfactant) From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants that the above-described photosensitive layer may contain, and preferred embodiments are the same.

[0188] The thermoplastic resin layer may contain a surfactant alone or in combination of two or more. The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass based on the total mass of the thermoplastic resin layer.

[0189] (Sensitizer) The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that the above-described photosensitive layer may contain.

[0190] The thermoplastic resin layer may contain a sensitizer alone or in combination of two or more. The content of the sensitizer can be appropriately selected according to the purpose. From the viewpoints of improving sensitivity to a light source and visibility of an exposed portion and a non-exposed portion, the range of 0.01% by mass to 5% by mass is preferred, and the range of 0.05% by mass to 1% by mass is more preferred based on the total mass of the thermoplastic resin layer.

[0191] (Additives, etc.) The thermoplastic resin layer may contain known additives as necessary in addition to the above components. Regarding the thermoplastic resin layer, it is described in paragraphs 0189 to 0193 of JP-A-2014-85643, and the content described in this publication is incorporated herein.

[0192] (Physical properties, etc.) The layer thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion to an adjacent layer, 1 μm or more is preferable, and 2 μm or more is more preferable. The upper limit is not particularly limited, but from the viewpoints of developability and resolution, 20 μm or less is preferable, 10 μm or less is more preferable, and 5 μm or less is still more preferable.

[0193] (Forming method) The method for forming the thermoplastic resin layer is not particularly limited as long as it can form a layer containing the above components. Examples of the method for forming the thermoplastic resin layer include preparing a thermoplastic resin composition containing the above components and a solvent, applying the thermoplastic resin composition onto the surface of a support or the like, and drying the coating film of the thermoplastic resin composition. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

[0194] - Solvent - The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above components contained in the thermoplastic resin layer. Examples of the solvent contained in the thermoplastic resin composition include solvents that may be contained in the above-described photosensitive composition, and the preferred embodiments are the same.

[0195] The solvent contained in the thermoplastic resin composition may be a single type or two or more types. When applying the thermoplastic resin composition, the content of the solvent is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition.

[0196] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the preparation method of the photosensitive composition and the formation method of the photosensitive layer described above. For example, after preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in the above solvent and mixing the obtained solutions at a predetermined ratio to prepare a thermoplastic resin composition, the obtained thermoplastic resin composition is applied to the surface of the support, and the coating film of the thermoplastic resin composition is dried to form a thermoplastic resin layer. Further, after forming the photosensitive layer and the intermediate layer on the cover film described later, a thermoplastic resin layer may be formed on the surface of the intermediate layer.

[0197] 〔Intermediate layer〕 The above laminate may have an intermediate layer between the thermoplastic resin layer and the photosensitive layer. The photosensitive transfer member preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive layer. By having an intermediate layer, mixing of components during application of a plurality of layers and during storage after application can be suppressed. The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppression of mixing of components during application of a plurality of layers and during storage after application. 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.

[0198] Examples of the intermediate layer include an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in JP-A-5-72724. It is preferable that the intermediate layer is an oxygen barrier layer because the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and productivity is improved. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications and the like. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1% by mass aqueous solution of sodium carbonate at 22°C) is preferable.

[0199] The intermediate layer preferably contains a resin. Examples of the resin contained in the intermediate layer include resins such as polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. As the resin contained in the intermediate layer, a water-soluble resin is preferable. Also, from the viewpoint of suppressing the mixing of components between multiple layers, the resin contained in the intermediate layer is preferably a resin different from both the polymer A contained in the photosensitive layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0200] The intermediate layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinyl pyrrolidone, from the viewpoints of oxygen barrier properties and suppressing the mixing of components during the application of multiple layers and during storage after application.

[0201] The intermediate layer may contain one of the above resins alone or two or more of them. The content of the resin in the intermediate layer is not particularly limited, but from the viewpoints of oxygen barrier properties and suppressing the mixing of components during the application of multiple layers and during storage after application, 50% by mass to 100% by mass is preferable, 70% by mass to 100% by mass is more preferable, 80% by mass to 100% by mass is still more preferable, and 90% by mass to 100% by mass is particularly preferable, based on the total mass of the intermediate layer. Also, the intermediate layer may contain additives such as surfactants as necessary.

[0202] The layer thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier properties are not deteriorated, the mixing of components during the application of multiple layers and during storage after application can be suppressed, and an increase in the removal time of the intermediate layer during development can be suppressed.

[0203] The method for forming the intermediate layer is not particularly limited. For example, a method of preparing an intermediate layer composition containing the above resin and optional additives, applying it to the surface of the thermoplastic resin layer or the photosensitive layer, and drying the coating film of the intermediate layer composition to form the intermediate layer can be mentioned. The intermediate layer composition preferably contains a solvent in order to adjust the viscosity of the intermediate layer composition and facilitate the formation of the intermediate layer.

[0204] The solvent contained in the intermediate layer composition is not particularly limited as long as it can dissolve or disperse the above resin. At least one selected from the group consisting of water and water-miscible organic solvents is preferable, and a mixed solvent of water or a water-miscible organic solvent and water is more preferable. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.

[0205] [[Cover Film]] The above laminate preferably has a cover film in contact with the surface not facing the support of the photosensitive layer. The photosensitive transfer member preferably has a cover film in contact with the surface not facing the support of the photosensitive layer. Hereinafter, in this specification, the surface facing the support of the photosensitive layer is also referred to as the "first surface", and the surface opposite to the first surface is also referred to as the "second surface".

[0206] Examples of the material constituting the cover film include resin films and paper. From the viewpoints of strength and flexibility, a resin film is preferable. Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, triacetate cellulose film, polystyrene film, and polycarbonate film. Among them, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable.

[0207] The thickness (layer thickness) of the cover film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and particularly preferably 10 μm to 20 μm. In addition, the arithmetic mean roughness Ra value of the surface of the cover film that contacts the photosensitive layer (hereinafter also simply referred to as "the surface of the cover film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less from the viewpoint of excellent resolution. It is considered that when the Ra value of the surface of the cover film is within the above range, the uniformity of the layer thickness of the photosensitive layer and the formed resin pattern is improved. The lower limit of the Ra value of the surface of the cover film is not particularly limited, but is preferably 0.001 μm or more.

[0208] The photosensitive transfer member may include layers other than the layers described above (hereinafter also referred to as "other layers"). Examples of the other layers include a contrast enhancement layer. The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018 / 179640. The other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of these publications are incorporated herein.

[0209] From the viewpoint of more effectively exhibiting the effects in the present disclosure, the total thickness of the layers other than the support and the cover film in the photosensitive transfer member is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less. From the viewpoint of more effectively exhibiting the effects in the present disclosure, the total thickness of the photosensitive layer, the intermediate layer, and the thermoplastic resin layer in the photosensitive transfer member is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[0210] (Relationship between the support, the photosensitive layer, and the cover film) The laminate having a photosensitive layer used in the present disclosure is such that the elongation at break of the cured film obtained by curing the photosensitive layer at 120°C is 15% or more, the arithmetic mean roughness Ra of the surface of the support on the photosensitive layer side is 50 nm or less, and preferably, the arithmetic mean roughness Ra of the surface of the cover film on the photosensitive layer side is 150 nm or less.

[0211] In addition, the laminate having a photosensitive layer used in the present disclosure preferably satisfies the following formula (R1). X × Y < 1,500 Formula (R1) Here, in the above formula (R1), X represents the value (%) of the elongation at break of the cured film obtained by curing the photosensitive layer at 120°C, and Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the support on the photosensitive layer side. More preferably, X × Y is 750 or less.

[0212] Preferably, 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 layer. The elongation at break is measured by a tensile test using a cured film obtained by exposing a photosensitive layer having a thickness of 20 μm to light with an ultra-high pressure mercury lamp at 120 mJ / cm 2 for curing, followed by additional exposure with a high pressure mercury lamp at 400 mJ / cm 2 and then heating at 145°C for 30 minutes.

[0213] In addition, the laminate having a photosensitive layer used in the present disclosure preferably satisfies the following formula (R2). Y ≤ Z Formula (R2) Here, in the above formula (R2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the support on the photosensitive layer side, and Z represents the value (nm) of the arithmetic mean roughness Ra of the surface of the cover film on the photosensitive layer side.

