WO2021166719A1

WO2021166719A1 - Method for manufacturing cut article, and layered body

Info

Publication number: WO2021166719A1
Application number: PCT/JP2021/004622
Authority: WO
Inventors: 洋行海鉾
Original assignee: 富士フイルム株式会社
Priority date: 2020-02-17
Filing date: 2021-02-08
Publication date: 2021-08-26
Also published as: JPWO2021166719A1; CN114901442A

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

Manufacturing method of cut material and laminated body

This disclosure relates to a method for producing a cut product and a laminate.

In display devices equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. A conductive layer pattern such as is provided inside the touch panel.
Generally, in forming a patterned layer, the number of steps for obtaining the required pattern shape is small, so that a layer of a photosensitive composition provided on an arbitrary substrate using a photosensitive transfer member is used. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.

Further, as a conventional film cutting method, the one described in Patent Document 1 is known.
In Japanese Patent Application Laid-Open No. 2010-228023, a continuously traveling film is inserted between an upper blade and a lower blade that rotate so that one side surface of each blade edge is in sliding contact with each other, and along the traveling direction. A method for cutting a film so as to be divided in the width direction, wherein the upper blade has a cutting edge angle of 80 to 90 ° in sliding contact with the lower blade, and the lower blade is the upper blade. A method for cutting a film is described, wherein a blade having a blade edge angle of 80 to 90 ° in sliding contact with the blade is used.

An object to be solved by one embodiment of the present invention is to provide a method for producing a cut product capable of suppressing a dent failure in the obtained cut product.
Further, an object to be solved by another embodiment of the present invention is to provide a laminated body having few dent failures.

Means for solving the above problems include the following aspects.
<1> A method for producing a cut product, which comprises a step of sandwiching and cutting a laminate having a photosensitive layer between an upper blade and a lower blade, 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 chamfering angle θ1 which is an inclination angle of the lower blade side at the cutting edge of the upper blade in a cross section perpendicular to the feed direction of the laminated body of the upper blade is 3 ° or less. Method of manufacturing cut pieces.
<3> The method for producing a cut product according to <1> or <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 laminated body of the upper blade.
<4> The method for producing 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 producing 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 producing a cut product according to any one of <1> to <5>, wherein the laminated body is a laminated body having a support, the photosensitive layer, and a cover film.
<7> The method for producing a cut product according to <6>, wherein the thickness of the support and the cover film are independently 10 μm to 20 μm.
<8> The method for producing a cut product according to <6> or <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 producing a cut product according to any one of <6> to <8>, wherein the arithmetic average 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 producing a cut product according to any one of <1> to <9>, which comprises a step of winding at least a part of the cut product of the obtained laminated body 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. Laminated body.
<12> A laminate having a photosensitive layer, wherein the laminate has a cut surface formed by at least being cut, and the number of dent failures in the laminate is 60 / m ² or less. ..

According to one embodiment of the present invention, it is possible to provide a method for producing a cut product capable of suppressing a dent failure in the obtained cut product.
Further, according to another embodiment of the present invention, it is possible to provide a laminated body having few dent failures.

FIG. 1 is a schematic cross-sectional view showing an example of an upper blade and a lower blade of a disk-shaped rotary slitter used in the present disclosure. FIG. 2 is a schematic view showing an example of the layer structure of the photosensitive transfer member used in the present disclosure. FIG. 3 is an enlarged view of an example of an end portion of a cut surface obtained by cutting a laminate having a support, a photosensitive layer, and a cover film.

The contents of the present disclosure will be described below. Although the description will be given with reference to the attached drawings, the reference numerals may be omitted.
In addition, the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate" represents both acrylate and methacrylate, or either.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of applicable substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means quantity.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam. The light used for exposure generally includes the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and active rays (active energy rays) such as electron beams. Can be mentioned.
Further, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.). It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and using polystyrene as a standard substance.
In the present specification, unless otherwise specified, the content of the metal element is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer.
In the present specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
In the present specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
As used herein, the term "alkali-soluble" means that the solubility of sodium carbonate having a liquid temperature of 22 ° C. in 100 g of a 1% by mass aqueous solution is 0.1 g or more.
As used herein, the term "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more. Therefore, for example, the water-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.
In the present specification, the "solid content" of the composition means a component forming a layer produced by using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent is removed. Means all ingredients. Further, if the component forms the above layer, the liquid component is also regarded as a solid content.
In the present specification, the layer thickness of each layer included in the photosensitive transfer member is based on an observation image obtained by observing a cross section in a direction perpendicular to the main surface of the photosensitive transfer member with a scanning electron microscope (SEM). The thickness of each layer is measured at an arbitrary 5 points or more, and the average value thereof is calculated to measure the thickness.

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

In principle, it is advantageous for a resist material such as a photosensitive transfer member to narrow the gap between the mask and the resist material in order to form a resist faithful to the patterning mask by exposure. The narrower the gap, the shorter the optical path length, the less affected by diffraction and scattering, and the more faithful the resist to the mask can be realized. At high resolutions, the gap distances are noticeable and it is important to control them. Since the dry film is exposed through the support from the viewpoint of preventing mask contamination, it is necessary to reduce the thickness of the support, and the total film thickness is decreasing accordingly. It cannot be cut well under the conventional cutting conditions, and many chips are generated. When the chips adhere to the cut laminate (cut piece) having the photosensitive layer, a dent failure occurs. The present inventor has found that it occurs. For example, chips adhere to a laminate having a photosensitive layer, and then the cut pieces are stacked for storage, resulting in a dent failure. Further, when the laminate having the photosensitive layer is wound in a roll shape, a dent failure occurs due to the inclusion of chip pieces.

As a result of diligent studies, the present inventor has found that dent failure in the obtained cut product can be suppressed by adopting the method for producing the cut product having the above configuration.
Although the detailed mechanism for exhibiting the above effects is unknown, the clearance between the cutting edge of the upper blade and the cutting edge of the lower blade is 5 μm or less, so that chips are formed when the laminate having the photosensitive layer is cut. It is presumed that the generation of dents can be suppressed and the dent failure caused by the adhesion of chips to the laminate can be suppressed.

The laminate having the photosensitive layer is preferably a photosensitive transfer member.
The photosensitive transfer member used in the present disclosure is preferably a negative type photosensitive transfer member.
A preferred embodiment of the laminate having the photosensitive layer will be described later.

<Cut process>
The method for producing a cut product according to the present disclosure includes a step of sandwiching and cutting a laminate having a photosensitive layer between an upper blade and a lower blade, and a clearance between the cutting edge of the upper blade and the cutting edge of the lower blade is 5 μm. It is as follows.
The cutting means having an upper blade and a lower blade used in the present disclosure is not particularly limited, and examples thereof include a cutting machine and a slitter. The cutting means is preferably a rotary slitter, and more preferably a disk-shaped rotary slitter, from the viewpoint that it can be continuously cut and can be wound in a roll shape.

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 cut surface of the laminated body.
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.
Further, at the time of cutting, the laminate having the photosensitive layer (not shown) 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 to have the photosensitive layer. The laminate is cut. In FIG. 1, it is sandwiched between the upper blade 102 and the lower blade 104, and the laminated body having the photosensitive layer is cut so as to be separated into the left and right.

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, preferably 1 μm or more and 5 μm or less, and 2 μm or more and 4.5 μm or less from the viewpoint of suppressing dent defects. Is more preferable, and it is 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.

In the cross section of the upper blade 102 on the plane perpendicular to the feed direction of the laminated body, the chamfer length R1 of the upper blade 102 is preferably 0.5 μm or more and 3 μm or less from the viewpoint of suppressing dent defects. It is more preferably 5 μm or more and 2.5 μm or less, further 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.
Further, in the cross section of the lower blade 104 on the plane perpendicular to the feed direction of the laminated body, the chamfer length R2 of the lower blade 104 is preferably 0.5 μm or more and 3 μm or less from the viewpoint of suppressing dent defects. It is 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.

In the cross section of the upper blade 102 perpendicular to the feed direction of the laminated body, the chamfer angle θ1 which is the inclination angle of the lower blade side of the cutting edge 102a of the upper blade 102 shall be 15 ° or less from the viewpoint of suppressing dent defects. Is more preferable, 10 ° or less is more preferable, 3 ° or less is further preferable, and 1 ° or more and 3 ° or less is particularly preferable.
Further, the chamfer angle θ1 is preferably an angle exceeding 0 ° from the viewpoint of suppressing dent defects.

In the cross section of the upper blade 102 perpendicular to the feed direction of the laminated body, the cutting edge angle θ2 of the upper blade 102 is preferably 45 ° or less, more preferably 40 ° or less, from the viewpoint of suppressing dent defects. , 33 ° or less, and particularly preferably 20 ° or more and 33 ° or less.
Further, the cutting edge angle θ2 is preferably an angle of 2 times or more of the chamfering angle θ1, more preferably 5 times or more of the chamfering angle θ1, and 10 of the chamfering angle θ1 from the viewpoint of suppressing dent defects. It is particularly preferable that the angle is double or more.

In the cross section of the lower blade 104 perpendicular to the feed direction of the laminated body, the cutting edge angle θ3 of the lower blade 104 is preferably 75 ° or more and 120 ° or less, and 80 ° or more and 110 ° or less from the viewpoint of suppressing dent defects. It is more preferably 85 ° or more and 105 ° or less, and particularly preferably 90 ° or more and 100 ° or less.

The materials of the upper blade 102 and the lower blade 104 are not particularly limited, and known materials can be used. For example, high-speed tool steel (SKH), alloy tool steel (for example, SKD), cemented carbide and the like are preferable. It is appropriately set depending on the thickness of the laminated body, cutting conditions, and the like. Further, 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 can be appropriately set according to the thickness of the laminated body and the like.
Further, in the cutting step, the upper blade 102 is preferably located above the lower blade 104 in the direction of gravity.

The penetration depth T of the upper blade 102 with respect to the lower blade 104 at the time of cutting in the above-mentioned cutting step is not particularly limited as long as it can be cut, but from the viewpoint of cutting speed and suppression of dent defects, the rotary slitter Is preferably 0.4 mm to 0.6 mm.
Further, in the rotary slitter, it is preferable that the upper blade 102 and the lower blade 104 in the cutting step are in sliding contact with each other at least in a part.

In the above-mentioned cutting step, the shape and size of the cut product obtained by cutting the laminated body are not particularly limited, and may be cut into a desired shape and size.
Further, the materials and sizes of the upper blade and the lower blade can be appropriately selected according to the laminated body and the obtained cut piece.
Further, in the cutting step, it is preferable to cut the laminated body in the thickness direction.

Further, the cutting speed in the above-mentioned cutting step is not particularly limited and can be appropriately selected as desired.

<Rolling process>
The method for producing a cut product according to the present disclosure preferably includes a step of winding at least a part of the obtained cut product of the laminated body after the cutting step.
When the cut piece is wound up, dent defects due to the adhesion of chips are likely to occur, so that the effect according to the present disclosure can be further exerted.
The winding method is not particularly limited, and a known method can be used, but in the winding step, it is preferable to wind the cut piece in a roll shape.

<Other processes>
The method for producing a 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.

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

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

<Laminate with 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 a laminate having at least a support and a photosensitive layer. Is preferable, and a laminate having a support, a photosensitive layer, and a cover film is more preferable.
Further, the laminate having the photosensitive layer is preferably a photosensitive transfer member.
In the photosensitive transfer member, the support and the photosensitive layer may be directly laminated without interposing another layer, or may be laminated through another layer. Further, another layer may be laminated on the surface of the photosensitive layer opposite to the surface facing the support.
Examples of layers other than the support and the photosensitive layer include a thermoplastic resin layer, an intermediate layer, a refractive index adjusting layer, and a cover film.
Further, each layer may be a single layer or a plurality of layers or more.

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, from the viewpoint of further exerting the effects in the present disclosure.

An example of the embodiment of the laminate having a photosensitive layer used in the present disclosure is shown below, but the present invention 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. It is also preferable that the photosensitive layer is a colored resin layer. The laminate having a photosensitive layer used in the present disclosure may be used as a photosensitive transfer material member for a wiring protective film or as a photosensitive transfer member for an etching resist, as will be described later.
When the photosensitive transfer member for a wiring protective film is used, the structure of the laminated body is preferably, for example, the above-mentioned structure (1) or (2).
Further, in the case of a photosensitive transfer member for an etching resist, the structure of the laminated body is preferably, for example, the above-mentioned structures (2) to (4).

In the case of the laminate having the photosensitive layer used in the present disclosure, in the case of a configuration in which another layer is further provided on the side opposite to the support side of the photosensitive layer, the laminate is arranged on the side opposite to the support side of the photosensitive layer. The total thickness of the layers is preferably 0.1% to 30%, more preferably 0.1% to 20%, based on the thickness of the photosensitive layer.

From the viewpoint of suppressing the generation of air bubbles during bonding, the maximum width of the waviness of the laminate having the photosensitive layer used in the present disclosure is preferably 300 μm or less, more preferably 200 μm or less, and 60 μm or less. It is more preferable to have. The lower limit of the maximum width of the waviness 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 waviness of the laminate having the 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 stage having a smooth and horizontal surface so that the surface of the support faces the stage. After standing, the surface of the test sample was scanned with a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) for a range of 10 cm square at the center of the test sample to obtain a three-dimensional surface image, and the obtained three-dimensional image was obtained. Subtract the minimum concave height from the maximum convex height observed in the surface image. The above operation is performed on 10 test samples, and the arithmetic mean value thereof is defined as the "maximum width of waviness of the photosensitive transfer member".

Hereinafter, the laminate having a photosensitive layer used in the present disclosure will be described. The laminate of the following embodiment A has a configuration that can be suitably used for a photosensitive transfer member for an etching resist, and the laminate of the following embodiment B is suitably used for a photosensitive transfer member for a wiring protective film. It is a configuration that can be done.

[[Laminate of Embodiment A]]
Hereinafter, the laminated body of the embodiment A will be described.

[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 is a support that supports a photosensitive layer or a laminated body including the photosensitive layer and can be peeled off.

