Wound body, method for manufacturing laminate having resin pattern, and method for manufacturing laminate having conductor pattern

Abstract

To provide a wound body which is excellent in peelability of a protective film in a transfer film unwound from the wound body, and a laminating property of an end, a method for manufacturing a laminate having a resin pattern using the wound body, and a method for manufacturing a laminate having a conductor pattern.SOLUTION: A wound body of a transfer film has a temporary support body, a composition layer and a protective film in this order, wherein the composition layer contains a photosensitive composition layer, as for the transfer film unwound from the wound body, when cross-section observation is performed on five different places at an interval of 8 cm in a longitudinal direction of the transfer film, both a minimum value and a maximum value of five positions X and five positions Y obtained in the respective cross-section observation are within a range of -40 to 40 μm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a roll. Specifically, the present invention relates to a roll of a transfer film having a support, a composition layer, and a protective film in this order, in which the composition layer includes a photosensitive composition layer. The present invention also relates to a method for producing a laminate having a resin pattern using the above-mentioned wound body, and a method for producing a laminate having a conductor pattern. [Background technology]

[0002] In display devices (such as organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with touch panels such as capacitance-type input devices, conductive layer patterns such as electrode patterns corresponding to the sensors of the visual recognition area, peripheral wiring parts, and wiring of the extraction wiring parts are provided inside the touch panel. Also, wiring patterns are formed in printed circuit board wiring and the like by etching and plating processes. Generally, in forming a patterned layer, the number of steps required to obtain the required pattern shape is small, and therefore a method in which a photosensitive composition layer is placed on any substrate using a transfer film, and the photosensitive composition layer is exposed to light through a mask and then developed is widely used.

[0003] For example, Patent Document 1 discloses a photosensitive element (transfer film) consisting of a support film (support), a photosensitive resin composition layer (photosensitive composition layer), and a protective film, which satisfies certain requirements. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2003-248320 A Summary of the Invention [Problem to be solved by the invention]

[0005] The transfer film has, for example, a temporary support, a composition layer, and a protective film in this order, and is supplied as a roll. When the composition layer is disposed on the substrate using the transfer film, the transfer film is first unwound from the roll, and the protective film is peeled off from the unwound transfer film to expose the composition layer (e.g., photosensitive composition layer). Then, the transfer film from which the protective film has been peeled off is laminated to the substrate so that the exposed composition layer faces the desired surface of the substrate. In the above process, when the protective film is peeled off from the transfer film, it is necessary that the protective film has excellent peelability. If the protective film has poor peelability, peeling also occurs between the temporary support and the composition layer when the protective film is peeled off from the transfer film, resulting in a situation in which the composition layer cannot be normally laminated to another substrate.

[0006] In addition, after the composition layer is transferred to the substrate, the laminated composition layer is required to have excellent surface properties, and in particular, it is required that the occurrence of wrinkles, etc., is suppressed at the ends of the laminated composition layer. Hereinafter, the suppression of the occurrence of wrinkles, etc., at the ends of the laminated composition layer as described above is referred to as excellent end lamination.

[0007] The inventors of the present invention have examined the transfer film (photosensitive element) described in Patent Document 1 as a rolled body and found that at least one of the peelability and end lamination properties of the protective film described above may not meet the currently required standards, and that improvement is necessary.

[0008] Therefore, an object of the present invention is to provide a roll that is excellent in peelability of the protective film in the transfer film unwound from the roll and in lamination properties at the ends. Another object of the present invention is to provide a method for producing a laminate having a resin pattern using the above-mentioned wound body, and a method for producing a laminate having a conductor pattern. [Means for solving the problem]