[0214] 〔Method for manufacturing a photosensitive transfer member〕 The method for manufacturing the photosensitive transfer member (laminate having a photosensitive layer) used in the present disclosure is not particularly limited, and known manufacturing methods, for example, known methods for forming each layer can be used. Hereinafter, a method for manufacturing a photosensitive transfer member used in the present disclosure will be described with reference to FIG. 2. However, the photosensitive transfer member used in the present disclosure is not limited to having the configuration shown in FIG. 2. FIG. 2 is a schematic diagram showing an example of the configuration of a photosensitive transfer member used in the present disclosure. The photosensitive transfer member 100 shown in FIG. 2 has a configuration in which a support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive layer 16, and a cover film 18 are laminated in this order.

[0215] As a method for manufacturing the above-described photosensitive transfer member 100, for example, after applying a thermoplastic resin composition to the surface of the support 10, the thermoplastic resin layer 12 is formed by drying the coating film of the thermoplastic resin composition; after applying an intermediate layer composition to the surface of the thermoplastic resin layer 12, the intermediate layer 14 is formed by drying the coating film of the intermediate layer composition; and after applying a photosensitive composition containing a binder polymer and a polymerizable compound to the surface of the intermediate layer 14, the photosensitive layer 16 is formed by drying the coating film of the photosensitive composition. In the above manufacturing method, it is preferable to use a thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, an intermediate layer composition containing at least one selected from the group consisting of water and a water-miscible organic solvent, and a photosensitive composition containing a binder polymer, a polymerizable compound, and at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Thereby, it is possible to suppress the mixing of the components contained in the thermoplastic resin layer 12 and the components contained in the intermediate layer 14 during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and / or during the storage period of the laminate having the coating film of the intermediate layer composition, and further suppress the mixing of the components contained in the intermediate layer 14 and the components contained in the photosensitive layer 16 during the application of the photosensitive composition to the surface of the intermediate layer 14 and / or during the storage period of the laminate having the coating film of the photosensitive composition.

[0216] A photosensitive transfer member 100 is manufactured by pressing a cover film 18 onto the photosensitive layer 16 of the laminate manufactured by the above manufacturing method. As a method for manufacturing the photosensitive transfer member used in the present disclosure, it is preferable to manufacture a photosensitive transfer member 100 including a support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive layer 16, and a cover film 18 by including a step of providing a cover film 18 so as to be in contact with the second surface of the photosensitive layer 16. After manufacturing the photosensitive transfer member 100 by the above manufacturing method, the photosensitive transfer member 100 may be wound up to produce and store a photosensitive transfer member in a roll form. The photosensitive transfer member in a roll form can be provided in its original form for bonding to a substrate in a roll-to-roll method.

[0217] In addition, the photosensitive transfer member obtained by the manufacturing method of the cut product according to the present disclosure can be suitably used for manufacturing circuit wirings and manufacturing display devices such as touch panels.

[0218] In addition, the photosensitive transfer member obtained by the manufacturing method of the cut product according to the present disclosure can be suitably used for various applications that require precision microfabrication by photolithography. After patterning the photosensitive layer, the photosensitive layer may be etched as a film, or electroforming mainly based on electroplating may be performed. Further, the cured film obtained by patterning may be used as a permanent film, for example, as an interlayer insulating film, a wiring protection film, a wiring protection film having an index matching layer, or the like. In addition, the photosensitive transfer member obtained by the manufacturing method of the cut product according to the present disclosure can be suitably used for various wiring formation applications of semiconductor packages, printed circuit boards, and sensor boards, touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, formation of structures in the field of micromachines or microelectronics, and the like.

[0219] In addition, a preferred embodiment of the laminate of Embodiment A is also an aspect in which the photosensitive layer is a colored resin layer containing a pigment. As uses of the colored resin layer, in addition to those described above, for example, it is suitable for uses such as forming colored pixels or black matrices such as color filters used in liquid crystal display devices (LCDs) and solid-state imaging devices [e.g., CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor)]. In recent years, in liquid crystal display windows of electronic devices, in order to protect the liquid crystal display window, a cover glass having a black frame-shaped light-shielding layer formed on the peripheral portion of the back surface of a transparent glass substrate or the like may be attached. A colored resin layer can be used to form such a light-shielding layer. Regarding aspects other than pigments in the colored resin layer, they are the same as the aspects described above.

[0220] <Pigment> The pigment used in the colored resin layer may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and colored pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.

[0221] As the black pigment, as long as the effects in the present disclosure are not impaired, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected. Among them, from the viewpoint of optical density, examples of the black pigment include carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, and carbon black is particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black having at least a part of its surface coated with resin is preferred.

[0222] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 μm to 0.1 μm in number average particle size, and more preferably 0.01 μm to 0.08 μm. Here, the particle size refers to the diameter of a circle obtained by determining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. The number-average particle size is an average value obtained by determining the above-described particle size for any 100 particles and averaging the 100 obtained particle sizes.

[0223] As pigments other than the black pigment, for the white pigment, the white pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used. Specifically, among the white pigments, as the inorganic pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, titanium oxide or zinc oxide is more preferable, and titanium oxide is still more preferable. As the inorganic pigment, rutile-type or anatase-type titanium oxide is still more preferable, and rutile-type titanium oxide is particularly preferable. Further, the surface of the titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, or two or more treatments may be performed. Thereby, the catalytic activity of the titanium oxide is suppressed, and the heat resistance, lightfastness, etc. are improved. From the viewpoint of reducing the thickness of the photosensitive layer after heating, as the surface treatment of the surface of the titanium oxide, at least one of alumina treatment and zirconia treatment is preferable, and both alumina treatment and zirconia treatment are particularly preferable.

[0224] Further, when the photosensitive layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive layer further contains a colored pigment other than the black pigment and the white pigment. When a colored pigment is contained, the particle size of the colored pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, in terms of better dispersibility. Examples of colored pigments include Victoria Pure Blue BO (Color Index (hereinafter C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hostaperm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fast Pink B Spr (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1), and carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, and C.I. Pigment Violet 23, etc. Among them, C.I. Pigment Red 177 is preferred.

[0225] When the photosensitive layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, still more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less with respect to the total mass of the photosensitive layer.

[0226] When the photosensitive layer contains pigments other than black pigments (white pigments and colored pigments), the content of the pigments other than black pigments is preferably 30% by mass or less, more preferably 1% by mass to 20% by mass, and still more preferably 3% by mass to 15% by mass with respect to the black pigment.

[0227] In addition, when the photosensitive layer contains a black pigment and the photosensitive layer is formed of a photosensitive composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion liquid. The dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle refers to the part of the medium in which the pigment is dispersed when the pigment dispersion liquid is formed, is liquid, and includes a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0228] There is no particular limitation on the dispersing machine, and examples thereof include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Further, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For the dispersing machine and fine pulverization, reference can be made to the description in "Dictionary of Pigments" (written by Kunizo Asakura, first edition, Asakura Shoten, 2000, pages 438 and 310).

[0229] [[Embodiment B laminate]] Hereinafter, an example of the laminate of Embodiment B will be described. Hereinafter, each element constituting the laminate of Embodiment B will be described. The support and the cover film used in the laminate of Embodiment B are the same as the support and the cover film in the laminate of Embodiment A, and the preferred embodiments are also the same.

[0230] [[Photosensitive layer]] The photosensitive transfer member has a photosensitive layer. After transferring the photosensitive layer onto the object to be transferred, exposure and development are performed to form a pattern on the object to be transferred. Hereinafter, the components that can be contained in the photosensitive layer will be described in detail.

[0231] (Binder polymer) The photosensitive layer preferably contains a binder polymer. Examples of the binder polymer include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by the reaction of an epoxy resin and (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of an epoxy acrylate resin and an acid anhydride. Also, the binder polymer is preferably an alkali-soluble resin.

[0232] 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 a (meth)acrylic compound, or may have structural units derived from a polymerizable monomer 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.