The support preferably has light transmission property from the viewpoint of enabling exposure of the photosensitive layer through the support when pattern-exposing the photosensitive layer. In addition, in this specification, "having light transmittance" means that the transmittance of light of the wavelength used for pattern exposure is 50% or more.
From the viewpoint of improving the exposure sensitivity of the photosensitive layer, the support preferably has a light transmittance of 60% or more, preferably 70% or more, at a wavelength (more preferably 365 nm) used for pattern exposure. More preferred.
The transmittance of the layer included in the photosensitive transfer member refers to the light emitted through the layer with respect to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer (thickness direction). It is a ratio of the intensity of light emission, and is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

The support may have a single-layer structure or a multi-layer structure.
Examples of the material constituting the support include a glass substrate, a resin film and paper, and a resin film is preferable from the viewpoint of strength, flexibility and light transmission.
Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.

The thickness (layer thickness) of the support is not particularly limited, and the strength as the support, the flexibility required for bonding to the circuit wiring forming substrate, and the light transmission required in the first exposure step are not particularly limited. From the viewpoint of sex, it may be selected according to the material.
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, further preferably in the range of 10 μm to 20 μm, and particularly preferably in the range of 10 μm to 16 μm from the viewpoint of ease of handling and versatility. preferable.
The average thickness of the support is preferably 50 μm or less, more preferably 25 μm or less, from the viewpoint of resolution and linearity when exposed through the support.

Examples of the support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

Further, it is preferable that the film used as the support has no deformation such as wrinkles, scratches, defects and the like.
From the viewpoint of pattern formation during pattern exposure via the support and transparency of the support, it is preferable that the number of fine particles, foreign substances, defects, precipitates, etc. contained in the support is small. The number of the above fine particles and foreign matter and defect diameter 1μm is preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, further preferably 3/10 mm ² or less , 0 pieces / 10 mm ² is particularly preferable.

Preferred embodiments of the support include, for example, paragraphs 0017 to 0018 of JP2014-85643, paragraphs 0019 to 0026 of JP2016-27363, and paragraphs 0041 to 0057 of International Publication No. 2012/081680. It is described in paragraphs 0029 to 0040 of International Publication No. 2018/179370 and paragraphs 0012 to 0032 of JP-A-2019-101405, and the contents of these publications are incorporated in the present specification.

Further, the arithmetic mean roughness Ra value of the surface of the support on the photosensitive layer side is preferably 0.3 μm or less, and more preferably 0.1 μm or less, from the viewpoint of more exerting the effect in the present disclosure. It is preferably 0.05 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.

The Ra value on the surface of the support and the cover film is measured by the following method.
Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the support or cover film is measured under the following conditions to obtain a surface profile of the optical film.
As the measurement / analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed with the above analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated, and the Ra value of the surface of the support or the cover film is obtained.
When the support or cover film is attached to the photosensitive layer or the like, the support or cover film may be peeled from the photosensitive layer, and the Ra value of the surface on the peeled side may be measured.

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

[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.

The photosensitive layer is preferably a negative photosensitive layer in which the solubility of the exposed portion in the developing solution is reduced by exposure and the non-exposed portion is removed by development. However, the photosensitive layer is not limited to the negative photosensitive layer, and may be a positive photosensitive layer in which the solubility of the exposed portion in the developing solution is improved by exposure and the exposed portion is removed by development.

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 contains the polymer A, the polymerizable compound, and light. It is particularly preferable to include a polymerization initiator. The photosensitive layer is based on the total mass of the photosensitive layer, and the binder polymer: 10% by mass to 90% by mass; the polymerizable compound: 5% by mass to 70% by mass; and the photopolymerization initiator: 0.01% by mass to It preferably contains 20% by mass.
Hereinafter, each component will be described in order.

(Binder polymer)
The photosensitive layer preferably contains a binder polymer.
The binder polymer is not particularly limited, and for example, a known binder polymer used for an etching resist is preferably used.
Moreover, as a binder polymer, an alkali-soluble polymer can be mentioned.
The alkali-soluble polymer is preferably an alkali-soluble polymer having an acid group.
Among them, as the binder polymer, the polymer A described later is preferable.

-Polymer A-
The binder polymer preferably contains the polymer A.
The polymer A is preferably an alkali-soluble polymer. Alkali-soluble polymers include polymers that are easily soluble in alkaline substances.

The acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and less than 190 mgKOH / g, from the viewpoint of better resolution by suppressing the swelling of the photosensitive layer due to the developing solution. Is more preferable.
The lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, 60 mgKOH / g or more is preferable, 120 mgKOH / g or more is more preferable, 150 mgKOH / g or more is further preferable, and 170 mgKOH / g or more is preferable. Especially preferable.

The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
In the present 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 the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.

The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolution and developability. The weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 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 aggregate and the properties of the unexposed film such as edge fuse property and cut chip property. The weight average molecular weight is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property refers to the degree to which the photosensitive layer easily protrudes from the end face of the roll when the photosensitive transfer member is wound in a roll shape. The cut chip property refers to the degree of ease with which the chip flies when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive transfer member or the like, it will be transferred to the mask in a later exposure step or the like, causing a defective product. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is more preferably 0.0 to 3.0. In the present disclosure, the molecular weight is a value measured using gel permeation chromatography. The degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

The polymer A preferably has an aromatic hydrocarbon group, and has a structural unit having an aromatic hydrocarbon group, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure. Is more preferable. 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, based on the total mass of the polymer A, and is 40%. It is more preferably mass% or more, particularly preferably 45 mass% or more, and most preferably 50 mass% or more. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. When 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.

Examples of the monomer forming 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, acetoxy). Styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.) can be mentioned. Of these, a monomer having an aralkyl group or styrene is preferable. In one embodiment, when the monomer forming 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 20 based on the total mass of the polymer A. It is preferably mass% to 50% by mass, more preferably 25% by mass to 45% by mass, further preferably 30% by mass to 40% by mass, and 30% by mass to 35% by mass. Is particularly preferable. When the photosensitive layer contains a plurality of types of polymers A, the content of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.

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

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

As the monomer having a substituted or unsubstituted benzyl group, a (meth) acrylate having a substituted or unsubstituted benzyl group (for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, etc.); having a benzyl group. Vinyl monomers (eg, vinylbenzyl chloride, vinylbenzyl alcohol, etc.) can be mentioned. Of these, benzyl (meth) acrylate is preferable. In one embodiment, when the monomer forming the structural unit having an aromatic hydrocarbon group in the polymer A is benzyl (meth) acrylate, the content ratio of the structural unit derived from the benzyl (meth) acrylate is the polymer A. It is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and 75% by mass, based on the total mass of the above. It is particularly preferably% to 90% by mass.

The polymer A having a structural unit having an aromatic hydrocarbon group is a monomer having an aromatic hydrocarbon group, at least one of the first monomers described later, and / or a second single amount described later. It is preferably obtained by polymerizing with at least one of the bodies.

The polymer A having no structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and at least one of the first monomers. It is more preferable to obtain it by copolymerizing with at least one of the second monomers described later.

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, preferably 10% by mass to 40% by mass, based on the total mass of the polymer A. It is more preferable, and it is further preferable that it is 15% by mass to 30% by mass.

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. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of exhibiting good developability and controlling edge fuseability, more preferably 15% by mass or more, still more preferably 20% by mass or more. .. It is preferable that the content ratio is 50% by mass or less from the viewpoint of high resolution of the resist pattern and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, it is 35% by mass or less. Is more preferable, 30% by mass or less is further preferable, and 27% by mass or less is particularly preferable.

The second monomer is a monomer that is non-acidic and has at least one ethylenically unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other (meth) acrylates; vinyl acetate Such as vinyl alcohol esters; as well as (meth) acrylonitrile and the like. Of these, 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 constituent unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, preferably 15% by mass to 50% by mass, based on the total mass of the polymer A. It is more preferably 20% by mass to 45% by mass.

Further, the polymer A contains at least one structural unit selected from the group consisting of a structural unit having an aralkyl group and a structural unit derived from styrene, when the focal position at the time of exposure is deviated. It is preferable from the viewpoint of suppressing the line width thickening and the deterioration of the resolution. 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 and the like are preferable.
In one embodiment, the polymer A contains 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 the first monomer, and a second. It is preferable that the polymer contains 30% by mass to 45% by mass of the structural unit derived from the monomer of. In another embodiment, the polymer contains 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 the first monomer. Is preferable.

The polymer A may have any of a linear structure, a branched structure, and 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 by using a monomer having a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. .. 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, and t (meth) acrylate. -Butyl, i-amyl (meth) acrylate, t-amyl (meth) acrylate, isoamyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and (meth) Examples thereof include t-octyl acrylate. Among these, i-propyl (meth) acrylate, i-butyl (meth) acrylate, or t-butyl methacrylate are preferable, and i-propyl methacrylate or t-butyl methacrylate are more preferable.
Specific examples of the monomer having 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. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (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). -3-Methyl-1-adamantyl acrylate, -3,5-dimethyl-1-adamantyl (meth) acrylate, -3-ethyladamantyl (meth) acrylate, -3-methyl-5-methyl (meth) acrylate 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, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-mentanoindene (meth) acrylate-5- Il, Octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, -1-mentyl (meth) acrylate, tricyclodecane (meth) acrylate, -3-hydroxy- (meth) acrylate 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 Examples thereof include acid (nor) bornyl, (meth) acrylate isobornyl, (meth) acrylate fentyl, (meth) acrylate-2,2,5-trimethylcyclohexyl, and (meth) acrylate cyclohexyl.
Among these (meth) acrylic acid esters, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, fentyl (meth) acrylate, -1-mentyl (meth) acrylate or tricyclodecane (meth) acrylate are preferred, cyclohexyl (meth) acrylate, (nor) bornyl (nor) acrylate, ( More preferred are isobornyl acrylate, -2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate.

The photosensitive layer may contain the polymer A alone or in combination of two or more. When two or more kinds are contained, two kinds of the polymer A having an aromatic hydrocarbon group are mixed and used, or the polymer A having an aromatic hydrocarbon group and the polymer A having no aromatic hydrocarbon group are not used. It is preferable to use the polymer A in combination. 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, based on the total mass of the polymer A. It is more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

In the synthesis of polymer A, a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile is prepared by diluting the one or more monomers described above with a solvent such as acetone, methyl ethyl ketone or isopropanol. Is preferably added in an appropriate amount and heated and stirred. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

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 the resolution when the focal position at the time of exposure is deviated. From this viewpoint, the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower. Further, it is preferable to use the polymer A having a Tg of 30 ° C. or higher 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, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. ..

The photosensitive layer may contain a resin other than the polymer A.
Resins other than polymer A include acrylic resins, styrene-acrylic copolymers (however, those having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohols, polyvinyl formal, polyamide resins, polyester resins, and polyamides. Examples thereof include resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The content of the structural unit formed from methacrylic acid in the binder polymer is 40% by mass with respect to the total mass of the binder polymer from the viewpoint of the resolution of the obtained etching pattern and the residue suppression property during development. It is preferably 5% by mass or more and 40% by mass or less, 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. preferable.
Furthermore, the acid value of the binder polymer is preferably 100 mgKOH / g to 200 mgKOH / g from the viewpoint of the resolution of the obtained etching pattern and the residue inhibitory property during development.

The binder polymer may be used alone or in combination of two or more.
The ratio of the binder polymer to 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 further preferably 40% by mass to 60% by mass. %. It is preferable that the ratio of the binder polymer to the photosensitive layer is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the ratio of the binder polymer to the photosensitive layer is 10% by mass or more from the viewpoint of improving the edge fuse resistance.

(Polymerizable compound)
The photosensitive layer preferably contains a polymerizable compound.
As used herein, the term "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.

As the polymerizable compound, an ethylenically unsaturated compound is preferable.
The ethylenically unsaturated compound is a component that contributes to the photosensitivity (that is, photocurability) of the negative photosensitive layer and the strength of the cured film.
The ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.
The photosensitive layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound as the ethylenically unsaturated compound.
Here, the bifunctional or higher functional 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.

The photosensitive layer preferably contains a polymerizable compound having a polymerizable group.
The polymerizable group contained in the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction, and has, for example, an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group. Groups; and groups having a cationically 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 metaacryloyl group is more preferable.

As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferable in that the photosensitive layer is more photosensitive, and two or more ethylenically in one molecule. A compound having an unsaturated group (polyfunctional ethylenically unsaturated compound) is more preferable.
Further, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.

The photosensitive layer is bifunctional or trifunctional ethylenically having two or three ethylenically unsaturated groups in one molecule in that the photosensitive layer has a better balance of photosensitivity, resolution and peelability. It is preferable to contain an unsaturated compound, and more preferably to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.
The content of the bifunctional ethylenically unsaturated compound in the photosensitive layer with respect to the content of the polymerizable compound is preferably 60% by mass or more, more preferably more than 70% by mass, and more preferably 90% by mass or more from the viewpoint of excellent peelability. Is more preferable. 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.
Further, as the ethylenically unsaturated compound, a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.

-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-mentioned polymerizable compounds.

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

Examples of the aromatic ring contained in the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring. Heterocycles and fused rings thereof are mentioned, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable. The aromatic ring may have a substituent.
The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive layer due to the developing solution.
Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane). Examples thereof include an F structure and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and a bisphenol A structure is preferable.

Examples of the polymerizable compound B1 having a bisphenol structure include a compound 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 alkyleneoxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferable, and 6 to 14 is more preferable.
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 in the present specification.

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 the 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.). Co., Ltd.), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, Shin-Nakamura Chemical Industry Co., Ltd.) (Manufactured by Co., Ltd.), 2,2-bis (4- (methacryloxidodecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, manufactured by Hitachi Kasei Co., Ltd.), 2,2-bis (4- (methacryloxypentadeca) Ethoxy) phenyl) propane (BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ), And ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

The polymerizable compound B1 has the following general formula (I):

{In the equation, R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ and n ₃ are independent, respectively. An integer of 1 to 39, n ₁ + n ₃ _{is an integer of 2 to 40, n 2 and n 4} are independently integers of 0 to 29, and n 2 + n 4 is an integer of 0 to 30. The sequence of repeating units of-(AO)-and-(BO)-may be random or block. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side. }
The compound represented by is used.
In one embodiment, n ₁ + n ₂ + n ₃ + n ₄ is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n ₂ + n ₄ is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.

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 more excellent resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which components in the photosensitive layer, particularly binder polymer, etc., exude from the end of the transfer member). Is more preferable.

The photosensitive layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.
The polymerizable compound other than the polymerizable compound B1 is not particularly limited, and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound. Examples include compounds.

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

Examples of the bifunctional 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. Be done.
Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). ), 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry 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. 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) Can be mentioned.