[0009] As a result of intensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0010] [1] A roll of a transfer film having a temporary support, a composition layer, and a protective film in this order, the composition layer comprises a photosensitive composition layer, A roll, in which the following cross-sectional observation is performed on the transfer film unwound from the roll at five different locations spaced 8 cm apart along the longitudinal direction of the transfer film, and the minimum and maximum values ​​of five positions X and five positions Y obtained in each cross-sectional observation are all within the range of -40 to 40 μm. Cross-sectional observation: The transfer film unwound from the roll is cut along the width direction of the transfer film, and one of the two exposed cross sections is observed from the normal direction of the one cross section. In the exposed cross section, the position of one end located on the outermost side of the temporary support in the width direction of the transfer film is defined as a first position, the position of one end located on the outermost side of the protective film in the width direction of the transfer film and on the same side as the first position is defined as a second position, and the position of the second position is defined as position X when the position on the outer side along the width direction of the transfer film from the first position as a reference is expressed as a positive value in the width direction of the transfer film, The position of the other end of the exposed cross-section that is located at the outermost position of the temporary support in the width direction of the transfer film is defined as a third position, the position of the other end of the protective film that is located at the outermost position in the width direction of the transfer film and is on the same side as the third position is defined as a fourth position, and the position of the fourth position is defined as position Y when the position outside the third position along the width direction of the transfer film is expressed as a positive value based on the third position. [2] The wound body according to [1], wherein the minimum value is within a range of 0.1 to 40 μm. [3] The roll according to [1] or [2], wherein the photosensitive composition layer has a thickness of 2 to 20 μm. [4] The roll according to any one of [1] to [3], wherein the composition layer has at least one of an intermediate layer and a thermoplastic resin layer between the temporary support and the photosensitive composition layer. [5] The wound body according to [4], wherein the intermediate layer has a thickness of 0.1 to 10 μm. [6] The wound body according to [4], wherein the thermoplastic resin layer has a thickness of 0.1 to 10 μm. [7] An unwinding step of unwinding the transfer film from the roll described in any one of [1] to [6]; a peeling step of peeling the protective film from the transfer film to expose a surface of the composition layer; a lamination step of laminating the transfer film and a substrate having a conductive layer such that the exposed surface of the composition layer is in contact with the conductive layer of the substrate having a conductive layer on a surface thereof; an exposure step of exposing the photosensitive composition layer contained in the composition layer; a development step of performing a development treatment on the exposed photosensitive composition layer to form a resin pattern, A method for producing a laminate having a resin pattern, further comprising a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step. [8] An unwinding step of unwinding the transfer film from the roll described in any one of [1] to [6]; a peeling step of peeling the protective film from the transfer film to expose a surface of the composition layer; a lamination step of laminating the transfer film and a substrate having a conductive layer such that the exposed surface of the composition layer is in contact with the conductive layer of the substrate having a conductive layer on a surface thereof; an exposure step of exposing the photosensitive composition layer contained in the composition layer; a developing step of performing a development treatment on the exposed photosensitive composition layer to form a resist pattern; one of an etching step of performing an etching process on the conductive layer in an area where the resist pattern is not disposed, and a plating step of performing a plating process on the conductive layer in an area where the resist pattern is not disposed; a resist pattern stripping step of stripping the resist pattern; In the case where the plating treatment step is further included, a removal step of removing the conductive layer exposed by the resist pattern peeling step to form a conductive pattern on the substrate is also included in the method for producing a laminate having a conductive pattern, A method for producing a laminate having a conductor pattern, further comprising a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step. Effect of the Invention

[0011] According to the present invention, it is possible to provide a roll that is excellent in peelability of the protective film in the transfer film unwound from the roll and in lamination properties of the end portions. The present invention also provides a method for producing a laminate having a resin pattern using the above-mentioned wound body, and a method for producing a laminate having a conductor pattern. [Brief description of the drawings]

[0012] [Figure 1] 11 is a schematic diagram showing the process of unwinding the transfer film from the roll. FIG. [Diagram 2] 11 is a schematic diagram showing an example of a cross-sectional end portion of a transfer film when the position X has a positive value. FIG. [Diagram 3] 11 is a schematic diagram showing an example of a cross-sectional end portion of a transfer film when the position X has a negative value. FIG. [Figure 4] 11 is a schematic diagram showing an example of both ends of a cross section of a transfer film when position X and position Y take positive values. FIG. [Diagram 5] 11 is a schematic diagram showing an example of both ends of a cross section of a transfer film when position X and position Y take negative values. FIG. [Figure 6] FIG. 2 is a schematic diagram showing an example of the configuration of the transfer film of the first embodiment. [Figure 7]FIG. 11 is a schematic diagram showing an example of the configuration of a transfer film according to a second embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. The following description of the configuration may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0014] The following describes the meaning of each description in this specification. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present specification, in the numerical ranges described stepwise, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical ranges described in the present specification, the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

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

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

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

[0018] In this specification, "(meth)acrylic" is a concept that includes both acrylic and methacrylic, and "(meth)acryloxy group" is a concept that includes both acryloxy group and methacryloxy group.