[0233] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile. Examples of the (meth)acrylic acid ester include alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate. Among them, alkyl (meth)acrylate is preferred. Examples of the (meth)acrylamide include acrylamides such as diacetone acrylamide.

[0234] Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 12 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. As the (meth)acrylic acid ester, an alkyl (meth)acrylate having an alkyl group with 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0235] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. 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 can be mentioned. These polymerizable monomers may be used alone or in combination of two or more.

[0236] 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.

[0237] 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 with respect to 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.

[0238] In addition, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned (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 50% by mass to 90% by mass, more preferably 60% by mass to 90% by mass, and further preferably 65% by mass to 90% by mass with respect to all the structural units of the (meth)acrylic resin.

[0239] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from (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 (meth)acrylic acid alkyl ester is more preferable. In addition, 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.

[0240] From the viewpoint of resolution, 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 methacrylic acid alkyl ester, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester. From the viewpoint of resolution, the total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on all the structural units of the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, preferably 80% by mass or less.

[0241] From the viewpoint of resolution, 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 methacrylic acid alkyl ester, and at least one selected from the group consisting of a structural unit derived from acrylic acid and a structural unit derived from acrylic acid alkyl ester. From the viewpoint of resolution, the mass ratio of the total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester to the total content of the structural unit derived from acrylic acid and the structural unit derived from acrylic acid alkyl ester is preferably 60 / 40 to 80 / 20.

[0242] (Meta)acrylic resin preferably has an ester group at its terminal in terms of excellent developability of the photosensitive layer after transfer. Note that the terminal part of the (meta)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. The (meta)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0243] Also, 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. Also, the binder polymer is more preferably a resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing resin), for example, from the viewpoint of being easily cross-linked with a cross-linking component by heating to form a strong film, and even more preferably a (meta)acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing (meta)acrylic resin). When the binder polymer is a resin having a carboxyl group, for example, the three-dimensional cross-linking density can be increased by adding a thermally cross-linkable compound such as a blocked isocyanate compound and performing thermal cross-linking. Also, when the carboxyl group of the resin having a carboxyl group is anhydrified and hydrophobized, the wet heat resistance can be improved.

[0244] The carboxyl group-containing (meta)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above acid value conditions, and can be appropriately selected from known (meta)acrylic resins. For example, among the polymers described in paragraph 0025 of JP-A-2011-095716, a carboxyl 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 carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, etc. can be preferably used.

[0245] Other suitable embodiments of the binder polymer include styrene-acrylic copolymers. In this 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. 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. In addition, 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, and still more preferably 5% by mass to 80% by mass, based on all the structural units of the copolymer. In addition, 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, and still more preferably 20% by mass to 95% by mass, based on all the structural units of the copolymer.

[0246] From the viewpoints of the moisture permeability and strength of the resulting cured film, the binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure. Examples of the monomer that forms the structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth)acrylate. Among them, styrene compounds are preferred, and styrene is more preferred. In addition, from the viewpoints of the moisture permeability and strength of the resulting cured film, the binder polymer more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0247]

Chemical formula

[0248] 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% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and still more preferably 20% by mass to 60% by mass, based on all the structural units of the binder polymer, from the viewpoints of the moisture permeability and strength of the resulting cured film. Also, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 60 mol%, based on all the structural units of the binder polymer, from the viewpoints of the moisture permeability and strength of the resulting cured film. Furthermore, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, based on all the structural units of the binder polymer, from the viewpoints of the moisture permeability and strength of the resulting cured film. 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.

[0249] The binder polymer preferably has an aliphatic hydrocarbon ring structure from the viewpoints of development residue suppression, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. Among them, the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

[0250] 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 isophorone ring. Among them, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, a ring formed by condensing an aliphatic hydrocarbon ring having two or more rings is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 decane ring) is more preferable. Examples of the monomer that forms a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Further, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the binder polymer 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).

[0251]

Chemical formula

[0252] 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.

[0253] 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 even more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film. The aliphatic hydrocarbon ring structure in R Cy of formula (Cy) may be a monocyclic structure or a polycyclic structure. Further, R CyThe aliphatic hydrocarbon ring structure in [the compound] is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isobornyl ring structure from the viewpoints of development residue suppression property, strength of the resulting cured film, and tackiness of the resulting uncured film. More preferably, it is a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably, it is a tetrahydrodicyclopentadiene ring structure. Furthermore, R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in [the compound] is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused from the viewpoints of development residue suppression property, strength of the resulting cured film, and tackiness of the resulting uncured film. More preferably, it is a ring in which 2 to 4 aliphatic hydrocarbon rings are fused. Furthermore, R in formula (Cy) Cy is preferably a group in which the oxygen atom of -C(=O)O- in formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group from the viewpoints of development residue suppression property, strength of the resulting cured film, and tackiness of the resulting uncured film. More preferably, it is a cyclohexyl group or a dicyclopentanyl group, and still more preferably, it is a dicyclopentanyl group.

[0254] 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, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and still more preferably 20% by mass to 70% by mass with respect to all the structural units of the binder polymer from the viewpoints of development residue suppression property, strength of the resulting cured film, and tackiness of the resulting uncured film. Further, from the viewpoints of development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 50 mol% with respect to all the structural units of the binder polymer. Furthermore, from the viewpoints of development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 50 mol% with respect to all the structural units of the binder polymer.

[0255] When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, 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% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 40% by mass to 75% by mass with respect to all the structural units of the binder polymer, from the viewpoints of development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film. Further, from the viewpoints of development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, 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 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and still more preferably 40 mol% to 60 mol% with respect to all the structural units of the binder polymer. Furthermore, from the viewpoints of the present development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, 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 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and still more preferably 40 mol% to 60 mol% with respect to all the structural units of the binder polymer. Further, from the viewpoints of development residue suppression, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, 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 even 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)

[0256] The binder polymer preferably has a structural unit having an acid group from the viewpoints of developability and adhesion to the substrate. 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.

[0257]

Chemical formula

[0258] 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% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 30% by mass with respect to all the structural units of the binder polymer from the viewpoints of developability and adhesion to the substrate. In addition, from the viewpoints of developability and adhesion to a substrate, the content of the constitutional unit having an acid group in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and still more preferably 20 mol% to 40 mol% with respect to all the constitutional units of the binder polymer. Furthermore, from the viewpoints of developability and adhesion to a substrate, the content of the constitutional unit derived from (meth)acrylic acid in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and still more preferably 20 mol% to 40 mol% with respect to all the constitutional units of the binder polymer.

[0259] From the viewpoints of curability and the strength of the resulting cured film, the binder polymer preferably has a reactive group, and more preferably has a constitutional unit having a reactive group. 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 constitutional unit having an ethylenically unsaturated group in a side chain. 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 constitutional unit having a reactive group include, but are not limited to, those shown below.

[0260]

Chemical formula

[0261] The binder polymer may have one kind of constitutional unit having a reactive group alone or two or more kinds thereof. 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% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and still more preferably 20% by mass to 40% by mass with respect to all the structural units of the binder polymer from the viewpoints of curability and the strength of the resulting cured film. Also, the content of the structural unit having a reactive group in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 50 mol% with respect to all the structural units of the binder polymer from the viewpoints of curability and the strength of the resulting cured film.

[0262] Examples of the means for introducing a reactive group into the binder polymer include methods of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group with a compound 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 means of synthesizing a polymer having a carboxy group by a polymerization reaction and then reacting glycidyl (meth)acrylate with a part of the carboxy groups of the obtained resin 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°C to 100°C, more preferably 80°C to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fuji Film Wako Pure Chemical Corporation is more preferred. The above polymer reaction is preferably carried out under temperature conditions of 80°C to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0263] As the binder polymer, the following resins are preferable from the viewpoints of developability, curability, and the strength of the resulting cured film. The content ratios (a to d) of the respective structural units shown below, the weight average molecular weight Mw, etc. can be appropriately changed according to the purpose.

[0264]

Chemical formula

[0265] In the above resin, it is preferable that a is 20% by mass to 60% by mass, b is 10% by mass to 50% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass.

[0266]

Chemical formula

[0267] In the above resin, it is preferable that a is 20% by mass to 60% by mass, b is 10% by mass to 50% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass.