Examples of trifunctional or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples thereof include acrylates, ditrimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, tri (meth) acrylates of isocyanurates, glycerintri (meth) acrylates, and modified alkylene oxides 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. , "(Tri / tetra) (meth) acrylate" is a concept that includes tri (meth) acrylate and tetra (meth) acrylate. In one embodiment, the photosensitive layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. More preferably, it contains a compound. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound is (total mass of the polymerizable compound B1): (total mass of the trifunctional or higher ethylenically unsaturated compound) = 1: 1. It is preferably ~ 5: 1, more preferably 1.2: 1 to 4: 1, and even more preferably 1.5: 1 to 3: 1.
In one embodiment, the photosensitive layer preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified product of the trifunctional or higher-functional ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). -9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. (Registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toa Synthetic Co., Ltd.), Aronix M- 520 (manufactured by Toa Synthetic Co., Ltd.) and Aronix M-510 (manufactured by Toa Synthetic Co., Ltd.) can be mentioned.

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

The value of the ratio Mm / Mb of the content Mm of the polymerizable compound and the content Mb of the binder polymer in the photosensitive layer is 1.0 from the viewpoint of the resolution of the obtained etching pattern and the residue suppression property during development. It is preferably less than or equal to, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less.
Further, the polymerizable compound in the photosensitive layer preferably contains a (meth) acrylic compound from the viewpoint of curability and the resolution of the obtained etching pattern.
Further, the polymerizable compound in the photosensitive layer contains a (meth) acrylic compound and is contained in the photosensitive layer from the viewpoint of curability, resolution of the obtained etching pattern, and residue suppression during development. It is more preferable that the content of the acrylic compound with respect to the total mass of the (meth) acrylic compound is 60% by mass or less.

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% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and 20% by mass to 50% by mass with respect to the total mass of the photosensitive layer. More preferred.

The weight average molecular weight (Mw) of the polymerizable compound containing the polymerizable compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

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

-Photopolymerization initiator-
The photosensitive layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound by receiving active rays such as ultraviolet rays, visible rays and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.

Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.

Further, the photosensitive layer is a 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolvability, and a dimer thereof. It preferably contains at least one selected from the group consisting of derivatives. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2 -(P-Methenylphenyl) -4,5-diphenylimidazole dimer can be mentioned.

As the photoradical polymerization initiator, for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783 may be used.

Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and TAZ-110 (trade name:). Midori Kagaku Co., Ltd., Benzoinone, TAZ-111 (trade name: Midori Kagaku Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (BASF), Omnirad 651 and 369 (trade name: IGM Resins B.V.) , And 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) Be done.

Examples of commercially available photoradical polymerization initiators include 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-. 01, manufactured by BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (Product name: Omnirad 379EG, IGM Resins BV), 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Product name: Omnirad 907, IGM Resins BV) , 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins B. V.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: Omnirad 369, IGM Resins B.V.), 2-hydroxy-2-methyl- 1-Phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins VV), 1-hydroxycyclohexylphenylketone (trade name: Omnirad 184, manufactured by IGM Resins VV), 2,2- Dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins VV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H,) IGM Resins B.V.), Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name: Omnirad 819, IGM Resins B.V.), Oxime ester-based photopolymerization initiator ( Product 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 ) (Product name: B-CIM, manufactured by Hampford) and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.). ..

A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid by receiving active light. As the photocationic polymerization initiator, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable, but its chemical structure is not limited. In addition, a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is used. The generated photocationic polymerization initiator is particularly preferable. The lower limit of pKa is not particularly defined, but is preferably -10.0 or higher, for example.

Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, the diazomethane compound and the imide sulfonate compound, the compounds described in paragraphs 0083 to 0088 of JP2011-221494 may be used. Further, as the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.

The photosensitive layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

The photosensitive layer may contain one type of photopolymerization initiator alone, or may contain two or more types of photopolymerization initiators.
The content of the photopolymerization 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 1.0% by mass, based on the total mass of the photosensitive layer. % Or more is more preferable. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

-Dye-
The photosensitive layer has 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 from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. , It is preferable to contain a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (also simply referred to as "dye N"). When the dye N is contained, the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, the support and the intermediate layer) is improved, and the resolution is more excellent.

In the present specification, the term "the maximum absorption wavelength is changed by an acid, a base or a radical" means that the dye in a color-developing state is decolorized by an acid, a base or a radical, and the dye in a decolorized state is an acid. It may mean any aspect of a mode in which a color is developed by a base or a radical, or a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
Specifically, the dye N may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize. In this case, the dye may change the state of color development or decolorization by generating and acting on the acid, base or radical in the photosensitive layer by exposure, and the state in the photosensitive layer by the acid, base or radical (for example). It may be a dye whose color development or decolorization state changes by changing pH). Further, it may be a dye that changes the state of color development or decolorization by directly receiving an acid, a base or a radical as a stimulus without exposure.

Among them, from the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.
From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the photosensitive layer preferably contains both a dye whose maximum absorption wavelength is changed by radicals as dye N and a photoradical polymerization initiator. ..
Further, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by an acid, a base, or a radical.

As an example of the color development mechanism of the dye N in the present disclosure, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive layer, and photoradical polymerization is started after exposure. Examples thereof include an embodiment in which a radical-reactive dye, an acid-reactive dye or a base-reactive dye (for example, a leuco dye) is colored by a radical, acid or base generated from an agent, a photocationic polymerization initiator or a photobase generator.

From the viewpoint of visibility of the exposed and unexposed areas, the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, more preferably 550 nm to 700 nm. It is more preferably about 650 nm.
Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of the dye N is transmitted by a solution containing the dye N (liquid temperature 25 ° C.) in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere. It is obtained by measuring the spectrum and detecting the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength).

Examples of the dye that develops or decolorizes by exposure include leuco compounds.
Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes and anthraquinone dyes.
As the dye N, a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton. Leuco compounds (diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (rodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide dyes), and leukooramine skeletons. Examples thereof include leuco compounds having leuco compounds (leuco auramine dyes).
Among them, a triarylmethane dye or a fluorane dye is preferable, and a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye is more preferable.

The leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion. As a result, the lactone ring, sultin ring, or sulton ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a ring-closed state. The color can be decolorized or the leuco compound can be changed to an open ring state to develop a color. The leuco compound preferably has a lactone ring, a sultone ring or a sultone ring, and the lactone ring, the sultone ring or the sultone ring is opened by a radical or an acid to develop a color. A compound in which the lactone ring is opened to develop color is more preferable.

Examples of the dye N include the following dyes and leuco compounds.
Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuxin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, timol sulfophthalein, xylenol blue, and methyl. Orange, paramethyl red, congofred, benzopurpurin 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl violet, malakite green, parafuxin, Victoria pure blue-naphthalene sulfonate, Victoria pure blue BOH Tsuchiya Chemical Industry Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green # 502 (manufactured by Orient Chemical Industry Co., Ltd.) ), Spiron Red BEH Special (manufactured by Hodoya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rodamine B, rodamine 6G, sulfolodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxy Anilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylamino Examples thereof include phenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the leuco compound among the dyes N include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, and malakite green lactone. Benzoyl leucomethylene blue, 2- (N-phenyl-N-methylamino) -6- (Np-tolyl-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p) -Truizino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methyl) Amino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7 -Xylidinofluorane, 3- (N, N-diethylamino) -6-methyl-7-chlorofluorane, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N) , N-diethylamino) -7- (4-chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7,8-benzofluorolane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6 -Methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl- 2-Methylindole-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethyl Aminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-zaphthalide, 3- (4-diethylaminophenyl) -3-( 1-ethyl-2-methylindole-3-yl) phthalide and 3', 6'-bis (diphenylamino) spirisobenzofuran-1 (3H), 9'-[9H] xanthen-3-one. Be done.

The dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. Is more preferable.
As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate is preferable.

The dye N may be used alone or in combination of two or more.
The content of the dye N is preferably 0.1% by mass or more with respect to the total mass of the photosensitive layer from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution. , 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.

The content of the dye N means the content of the dye when all of the dye N contained in the photosensitive layer is in a colored state. Hereinafter, a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
Two kinds of solutions in which 0.001 g and 0.01 g of the dye are dissolved in 100 mL of methyl ethyl ketone are prepared. A photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Then, in an atmospheric atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive layer, the content of the dye contained in the photosensitive layer is calculated based on the calibration curve.

-Thermal crosslinkable compound-
The photosensitive layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In this specification, the heat-crosslinkable compound having a polymerizable group described later is not treated as a polymerizable compound, but is treated as a heat-crosslinkable compound.
Examples of the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the binder polymer and / or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film becomes There is a tendency for the function to be enhanced when a film obtained by lowering and curing the photosensitive layer is used as a protective film.
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".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 ° C. to 160 ° C., more preferably 130 ° C. to 150 ° C.
The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with 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 to this.

Examples of the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. include active methylene compounds [malonic acid diester (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonate, etc.)] and oxime compounds. (A compound having a structure represented by -C (= N-OH)-in the molecule such as formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, and cyclohexanoneoxime) can be mentioned.
Among these, the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. preferably contains, for example, an oxime compound from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred material.
The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurate-forming and protecting hexamethylene diisocyanate.
Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and has a smaller development residue. It is preferable from the viewpoint of ease.

The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferable.
Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group and a styryl group, and a group having an epoxy group such as a 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 further preferable.

As the blocked isocyanate compound, a commercially available product can be used.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and block. Duranate series of types (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.) can be mentioned.
Further, as the blocked isocyanate compound, a compound having the following structure can also be used.

The heat-crosslinkable compound may be used alone or in combination of two or more.
When the photosensitive layer contains a heat-crosslinkable compound, the content of the heat-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. preferable.

-Surfactant-
The photosensitive layer preferably contains a surfactant from the viewpoint of thickness uniformity.
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, silicone-based nonionic surfactants, and fluorine-based nonionics. Examples include sex surfactants.
The photosensitive layer preferably contains a fluorine-based nonionic surfactant from the viewpoint of being more excellent in resolution. It is considered that the photosensitive layer contains a fluorine-based nonionic surfactant to suppress the penetration of the etching solution into the photosensitive layer and reduce the side etching.
Examples of commercially available fluorine-based nonionic surfactants include Megafuck F-551-A, F-552 and F-554 (all manufactured by DIC Corporation).

Examples of the surfactant include the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and JP-A-2009-237362. The surfactants described in paragraphs 0060 to 0071 can also be used.
Further, as the surfactant, a nonionic surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.

Commercially available products of fluorine-based surfactants include, for example, Megafuck (trade names) 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 (above, manufactured by DIC Co., Ltd.), Florard (trade name) FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Co., Ltd.), PolyFox (Product Name) PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), Futagent (Product Name) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F , 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by Neos Co., Ltd.) and the like.
In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cut and the fluorine atom is volatilized. Can be preferably used. Examples of such fluorine-based surfactants include Megafuck (trade name) DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)). For example, Megafuck (trade name) DS-21 can be mentioned.

Further, as the fluorine-based surfactant, 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.
A block polymer can also be used as the fluorine-based surfactant. The fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a structural unit derived from an acrylate compound can also be preferably used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Megafuck (trade name) RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
As the fluorine-based surfactant, 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 a substitute material of perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) as the fluorine-based surfactant.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and the like. 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 (above, manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (above, manufactured by BASF), Solspers (trade name) 20000 (above, Nippon Lubrizol Co., Ltd.) , NCW-101, NCW-1001, NCW-1002 (above, manufactured by Fujifilm Wako Junyaku Co., Ltd.), Pionin (trade name) D-6112, D-6112-W, D-6315 (above, Takemoto) Oils and fats (manufactured by Nissin Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.) and the like can be mentioned.

Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.
Specific examples of silicone-based surfactants include DOWNSIL (trade name) 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400. (The above is manufactured by Toray Dow Corning Co., Ltd.), X-22-4952, X-22-2272, 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 Industry Co., Ltd.), F-4440 , TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like.

The photosensitive layer may contain one type of surfactant alone or two or more types.
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.

-Additive-
In addition to the above components, the photosensitive layer may contain a known additive, if necessary.
Examples of the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, benzotriazoles, carboxybenzotriazoles, a resin other than polymer A, and a solvent. The photosensitive layer may contain each additive alone or in combination of two or more.

The photosensitive layer may contain a radical polymerization inhibitor.
Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Of these, phenothiazine, phenothiazine or 4-methoxyphenol is preferable. Examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. It is preferable to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the photosensitive layer.

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

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole and the like. As the carboxybenzotriazoles, for example, a commercially available product such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.

The total content of the radical polymerization inhibitor, benzotriazols, and carboxybenzotriazols is preferably 0.01% by mass to 3% by mass when the total mass of the photosensitive layer is 100% by mass. Yes, more preferably 0.05% by mass to 1% by mass. It is preferable that the content is 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive layer. On the other hand, it is preferable to set the content to 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.

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, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclydin compounds.

The photosensitive layer may contain one kind of sensitizer alone or two or more kinds.
When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing 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 with respect to the total mass of the photosensitive layer.

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 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.

The photosensitive layer may contain a solvent. When the photosensitive layer is formed by a photosensitive composition containing a solvent, the solvent may remain in the photosensitive layer.

In addition, the photosensitive layer includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, etc. It may further contain known additives such as cross-linking agents and organic or inorganic anti-precipitation agents.
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 in the present specification.

(Physical characteristics, etc.)
The thickness (layer thickness) of the photosensitive layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, further preferably 0.5 μm to 50 μm, further preferably 0.5 μm to 30 μm, and 1 μm to 1 μm. 20 μm is particularly preferable, and 2 μm to 10 μm is most preferable. As a result, the developability of the photosensitive layer can be improved, and the resolvability can be improved.
The thickness of each layer included in the photosensitive transfer member was obtained 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). It is measured by measuring the thickness of each layer at 10 points or more based on the image and calculating the average value thereof.

Further, from the viewpoint of excellent adhesion, the transmittance of light having a wavelength of 365 nm in 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.

(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. Of these, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.

The content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, 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.

As a method of setting impurities in the above range, it is possible to select a material having a low content of impurities as a raw material of the photosensitive layer, prevent impurities from being mixed in when forming the photosensitive layer, and wash and remove the impurities. Can be mentioned. By such a method, the amount of impurities can be kept within the above range.

The impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

The content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive layer should be low. Is preferable. The content of these compounds in the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis. The lower limit is based on mass and can be 10 ppb or more, and can be 100 ppb or more. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measurement method.

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 laminateability.

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

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

(Formation method)
The method for forming the photosensitive layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
As a method for forming the photosensitive layer, for example, a photosensitive composition containing a binder polymer, a polymerizable compound and a solvent is prepared, the photosensitive composition is applied to the surface of a support or the like, and the photosensitive composition is applied. Examples thereof include a method of forming the film by drying it.

Examples of the photosensitive composition used for forming the photosensitive layer include a binder polymer, a polymerizable compound, and a composition containing the above-mentioned 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.

-solvent-
The solvent contained in the photosensitive composition is not particularly limited as long as the binder polymer, the polymerizable compound and the above optional components can be dissolved or dispersed, and known solvents can be used.
Examples of the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (methanol, ethanol, etc.), a ketone solvent (acetone, methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (toluene, etc.), and an aprotonic polar solvent. Examples thereof include (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetrahydrofuran, etc.), an ester solvent, an amide solvent, a lactone solvent, and a mixed solvent 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 is at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It preferably contains seeds. Among them, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable. A mixed solvent containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and at least three cyclic ether solvents is more preferable.

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 solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used, and the contents thereof are described in the present specification. Incorporated into the book.

The photosensitive composition may contain one type of solvent alone, or may contain two or more types of solvent.
The content of the solvent when the photosensitive composition is applied is preferably 50 parts by mass to 1,900 parts by mass, 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. More preferred.

The method for preparing the photosensitive composition is not particularly limited. For example, a photosensitive composition is prepared by preparing a solution in which each component is dissolved in the above solvent in advance and mixing the obtained solution in a predetermined ratio. There is a way to do it.
The photosensitive composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the photosensitive layer.

The method for applying the photosensitive composition is not particularly limited, and the photosensitive composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating and inkjet coating.
Further, the photosensitive layer may be formed by applying the photosensitive composition on a cover film described later and drying it.

[Thermoplastic resin layer]
The 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 the photosensitive transfer member with a thermoplastic resin layer between the support and the photosensitive layer, the followability to the substrate at the time of bonding to the substrate is improved, and the space between the substrate and the photosensitive transfer member is improved. This is because the mixing of air bubbles is suppressed and the adhesion to the adjacent layer (for example, the support) is improved.

(Alkali-soluble resin)
The thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin.
In the present specification, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution 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, and polyhydroxystyrene resin. Examples thereof include polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
Here, the acrylic resin was 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) acrylic acid amide. It means a resin having at least one structural unit.
As the acrylic resin, the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is that of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass.
Above all, the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. , 50% by mass to 100% by mass, more preferably.

Further, 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, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and further preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more.
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.

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, among the polymers described in paragraphs 0025 of JP2011-95716A, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, described in paragraphs 0033 to 0052 of JP2010-237589. Acrylic resin containing a carboxy group having an acid value of 60 mgKOH / g or more, and a carboxy group having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP2016-224162A. Acrylic resin can be mentioned.
The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 12 by mass, based on the total mass of the acrylic resin. More preferably, it is by mass% to 30% by mass.
As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.

The alkali-soluble resin may have a reactive group. The reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; and a polyadditive reactive group such as an epoxy group and a (block) isocyanate group are used. Can be mentioned.

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 even more preferably 20,000 to 50,000.

The thermoplastic resin layer may contain one kind of alkali-soluble resin alone or two or more kinds.
The content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, preferably 20% by mass to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. Is more preferable, 40% by mass to 80% by mass is further preferable, and 50% by mass to 70% by mass is particularly preferable.

(Dye)
The thermoplastic resin layer 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 is changed by an acid, a base, or a radical. It is preferable to do so.
The preferred embodiment of the dye B is the same as the preferred embodiment of the dye N except for the points described later.

From the viewpoint of visibility and resolution of the exposed and unexposed areas, the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid. ..
The thermoplastic resin layer is both a dye whose maximum absorption wavelength changes depending on the acid as the dye B and a compound that generates an acid by light, which will be described later, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. Is preferably contained.

The dye B may be used alone or in combination of two or more.
The content of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass to 6% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed part and the non-exposed part. More preferably, 0.2% by mass to 5% by mass is further preferable, and 0.25% by mass to 3.0% by mass is particularly preferable.

Here, the content of the dye B means the content of the dye when all the dyes B contained in the thermoplastic resin layer are in a colored state. Hereinafter, a method for quantifying the content of dye B will be described by taking a dye that develops color by radicals as an example.
A solution in which 0.001 g and 0.01 g of the dye are dissolved in 100 mL of methyl ethyl ketone is prepared. A photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Then, in an atmospheric atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.

(Compounds that generate acids, bases or radicals with light)
The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (also simply referred to as “Compound C”).
As the compound C, a compound that generates an acid, a base, or a radical by receiving active rays such as ultraviolet rays and visible rays is preferable.
As the compound C, a known photoacid generator, photobase generator, and photoradical polymerization initiator (photoradical generator) can be used. Of these, a photoacid generator is preferred.

-Photoacid generator-
The thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution.
Examples of the photoacid generator include a photocationic polymerization initiator that may be contained in the above-mentioned photosensitive layer, and the preferred embodiments are the same except for the points described below.

The photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and preferably contains sensitivity, resolution and resolution. From the viewpoint of adhesion, it is more preferable to contain an oxime sulfonate compound.
Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.

-Photoradical polymerization initiator-
The thermoplastic resin layer may contain a photoradical polymerization initiator (photoradical polymerization initiator).
Examples of the photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the photosensitive layer described above, and the preferred embodiment is also the same.

-Photobase generator-
The thermoplastic resin layer may contain a photobase generator.
The photobase generator is not particularly limited as long as it is a known photobase generator, and for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyloxime, [[(2,2). 6-Dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4) -Morphorinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 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 can be mentioned.

The thermoplastic resin layer may contain the compound C alone or in combination of two or more.
The content of compound C is preferably 0.1% by mass to 10% by mass, preferably 0.5% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility and resolution of the exposed and unexposed areas. More preferably, it is by mass% to 5% by mass.

(Plasticizer)
The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
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 of the plasticizer (weight average molecular weight (Mw)) 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, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and is a polyalkylene glycol. Compounds are more preferred. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

Further, the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution and adhesion to the 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 a plasticizer include the (meth) acrylate compound described as the polymerizable compound 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 the thermoplastic resin layer and the photosensitive layer contain the same (meth) acrylate compound, respectively, so that the diffusion of components between the layers is suppressed and the storage stability is improved.

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

The thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizer.
The content of the plasticizer is preferably 1% by mass to 70% by mass and 10% by mass to 60% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of resolution, adhesion to adjacent layers and developability. By mass% is more preferable, and 20% by mass to 50% by mass is particularly preferable.

(Surfactant)
The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
Examples of the surfactant include surfactants that may be contained in the above-mentioned photosensitive layer, and the preferred embodiment is the same.

The thermoplastic resin layer may contain one type of surfactant alone or two or more types.
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.

(Sensitizer)
The thermoplastic resin layer may contain a sensitizer.
The sensitizer is not particularly limited, and examples thereof include a sensitizer that may be contained in the above-mentioned photosensitive layer.

The thermoplastic resin layer may contain one type of sensitizer alone or two or more types.
The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and non-exposed areas, 0.01 mass with respect to the total mass of the thermoplastic resin layer. The range of% to 5% by mass is preferable, and the range of 0.05% by mass to 1% by mass is more preferable.

(Additives, etc.)
In addition to the above components, the thermoplastic resin layer may contain known additives, if necessary.
Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-85643, and the contents described in this publication are incorporated in the present specification.

(Physical characteristics, etc.)
The layer thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers. The upper limit is not particularly limited, but from the viewpoint of developability and resolution, 20 μm or less is preferable, 10 μm or less is more preferable, and 5 μm or less is further preferable.

(Formation method)
The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
As a method for forming the thermoplastic resin layer, for example, a thermoplastic resin composition containing the above components and a solvent is prepared, the thermoplastic resin composition is applied to the surface of a support or the like, and the thermoplastic resin composition is formed. Examples thereof include a method of forming the coating film by drying.
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.

-solvent-
The solvent contained in the thermoplastic resin composition is not particularly limited as long as the above-mentioned components contained in the thermoplastic resin layer can be dissolved or dispersed.
Examples of the solvent contained in the thermoplastic resin composition include solvents that may be contained in the above-mentioned photosensitive composition, and preferred embodiments are also the same.

The solvent contained in the thermoplastic resin composition may be one kind alone or two or more kinds.
The content of the solvent when the thermoplastic resin composition is applied is preferably 50 parts by mass to 1,900 parts by mass, preferably 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition. The portion is more preferable.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the method for preparing the photosensitive composition and the method for forming the photosensitive layer described above.
For example, a solution in which each component contained in the thermoplastic resin layer is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to prepare a thermoplastic resin composition.
The thermoplastic resin layer is formed by applying the obtained thermoplastic resin composition to the surface of the support and drying the coating film of the thermoplastic resin composition.
Further, after forming the photosensitive layer and the intermediate layer on the cover film described later, the thermoplastic resin layer may be formed on the surface of the intermediate layer.

[Middle layer]
The laminate may have an intermediate layer between the thermoplastic resin layer and the photosensitive layer. The photosensitive transfer member has an intermediate layer between the thermoplastic resin layer and the photosensitive layer. Is preferable. By having the intermediate layer, it is possible to suppress the mixing of the components when the plurality of layers are applied and when the layers are stored after application.
The intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application.
In the present specification, "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.

Examples of the intermediate layer include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-72724. When the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, which is preferable.
The oxygen blocking layer used as the intermediate layer may be appropriately selected from the known layers described in the above publications and the like. Of these, an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.

The intermediate layer preferably contains a resin.
Examples of the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and their common weights. Examples include resins such as coalescence.
As the resin contained in the intermediate layer, a water-soluble resin is preferable.
Further, the resin contained in the intermediate layer includes the polymer A contained in the photosensitive layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer from the viewpoint of suppressing the mixing of the components between the plurality of layers. ), It is preferable that the resin is different from any of the above.

The intermediate layer preferably contains polyvinyl alcohol from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application, and contains both polyvinyl alcohol and polyvinylpyrrolidone. It is more preferable to contain it.

The intermediate layer may contain the above resin alone or in combination of two or more.
The content of the resin in the intermediate layer is not particularly limited, but is based on the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing the mixing of components during application of the plurality of layers and storage after application. , 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
Further, the intermediate layer may contain an additive such as a surfactant, if necessary.

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 blocking property is not lowered, the mixing of the components at the time of applying the plurality of layers and at the time of storage after application can be suppressed, and the intermediate during development. This is because an increase in layer removal time can be suppressed.

The method for forming the intermediate layer is not particularly limited, and for example, an intermediate layer composition containing the above resin and any additive is prepared and applied to the surface of the thermoplastic resin layer or the photosensitive layer to form the intermediate layer composition. A method of forming an intermediate layer by drying the coating film of the above 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.

The solvent contained in the intermediate layer composition is not particularly limited as long as the above resin can be dissolved or dispersed, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water or water or water is preferable. 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, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.

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

Examples of the material constituting the cover film include a resin film and paper, and a resin film is preferable from the viewpoint of strength and flexibility.
Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable.

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.
Further, the arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive layer (hereinafter, also simply referred to as “the surface of the cover film”) is preferably 0.3 μm or less from the viewpoint of excellent resolution. It is more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. It is considered that when the Ra value on 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 on the surface of the cover film is not particularly limited, but is preferably 0.001 μm or more.

The photosensitive transfer member may include a layer other than the above-mentioned layer (hereinafter, also referred to as “other layer”). Other layers include, for example, a contrast enhancement layer.
The contrast enhancement layer is described in paragraph 0134 of WO 2018/179640. Further, 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 by reference.

The total thickness of each layer of the photosensitive transfer member excluding the support and the cover film is preferably 20 μm or less, more preferably 10 μm or less, and 8 μm or less from the viewpoint of further exerting the effects in the present disclosure. It is more preferably 2 μm or more and 8 μm or less.
Further, 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, and more preferably 10 μm or less, from the viewpoint of further exerting the effects in the present disclosure. It is more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

(Relationship between support, photosensitive layer and cover film)
The laminate having a photosensitive layer used in the present disclosure is
The breaking elongation 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.
The arithmetic mean roughness Ra of the surface of the cover film on the photosensitive layer side is preferably 150 nm or less.

Further, 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 at 120 ° C. of the cured film obtained by curing the photosensitive layer, and Y is the arithmetic mean of the surface of the support on the photosensitive layer side. Represents the value of roughness Ra (nm).
X × Y is more preferably 750 or less.

It is preferable that the breaking elongation at 120 ° C. is twice or more larger than the breaking elongation at 23 ° C. of the cured film obtained by curing the photosensitive layer.
The elongation at break was determined by exposing a photosensitive layer having a thickness of 20 μm to 120 mJ / cm ² with an ultra-high pressure mercury lamp and curing it, then further exposing it to 400 mJ / cm ² with a high pressure mercury lamp and heating it at 145 ° C. for 30 minutes. Measured by a tensile test using the cured film of.

Further, 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 arithmetic mean roughness Ra value (nm) of the surface of the support on the photosensitive layer side, and Z is the arithmetic of the surface of the cover film on the photosensitive layer side. It represents the value (nm) of the average roughness Ra.

[Manufacturing method of photosensitive transfer member]
The method for producing the photosensitive transfer member (laminate having the photosensitive layer) used in the present disclosure is not particularly limited, and a known production method, for example, a known method for forming each layer can be used.
Hereinafter, a method for manufacturing the photosensitive transfer member used in the present disclosure will be described with reference to FIG. However, the photosensitive transfer member used in the present disclosure is not limited to the one having the configuration shown in FIG.
FIG. 2 is a schematic view showing an example of the configuration of the photosensitive transfer member used in the present disclosure. The photosensitive transfer member 100 shown in FIG. 2 has a structure 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.