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

[0020] In this specification, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0021] In this specification, the "solid content" of a composition means the components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. In addition, liquid components are also considered to be solid contents as long as they form a composition layer.

[0022] Unless otherwise specified, the compounds described herein may contain structural isomers, optical isomers, and isotopes. In addition, the compounds may contain one or more structural isomers, optical isomers, and isotopes. In this specification, unless otherwise specified, the bonding direction of a divalent group (e.g., -COO-) may be either "XO-CO-Z" or "X-CO-OZ" when Y in a compound represented by "XYZ" is -COO-.

[0023] [Rolled body] The wound body of the present invention will be described in detail below. The roll of the present invention is a roll of a transfer film having a temporary support, a composition layer, and a protective film in this order, the composition layer including a photosensitive composition layer. In addition, for the roll of the present invention, cross-sectional observation, which will be described later, is performed on the transfer film unwound from the roll at five different locations spaced 8 cm apart along the longitudinal direction of the transfer film, and the minimum and maximum values ​​of the five positions X and five positions Y obtained in each cross-sectional observation are all within the range of -40 to 40 μm.

[0024] The above positions X and Y are obtained by observing the cross section as described below. Cross-sectional observation: The transfer film unwound from the roll is cut along the width direction of the transfer film, and one of the two exposed cross sections is observed from the normal direction of the one cross section. In the exposed cross-section, the position of one end that is located on the outermost side of the temporary support in the width direction of the transfer film is defined as a first position, the position of one end that is located on the outermost side of the protective film in the width direction of the transfer film and is on the same side as the first position is defined as a second position, and the position of the second position is defined as position X when a position outside the first position along the width direction of the transfer film is expressed as a positive value based on the first position. In addition, the position of the other end of the exposed cross-section that is located at the outermost position of the temporary support in the width direction of the transfer film is defined as a third position, the position of the other end of the protective film that is located at the outermost position in the width direction of the transfer film and is on the same side as the third position is defined as a fourth position, and the position of the fourth position is defined as position Y when the position outside the third position along the width direction of the transfer film is expressed as a positive value based on the third position.

[0025] A specific procedure for observing the cross section will be described with reference to Fig. 1. Fig. 1 is a schematic diagram showing the process of unwinding the transfer film from the roll. First, the transfer film 12 is unwound from the roll 10, and the unwound transfer film 12 is cut along the width direction. More specifically, as shown in FIG. 1, when cutting the transfer film 12 in the width direction, the transfer film 12 is unwound and cut along a cutting line CL1 extending in the width direction of the transfer film 12. The transfer film 12 is also cut along cutting lines CL2 to CL5 spaced apart from the cutting line CL1 by a width W. Next, as described later, one of the two cross sections exposed by the cutting is observed from the normal direction of the one cross section, and the positions X and Y are measured for each cross section. As described later, five positions X and five positions Y are measured from five cross sections generated and observed along the five cutting lines CL1 to CL5.

[0026] Next, a method for measuring the position X will be described with reference to FIGS. FIG. 2 shows an example of a cut surface of a transfer film. FIG. 2 shows a partially enlarged view of the cut surface of the transfer film 12A cut by the above-mentioned procedure, which corresponds to an enlarged view of one end of the transfer film 12A. As shown in FIG. 2, the transfer film 12A has a temporary support 14A, a composition layer 16A, and a protective film 18A in this order. The composition layer 16A is a layer including a photosensitive composition layer. As shown in FIG. 2, at one end of the transfer film 12A, a protective film 18A protrudes outward beyond the temporary support 14A and the composition layer 16A. 2, the position of one end located on the outermost side of the temporary support 14A in the width direction of the transfer film 12A is defined as a first position P1A, the position of one end located on the outermost side of the protective film 18A in the width direction of the transfer film 12A and located on the same side as the first position P1A is defined as a second position P2A, and when a position on the outer side of the first position P1A in the width direction of the transfer film 12A is expressed as a positive value as shown by an arrow with the first position P1A as the reference, position X is shown as a positive value. In other words, position X, which is the position of the second position P2A based on the first position P1A, is shown as a positive value.