[0268]

Chemical formula

[0269] In the above resin, it is preferable that a is 30% by mass to 65% by mass, b is 1.0% by mass to 20% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass.

[0270]

Chemical formula

[0271] In the above compound, it is preferable that a is 1.0% by mass to 20% by mass, b is 20% by mass to 60% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass.

[0272] Further, the binder polymer may contain a polymer having a structural unit having 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-membered ring to 7-membered ring is preferable, a 5-membered ring or 6-membered ring is more preferable, and a 5-membered ring is still more preferable.

[0273] 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 monovalent group obtained by removing one hydrogen atom from the compound represented by the following formula P-1 is directly or via a divalent linking group bonded to the main chain.

[0274] [Chemical formula]

[0275] In formula P-1, R A1a represents a substituent, and n 1a R's of A1a may be the same or different, and Z 1a represents a divalent group that forms a ring containing -C(=O)-O-C(=O)-, and n 1a represents an integer of 0 or more.

[0276] Examples of the substituent represented by R A1a include, for example, an alkyl group. As Z 1a a C2-C4 alkylene group is preferable, a C2 or C3 alkylene group is more preferable, and a C2 alkylene group is still more preferable. n 1a represents an integer of 0 or more. When Z 1a represents a C2-C4 alkylene group, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still 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.

[0277] 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.

[0278] 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.

[0279]

Chemical formula

[0280]

Chemical formula

[0281] The structural unit having a carboxylic anhydride structure in polymer X may be a single kind or two or more kinds.

[0282] The total content of the structural unit having a carboxylic anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, still more preferably 10 mol% to 35 mol% with respect to all the structural units of polymer X.

[0283] The photosensitive layer may contain only one kind of polymer X or may contain two or more kinds. When the photosensitive layer contains polymer X, from the viewpoints of resolution and developability, the content of polymer X is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, still more preferably 0.5% by mass to 20% by mass, and still more preferably 1% by mass to 20% by mass, based on the total mass of the photosensitive layer.

[0284] 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 20,000 to 30,000, from the viewpoints of improving resolution and developability.

[0285] The acid value of the binder polymer is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, still more preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 60 mgKOH / g to 110 mgKOH / g. Note that the acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992. The dispersity (weight average molecular weight / number average molecular weight) 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, from the viewpoint of developability.

[0286] The photosensitive layer may contain only one kind of binder polymer or may contain two or more kinds of binder polymers. The content of the binder polymer is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass, based on the total mass of the photosensitive layer, from the viewpoints of photosensitivity, resolution, and developability.

[0287] (Polymerizable compound) The photosensitive layer may contain a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, and a radical polymerizable group is preferred.

[0288] The polymerizable compound preferably contains a polymerizable 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. The ethylenically unsaturated compound in the present specification is a compound other than the above binder polymer, and preferably has a molecular weight of less than 5,000. Moreover, as a preferable aspect of the ethylenically unsaturated compound used in the second embodiment, the preferable aspect of the ethylenically unsaturated compound used in the above-described first embodiment can be mentioned.

[0289] As one of the preferable aspects of the ethylenically unsaturated compound, a compound represented by the following formula (M) (simply also 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.

[0290] 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. Moreover, Q in formula (M) 1 and Q 2 are preferably acryloyloxy groups from the viewpoint of reactivity. R in formula (M) 1 is, from the viewpoints of development residue suppression property, rust prevention property, and bending resistance of the obtained cured film, an alkylene group, an alkyleneoxyalkylene group (-L 1 -O-L 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1-), preferably a hydrocarbon group having 2 to 20 carbon atoms, more preferably a polyalkyleneoxyalkylene group, still more preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms. 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 a branched chain, cyclic, or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or any combination thereof. 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 still 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, and 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.

[0291] Also, in compound M, Q 1 and Q 2 The number of atoms in the shortest connecting chain connecting between them is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, and particularly preferably 8 to 12 from the viewpoints of development residue suppression property, rust prevention property, and bending resistance of the obtained cured film. In this specification, "the number of atoms in the shortest connecting chain connecting between 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

[0292] 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 viewpoints of development residue suppression property, rust prevention property, and bending resistance of the obtained cured film, 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 still 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.

[0293] Also, as one of the preferred embodiments of the ethylenically unsaturated compound, ethylenically unsaturated compounds having two or more functional groups are exemplified. In this specification, the "ethylenically unsaturated compound having two or more functional groups" 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.

[0294] There is no particular limitation on the bifunctional ethylenically unsaturated compound, and it can be appropriately selected from known compounds. Examples of the bifunctional ethylenically unsaturated compound other than the above compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0295] Examples of commercially available products of the bifunctional ethylenically unsaturated compound 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.), and 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0296] 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.

[0297] Examples of ethylenically unsaturated compounds 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., etc.), ethoxylated glycerol triacrylate (such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0298] Examples of ethylenically unsaturated compounds 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 also include urethane (meth)acrylate having a functionality of 3 or more. The lower limit of the functionality is more preferably 6 or more, and even more preferably 8 or more. The upper limit of the functionality is preferably 20 or less. Examples of urethane (meth)acrylate having a functionality of 3 or more 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.), etc.

[0299] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group. Examples of the acid group include a phosphate group, a sulfo group, and a carboxy group. Among these, as the acid group, a carboxy group is preferred. Examples of the ethylenically unsaturated compound having an acid group include 3- to 4-functional ethylenically unsaturated compounds having an acid group [compounds in which a carboxy group is introduced into a pentaerythritol tri- and tetraacrylate (PETA) skeleton (acid value: 80 mgKOH / g to 120 mgKOH / g)], 5- to 6-functional ethylenically unsaturated compounds having an acid group [compounds in which a carboxy group is introduced into a dipentaerythritol penta- and hexaacrylate (DPHA) skeleton (acid value: 25 mgKOH / g to 70 mgKOH / g)], and the like. These ethylenically unsaturated compounds having 3 or more functional groups with an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

[0300] As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of a bifunctional or higher-functional ethylenically unsaturated compound having a carboxy group and its carboxylic anhydride is preferable. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher-functional ethylenically unsaturated compound having a carboxy group and its carboxylic anhydride, the developability and film strength are further enhanced. The bifunctional or higher-functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of the bifunctional or higher-functional 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.).

[0301] As the ethylenically unsaturated compound having an acid group, the polymerizable 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.

[0302] Examples of the ethylenically unsaturated compound include a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, a urethane monomer such as a (meth)acrylate compound having a urethane bond, a phthalic acid-based compound 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 an alkyl (meth)acrylate ester. These may be used alone or in combination of two or more.

[0303] 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.

[0304] Examples of the ethylenically unsaturated compound 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., etc.), ethoxylated glycerol triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

[0305] From the viewpoint of excellent developability, ethylenically unsaturated compounds containing an ester bond are also preferable as the ethylenically unsaturated compound. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule. From the viewpoints of excellent curability and developability, 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. From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group with 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 with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0306] One preferred embodiment of the ethylenically unsaturated compound includes 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 viewpoints of the moisture permeability and bending resistance of the obtained cured film and the adhesiveness of the obtained uncured film, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isobornyl structure is preferable.

[0307] 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 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 layer.

[0308] As one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a bifunctional or higher-functional ethylenically unsaturated compound, more preferably contains a trifunctional or higher-functional ethylenically unsaturated compound, and even more preferably contains a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0309] Also, as one of the preferred embodiments of the photosensitive layer, the photosensitive 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.

[0310] As one of the preferred embodiments of the photosensitive layer, the photosensitive 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 dipentaerythritol pentaacrylate.

[0311] As one of the preferred embodiments of the photosensitive layer, the photosensitive 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.

[0312] As one of the preferred embodiments of the photosensitive layer, from the viewpoints of development residue suppression and rust prevention, the photosensitive 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% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass. The content of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 10% by mass to 60% by mass, and more preferably 15% by mass to 40% by mass, based on the total mass of the photosensitive layer.