As a method for producing the photosensitive transfer member 100, for example, the thermoplastic resin layer 12 is formed by applying the thermoplastic resin composition to the surface of the support 10 and then drying the coating film of the thermoplastic resin composition. And the step of applying the intermediate layer composition to the surface of the thermoplastic resin layer 12 and then drying the coating film of the intermediate layer composition to form the intermediate layer 14, and the step of forming the intermediate layer 14 and the binder on the surface of the intermediate layer 14. Examples thereof include a method including a step of applying a photosensitive composition containing a polymer and a polymerizable compound, and then drying a coating film of the photosensitive composition to form a photosensitive layer 16.
In the above production method, it is selected from the group consisting of 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, and a water- and water-mixable organic solvent. An intermediate layer composition containing at least one of the above, and a photosensitive composition containing at least one selected from the group consisting of a binder polymer, a polymerizable compound, and an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to use. As a result, the components contained in the thermoplastic resin layer 12 during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and / or the storage period of the laminate having the coating film of the intermediate layer composition. Mixing with the components contained in the intermediate layer 14 can be suppressed, and the coating of the photosensitive composition on the surface of the intermediate layer 14 and / or the storage period of the laminate having the coating film of the photosensitive composition. In, the mixing of the component contained in the intermediate layer 14 and the component contained in the photosensitive layer 16 can be suppressed.

The photosensitive transfer member 100 is manufactured by pressing the cover film 18 onto the photosensitive layer 16 of the laminate manufactured by the above manufacturing method.
The method for manufacturing the photosensitive transfer member used in the present disclosure includes a step of providing a cover film 18 so as to be in contact with the second surface of the photosensitive layer 16, thereby including a support 10, a thermoplastic resin layer 12, and an intermediate layer. 14. It is preferable to manufacture the photosensitive transfer member 100 including the photosensitive layer 16 and the cover film 18.
After manufacturing the photosensitive transfer member 100 by the above manufacturing method, the photosensitive transfer member 100 in the form of a roll may be manufactured and stored by winding the photosensitive transfer member 100. The roll-type photosensitive transfer member can be provided as it is for bonding with a substrate in a roll-to-roll method.

Further, the photosensitive transfer member obtained by the method for manufacturing a cut product according to the present disclosure can be suitably used for manufacturing a circuit wiring and a display device such as a touch panel.

Further, the photosensitive transfer member obtained by the method for producing a cut product according to the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography. After patterning the photosensitive layer, the photosensitive layer may be used as a coating for etching, or electroforming may be performed mainly by electroplating. Further, the cured film obtained by patterning may be used as a permanent film, or may be used as, for example, an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, or the like. Further, the photosensitive transfer member obtained by the method for manufacturing a cut product according to the present disclosure includes various wiring forming applications for semiconductor packages, printed circuit boards, sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, and the like. It can be suitably used for applications such as formation of structures in the fields of liquid crystal sealing materials, micromachines or microelectronics.

Further, as the laminate of the embodiment A, an embodiment in which the photosensitive layer is a colored resin layer containing a pigment is also preferably mentioned.
In addition to the above, the colored resin layer is used for, for example, a liquid crystal display (LCD) and a color used for a solid-state image sensor [for example, a CCD (charge-coupled device) and a CMOS (complementary metal oxide semiconductor)]. It is suitable for forming colored pixels such as filters or a black matrix.
In recent years, the liquid crystal display window of an electronic device may be provided with a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like in order to protect the liquid crystal display window. be. A colored resin layer can be used to form such a light-shielding layer.
Aspects other than the pigment in the colored resin layer are the same as those described above.

<Pigment>
The pigment used for the colored resin layer may be appropriately selected according to a desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Above all, when forming a black pattern, a black pigment is preferably selected as the pigment.

As the black pigment, a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effect in the present disclosure is not impaired. 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 preferable. As the carbon black, from the viewpoint of surface resistance, carbon black in which at least a part of the surface is coated with a resin is preferable.

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

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

When the photosensitive layer is a colored resin layer, it is also preferable that the photosensitive layer further contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, in that the dispersibility is more excellent.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite. -Errow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (C) I. Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment) Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Above all, C.I. I. Pigment Red 177 is preferred.

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, based on the total mass of the photosensitive layer. It is 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.

When the photosensitive layer contains a pigment other than the black pigment (white pigment and chromatic pigment), the content of the pigment other than the black pigment is preferably 30% by mass or less, preferably 1% by mass to 20% by mass, based on the black pigment. The mass% is more preferable, and 3% by mass to 15% by mass is further preferable.

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 introduced into the photosensitive composition in the form of a pigment dispersion. Is preferable.
The dispersion liquid may be prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser. 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 portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.

The disperser is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force. For the disperser and fine pulverization, the description in "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310) can be referred to.

[[Laminate of Embodiment B]]
Hereinafter, the laminated body of the embodiment B will be described with an example.
Hereinafter, each element constituting the laminated body of the embodiment B will be described.
The support and cover film used for the laminate of Embodiment B are the same as the support and cover film of the laminate of Embodiment A, and the preferred embodiment is also the same.

[Photosensitive layer]
The photosensitive transfer member has a photosensitive layer.
A pattern can be formed on the transfer target by transferring the photosensitive layer onto the transfer target and then exposing and developing the photosensitive layer.
Hereinafter, the components that can be contained in the photosensitive layer will be described in detail.

(Binder polymer)
The photosensitive layer preferably contains a binder polymer.
Examples of the binder polymer include (meth) acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and the reaction of epoxy resin with (meth) acrylic acid. Examples thereof include the obtained epoxy acrylate resin and the acid-modified epoxy acrylate resin obtained by reacting the epoxy acrylate resin with the acid anhydride.
Further, the binder polymer is preferably an alkali-soluble resin.

One of the preferred embodiments of the binder polymer is a (meth) acrylic resin in that it is excellent in alkali developability and film forming property.
In the present specification, the (meth) acrylic resin means a resin having a structural unit derived from the (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, 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 of only structural units derived from the (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 with respect to all the structural units of the (meth) acrylic resin.

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 (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester. ) Acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate. Meta) Acrylic acid alkyl esters are preferred.
Examples of (meth) acrylamide include acrylamide such as diacetone acrylamide.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth). Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as dodecyl (meth) acrylic acid.
As the (meth) acrylic acid ester, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.

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 the (meth) acrylic compound that is copolymerizable with the (meth) acrylic compound, and is, for example, styrene, vinyltoluene, and α. -Styrene compounds such as methylstyrene which may have a substituent at the α-position or aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic acid anhydride, monomethyl maleate, maleic acid Examples thereof include monoethyl and maleic acid monoesters such as monoisopropyl maleate, fumaric acid, silicic acid, α-cyanosilicic acid, itaconic acid, and crotonic acid.
These polymerizable monomers may be used alone or in combination of two or more.

Further, the (meth) acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving the alkali developability. 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.

The content of the constituent unit having an acid group (preferably the constituent unit derived from (meth) acrylic acid) in the (meth) acrylic resin is excellent in developability with respect to the total mass of the (meth) acrylic resin. 10% by mass or more is preferable. 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.

Further, it is more preferable that the (meth) acrylic resin 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, preferably 60% by mass or more, based on all the structural units of the (meth) acrylic resin. 90% by mass is more preferable, and 65% by mass to 90% by mass is further preferable.

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

Further, 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 from the viewpoint of resolvability, and methacrylic acid. It is preferable to have both a structural unit derived from an acid and a structural unit derived from an alkyl methacrylate ester.
The total content of the methacrylic acid-derived structural unit and the methacrylic acid alkyl ester-derived structural unit in the (meth) acrylic resin is 40 with respect to all the structural units of the (meth) acrylic resin from the viewpoint of resolution. It is preferably mass% or more, and more preferably 60% by mass or more. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

Further, the (meth) acrylic resin is derived from 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 from the viewpoint of resolution, and acrylic acid. It is also preferable to have at least one selected from the group consisting of a structural unit and a structural unit derived from an acrylic 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 is the total content of the structural unit derived from acrylic acid and the structural unit derived from acrylic acid alkyl ester. The mass ratio is preferably 60/40 to 80/20 with respect to the amount.

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

Further, the binder polymer is preferably, for example, a binder polymer having an acid value of 60 mgKOH / g or more from the viewpoint of developability.
Further, the binder polymer is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with a crosslinked component by heating to form a strong film. More preferably, it is a (meth) acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth) acrylic resin).
When the binder polymer is a resin having a carboxy group, the three-dimensional crosslink density can be increased by adding a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking the binder polymer. Further, when the carboxy group of the resin having a carboxy group is anhydrous and hydrophobized, the wet heat resistance can be improved.

The carboxy group-containing (meth) acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth) acrylic resins.
For example, among the polymers described in paragraphs 0025 of JP2011-095716A, carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and the polymers described in paragraphs 0033 to 0052 of JP2010-237589A. , A carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.

Another preferred embodiment of the binder polymer is a styrene-acrylic copolymer. In the present specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and a structural unit derived from the styrene compound. The total content of the structural units 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.
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 further preferably 5% by mass to 80% by mass, based on all the structural units of the copolymer. preferable.
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 20% by mass to 95% by mass, based on all the structural units of the copolymer. Mass% is more preferred.

The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint of moisture permeability and strength of the obtained cured film.
Examples of the monomer forming a structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth) acrylate.
Of these, styrene compounds are preferable, and styrene is more preferable.
Further, the binder polymer more preferably has a structural unit (constituent unit derived from styrene) represented by the following formula (S) from the viewpoint of moisture permeability and strength of the obtained cured film.

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 5 with respect to all the structural units of the binder polymer from the viewpoint of the moisture permeability and strength of the obtained cured film. It is preferably from mass% to 90% by mass, more preferably from 10% by mass to 70% by mass, and even more preferably from 20% by mass to 60% by mass.
The content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 mol% to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of the moisture permeability and strength of the obtained cured film. 10 mol% to 60 mol% is more preferable, and 20 mol% to 60 mol% is further preferable.
Further, the content of the structural unit represented by the above formula (S) in the binder polymer is 5 mol% to 70 mol with respect to all the structural units of the binder polymer from the viewpoint of the moisture permeability and strength of the obtained cured film. % Is preferable, 10 mol% to 60 mol% is more preferable, 20 mol% to 60 mol% is further preferable, and 20 mol% to 50 mol% is particularly preferable.
In the present specification, when the content of the "constituent unit" is defined by the molar ratio, the above "constituent unit" is synonymous with the "monomer unit". Further, in the present specification, the above-mentioned "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The binder polymer preferably has an aliphatic hydrocarbon ring structure from the viewpoint of suppressing development residue, strength of the obtained cured film, and adhesiveness of the obtained uncured film. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. Above all, it is more preferable that the binder polymer has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
Among them, a ring in which two or more aliphatic hydrocarbon rings are fused is preferable, and a tetrahydrodicyclopentadiene ring is preferable, from the viewpoints of suppressing the development residue, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film. (Tricyclo [5.2.1.0 ^2,6 ] decan ring) is more preferable.
Examples of the monomer forming a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Further, the binder polymer more preferably has a structural unit represented by the following formula (Cy) from the viewpoint of suppressing development residue, strength of the obtained cured film, and adhesiveness of the obtained uncured film. It is more preferable to have a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

Wherein (Cy), R ^M represents a hydrogen atom or a methyl group, R ^Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

^{R M} in the formula (Cy) is preferably a methyl group.
One R ^Cy in Formula (Cy), which has developed residual渣抑system, strength of the obtained cured film, and, in view of the tackiness of the uncured film obtained, an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms It is preferably a valent group, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms. It is more preferable that it is a group of.
Aliphatic hydrocarbon cyclic structure in the R ^Cy of formula (Cy) can be a single ring structure or may be a polycyclic structure.
Further, the aliphatic hydrocarbon cyclic structure in the R ^Cy of formula (Cy), the development residue渣抑system, strength of the obtained cured film, and, in view of the tackiness of the uncured film obtained, a cyclopentane ring, cyclohexane It is preferably a ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and a tetrahydrodicyclopentadiene ring structure. Is more preferable.
Moreover, aliphatic hydrocarbon cyclic structure in the R ^Cy of formula (Cy), the development residue渣抑system, strength of the obtained cured film, and, in view of the tackiness of the uncured film obtained, bicyclic or more aliphatic A ring structure in which the hydrocarbon ring is fused is preferable, and a ring in which 2 to 4 aliphatic hydrocarbon rings are fused is more preferable.
Furthermore, ^{R Cy} in the formula (Cy), the intensity of the development residual渣抑system resistance, the resulting cured film, and, in view of the tackiness of the uncured film obtained, -C in the formula (Cy) (= O) O- The group in which the oxygen atom of the above and the aliphatic hydrocarbon ring structure are directly bonded, that is, an aliphatic hydrocarbon ring group is preferable, and a cyclohexyl group or a dicyclopentanyl group is more preferable. It is more preferably a pentanyl group.

The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types.
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 the development residue inhibitory property, the strength of the obtained cured film, and the obtained uncured film. From the viewpoint of film adhesiveness, 5% by mass to 90% by mass is preferable, 10% by mass to 80% by mass is more preferable, and 20% by mass to 70% by mass is further preferable, based on all the constituent units of the binder polymer.
In addition, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is the total of the binder polymer from the viewpoint of suppressing the development residue, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film. With respect to the constituent unit, 5 mol% to 70 mol% is preferable, 10 mol% to 60 mol% is more preferable, and 20 mol% to 50 mol% is further preferable.
Further, the content of the structural unit represented by the above formula (Cy) in the binder polymer is determined from the viewpoint of the inhibitory property of developing residue, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film. With respect to all the constituent units, 5 mol% to 70 mol% is preferable, 10 mol% to 60 mol% is more preferable, and 20 mol% to 50 mol% is further preferable.

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 developed. From the viewpoint of residue suppression, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, 10% by mass to 90% by mass is preferable, and 20% by mass to 80% by mass, based on all the constituent units of the binder polymer. The mass% is more preferable, and 40% by mass to 75% by mass is further preferable.
Further, 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 the development residue inhibitory property, the strength of the obtained cured film, and the adhesion of the obtained uncured film. From the viewpoint of properties, 10 mol% to 80 mol% is preferable, 20 mol% to 70 mol% is more preferable, and 40 mol% to 60 mol% is further preferable with respect to all the constituent units of the binder polymer.
Further, 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 the present development residue inhibitory property, the strength of the obtained cured film, and the obtained. From the viewpoint of the adhesiveness of the uncured film, 10 mol% to 80 mol% is preferable, 20 mol% to 70 mol% is more preferable, and 40 mol% to 60 mol% is preferable with respect to all the constituent units of the binder polymer. More preferred.
Further, 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 are the development residue inhibitory property and the strength of the obtained cured film. From the viewpoint of the adhesiveness of the obtained uncured film, it is preferable to satisfy the relationship shown in the following formula (SCy), more preferably the following formula (SCy-1) is satisfied, and the following formula (SCy-2) is used. It is more preferable to meet.
0.2 ≦ nS / (nS + nCy) ≦ 0.8 formula (SCy)
0.30 ≤ nS / (nS + nCy) ≤ 0.75 Equation (SCy-1)
0.40 ≤ nS / (nS + nCy) ≤ 0.70 equation (SCy-2)

The binder polymer preferably has a structural unit having an acid group from the viewpoint of developability and adhesion to the substrate.
Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable.
As the structural unit having the acid group, the structural unit derived from (meth) acrylic acid, which is shown below, is preferable, and the structural unit derived from methacrylic acid is more preferable.