[0027] Also, Fig. 3 shows another example of a cut surface of a transfer film. Fig. 3 shows a partially enlarged view of the cut surface of a transfer film 12B cut by the above-mentioned procedure, which corresponds to an enlarged view of one end of the transfer film 12B. As shown in Fig. 3, the transfer film 12B has a temporary support 14B, a composition layer 16B, and a protective film 18B in this order. The composition layer 16B is a layer including a photosensitive composition layer. As shown in FIG. 3, at one end of the transfer film 12B, the temporary support 14B and the composition layer 16B protrude beyond the protective film 18B. 3, the position of one end located on the outermost side of the temporary support 14B in the width direction of the transfer film 12B is defined as a first position P1B, the position of one end located on the outermost side of the protective film 18B in the width direction of the transfer film 12B and located on the same side as the first position P1B is defined as a second position P2B, and when a position on the outer side of the first position P1B in the width direction of the transfer film 12B is expressed as a positive value with the first position P1B as the reference, the position X is shown as a negative value. In other words, the position X, which is the position of the second position P2B with the first position P1B as the reference, is shown as a negative value.

[0028] The measurement of position Y can be performed according to the same procedure as the measurement method of position X. Hereinafter, a description will be given with reference to Figs. Next, an example of both ends of the cut surface of the transfer film is shown in Fig. 4. Fig. 4 shows an overall view of the cut surface of the transfer film 12A cut by the above-mentioned procedure, and both ends of the transfer film 12A are shown. 14A, 16A, and 18A shown in Fig. 4 are synonymous with 14A, 16A, and 18A in Fig. 2. As shown in FIG. 4, at both ends of the transfer film 12A, protective films 18A protrude outward beyond the temporary support 14A and the composition layer 16A. As described above, the position X can be measured by the procedure described with reference to FIG. Also, in Figure 4, the position of the other end that is located at the outermost position of the temporary support 14A in the width direction of the transfer film 12A is designated as a third position P3A, and the position of the other end that is located at the outermost position of the protective film 18A in the width direction of the transfer film 12A and is on the same side as the third position P3A is designated as a fourth position P4A, and when a position that is outer than the third position P3A in the width direction of the transfer film 12A is represented as a positive value, as shown by the arrow, using the third position P3A as a reference, position Y is represented as a positive value. The third position P3A is located on the opposite side to the first position P1A in the width direction of the transfer film 12A, and corresponds to the position of one end located on the outermost side of the temporary support 14A. The fourth position P4A is located on the opposite side to the first position P1A in the width direction of the transfer film 12A, and corresponds to the outermost end position of the protection film 18A.

[0029] Also, another example of the cut surface of the transfer film is shown in Fig. 5. Fig. 5 shows an overall view of the cut surface of the transfer film 12B cut by the above-mentioned procedure, and both ends of the transfer film 12B are shown. 14B, 16B, and 18B shown in Fig. 5 are the same as 14B, 16B, and 18B in Fig. 3. As shown in FIG. 5, at both ends of the transfer film 12B, the temporary support 14B and the composition layer 16B protrude beyond the protective film 18B. As described above, the position X can be measured by the procedure described with reference to FIG. Also, in Figure 5, the position of the other end that is located at the outermost position of the temporary support 14B in the width direction of the transfer film 12B is designated as the third position P3B, and the position of the other end that is located at the outermost position of the protective film 18B in the width direction of the transfer film 12B and is on the same side as the third position P3B is designated as the fourth position P4B, and when a position that is outer than the third position P3B in the width direction of the transfer film 12B is represented as a positive value using the third position P3B as the reference, position Y is shown as a negative value.

[0030] As in the embodiment shown in FIGS. 2 to 5 described above, five cross-sectional points of the transfer film unwound from the roll are observed, and the value of position X at one end of the transfer film and the value of position Y at the other end of the transfer film are measured, thereby measuring the five position X values ​​and the five position Y values. From the five X positions and five Y positions thus obtained, the minimum and maximum values ​​are selected. As a specific method for measuring the positions X and Y, the cross section is observed with a scanning electron microscope to measure the above positions.

[0031] As described above, in the wound body of the present invention, the minimum and maximum values ​​among the five positions X and the five positions Y measured by the above procedure are all within the range of −40 to 40 μm. In addition, in terms of obtaining a more excellent effect of the present invention, the minimum and maximum values ​​of the five positions X and the five positions Y are preferably not less than -20 μm, more preferably not less than -1 μm, and even more preferably not less than 0.1 μm. In other words, in terms of obtaining a more excellent effect of the present invention, the minimum values ​​are preferably within the range of 0.1 to 40 μm. The minimum and maximum values ​​of the five positions X and the five positions Y are not particularly limited as long as they are 40 μm or less, but are preferably 25 μm or less.