[0313] As one of the preferred embodiments of the photosensitive layer, from the viewpoint of rust prevention, the photosensitive layer preferably contains Compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure. As one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains Compound M and an ethylenically unsaturated compound having an acid group from the viewpoints of substrate adhesion, development residue suppression, and rust prevention. More preferably, it contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group. Even more preferably, it 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. Particularly preferably, it 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. As one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group from the viewpoints of substrate adhesion, development residue suppression, and rust prevention. More preferably, it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. Even more preferably, it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group. Particularly preferably, it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0314] The photosensitive 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% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass based on the total content of all the ethylenically unsaturated compounds contained in the photosensitive layer.

[0315] The ethylenically unsaturated compound may be used alone or in combination of two or more kinds. The content of the ethylenically unsaturated compound in the photosensitive layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, still more preferably 5% by mass to 60% by mass, and particularly preferably 5% by mass to 50% by mass based on the total mass of the photosensitive layer.

[0316] (Polymerization initiator) The photosensitive layer preferably contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferred. Preferred embodiments of the polymerization initiator used in Embodiment B include the preferred embodiments of the polymerization initiator used in Embodiment A described above. The polymerization initiator may be used alone or in combination of two or more kinds. The content of the polymerization initiator 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 based on the total mass of the photosensitive layer. Further, the upper limit value is preferably 10% by mass or less, more preferably 5% by mass or less based on the total mass of the photosensitive layer.

[0317] (Heterocyclic compound) The photosensitive 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 of 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.

[0318] Examples of the heterocyclic ring compound include, for example, 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 these, as the heterocyclic ring 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.

[0319] Preferable specific examples of the heterocyclic ring compound are shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

[0320]

Chemical formula

[0321]

Chemical formula

[0322] Examples of the tetrazole compound include the following compounds.

[0323]

Chemical formula

[0324]

Chemical formula

[0325] Examples of the thiadiazole compound include the following compounds.

[0326]

Chemical formula

[0327] Examples of the triazine compound include the following compounds.

[0328]

Chemical formula

[0329] Examples of the rhodanine compound include the following compounds.

[0330]

Chemical formula

[0331] Examples of the thiazole compound include the following compounds.

[0332]

Chemical formula

[0333] Examples of the benzothiazole compound include the following compounds.

[0334]

Chemical formula

[0335] Examples of the benzimidazole compound include the following compounds.

[0336]

Chemical formula

[0337]

Chemical formula

[0338] Examples of the benzoxazole compound include the following compounds.

[0339] [Chemical formula]

[0340] The heterocyclic compound may be used alone or in combination of two or more. When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, more preferably 0.10% by mass to 10.0% by mass, still more preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass with respect to the total mass of the photosensitive layer.

[0341] (Aliphatic thiol compound) The photosensitive layer may contain an aliphatic thiol compound. When the photosensitive layer contains an aliphatic thiol compound, the en-thiol reaction between the aliphatic thiol compound and the ethylenically unsaturated compound suppresses the curing shrinkage of the formed film and relaxes the stress.

[0342] 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. Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is more preferable from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure). In this 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.

[0343] 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 still more preferably 150 to 1,000.

[0344] 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 still more preferable.

[0345] Examples of the polyfunctional aliphatic thiol compound 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.

[0346] Among the above, 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.

[0347] Examples of the monofunctional aliphatic thiol compound 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.

[0348] The photosensitive layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds. When the photosensitive 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 layer.

[0349] (Thermally crosslinkable compound) The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. As the thermally crosslinkable compound used in the photosensitive layer of Embodiment B, the thermally crosslinkable compound described above in the photosensitive layer of Embodiment A is preferably used. The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive 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 layer.

[0350] (Surfactant) The photosensitive layer may contain a surfactant. As the surfactant used in the photosensitive layer of Embodiment B, the surfactant described above in the photosensitive layer of Embodiment A is preferably used. The surfactant may be used alone or in combination of two or more. When the photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, more preferably 0.01% by mass to 1.0% by mass, and still more preferably 0.05% by mass to 0.80% by mass with respect to the total mass of the photosensitive layer.

[0351] (Radical polymerization inhibitor) The photosensitive layer may contain a radical polymerization inhibitor. As the radical polymerization inhibitor used in the photosensitive layer of Embodiment B, the radical polymerization inhibitor described above in the photosensitive layer of Embodiment A is preferably used. The radical polymerization inhibitor may be used alone or in combination of two or more. When the photosensitive layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass with respect to the total mass of the photosensitive layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and the suppression of decolorization of the dye are more excellent.

[0352] (Hydrogen donating compound) The photosensitive layer may contain a hydrogen donating compound. The hydrogen donating compound has functions such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound by oxygen. Examples of the hydrogen donating compound include amines and amino acid compounds.

[0353] Examples of amines include 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 Unexamined Patent Application Publication No. 51-082102, Japanese Unexamined Patent Application Publication No. 52-134692, Japanese Unexamined Patent Application Publication No. 59-138205, Japanese Unexamined Patent Application Publication No. 60-084305, Japanese Unexamined Patent Application Publication No. 62-018537, Japanese Unexamined Patent Application Publication No. 64-033104, and Research Disclosure No. 33825. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline can be mentioned. Among them, from the viewpoints of sensitivity, curing rate, and curability, as amines, at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferable.

[0354] Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, from the viewpoints of sensitivity, curing rate, and curability, as the amino acid compound, N-phenylglycine is preferable.

[0355] Examples of hydrogen-donating compounds also include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithiane) described in Japanese Unexamined Patent Application Publication No. 6-308727.

[0356] The hydrogen-donating compounds may be used alone or in combination of two or more. When the photosensitive layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and still more preferably 0.03% by mass to 5.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer.

[0357] (Impurities, etc.) The photosensitive layer may contain a predetermined amount of impurities. Regarding the impurities in the photosensitive layer of Embodiment B, they are the same as the preferred embodiments of the impurities described above in the photosensitive layer of Embodiment A.

[0358] (Residual monomers) The photosensitive layer may contain residual monomers corresponding to each structural unit of the binder polymer described above. Regarding the residual monomers corresponding to each structural unit of the binder polymer in the photosensitive layer of Embodiment B, they are the same as the preferred embodiments of the residual monomers corresponding to each structural unit of the binder polymer described above in the photosensitive layer of Embodiment A.

[0359] (Other components) The photosensitive layer may contain components other than the components described above (hereinafter also referred to as "other components"). Examples of the other components include colorants, antioxidants, and particles (e.g., metal oxide particles). In addition, as the other components, other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 are also included.

[0360] -Particles- As the particles, metal oxide particles are preferred. 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 nm to 200 nm, more preferably 3 nm 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 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.

[0361] When the photosensitive layer contains particles, it may contain only one kind of particles with different metal species, sizes, etc., or may contain two or more kinds. The photosensitive layer either does not contain particles, or when the photosensitive 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, even 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 layer.

[0362] -Colorant- The photosensitive layer may contain a colorant (such as a pigment or a dye), but for example, from the viewpoint of transparency, it is preferably substantially free of a colorant. When the photosensitive 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 layer.

[0363] -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, parahydroxyphenylglycine, and paraphenylenediamine. Among them, from the viewpoints of storage stability and curability, 3 - pyrazolidones are preferred as antioxidants, and 1 - phenyl - 3 - pyrazolidone is more preferred.

[0364] When the photosensitive 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, based on the total mass of the photosensitive layer. The upper limit is not particularly limited, but preferably 1% by mass or less.

[0365] (Thickness of the photosensitive layer) The thickness (layer thickness) of the photosensitive layer is not particularly limited, but from the viewpoints of developability and resolution, it is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, particularly preferably 10 μm or less, and most preferably 5.0 μm or less. As the lower limit, from the viewpoint of excellent strength of the film obtained by curing the photosensitive layer, it is preferably 0.60 μm or more, and more preferably 1.5 μm or more.

[0366] (Refractive index of the photosensitive layer) The refractive index of the photosensitive layer is preferably 1.47 to 1.56, and more preferably 1.49 to 1.54.

[0367] (Color of the photosensitive layer) The photosensitive 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 10 to 90, the a * value is preferably - 1.0 to 1.0, and the b * value is preferably - 1.0 to 1.0.