The binder polymer may have one type of structural unit having an acid group alone or two or more types.
When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is 5% by mass with respect to all the structural units of the binder polymer from the viewpoint of developability and adhesion to the substrate. % To 50% by mass is preferable, 5% by mass to 40% by mass is more preferable, and 10% by mass to 30% by mass is further preferable.
The content of the constituent unit having an acid group in the binder polymer is preferably 5 mol% to 70 mol% with respect to all the constituent units of the binder polymer from the viewpoint of developability and adhesion to the substrate. More preferably, mol% to 50 mol%, still more preferably 20 mol% to 40 mol%.
Further, the content of the (meth) acrylic acid-derived structural unit in the binder polymer is 5 mol% to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of developability and adhesion to the substrate. Is preferable, 10 mol% to 50 mol% is more preferable, and 20 mol% to 40 mol% is further preferable.

The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint of curability and the strength of the obtained cured film.
As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain.
In the present specification, the "main chain" represents a relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to an atomic group branched from the main chain. show.
As the ethylenically unsaturated group, an allyl group or a (meth) acryloxy group is more preferable.
Examples of the structural unit having a reactive group include, but are not limited to, those shown below.

The binder polymer may have one type of structural unit having a reactive group alone or two or more types.
When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is relative to all the structural units of the binder polymer from the viewpoint of curability and the strength of the obtained cured film. 5, 70% by mass is preferable, 10% by mass to 50% by mass is more preferable, and 20% by mass to 40% by mass is further preferable.
The content of the structural unit having a reactive group in the binder polymer is 5 mol% to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of curability and the strength of the obtained cured film. Preferably, 10 mol% to 60 mol% is more preferable, and 20 mol% to 50 mol% is further preferable.

As a means for introducing a reactive group into a binder polymer, functional groups such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate are used. Examples thereof include a method of reacting a compound such as a compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.
A preferable example of the means for introducing a reactive group into a binder polymer is that a polymer having a carboxy group is synthesized by a polymerization reaction and then glycidyl (meth) acrylate is added to a part of the carboxy groups of the obtained resin by the polymer reaction. Can be mentioned as a means for introducing a (meth) acryloxy group into a polymer by reacting. By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained.
The polymerization reaction is preferably carried out under a temperature condition of 70 ° C. to 100 ° C., and more preferably carried out under a temperature condition of 80 ° C. to 90 ° C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. is more preferable. The 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.

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

In the above resin, a is preferably 20% by mass to 60% by mass, b is preferably 10% by mass to 50% by mass, c is preferably 5.0% by mass to 25% by mass, and d is preferably 10% by mass to 50% by mass. ..

In the above resin, 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. Is preferable.

In the above compound, 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. Is preferable.

Further, the binder polymer may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer X”).
The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
As the ring having a cyclic carboxylic acid anhydride structure, a 5-membered ring to a 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.

The structural unit having a carboxylic acid anhydride structure is 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 the following formula P-1. It is preferable that the monovalent group obtained by removing one hydrogen atom from the represented compound is a structural unit bonded to the main chain directly or via a divalent linking group.

In the formula P-1, R ^A1a represents a substituent, n ^1a R ^A1a may be the same or different, and Z ^1a is −C (= O) −OC (= O) −. Represents a divalent group forming a ring containing, and n ^1a represents an integer of 0 or more.

Examples of the substituent represented by ^{RA1a include an alkyl group.}
As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.
n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
When n ^1a represents an integer of 2 or more, a plurality of ^RA1a may be the same or different. Further, the plurality of ^RA1a may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

As the structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable. A structural unit derived from an acid anhydride is 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.

Hereinafter, specific examples of the structural unit having a carboxylic acid anhydride structure will be given, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group, or CF ₃ groups, and Me represents a methyl group.

The structural unit having the carboxylic acid anhydride structure in the polymer X may be one kind alone or two or more kinds.

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

The photosensitive layer may contain only one type of polymer X, or may contain two or more types of polymer X.
When the photosensitive layer contains the polymer X, the content of the polymer X is preferably 0.1% by mass to 30% by mass with respect to the total mass of the photosensitive layer from the viewpoint of resolution and developability. , 0.2% by mass to 20% by mass, more preferably 0.5% by mass to 20% by mass, further preferably 1% by mass to 20% by mass.

The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and 20, from the viewpoint of improving resolution and developability. 000 to 30,000 is particularly preferable.

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, further preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 60 mgKOH / g to 110 mgKOH / g.
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, and 1.0 to 4.0 from the viewpoint of developability. Is more preferable, and 1.0 to 3.0 is particularly preferable.

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, based on the total mass of the photosensitive layer from the viewpoint of photosensitivity, resolution and developability. , 30% by mass to 70% by mass is more preferable.

(Polymerizable compound)
The photosensitive layer may contain a polymerizable compound.
A polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable.

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 binder polymer, and preferably has a molecular weight of less than 5,000.
In addition, preferred embodiments of the ethylenically unsaturated compound used in the second embodiment include preferred embodiments of the ethylenically unsaturated compound used in the first embodiment described above.

As one of the preferred embodiments 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 represent a (meth) acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

^{Q 1} and ^{Q 2} in the formula (M), from the viewpoint of ease of synthesis, it is preferred that ^{Q 1} and ^{Q 2} are the same group.
^{Further, Q 1} and Q ² in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
The ^{R 1} in the formula (M), the development residue渣抑system resistance, rust resistance, from the viewpoint of bending resistance of the obtained cured film, an alkylene group, an alkylene oxyalkylene group ^{^{(-L 1 -O-L 1 -}} ), or , Polyalkyleneoxyalkylene group (-(L ^1- O) _p- L ^1- ) is preferable, hydrocarbon group having 2 to 20 carbon atoms or polyalkyleneoxyalkylene group is more preferable, and polyalkyleneoxyalkylene group has 4 to 20 carbon atoms. An alkylene group is more preferable, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferable.
The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited, and is, for example, branched chain, cyclic, or having 1 to 1 to carbon atoms. It may be any of 5 linear alkylene groups, arylene groups, ether bonds, and combinations thereof, and alkylene groups or groups in which two or more alkylene groups and one or more arylene groups are combined are preferable. , The alkylene group is more preferable, and the linear alkylene group is further preferable.
The above L ¹ 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, and is preferably an integer of 2 to 10.

The atomic number of the connecting chain of the shortest for connecting the Q ^1, Q ² in the compound M is developing residual渣抑system resistance, rust resistance, from the viewpoint of bending resistance of the obtained cured film, 3 to 50 Is preferable, 4 to 40 pieces are more preferable, 6 to 20 pieces are further preferable, and 8 to 12 pieces are particularly preferable.
In the present specification, the "Q ^1, Q atoms linking chain shortest connecting between the ^2", connecting the atoms in R ¹ be linked to Q ¹ to atom in R ¹ be linked to Q ² It is the shortest number of atoms.

Specific examples of the compound M include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 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, hydrogenated Di (meth) acrylate of bisphenol A, di (meth) acrylate of hydrogenated bisphenol F, polyethylene glycol di (meth) acrylate, polypropylenelen glycol di (meth) acrylate, poly (ethylene glycol / propylene glycol) di (meth) acrylate , And polybutylene glycol di (meth) acrylate. The ester monomer can also be used as a mixture.
Among the above compounds, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1 , 10-Decandiol di (meth) acrylate, and at least one compound selected from the group consisting of neopentyl glycol di (meth) acrylate, preferably 1,6-hexanediol di (meth) acrylate. , 1,9-Nonandiol di (meth) acrylate, and at least one compound selected from the group consisting of 1,10-decanediol di (meth) acrylate, more preferably 1,9-nonane. More preferably, it is at least one compound selected from the group consisting of diol di (meth) acrylate and 1,10-decanediol di (meth) acrylate.

Further, as one of the preferred embodiments of the ethylenically unsaturated compound, a bifunctional or higher functional ethylenically unsaturated compound can be mentioned.
As used herein, the term "bifunctional or higher functional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth) acryloyl group is preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and 1,4-cyclohexanediol di (meth) acrylate.

Commercially available products of bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimenanol dimethacrylate (trade name: NK ester A-DCP). Product name: NK ester DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., 1,9-nonanediol diacrylate (trade name: NK ester A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6 -Hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can be mentioned.

The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of trifunctional or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Examples thereof include ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compound having a glycerin tri (meth) acrylate skeleton.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.). (Meta) acrylate compound alkylene oxide-modified compound (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. (Registered trademark) 135, etc.), ethoxylated glycerin triacrylate (NK ester A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can also be mentioned.

Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds.
Examples of the urethane (meth) acrylate include urethane di (meth) acrylate, and examples thereof include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
Further, as the urethane (meth) acrylate, a urethane (meth) acrylate having trifunctionality or higher can also be mentioned. As the lower limit of the number of functional groups, 6-functionality or more is more preferable, and 8-functionality or more is further preferable. The upper limit of the number of functional groups is preferably 20 functional or less. Examples of trifunctional or higher functional urethane (meth) acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ), UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H. , And UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.) and the like.

One of the preferred embodiments of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group.
Examples of the acid group include a phosphoric acid group, a sulfo group, and a carboxy group.
Among these, the carboxy group is preferable as the acid group.
As the ethylenically unsaturated compound having an acid group, a trifunctional to tetrafunctional ethylenically unsaturated compound having an acid group [pentaerythritol tri and tetraacrylate (PETA) having a carboxy group introduced into the skeleton (acid value: 80 mgKOH) / G to 120 mgKOH / g)], a pentafunctional to hexafunctional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA)) with a carboxy group introduced into the skeleton [acid value: 25 mgKOH / g] ~ 70 mgKOH / g)] and the like.
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

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 a carboxylic acid anhydride thereof 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 a carboxylic acid anhydride thereof, the developability and film strength are higher. Increase.
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 the like. Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.) can be mentioned.

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 contents described in this publication are incorporated in the present specification. Is done.

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

Examples of the compound obtained by reacting a polyvalent alcohol with α, β-unsaturated carboxylic acid include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis. Bisphenol A-based (meth) acrylate compounds such as (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, and 2 to 14 ethylene oxide groups. , Polyethylenepolypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate having 2 to 14 propylene oxide groups. , Trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, trimethylolpropane ) Tetraacrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Can be mentioned.
Among them, an ethylene unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and a tetramethylolmethanetri (meth) acrylate, a tetramethylolmethanetetra (meth) acrylate, a trimethylolpropane tri (meth) acrylate, or a di (Trimethylolpropane) Tetraacrylate is more preferable.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc. ), Ethylene unsaturated compound alkylene oxide-modified compound (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. (Registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like can also be mentioned.

As the ethylenically unsaturated compound, those containing an ester bond are also preferable from the viewpoint of excellent developability.
The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the viewpoint of excellent curability and developability, ethylene having a tetramethylolmethane structure or a trimethylolpropane structure is used. Unsaturated compounds are preferred, and tetramethylolmethanetri (meth) acrylates, tetramethylolmethanetetra (meth) acrylates, trimethylolpropane tri (meth) acrylates, or di (trimethylolpropane) tetraacrylates are more preferred.
From the viewpoint of imparting reliability, the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylene unsaturated compound having a tetramethylol methane structure or a trimethylol propane structure. It preferably contains a compound.
Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, and tricyclodecanedimethanoldi. Examples include (meth) acrylate.

One of the preferred embodiments of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
The ethylenically unsaturated compound is ethylenically 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). Unsaturated compounds are preferable, bifunctional ethylenically unsaturated compounds having a ring structure in which two or more aliphatic hydrocarbon rings are fused are more preferable, and tricyclodecanedimethanol di (meth) acrylate is further preferable.
The aliphatic hydrocarbon ring structure includes a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, and a tricyclodecene from the viewpoints of the moisture permeability and bending resistance of the obtained cured film and the adhesiveness of the obtained uncured film. A structure, a norbornane structure, or an isoborone structure is preferable.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.
The ratio of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less to the content of all the ethylenically unsaturated compounds contained in the photosensitive layer is based on the content of all the ethylenically unsaturated compounds contained in the photosensitive layer. It is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

As one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound, and more preferably contains a trifunctional or higher functional ethylenically unsaturated compound. It is more preferable to contain a tetrafunctional ethylenically unsaturated compound.

Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer comprises a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring. It is preferable to include it.

Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, and 1,9-nonane. It is more preferable to contain a diol diacrylate, a tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and 1,9-nonane diol diacrylate and a tricyclodecanedimethanol diacrylate. More preferably, it contains an acrylate and a succinic acid-modified form of dipentaerythritol pentaacrylate.

Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later. It is more preferable to contain the compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer is a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)) from the viewpoint of suppressing development residue and preventing rust. It is preferable to contain an acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher (meth) acrylate compound).
The mass ratio of the contents of the bifunctional ethylenically unsaturated compound and the trifunctional or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.
The content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass, based on the total amount of all the ethylenically unsaturated compounds.
The content of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 40% by mass, based on the total mass of the photosensitive layer.

Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. ..
Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer is composed of compound M and an ethylenically unsaturated compound having an acid group from the viewpoints of substrate adhesion, development residue inhibitory property, and rust prevention property. It is more preferable to contain compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, and more preferably compound M, an aliphatic hydrocarbon. It is more preferable to contain a bifunctional ethylenically unsaturated compound having a ring structure, a trifunctional or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and the compound M has an aliphatic hydrocarbon ring structure. It is particularly preferable to contain a bifunctional ethylenically unsaturated compound having a trifunctional or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound.
Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer is composed of 1,9-nonanediol diacrylate, from the viewpoints of substrate adhesion, development residue inhibitory property, and rust prevention. And, it is preferable to contain a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. It preferably contains a compound, more preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group. , 9-Nonandiol diacrylate, tricyclodecanedimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound are particularly preferable.