[0032] The mechanism by which the minimum and maximum values ​​of the five positions X and the five positions Y in the transfer film unwound from the roll of the present invention are all within the range of −40 to 40 μm is not necessarily clear, but the present inventors speculate as follows. The mechanism by which the effects are obtained is not limited by the following speculation. In other words, even if the effects are obtained by a mechanism other than the following, it is included in the scope of the present invention. When the position X is more than 40 μm, the protective film 18A is extremely protruding from the temporary support 14A, so that the protective film 18A is easily peeled off when handling the roll and when unwinding the transfer film 12A from the roll. When unwinding the transfer film 12A from the roll, the transfer film 12A is conveyed using a roll, and when the protective film 18A is once peeled off and then passes through a roll, the protective film 18A adheres to the composition layer 16A again, and air bubbles may be included between the composition layer 16A and the protective film 18A. When such air bubbles are included, the composition layer 16A is pressed by the air bubbles, and as a result, the thickness of the composition layer 16A near the end portion is varied. When the composition layer 16A having such a variation in thickness is attached to the object to be attached, it is presumed that wrinkles are generated at the end portion of the attached composition layer 16A due to the variation in thickness.

[0033] Furthermore, when the position X is less than −40 μm, the protective film 18B is recessed from the temporary support 14B, so that the edge of the composition layer is exposed. When laminating the transfer film 12B in such a state, when the protective film 18B is peeled off from the composition layer 16B using an adhesive tape or the like, the adhesive tape tends to adhere to a part of the composition layer 16B as well, which causes a problem that not only the protective film 18B but also the composition layer 16B is peeled off from the temporary support 14B. In other words, it is not easy to peel off only the protective film 18B. When the position Y is equal to or greater than 40 μm or less than −40 μm, the same problem as that in the case of the position X described above occurs. For the reasons described above, in the roll of the present invention, the minimum and maximum values ​​of the five positions X and the five positions Y in the transfer film unwound from the roll are all within the range of -40 to 40 μm, and therefore the end positions of the protective film are in an appropriate range at both ends of the protective film, resulting in excellent peelability of the protective film and excellent lamination of the ends when the transfer film is laminated.

[0034] The method for adjusting the position X and the position Y to be within a predetermined range is not particularly limited, and may be a known method. For example, a method of adjusting the widthwise lengths of the temporary support, the composition layer, and the protective film to be used and laminating them, and a method of adjusting by a cutting method and conditions when slit-cutting the end of the widthwise direction of the transfer film including the temporary support, the composition layer, and the protective film.

[0035] At one end of the cross section of the transfer film described above, the relationship between the above-mentioned first position and the position of one end that is located on the outermost side of the composition layer in the width direction of the transfer film and is located on the same side as the above-mentioned first position (hereinafter also referred to as "position Ca") is not particularly limited, but when a position outside the first position along the width direction of the transfer film is expressed as a positive value based on the first position, it is preferable that the position Ca relative to the first position is within the range of -0.5 to 0.5 μm. Furthermore, at the other end of the cross section of the transfer film described above, the relationship between the above-mentioned third position and the position of one end that is located on the outermost side of the composition layer in the width direction of the transfer film and is located on the same side as the above-mentioned third position (hereinafter also referred to as "position Cb") is not particularly limited, but when a position further outward in the width direction of the transfer film than the third position is expressed as a positive value based on the third position, it is preferable that the position Cb relative to the third position is within the range of -0.5 to 0.5 μm.

[0036] The transfer film constituting the roll will be described below. The preferred embodiments of the transfer film shown below are preferred embodiments of the transfer film constituting the roll.

[0037] [Transfer film] The transfer film constituting the roll of the present invention has a temporary support, a composition layer, and a protective film in this order. The composition layer is not particularly limited as long as it includes a photosensitive composition layer. The photosensitive composition layer may be a negative photosensitive composition layer or a chemically amplified photosensitive composition layer, but is preferably a negative photosensitive composition layer. The composition layer may have a single layer structure or a structure of two or more layers. When the composition layer includes a composition layer other than the photosensitive composition layer, the other composition layer may be a thermoplastic resin layer, an intermediate layer, a refractive index adjustment layer, etc. The intermediate layer is preferably disposed between the temporary support and the photosensitive composition layer.