[0368] Note that the pattern obtained by curing the photosensitive layer (cured film of the photosensitive 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* ) In the color space, the L value of the pattern is preferably from 10 to 90, the a value of the pattern is preferably from -1.0 to 1.0, and the b value of the pattern is preferably from -1.0 to 1.0. * * *

[0369] (Moisture permeability of the photosensitive layer) The moisture permeability at a layer thickness of 40 μm of the pattern (cured film of the photosensitive layer) obtained by curing the photosensitive layer is preferably 500 g / (m 2 ·24 hr) or less, more preferably 300 g / (m 2 ·24 hr) or less, and still more preferably 100 g / (m 2 ·24 hr) or less, from the viewpoint of rust prevention. Note that the moisture permeability is measured on the cured film obtained by curing the photosensitive layer by subjecting the photosensitive layer to post-baking at 145°C for 30 minutes after exposure at an exposure amount of 300 mJ / cm 2 with i-line.

[0370] 〔Refractive index adjustment layer〕 The above laminate preferably has a refractive index adjustment layer. As the refractive index adjustment layer, a known refractive index adjustment layer can be applied. Examples of the materials included in the refractive index adjustment layer include a binder polymer, a polymerizable compound, a metal salt, and particles. The method for controlling the refractive index of the refractive index adjustment 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.

[0371] Examples of the binder polymer and the polymerizable unsaturated compound include the binder polymer and the polymerizable unsaturated compound described in the above item of "photosensitive layer".

[0372] 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 metalloids such as B, Si, Ge, As, Sb, and Te.

[0373] From the viewpoint of, for example, the transparency of the cured film, the average primary particle diameter of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm. 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.

[0374] 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, from the viewpoint of being easy to adjust the refractive index, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable.

[0375] Commercially available products of 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.).

[0376] 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% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and still more preferably 40% by mass 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% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and still more preferably 40% by mass to 85% by mass, based on the total mass of the refractive index adjustment layer.

[0377] The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive 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 particularly preferably 1.78 or less.

[0378] The thickness of the refractive index adjustment layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and still more preferably 60 nm to 100 nm.

[0379] [Relationship among the support, the photosensitive layer, and the cover film] Also in Embodiment B, it is preferable to satisfy the relationship among the support, the photosensitive layer, and the cover film described in Embodiment A.

[0380] (Method for manufacturing the photosensitive transfer member of Embodiment B) The method for manufacturing the photosensitive transfer member (laminated body having a photosensitive layer) of Embodiment B is not particularly limited, and known methods can be used. Regarding the photosensitive composition and the method for forming the photosensitive layer in Embodiment B, they are the same as those of the photosensitive composition and the method for forming the photosensitive layer described above in Embodiment A, and the preferred embodiments are also the same. Also, regarding the support and the cover film, they are the same as those of the manufacturing method in Embodiment A, and the preferred embodiments are also the same.

[0381] -Composition for forming a refractive index adjustment layer and method for forming a refractive index adjustment layer- As the composition for forming the refractive index adjustment layer, it is preferable to include 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 preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable 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, and at least one selected from the group consisting of water and water-miscible organic solvents is preferable, and water or a mixed solvent of water and a water-miscible organic solvent is more preferable. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 parts by mass to 2,500 parts by mass, more preferably 50 parts by mass to 1,900 parts by mass, and still more preferably 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.

[0382] The method for forming the refractive index adjustment layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. For example, known coating methods (such as slit coating, spin coating, curtain coating, and inkjet coating) can be mentioned.

[0383] Further, the photosensitive transfer member of Embodiment B can be manufactured by bonding a cover film to the refractive index adjustment layer. The method for bonding the cover film to the refractive index adjustment layer is not particularly limited, and known methods can be mentioned. Examples of the apparatus for bonding the cover film to the refractive index adjustment layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator preferably includes an arbitrarily heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0384] [Laminate] A first embodiment of the laminate according to the present disclosure is a laminate having a photosensitive layer, the laminate having at least a cut surface, and the number of cracks per 10 cut surface portions with a cut surface width of 50 μm being 3 or less. A second embodiment of the laminate according to the present disclosure is a laminate having a photosensitive layer, the laminate having at least a cut surface, and the number of indentation failures in the laminate being 60 pieces / m 2 is as follows.

[0385] In this specification, unless otherwise specified, when simply referring to "the laminate according to the present disclosure", it shall describe both the above first embodiment and the above second embodiment. Also, unless otherwise specified, when simply referring to "the photosensitive layer" or the like, it shall describe the photosensitive layer or the like of both the above first embodiment and the above second embodiment.

[0386] A preferred embodiment of the laminate having the photosensitive layer in the laminate according to the present disclosure is the same as the preferred embodiment of the laminate having the photosensitive layer used in the method for manufacturing the cut product according to the present disclosure described above, except as described below.

[0387] In the first embodiment of the laminate according to the present disclosure, the number of cracks per 10 cut surface portions with a cut surface width of 50 μm is 3 or less, and from the viewpoint of defect suppression, it is preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less, and particularly preferably 0.1 or less. In the second embodiment of the laminate according to the present disclosure, the number of cracks per 10 cut surface portions with a cut surface width of 50 μm is preferably 3 or less, more preferably 2 or less, still more preferably 1 or less, particularly preferably 0.5 or less, and most preferably 0.1 or less, from the viewpoint of defect suppression.

[0388] FIG. 3 shows an example of cracks occurring in the cut surface of the laminate. FIG. 3 is an enlarged view of an end portion of a cut surface of a laminate having a support 10, a photosensitive layer 16, and a cover film 18. In the cut surface of FIG. 3, some cracks CR in the support 10 can be confirmed.

[0389] The measurement of the number of cracks in the present disclosure shall be performed as follows. Arbitrarily collect 10 locations on the cut surface of the cut laminate, and observe a cut surface portion with a cut surface width of 50 μm of the cut surface with a scanning electron microscope (SEM). The conditions were an acceleration voltage of 3 kV and an observation magnification of 1,700 times. Among the 10 locations, any layer of the support, photosensitive layer, or cover film that has a crack regardless of the number is counted as one, and it is evaluated by the number of cracks (crack number) in 10 cut surface portions with a cut surface width of 50 μm.

[0390] In the second embodiment of the laminate according to the present disclosure, the number of dents in the laminate is 60 pieces / m 2 or less, and from the viewpoint of defect suppression, it is preferably 45 pieces / m 2 or less, more preferably 30 pieces / m 2 or less, and particularly preferably 10 pieces / m 2 or less. In the first embodiment of the laminate according to the present disclosure, the number of dents in the laminate is preferably 60 pieces / m 2 or less from the viewpoint of defect suppression, more preferably 45 pieces / m 2 or less, still more preferably 30 pieces / m 2 or less, and particularly preferably 10 pieces / m 2 or less.

[0391] The measurement of the number of dents in the laminate in the present disclosure shall be performed as follows. Visually observe the surface of the laminate for 6 m 2 or more, measure the number of dents, and calculate the number of dent failures per 1 m 2

Example

[0392] Examples are given below to more specifically explain the embodiments of the present invention. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0393] (Examples 1 to 12, and Comparative Examples 1 and 2) <Fabrication of Photosensitive Transfer Member> -Formation of Photosensitive Layer- A polyethylene terephthalate (PET) film with the thickness described in Table 2 was prepared as the support. On the surface of the support, the photosensitive composition A-1 described in Table 1 was applied using a slit nozzle with a coating width of 1.0 m and a layer thickness after drying of the thickness described in Table 2. The coating film of the photosensitive composition A-1 was dried at 80 °C for 40 seconds to form a photosensitive layer.

[0394] [Table 1]

[0395] In Table 1, "Mm / Mb" represents the value of the ratio Mm / Mb of the content Mm of the polymerizable compound to the content Mb of the binder polymer in the photosensitive layer, and the "content of acrylic compound" represents the content of the acrylic compound relative to the total mass of the (meth)acrylic compounds contained in the photosensitive layer, with the unit being mass %.