The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
The content of the bifunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60% by mass to 100% by mass with respect to the total content of all the ethylenically unsaturated compounds contained in the photosensitive layer. , 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass.

The ethylenically unsaturated compound may be used alone or in combination of two or more.
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, and 5% by mass to 60% by mass, based on the total mass of the photosensitive layer. The mass% is more preferable, and 5% by mass to 50% by mass is particularly preferable.

(Initiator)
The photosensitive layer preferably contains a polymerization initiator.
As the polymerization initiator, a photopolymerization initiator is preferable.
Preferred embodiments of the polymerization initiator used in the B embodiment include preferred embodiments of the polymerization initiator used in the above-described embodiment A.
The polymerization initiator may be used alone or in combination of two or more.
The content of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, based on the total mass of the photosensitive layer. It is more preferable to have. The upper limit of the value is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

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

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, and a pyrimidine compound.
Among the above, as the heterocyclic compound, at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole 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 thiadiazol compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, and a benzoxazole compound is more preferable.

A preferable specific example of the heterocyclic compound is shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

Examples of the tetrazole compound include the following compounds.

Examples of thiadiazole compounds include the following compounds.

Examples of the triazine compound include the following compounds.

Examples of the loadonine compound include the following compounds.

Examples of the thiazole compound include the following compounds.

Examples of the benzothiazole compound include the following compounds.

Examples of the benzimidazole compound include the following compounds.

Examples of the benzoxazole compound include the following compounds.

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, preferably 0.10% by mass to 10% by mass, based on the total mass of the photosensitive layer. 0.0% by mass is more preferable, 0.30% by mass to 8.0% by mass is further preferable, and 0.50% by mass to 5.0% by mass is particularly preferable.

(Aliphatic thiol compound)
The photosensitive layer may contain an aliphatic thiol compound.
When the photosensitive layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an en-thiol reaction with an ethylenically unsaturated compound, so that the curing shrinkage of the formed film is suppressed and the stress is relaxed. NS.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound) is preferable.
Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is more preferable from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).
As used herein, the term "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

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

The number of functional groups of the polyfunctional aliphatic thiol compound is, for example, preferably bifunctional to 10 functional, more preferably bifunctional to 8 functional, and further preferably bifunctional to 6 functional, from the viewpoint of adhesion of the formed pattern. preferable.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropanthris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like. 1,3,5-Tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethanetris (3-mercaptobutyrate) ), Tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) Pionate), dipentaerythritol hexakis (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis (3-mercaptobutylyloxy) butane, 1,2-ethanedithiol, 1, Examples thereof include 3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio) diethanethiol, meso-2,3-dimercaptosuccinic acid, and di (mercaptoethyl) ether.

Among the above, the polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris. At least one compound selected from the group consisting of (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred.

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

The photosensitive layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of 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% by mass to 50% by mass, 5% by mass, based on the total mass of the photosensitive layer. It is more preferably from mass% to 30% by mass, and particularly preferably from 8% by mass to 20% by mass.

(Thermal crosslinkable compound)
The photosensitive layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
As the heat-crosslinkable compound used in the photosensitive layer of the embodiment B, the above-mentioned heat-crosslinkable compound is preferably used in the photosensitive layer of the embodiment A.
The heat-crosslinkable compound may be used alone or in combination of two or more.
When the photosensitive layer contains a heat-crosslinkable compound, the content of the heat-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. preferable.

(Surfactant)
The photosensitive layer may contain a surfactant.
As the surfactant used in the photosensitive layer of the embodiment B, the above-mentioned surfactant is preferably used in the photosensitive layer of the embodiment A.
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, preferably 0.01% by mass to 1% by mass, based on the total mass of the photosensitive layer. .0% by mass is more preferable, and 0.05% by mass to 0.80% by mass is further preferable.

(Radical polymerization inhibitor)
The photosensitive layer may contain a radical polymerization inhibitor.
As the radical polymerization inhibitor used in the photosensitive layer of the embodiment B, the radical polymerization inhibitor described above is preferably used in the photosensitive layer of the embodiment A.
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, preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive layer. More preferably by mass. 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 dye decolorization are more excellent.

(Hydrogen donating compound)
The photosensitive layer may contain a hydrogen donating compound.
The hydrogen-donating compound has actions such as further improving the sensitivity of the photopolymerization initiator to active light and suppressing inhibition of polymerization of the polymerizable compound by oxygen.
Examples of the hydrogen donating compound include amines and amino acid compounds.

Examples of amines include M.I. R. "Journal of Polymer Society" by Sander et al., Vol. 10, p. 3173 (1972), Japanese Patent Application Laid-Open No. 44-020189, Japanese Patent Application Laid-Open No. 51-082102, Japanese Patent Application Laid-Open No. 52-134692, Japanese Patent Application Laid-Open No. 59-138205 Examples thereof include the compounds described in Japanese Patent Application Laid-Open No. 60-084305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, Research Disclosure No. 33825, and the like. More specifically, 4,4'-bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (also known as leucocrystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl. Examples thereof include dimethylaniline and p-methylthiodimethylaniline.
Among them, from the viewpoint of sensitivity, curing rate, and curability, the amines are at least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane. Seeds are preferred.

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

Examples of the hydrogen donating compound include an organometallic compound (tributyltin acetate, etc.) described in JP-A-48-042465, a hydrogen donor described in JP-A-55-0344414, and JP-A-6. Sulfur compounds (Tritian and the like) described in JP-A-308727 are also mentioned.

The hydrogen donating compound 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 0 with respect to the total mass of the photosensitive layer in terms of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. It is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and even more preferably 0.03% by mass to 5.0% by mass.

(Impurities, etc.)
The photosensitive layer may contain a predetermined amount of impurities.
The impurities in the photosensitive layer of the embodiment B are the same as in the preferred embodiment of the impurities described above in the photosensitive layer of the embodiment A.

(Residual monomer)
The photosensitive layer may contain residual monomers corresponding to each structural unit of the binder polymer described above.
The residual monomer corresponding to each structural unit of the binder polymer in the photosensitive layer of the embodiment B is the same as the preferred embodiment of the residual monomer corresponding to each structural unit of the binder polymer described above in the photosensitive layer of the embodiment A. ..

(Other ingredients)
The photosensitive layer may contain components other than the components described above (hereinafter, also referred to as “other components”). Other components include, for example, colorants, antioxidants, and particles (eg, metal oxide particles). In addition, as other components, other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 can also be mentioned.

-particle-
As the particles, metal oxide particles are preferable.
The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
The average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, for example, from the viewpoint of transparency of the cured film.
The average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.

When the photosensitive layer contains particles, it may contain only one type of metal type and particles having different sizes and the like, or may contain two or more types.
The photosensitive layer 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 with respect to the total mass of the photosensitive layer. It is more preferable that the particles are not contained or the content of the particles is more than 0% by mass and 10% by mass or less with respect to the total mass of the photosensitive layer, and the particles are not contained or the content of the particles is photosensitive. More than 0% by mass and 5% by mass or less is more preferable with respect to the total mass of the layer, and particles are not contained or the content of particles is more than 0% by mass and 1% by mass or less based on the total mass of the photosensitive layer. It is more preferable, and it is particularly preferable that it does not contain particles.

-Colorant-
The photosensitive layer may contain a colorant (pigment, dye, etc.), but for example, from the viewpoint of transparency, it is preferable that the photosensitive layer contains substantially no 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.

-Antioxidant-
Examples of the antioxidant include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-. 3-Pyrazoridones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Be done.
Among them, 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant from the viewpoint of storage stability and curability.

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, based on the total mass of the photosensitive layer. 01% by mass or more is more preferable. The upper limit is not particularly limited, but is preferably 1% by mass or less.

(Thickness of photosensitive layer)
The thickness (layer thickness) of the photosensitive layer is not particularly limited, but is preferably 30 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, particularly preferably 10 μm or less, from the viewpoint of developability and resolvability. Most preferably, it is 0.0 μm or less. As the lower limit, 0.60 μm or more is preferable, and 1.5 μm or more is more preferable, because the strength of the film obtained by curing the photosensitive layer is excellent.

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

(Color of photosensitive layer)
The photosensitive layer is preferably achromatic. Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has ^{an L *} value of 10 to 90 in the ^{CIE1976 (L *} , a ^* , b ^* ) color space. The a ^* value is preferably −1.0 to 1.0, and the b ^* value is preferably −1.0 to 1.0.

The pattern (cured film of the photosensitive layer) obtained by curing the photosensitive layer is preferably achromatic.
Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has ^{a pattern L *} value of 10 to 90 in the ^{CIE1976 (L *} , a ^* , b ^* ) color space. ^{The a *} value of the pattern is preferably −1.0 to 1.0, and the b ^* value of the pattern is preferably −1.0 to 1.0.

(Humidity permeability of photosensitive layer)
Moisture permeability in the layer thickness 40μm pattern obtained by curing the photosensitive layer (cured film of the photosensitive layer), from the viewpoint of corrosion resistance, is preferably 500g / (m 2 · ^24hr) or less, more preferably 300g ^/ (m 2 · 24hr) or less, still more preferably 100g ^/ (m 2 · 24hr) or less.
The moisture permeability is measured with a cured film obtained by curing the photosensitive layer by exposing the photosensitive layer with an i-line at an exposure amount of 300 mJ / cm ² and then performing post-baking at 145 ° C. for 30 minutes. do.

[Refractive index adjustment layer]
The laminate preferably has a refractive index adjusting layer.
As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjusting layer include a binder polymer, a polymerizable compound, a metal salt, and particles.
The method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, 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. There is a method using.

Examples of the binder polymer and the polymerizable unsaturated compound include the binder polymer and the polymerizable unsaturated compound described in the above section "Photosensitive layer".

Examples of the particles include metal oxide particles and metal particles.
The type of the metal oxide particles is not particularly limited, and examples thereof include known metal oxide particles. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

The average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, for example, from the viewpoint of transparency of the cured film.
The average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.

Specific examples of the metal oxide particles include zirconium oxide particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles), silicon dioxide particles (SiO ₂ particles), and a composite thereof. At least one selected from the group consisting of particles is preferable.
Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable from the viewpoint that the refractive index can be easily adjusted.

Commercially available metal oxide particles include fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F04) and fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F74). ), Calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F76), zirconium oxide particles (nanouse OZ) -S30M, manufactured by Nissan Chemical Industry Co., Ltd.) and zirconium oxide particles (Nano Youth OZ-S30K, manufactured by Nissan Chemical Industry Co., Ltd.).

The particles may be used alone or in combination of two or more.
The content of particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and 40% by mass to 85% by mass with respect to the total mass of the refractive index adjusting layer. More preferred.
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, based on the total mass of the refractive index adjusting layer. , 40% by mass to 85% by mass is more preferable.

The refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive layer.
The refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, and particularly preferably 1.78 or less.

The thickness of the refractive index adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm.

[Relationship between support, photosensitive layer and cover film]
Also in the B embodiment, it is preferable to satisfy the relationship of the support, the photosensitive layer and the cover film described in the A embodiment.

(Method for Manufacturing Photosensitive Transfer Member of Embodiment B)
The method for producing the photosensitive transfer member (laminated body having a photosensitive layer) of the embodiment B is not particularly limited, and a known method can be used.
The method for forming the photosensitive composition and the photosensitive layer in the embodiment B is the same as the method for forming the photosensitive composition and the photosensitive layer described above in the embodiment A, and the preferred embodiment is also the same.
Further, the support and the cover film are the same as the manufacturing method in the A embodiment, and the preferred embodiment is also the same.

-Composition for forming a refractive index adjusting layer and a method for forming the refractive index adjusting layer-
The composition for forming the refractive index adjusting layer preferably contains various components forming the above-mentioned refractive index adjusting layer and a solvent. In the composition for forming a refractive index adjusting 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 refractive index adjusting layer described above. be.
The solvent is not particularly limited as long as the components contained in the refractive index adjusting layer can be dissolved or dispersed, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water or water and water. A mixed solvent with 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 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition. The portion is more preferable.

The method for forming the refractive index adjusting layer is not particularly limited as long as it can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). Be done.

Further, by attaching the cover film to the refractive index adjusting layer, the photosensitive transfer member of Embodiment B can be manufactured.
The method of attaching the cover film to the refractive index adjusting layer is not particularly limited, and known methods can be mentioned.
Examples of the device for attaching the cover film to the refractive index adjusting layer include a vacuum laminator and a known laminator such as an auto-cut laminator.
It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.

[Laminate]
The first embodiment of the laminate according to the present disclosure is a laminate having a photosensitive layer, wherein the laminate has a cut surface formed by at least being cut, and a cut surface portion having a cut surface width of 50 μm. The number of cracks per 10 locations is 3 or less.
A second embodiment of the laminate according to the present disclosure is a laminate having a photosensitive layer, wherein the laminate has at least a cut surface formed by cutting, and the number of dent failures in the laminate is large. , 60 pieces / m ² or less.

Note that, in the present specification, unless otherwise specified, the term "laminate according to the present disclosure" refers to both the first embodiment and the second embodiment. Further, unless otherwise specified, when the term "photosensitive layer" or the like is simply used, the photosensitive layers and the like of both the first embodiment and the second embodiment will be described.

A preferred embodiment of the laminate having a photosensitive layer in the laminate according to the present disclosure is a preferred embodiment of the laminate having a photosensitive layer used in the method for producing a cut product according to the present disclosure, except as described later. The same is true.

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

FIG. 3 shows an example of cracks generated on the cut surface of the laminated body.
FIG. 3 is an enlarged view at the end of a cut surface obtained by cutting the laminate having the support 10, the photosensitive layer 16 and the cover film 18, and in the cut surface of FIG. 3, a crack CR of a part of the support 10 is taken. Can be confirmed.

The number of cracks in the present disclosure shall be measured as follows.
Arbitrary 10 points on the cut surface of the cut laminate are collected, and the cut surface portion of the cut surface is observed with a scanning electron microscope (SEM) having a cut surface width of 50 μm. The conditions were an acceleration voltage of 3 kV and an observation magnification of 1,700 times. Of the 10 locations, any layer of the support, the photosensitive layer, and the cover film, which has cracks regardless of the number, is counted as one, and among the 10 locations of the cut surface portion having a cut surface width of 50 μm. Evaluate by the number of cracks (number of cracks).