[0038] An example of the embodiment of the transfer film constituting the roll of the present invention will be shown below, but the present invention is not limited thereto. (1) "Temporary support / photosensitive composition layer / refractive index adjusting layer / protective film" (2) "Temporary support / photosensitive composition layer / protective film" (3) "Temporary support / intermediate layer / photosensitive composition layer / protective film" (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film" In each of the above-mentioned configurations, the photosensitive composition layer is preferably a negative photosensitive composition layer, and is also preferably a colored resin layer. The transfer film of the present invention may be used as a transfer film for a wiring protective film, as described below, or as a transfer film for an etching resist. When the transfer film is used as a wiring protection film, the transfer film preferably has the above-mentioned configuration (1) or (2), and when the transfer film is used as an etching resist, the transfer film preferably has the above-mentioned configuration (2) to (4).

[0039] In the case where the composition layer of the transfer film further has other layers on the side opposite the temporary support side of the photosensitive composition layer, the total thickness of the other layers arranged on the side opposite the temporary support side of the photosensitive composition layer is preferably 0.1 to 30%, more preferably 0.1 to 20%, of the thickness of the photosensitive composition layer.

[0040] From the viewpoint of preventing the generation of air bubbles in the lamination step described later, the maximum waviness width of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit of the maximum waviness width is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the undulation of the transfer film is a value measured by the following procedure. First, the transfer film is cut in a direction perpendicular to the main surface to a size of 20 cm long x 20 cm wide, and the protective film is peeled off to prepare a test sample. Next, the test sample is placed on a flat and horizontal stage so that the surface of the temporary support faces the stage. After being placed, the surface of the sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) in a central 10 cm square range of the test sample to obtain a three-dimensional surface image, and the minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. The above operation is performed on 10 test samples, and the arithmetic average value is taken as the "maximum waviness width of the transfer film".

[0041] The transfer film of the present invention will be described below by taking an example of a specific embodiment. The transfer film of the first embodiment is preferably used as a transfer film for a wiring protection film, and the transfer film of the second embodiment is preferably used as a transfer film for a wiring protection film and an etching resist.

[0042] [Transfer film of the first embodiment] An example of the transfer film of the first embodiment will be described below. The transfer film 30 shown in FIG. 6 has a temporary support 32, a composition layer 38 including a photosensitive composition layer 34 and a refractive index adjusting layer 36, and a protective film 40, in this order. Although the transfer film 30 shown in FIG. 6 has a refractive index matching layer 36 arranged thereon, the refractive index matching layer 36 does not necessarily have to be arranged. Each element constituting the transfer film will be described below.

[0043] <<Temporary support>> The transfer film has a temporary support. The temporary support is a member that supports the composition layer, and is ultimately removed by a peeling treatment.

[0044] The temporary support may have a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film, which is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of the film include a polyethylene terephthalate film (eg, a biaxially oriented polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film. Among these, a polyethylene terephthalate film is preferable as the temporary support. Moreover, it is preferable that the film used as the temporary support is free from deformation such as wrinkles and scratches.

[0045] The temporary support is preferably highly transparent in view of being able to perform pattern exposure through the temporary support, and the transmittance at 313 nm, 365 nm, 313 nm, 405 nm and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. Preferable values ​​of the transmittance include, for example, 87%, 92%, 98%, etc. From the viewpoint of pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, even more preferably 0.4% or less, and particularly preferably 0.1% or less. However, when the temporary support is peeled off during exposure as described later, the haze of the temporary support is not limited to this. The haze of the temporary support is preferably 0.05% or more, and more preferably 0.1% or more, from the viewpoint of transportability during production of the temporary support. The above-mentioned haze is a total light haze (%) in accordance with JIS K 7136:2000, and can be measured as a total light haze using a haze meter (device name: HZ-2, manufactured by Suga Test Instruments Co., Ltd.). When the temporary support is subjected to a surface treatment or an undercoat treatment as described below, the haze is measured as a value obtained by measuring the temporary support after the above treatment.