[0396] The details of the abbreviations in Table 1 are shown below. BPE-500: Ethoxylated (10 molar equivalents) bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) SR-502: Ethoxylated (9 molar equivalents) trimethylolpropane triacrylate (manufactured by Arkema) A-9300-CL1: ε-Caprolactone-modified Tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.) B-CIM: 2,2’-Bis(2-chlorophenyl)-4,4’,5,5’-tetraphenyl-1,2’-bisimidazole (polymerization initiator, manufactured by Kurogane Kasei Co., Ltd.) SB-PI 701: 4,4’-Bis(diethylamino)benzophenone (sensitizer, manufactured by Sanyo Trading Co., Ltd.) CBT-1: Carboxybenzotriazole (rust inhibitor, manufactured by Johoku Chemical Industry Co., Ltd.)

[0397] -Attachment of Cover Film- On the surface of the formed photosensitive layer, a PET film or a polypropylene (PP) film with the thickness described in Table 2 was pressure-bonded as a cover film to produce the photosensitive transfer member A of each example. The obtained photosensitive transfer member A was wound up to produce a roll-shaped photosensitive transfer member A with a width of 1,580 mm and a roll length of 4,000 m.

[0398] <Dent Failure Evaluation> The cutting of the large roll of the photosensitive transfer member A was performed using a disk-shaped rotary slitter having an upper blade 102 and a lower blade 104 with the cross-sections shown in FIG. 1 and Table 2. Each parameter of the used upper blade 102 was R1, chamfer angle θ1, and cutting edge angle θ2 described in Table 2. Also, each parameter of the used lower blade 104 was fixed with R2 being 2 μm and the cutting edge angle θ3 being 90°. Furthermore, the penetration depth T of the upper blade 102 with respect to the lower blade 104 during cutting was 0.5 mm. Moreover, the radii of the disk-shaped upper blade 102 and lower blade 104 were each approximately 100 mm, and the cutting speed was 100 m / min. The cut photosensitive transfer member A was rewound into small rolls. Using the above rotary slitter, a large roll of the photosensitive transfer member A with a width of 1,580 mm and a roll length of 4,000 m was cut into small rolls of the photosensitive transfer member A with a width of 500 mm and a length of 100 m. 2 m was pulled out from the small roll of the cut photosensitive transfer member A, and the number of dents was visually inspected. The small rolls used in the above evaluation were a total of six small rolls cut from the above large roll, three small rolls from the width direction of the large roll and two small rolls from the longitudinal direction of the large roll. These were investigated and evaluated according to the following evaluation criteria based on the maximum number among them. A: The number of depressions is from 0 to 10. B: The number of depressions is from 11 to 30. C: The number of depressions is from 31 to 60. D: The number of depressions is 61 or more.

[0399] <Evaluation of crack number> Using a rotary slitter, a large roll of photosensitive transfer member A with a width of 1,580 mm and a winding length of 4,000 m was cut into small rolls of photosensitive transfer member A with a width of 500 mm and a length of 100 m. 2 m was pulled out from the cut small roll of photosensitive transfer member A, and a total of 10 places were sampled at any 5 places on both sides, and the cut surfaces were observed with a scanning electron microscope (SEM: Scanning Electron Microscope). The conditions were an acceleration voltage of 3 kV and an observation magnification of 1,700 times. Among the 10 places, any layer of the support, photosensitive layer, or cover film, and any one with a crack regardless of the number was counted as one, and the evaluation was made based on the number of cracks in the 10 places.

[0400]

Table 2

[0401] The base materials used as the support or cover film described in Table 2 are as follows. PET film (thickness 16 μm): Lumirror 16QS62 manufactured by Toray Industries, Inc. PET film (thickness 20 μm): A PET film with a thickness of 20 μm was produced according to the description in paragraphs 0119 to 0127 of International Publication No. 2017 / 208849. PET film (thickness 14 μm): A PET film with a thickness of 14 μm was produced according to the description in paragraphs 0119 to 0127 of International Publication No. 2017 / 208849. PP film (thickness: 12 μm): Torayfan 12KW37 manufactured by Toray Industries, Inc.

[0402] As shown in Table 2 above, the manufacturing methods of the cut products of Examples 1 to 12 can suppress the depression failure in the obtained cut products as compared with the manufacturing method of the cut product of the Comparative Example.

[0403] (Examples 13 to 28) <Preparation of Photosensitive Composition> Photosensitive compositions AA-1 to AA-10 were respectively prepared so as to have the compositions shown in Table 3 below. The numerical values in each component column of Table 3 represent parts by mass.

[0404]

Table 3

[0405] Details of the compounds other than those described above in Table 3 are shown below. Compound B and Compound C: The following compounds

[0406]

Chemical formula

[0407] <Preparation of 36.3 mass% solution of alkali-soluble resin P-1> A 36.3 mass% solution of polymer P-1 having the following structure (solvent: propylene glycol monomethyl ether acetate) was used. In P-1, the numerical value at the lower right of each structural unit indicates the content ratio (mol%) of each structural unit. The 36.3 mass% solution of P-1 was prepared by the polymerization step and addition step shown below.

[0408] - Polymerization step - Into a 2,000 mL flask, propylene glycol monomethyl ether acetate (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM-Ac) (60 g) and propylene glycol monomethyl ether (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM) (240 g) were introduced. The resulting liquid was heated to 90 °C while stirring at a stirring speed of 250 rpm (revolutions per minute). 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., Ltd., trade name MMA), and 231.42 g of cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name CHMA) were mixed and diluted with PGM-Ac (60 g) 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 Fujifilm Wako Pure Chemical Corporation, trade name V-601) was dissolved in PGM-Ac (136.56 g) to obtain the dropping solution (2). The dropping solution (1) and the dropping solution (2) were simultaneously dropped into the above-mentioned 2,000 mL flask (specifically, a 2,000 mL flask containing the liquid heated to 90 °C) over 3 hours. Next, the container of the dropping solution (1) was washed with PGM-Ac (12 g), and the washing solution was dropped into the above 2,000 mL flask. Next, the container of the dropping solution (2) was washed with PGM-Ac (6 g), and the washing solution was dropped into the above 2,000 mL flask. During these droppings, the reaction solution in the 2,000 mL flask was maintained at 90 °C and stirred at a stirring speed of 250 rpm. Further, as a post-reaction, it was stirred at 90 °C for 1 hour. To the reaction solution after the post-reaction, as the first additional addition of the initiator, V-601 (2.401 g) was added. Further, the container of V-601 was washed with PGM-Ac (6 g), 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, V-601 (2.401 g) was added to the reaction solution. Further, the container of V-601 was washed with PGM-Ac (6 g), 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, V-601 (2.401 g) was added to the reaction solution. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing solution was introduced into the reaction solution. Then, it was stirred at 90 °C for 3 hours.

[0409] -Addition Step- After stirring at 90 °C for 3 hours, PGM-Ac (178.66 g) was introduced into the reaction solution. Next, tetraethylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Corporation) (1.8 g) and hydroquinone monomethyl ether (manufactured by Fujifilm Wako Pure Chemical Corporation) (0.8 g) were added to the reaction solution. Further, each container was washed with PGM-Ac (6 g), 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, it was stirred at 100 °C for 6 hours. Next, the reaction solution was cooled and filtered through a dust removal mesh filter (100 mesh) to obtain a solution (1,158 g) of polymer D (solid content concentration: 36.3 mass%). The weight average molecular weight of the obtained polymer P-1 was 27,000, the number average molecular weight was 15,000, and the acid value was 95 mgKOH / g.

[0410] P-1 (hereinafter, the molar ratio of the constituent repeating units in the formula was 51.5:2:26.5:20 in order from the leftmost constituent repeating unit.)

[0411]

Chemical Formula

[0412] <Preparation of 36.3 Mass% Solution of Alkali-Soluble Resin P-2> 82.4 g of propylene glycol monomethyl ether was charged into a flask and heated to 90 °C under a nitrogen stream. To this liquid, a solution prepared by dissolving 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate, and 34.0 g of methacrylic acid in 20 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 5.4 g of polymerization initiator V-601 (manufactured by Fuji Film Wako Pure Chemical Corporation) in 43.6 g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 3 hours. After the addition was completed, 0.75 g of V-601 was added three times at 1-hour intervals. Thereafter, the reaction was continued for another 3 hours. Then, it was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. Under an air stream, the temperature of the reaction solution was raised to 100 °C, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. 25.5 g of glycidyl methacrylate (Blemmer GH manufactured by NOF Corporation) was added dropwise thereto over 20 minutes. This was reacted at 100 °C for 7 hours to obtain a solution of polymer P-2. The solid content concentration of the obtained solution was 36.5%. The weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersity was 2.4, and the acid value of the polymer was 94.5 mgKOH / g. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass with respect to the polymer solid content for any monomer.