In the second embodiment of the laminate according to the present disclosure, the number of dent failures in the laminate is 60 / m ² ^{or less, and preferably 45 / m 2} or less from the viewpoint of defect suppression. , 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 dent failures in the laminate ^{is preferably 60 / m 2} or less, and 45 / m ² or less, from the viewpoint of defect suppression. More preferably, it is more preferably 30 pieces / m ² or less, and ^{particularly preferably 10 pieces / m 2} or less.

The number of dent failures in the laminate in the present disclosure shall be measured as follows.
Visually observe the surface of the laminate for 6 m ² or more, measure the number of dents (dents), and calculate the number of dent failures per ^{1 m 2.}

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiment of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

(Examples 1 to 12 and Comparative Examples 1 and 2)
<Manufacturing of photosensitive transfer member>
-Formation of photosensitive layer-
As a support, a polyethylene terephthalate (PET) film having the thickness shown in Table 2 was prepared.
The photosensitive composition A-1 shown in Table 1 was applied to the surface of the support using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was the thickness shown in Table 2. It was applied. The coating film of the photosensitive composition A-1 was dried at 80 ° C. for 40 seconds to form a photosensitive layer.

“Mm / Mb” in Table 1 represents the value of the ratio Mm / Mb of the content Mm of the polymerizable compound and the content Mb of the binder polymer in the photosensitive layer, and “content of the acrylic compound” is the photosensitive layer. It represents the content of the acrylic compound with respect to the total mass of the (meth) acrylic compound contained in the layer, and the unit is mass%.

The details of the abbreviations in Table 1 are shown below.
BPE-500: Ethoxylation (10 molar equivalents) Bisphenol A dimethacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

SR-502: Ethoxylation (9 molar equivalents) Trimethylolpropane triacrylate (manufactured by Arkema)
A-9300-CL1: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (manufactured by Shin Nakamura Chemical Industry 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.)

-Attach cover film-
A PET film or polypropylene (PP) film having the thickness shown in Table 2 was pressure-bonded to the surface of the formed photosensitive layer as a cover film to prepare the photosensitive transfer member A of each example.
The obtained photosensitive transfer member A was wound up to prepare a roll-shaped photosensitive transfer member A having a width of 1,580 mm and a tape measure of 4,000 m.

<Dent failure evaluation>
The large roll of the photosensitive transfer member A was cut by using a disk-shaped rotary slitter having an upper blade 102 and a lower blade 104 having a cross section shown in FIGS. 1 and 2. The parameters of the upper blade 102 used are R1, the chamfer angle θ1 and the cutting edge angle θ2 shown in Table 2, and the parameters of the lower blade 104 used are R2 of 2 μm and the cutting edge angle of θ3 of 90. Fixed at °. Further, the penetration depth T of the upper blade 102 with respect to the lower blade 104 at the time of cutting was 0.5 mm. Furthermore, the radii of the disk-shaped upper blade 102 and the lower blade 104 were each about 100 mm, and the cutting speed was 100 m / min. The cut photosensitive transfer member A was rewound into a small roll.
The rotary slitter was used to cut a large roll of the photosensitive transfer member A having a width of 1,580 mm and a tape measure of 4,000 m into a small roll of the photosensitive transfer member A having a width of 500 mm and a length of 100 m. The number of dents (dents) was visually investigated by pulling out 2 m from the small roll of the cut photosensitive transfer member A.
Of the small rolls cut from the large rolls, the small rolls used in the above evaluation are three small rolls from the width direction of the large rolls and two small rolls from the longitudinal direction of the large rolls, for a total of six. This is the main part, and these were investigated and the maximum number was evaluated according to the following evaluation criteria.
A: The number of dents is 0 to 10 B: The number of dents is 11 to 30 C: The number of dents is 31 to 60 D: The number of dents is 61 or more

<Evaluation of the number of cracks>
A large roll of the photosensitive transfer member A having a width of 1,580 mm and a tape measure of 4,000 m was cut into a small roll of the photosensitive transfer member A having a width of 500 mm and a length of 100 m by a rotary slitter. 2 m was pulled out from the small roll of the cut photosensitive transfer member A, and a total of 10 points were collected at 5 arbitrary points on both sides, and the cut surface was observed with a scanning electron microscope (SEM). The conditions were an acceleration voltage of 3 kV and an observation magnification of 1,700 times. Of the 10 locations, any layer of the support, the photosensitive layer, and the cover film, which had cracks regardless of the number, was counted as one and evaluated by the number of cracks generated in the 10 locations.

The base materials used as the support or cover film shown in Table 2 are as follows.
PET film (thickness 16 μm): Toray Industries, Inc. Lumirror 16QS62
PET film (thickness 20 μm): A PET film having a thickness of 20 μm was prepared according to the description in paragraphs 0119 to 0127 of International Publication No. 2017/208849.
PET film (thickness 14 μm): A PET film having a thickness of 14 μm was prepared according to the description in paragraphs 0119 to 0127 of International Publication No. 2017/208849.
PP film (thickness 12 μm): Toray Industries, Inc. Trefan 12KW37

As shown in Table 2 above, the methods for producing the cut products of Examples 1 to 12 can suppress dent failures in the obtained cut products as compared with the methods for producing the cut products of the comparative example.

(Examples 13 to 28)
<Preparation of photosensitive composition>
The photosensitive compositions AA-1 to AA-10 were 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.

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

<Preparation of 36.3% by mass solid content solution of alkali-soluble resin P-1>
A 36.3% by mass solution of the 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.
A 36.3% by mass solution of P-1 solid content was prepared by the polymerization step and addition step shown below.

-Polymerization process-
Propylene glycol monomethyl ether acetate (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM-Ac) (60 g), propylene glycol monomethyl ether (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM) (240 g) in a 2,000 mL flask. Was introduced. The obtained liquid was heated to 90 ° C. while stirring at a stirring speed of 250 rpm (revolutions per minute).
As the preparation of the dropping liquid (1), 107.1 g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd., trade name Acryester M), methyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, trade name MMA) (5.46 g). , And cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name CHMA) (231.42 g) were mixed and diluted with PGM-Ac (60 g) to obtain a dropping liquid (1).
To prepare the dropping solution (2), dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name V-601) (9.637 g) was added to PGM-Ac. The dropping liquid (2) was obtained by dissolving with (136.56 g).
The dropping liquid (1) and the dropping liquid (2) are simultaneously added dropwise to the above-mentioned 2,000 mL flask (specifically, a 2,000 mL flask containing a liquid heated to 90 ° C.) over 3 hours. bottom.
Next, the container of the dropping liquid (1) was washed with PGM-Ac (12 g), and the washing liquid was dropped into the 2,000 mL flask. Next, the container of the dropping liquid (2) was washed with PGM-Ac (6 g), and the washing liquid was dropped into the above 2000 mL flask. During these droppings, the reaction solution in the 2,000 mL flask was kept at 90 ° C. and stirred at a stirring speed of 250 rpm. Further, as a post-reaction, the mixture was stirred at 90 ° C. for 1 hour.
V-601 (2.401 g) was added to the reaction solution after the post-reaction as the first additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 1 hour.
Next, V-601 (2.401 g) was added to the reaction solution as the second additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 1 hour.
Next, V-601 (2.401 g) was added to the reaction solution as the third additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 3 hours.

-Additional process-
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 Industries, Ltd.) (1.8 g) and hydroquinone monomethyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.8 g) were added to the reaction solution. Further, each container was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. 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 liquid was introduced into the reaction liquid. Then, as an addition reaction, the mixture was stirred at 100 ° C. for 6 hours.
Next, the reaction solution was cooled and filtered through a mesh filter (100 mesh) for removing dust to obtain a solution of polymer D (1,158 g) (solid content concentration: 36.3% by mass). The obtained polymer P-1 had a weight average molecular weight of 27,000, a number average molecular weight of 15,000, and an acid value of 95 mgKOH / g.

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 constituent repeating unit on the left side.)

<Preparation of 36.3% by mass solid content solution of alkali-soluble resin P-2>
82.4 g of propylene glycol monomethyl ether was placed in a flask and heated to 90 ° C. under a nitrogen stream. A solution prepared by dissolving 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate and 34.0 g of methacrylate in 20 g of propylene glycol monomethyl ether in this solution, and a polymerization initiator V-601 (Fuji Film Wako Pure Chemical Industries, Ltd.) )) A solution prepared by dissolving 5.4 g in 43.6 g of propylene glycol monomethyl ether acetate was simultaneously added dropwise over 3 hours. After completion of the dropping, 0.75 g of V-601 was added three times every hour. After that, it was reacted 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. The temperature of the reaction solution was raised to 100 ° C. under an air flow, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. To this, 25.5 g of glycidyl methacrylate (Blemmer GH manufactured by NOF Corporation) was added dropwise over 20 minutes. This was reacted at 100 ° C. for 7 hours to obtain a solution of the 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 by gas chromatography was less than 0.1% by mass with respect to the polymer solid content in any of the monomers.

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 left constituent repeating unit.)

<Preparation of 36.2% by mass solid content solution of alkali-soluble resin P-3>
113.5 g of propylene glycol monomethyl ether was placed in a flask and heated to 90 ° C. under a nitrogen stream. A solution in which 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylate were dissolved in 30 g of propylene glycol monomethyl ether in this solution, and a polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 27. A solution prepared by dissolving 0.6 g in 57.7 g of propylene glycol monomethyl ether was simultaneously added dropwise over 3 hours. After completion of the dropping, 2.5 g of V-601 was added three times every hour. After that, it was reacted 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. The temperature of the reaction solution was raised to 100 ° C. under an air flow, 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 by gas chromatography was less than 0.1% by mass with respect to the polymer solid content in any of the monomers.

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 left constituent repeating unit.)

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

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 left constituent repeating unit.)

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

Polymer A in Table 4 was synthesized as follows.
1-Methylenepropanol (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 Industries, Ltd.) and methacrylic acid (14.4 g) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are 1-methoxypropanol (Tokyo Chemical Industry Co., Ltd.). Dissolve in (270.0 g) (manufactured by Fuji Film Co., Ltd.), and further dissolve 3.94 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to prepare a dropping solution, and put it in a flask for 2.5 hours. The dropping liquid was dropped over. The reaction was carried out while maintaining the stirred state for 2.0 hours.
Then, the temperature was returned to room temperature, and the mixture was added dropwise to ion-exchanged water (2.7 L) in a stirred state, and reprecipitation was carried out to obtain a suspension. Filtration was carried out by introducing a turbid solution in Nutche with a filter paper, and the filtered material was further washed with ion-exchanged water to obtain a wet powder. It was dried by blowing air at 45 ° C., and it was confirmed that the amount became constant, and polymer A was obtained as a powder in a yield of 70%.
The ratio of methacrylic acid / allyl methacrylate of the obtained polymer A was 76/24% by mass. The weight average molecular weight Mw was 38,000.

<Preparation of transfer films 1 to 16 (photosensitive transfer member)>
Using a slit-shaped nozzle on a temporary support of a polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) with a thickness of 16 μm, the coating amount was adjusted to the coating amount at which the film thickness after drying becomes the thickness shown in Table 5. After adjustment, any one of the photosensitive composition materials AA-1 to AA-10 shown in Table 5 was applied to form a photosensitive layer.
After volatilizing the solvent in the drying zone at 100 ° C., using a slit-shaped nozzle, among the materials B-1 to B-4 for forming the refractive index adjusting layer shown in Table 5, the combinations shown in Table 3 are used. Using at least one type, the coating amount is adjusted so that the film thickness after drying becomes the film thickness shown in Table 5, the film is applied onto the photosensitive layer layer, and then dried at a drying temperature of 80 ° C. , A refractive index adjusting layer was formed. A protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded onto the refractive index adjusting layer to prepare transfer films 1 to 16.

<Evaluation>
Similarly, the number of dents and the number of cracks were evaluated for the transfer films 1 to 16. The evaluation results are shown in Table 6 below.

As shown in Table 6 above, the methods for producing the cut products of Examples 13 to 28 can suppress dent failures and crack failures in the obtained cut products.

Japanese patent application No. 2020-024650 filed on February 17, 2020, Japanese patent application No. 2020-172675 filed on October 13, 2020, and filed on December 15, 2020. The disclosure of Japanese Patent Application No. 2020-209961 is incorporated herein by reference in its entirety. Also, all documents, patent applications and technical standards described herein are to the same extent as if the individual documents, patent applications and technical standards were specifically and individually stated to be incorporated by reference. , Incorporated by reference herein.

Claims

It includes a step of sandwiching and cutting a laminate having a photosensitive layer between an upper blade and a lower blade.
A method for manufacturing a cut product, in which the clearance between the cutting edge of the upper blade and the cutting edge of the lower blade is 5 μm or less.
The cut product according to claim 1, wherein the chamfer angle θ1, which is the inclination angle of the upper blade on the lower blade side, is 3 ° or less in the cross section of the upper blade perpendicular to the feed direction of the laminated body. Production method.
The method for manufacturing a cut product according to claim 1 or 2, wherein the cutting edge angle θ2 of the upper blade is 33 ° or less in a cross section of the upper blade perpendicular to the feeding direction of the laminated body.
The method for producing a cut product according to any one of claims 1 to 3, wherein the thickness of the entire laminate is 50 μm or less.
The method for producing 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.
The method for producing 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.
The method for producing a cut product according to claim 6, wherein the thickness of the support and the cover film are independently 10 μm to 20 μm.
The method for producing a cut product according to claim 6 or 7, wherein the arithmetic average roughness Ra value of the surface of the support on the photosensitive layer side is 0.05 μm or less.
The method for producing a cut product according to any one of claims 6 to 8, wherein the arithmetic average roughness Ra value of the surface of the cover film on the photosensitive layer side is 0.1 μm or less.
The method for producing a cut product according to any one of claims 1 to 9, which comprises a step of winding at least a part of the cut product of the obtained laminated body after the cutting step.
A laminate having a photosensitive layer,
The laminate has a cut surface that is at least cut.
A laminate in which the number of cracks per 10 cut surface portions having a cut surface width of 50 μm is 3 or less.
A laminate having a photosensitive layer,
The laminate has a cut surface that is at least cut.
A laminate in which the number of dent failures in the laminate is 60 / m 2 or less.