[0046] From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects having a diameter of 1 μm or more in the temporary support is 50 / 10 mm. 2 Less than 10 pieces / 10mm is preferable. 2 Less than 3 pieces / 10mm is more preferable. 2 Less than 0 / 10mm is more preferable. 2 is particularly preferred.

[0047] The thickness of the temporary support is not particularly limited, but is preferably 5 to 300 μm, and from the viewpoints of ease of handling and versatility, is more preferably 5 to 150 μm, further preferably 5 to 50 μm, and most preferably 5 to 25 μm. The thickness of the temporary support is calculated as the average value of any five points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0048] In order to improve the adhesion between the temporary support and the composition layer, the side of the temporary support which comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like. When surface modification is performed by UV irradiation, the exposure dose is 10 to 2000 mJ / cm 2 is preferable, and 50 to 1000 mJ / cm 2 is more preferred. Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, light-emitting diodes (LEDs), etc. that emit light in the 150 to 450 nm wavelength range. As long as the light irradiation amount is within this range, there are no particular limitations on the lamp output or illuminance. In addition, the temporary support may be subjected to an undercoat treatment to form an undercoat layer containing polyvinylidene chloride resin, styrene butadiene rubber, gelatin, or the like, in terms of adhesion to the composition layer, etc.

[0049] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 25 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm.

[0050] Preferred forms of the temporary support are described, for example, in paragraphs

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

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

[0029] to

[0040] of WO 2018 / 179370 A, the contents of which are incorporated herein by reference.

[0051] In order to provide handleability, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include Lumirror 16KS40, Lumirror 25QS40, Lumirror 25QS60, Lumirror 16FB40 (all manufactured by Toray Industries, Inc.), Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0052] <<Photosensitive composition layer>> The transfer film has a photosensitive composition layer. After the photosensitive composition layer is transferred onto a receiving material, it is possible to form a pattern on the receiving material by carrying out exposure and development. The photosensitive composition layer is preferably a negative type. The negative type photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in a developer is reduced by exposure. When the photosensitive composition layer is a negative type photosensitive composition layer, the pattern formed corresponds to a cured layer.

[0053] Components that can be contained in the photosensitive composition layer will be described in detail below.

[0054] <Binder polymer> The photosensitive composition layer may contain 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, epoxy acrylate resin obtained by reacting an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resin obtained by reacting an epoxy acrylate resin with an acid anhydride.

[0055] One preferred embodiment of the binder polymer is a (meth)acrylic resin, which has excellent alkaline developability and film formability. In this specification, the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from a (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of structural units derived from (meth)acrylic compounds, or may contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of structural units derived from (meth)acrylic compounds is 100% by mass or less based on the total structural units of the (meth)acrylic resin.

[0056] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, (meth)acrylic acid glycidyl esters, (meth)acrylic acid benzyl esters, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl esters are preferred. Examples of (meth)acrylamides include acrylamides such as diacetoneacrylamide.

[0057] The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. As the (meth)acrylic acid ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0058] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer that forms the above-mentioned structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that is copolymerizable with a (meth)acrylic compound, and examples thereof include styrene compounds that may have a substituent at the α-position or aromatic ring, such as styrene, vinyl toluene, and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0059] In order to improve the alkaline developability, the (meth)acrylic resin preferably has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Among these, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0060] The content of the structural unit having an acid group in the (meth)acrylic resin (preferably a structural unit derived from (meth)acrylic acid) is preferably 10% by mass or more based on the total mass of the (meth)acrylic resin in terms of excellent developability. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.

[0061] Moreover, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester. When the (meth)acrylic resin has a structural unit derived from an alkyl (meth)acrylate, the content of the structural unit derived from an alkyl (meth)acrylate in the (meth)acrylic resin is preferably 1 to 90 mass%, more preferably 1 to 50 mass%, and even more preferably 1 to 30 mass%, based on the total structural units of the (meth)acrylic resin.

[0062] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferred, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is more preferred. Furthermore, 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 preferred.

[0063] In addition, in terms of better effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from an alkyl methacrylate ester, and more preferably has both structural units derived from methacrylic acid and structural units derived from an alkyl methacrylate ester. The total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl ester in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total structural units of the (meth)acrylic resin, in terms of the superior effect of the present invention. The upper limit is not particularly limited, and may be 100% by mass or less, and is preferably 80% by mass or less.