[0413] P-2 (hereinafter, the molar ratio of the constituent repeating units in the formula was 41.0:15.2:23.9:19.9 in order from the leftmost constituent repeating unit.)

[0414]

Chemical formula

[0415] <Preparation of a 36.2 mass% solution of alkali-soluble resin P-3> 113.5 g of propylene glycol monomethyl ether was charged into a flask and heated to 90 °C under a nitrogen stream. A solution prepared by dissolving 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid in 30 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 27.6 g of polymerization initiator V-601 (manufactured by Fuji Film Wako Pure Chemical Corporation) in 57.7 g of propylene glycol monomethyl ether were simultaneously added dropwise over 3 hours. After the addition was completed, 2.5 g of V-601 was added three times at 1-hour intervals. Thereafter, the reaction was continued for another 3 hours. Then, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. Under an air stream, the temperature of the reaction solution was raised to 100 °C, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (Blemmer G manufactured by NOF Corporation) was added dropwise thereto over 20 minutes. This was reacted at 100 °C for 7 hours to obtain a solution of resin P-3. The solid content concentration of the obtained solution was 36.2%. The weight average molecular weight in terms of standard polystyrene in GPC was 18,000, the dispersity was 2.3, and the acid value of the polymer was 124 mgKOH / g. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass with respect to the polymer solid content for any monomer.

[0416] P-3 (hereinafter, the molar ratio of the constituent repeating units in the formula was 55.1:26.5:1.6:16.8 in order from the leftmost constituent repeating unit.)

[0417]

Chemical formula

[0418] <Preparation of 36.2 mass% solution of alkali-soluble resin P-4> In the synthesis of P-3, a 36.2 mass% solid content solution of P-4 (solvent: propylene glycol monomethyl ether acetate) was prepared by changing the types and amounts of monomers. The weight average molecular weight of the obtained polymer P-4 was 18,000, the dispersity was 2.3, and the acid value was 114 mgKOH / g.

[0419] P-4 (hereinafter, the molar ratio of the constituent repeating units in the formula was 55.1:24.6:1.6:17.0:1.7 in order from the leftmost constituent repeating unit.)

[0420]

Chemical formula

[0421] <Preparation of the composition for forming the refractive index adjustment layer> Next, compositions B-1 to B-4 for forming a refractive index adjustment layer were prepared with the compositions described in Table 4 below. The numerical values in Table 4 represent "parts by mass".

[0422]

Table 4

[0423] The polymer A in Table 4 was synthesized as follows. 1-methoxypropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0 g) was introduced into a 1 L three-necked flask, and the temperature was raised to 70 °C under a nitrogen stream while stirring. On the other hand, allyl methacrylate (45.6 g) (manufactured by Fujifilm Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) (manufactured by Fujifilm Wako Pure Chemical Corporation) were dissolved in 1-methoxypropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0 g), and further 3.94 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Corporation) was dissolved to prepare a dropping solution, which was then dropped into the flask over 2.5 hours. The reaction was carried out while maintaining the stirring state for 2.0 hours. Thereafter, the temperature was returned to room temperature and it was dropped into ion-exchanged water (2.7 L) under stirring to perform reprecipitation, obtaining a suspension. Filtration was carried out by introducing the suspension into a Buchner funnel with filter paper drawn, and the filtrate was further washed with ion-exchanged water to obtain a wet powder. It was subjected to blow drying at 45 °C, confirmed to have reached a constant weight, and Polymer A was obtained as a powder with a yield of 70%. The ratio of methacrylic acid / allyl methacrylate of the obtained Polymer A was 76 / 24 mass%. The weight average molecular weight Mw was 38,000.

[0424] <Production of Transfer Films 1 to 16 (Photosensitive Transfer Members)> On a temporary support of a polyethylene terephthalate film with a thickness of 16 μm (Lumirror 16KS40, manufactured by Toray Industries, Inc.), using a slit nozzle, the coating amount was adjusted to a coating amount such that the film thickness after drying became the thickness shown in Table 5, and any one of the photosensitive composition materials AA-1 to AA-10 described in Table 5 was applied to form a photosensitive layer. After volatilizing the solvent in a drying zone at 100 °C, using a slit nozzle, in the combination shown in Table 3, at least one of the materials B-1 to B-4 for forming a refractive index adjustment layer described in Table 5 was used, and the coating amount was adjusted to an amount such that the film thickness after drying became the film thickness described in Table 5 and applied onto the photosensitive layer. Then, it was dried at a drying temperature of 80 °C to form a refractive index adjustment layer. A protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded onto the refractive index adjustment layer to produce Transfer Films 1 to 16.

[0425]

Table 5

[0426] <Evaluation> Similarly, the number of depressions and the number of cracks were evaluated for Transfer Films 1 to 16. The evaluation results are shown in Table 6 below.

[0427]

Table 6

[0428] As shown in Table 6 above, the manufacturing methods of the cut products of Examples 13 to 28 can suppress the depression failure and crack failure in the obtained cut products.

[0429] Note that the disclosures of Japanese Patent Application No. 2020-024650 filed on February 17, 2020, Japanese Patent Application No. 2020-172675 filed on October 13, 2020, and Japanese Patent Application No. 2020-207961 filed on December 15, 2020 are incorporated herein by reference in their entirety. Also, all documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A step of sandwiching a laminate having a photosensitive layer between an upper blade and a lower blade and cutting it, wherein the clearance between the cutting edge of the upper blade and the cutting edge of the lower blade is 5 μm or less, the lower blade side of the upper blade and the upper blade side of the lower blade are chamfered, in a cross section perpendicular to the feeding direction of the laminate of the upper blade and the lower blade, when the length in the direction orthogonal to the lamination direction of the laminate in the chamfered portion of the upper blade is defined as the chamfer length R1 of the upper blade, and the length in the direction orthogonal to the lamination direction of the laminate in the chamfered portion of the lower blade is defined as the chamfer length R2 of the lower blade, the clearance is the total value of the chamfer length R1 of the upper blade and the chamfer length R2 of the lower blade, A method for manufacturing a cut product.

2. The method for manufacturing a cut product according to claim 1, wherein the chamfer angle θ1, which is the inclination angle on the lower blade side at the cutting edge of the upper blade, is 3° or less in a cross section perpendicular to the feeding direction of the laminate of the upper blade.

3. The method for manufacturing a cut product according to claim 1 or claim 2, wherein the cutting edge angle θ2 of the upper blade is 33° or less in a cross section perpendicular to the feeding direction of the laminate of the upper blade.

4. The method for manufacturing a cut product according to any one of claims 1 to 3, wherein the thickness of the entire laminate is 50 μm or less.

5. The method for manufacturing a cut product according to any one of claims 1 to 4, wherein the thickness of the photosensitive layer is 1 μm to 20 μm.

6. The method for manufacturing a cut product according to any one of claims 1 to 5, wherein the laminate is a laminate having a support, the photosensitive layer, and a cover film.

7. The method for manufacturing a cut product according to claim 6, wherein the thicknesses of the support and the cover film are each independently 10 μm to 20 μm.

8. The method for manufacturing a cut product according to claim 6 or claim 7, wherein the arithmetic mean roughness Ra value of the surface of the support on the photosensitive layer side is 0.05 μm or less.

9. The method for manufacturing a cut product according to any one of claims 6 to 8, wherein the arithmetic mean roughness Ra value of the surface of the cover film on the photosensitive layer side is 0.1 μm or less.

10. The method for manufacturing a cut product according to any one of claims 1 to 9, including a step of winding up at least a part of the cut product of the laminate obtained after the cutting step.

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