[0064] In addition, in terms of the effects of the present invention being more excellent, it is also preferable that the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from an alkyl methacrylate ester, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from an alkyl acrylate ester. In order to obtain a more excellent effect of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from an alkyl methacrylate ester is preferably 60 / 40 to 80 / 20 in terms of mass ratio relative to the total content of the structural units derived from acrylic acid and the structural units derived from an alkyl acrylate ester.

[0065] The (meth)acrylic resin preferably has an ester group at the end, in view of excellent developability of the photosensitive composition layer after transfer. The terminal portion of the (meth)acrylic resin is composed of a portion derived from the polymerization initiator used in the synthesis. The (meth)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0066] Another preferred embodiment of the binder polymer is an alkali-soluble resin. From the viewpoint of developability, the binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more. In addition, the binder polymer is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin), and even more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth)acrylic resin), from the viewpoint of being easily thermally crosslinked with the crosslinking component by heating to form a strong film. When the binder polymer is a resin having a carboxy group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to thermally crosslink the resin. In addition, when the carboxy group of the resin having a carboxy group is dehydrated and hydrophobized, the humidity and heat resistance can be improved.

[0067] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above-mentioned acid value condition, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph

[0025] of JP2011-095716A, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs

[0033] to

[0052] of JP2010-237589A, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.

[0068] Another preferred embodiment of the binder polymer is a styrene-acrylic copolymer. In this specification, a styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and the total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic compound is preferably 30 mass% or more, and more preferably 50 mass% or more, based on the total structural units of the copolymer. The content of the structural units derived from a styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, based on all the structural units of the copolymer. The content of the structural units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, based on all structural units of the copolymer.

[0069] The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, in that the effects of the present invention are more excellent. Examples of monomers that form structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, monomers having an aralkyl group or styrene are preferred. Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0070] An example of the monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0071] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of these, benzyl (meth)acrylate is preferred.

[0072] In addition, the binder polymer more preferably has a constitutional unit represented by the following formula (S) (a constitutional unit derived from styrene), in that the effects of the present invention are more excellent.

[0073] [ka]

[0074] When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90 mass%, more preferably 10 to 70 mass%, and further preferably 20 to 60 mass%, based on the total structural units of the binder polymer, in terms of better effects of the present invention. In addition, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 60 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, even more preferably 20 to 60 mol %, and particularly preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. In this specification, when the content of the "structural unit" is specified by a molar ratio, the "structural unit" is synonymous with the "monomer unit". In addition, in this specification, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0075] The binder polymer preferably has an aliphatic hydrocarbon ring structure in terms of better effects of the present invention. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. In particular, the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

[0076] Examples of the ring that constitutes the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring. Among these, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred in terms of the effects of the present invention being more excellent, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 ]decane ring) is more preferred. Examples of monomers that form a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. In addition, in terms of better effects of the present invention, the binder polymer more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0077] [ka]

[0078] In the formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0079] R in formula (Cy) M is preferably a methyl group. R in formula (Cy) Cy is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms, in that the effects of the present invention are more excellent. In addition, R in formula (Cy) Cy In terms of achieving superior effects of the present invention, the aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane 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 even more preferably a tetrahydrodicyclopentadiene ring structure. Furthermore, R in formula (Cy) Cy In terms of achieving better effects of the present invention, the aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring in which two to four aliphatic hydrocarbon rings are condensed. Furthermore, R in formula (Cy) Cyis preferably a group in which the oxygen atom of -C(=O)O- in formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and further preferably a dicyclopentanyl group, in that the effects of the present invention are more excellent.

[0080] The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types of structural units having an aliphatic hydrocarbon ring structure. When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%, based on the total structural units of the binder polymer, in terms of better effects of the present invention. In addition, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention.

[0081] 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 units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 40 to 75 mass%, based on the total structural units of the binder polymer, in terms of better effects of the present invention. In addition, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 40 to 60 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 40 to 60 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. In addition, in order to obtain a more excellent effect of the present invention, it is preferable that the molar amount nS of the constitutional unit represented by the above formula (S) in the binder polymer and the molar amount nCy of the constitutional unit represented by the above formula (Cy) satisfy the relationship shown in the following formula (SCy), more preferably the following formula (SCy-1), and even more preferably the following formula (SCy-2). 0.2≦nS / (nS+nCy)≦0.8 Formula (SCy) 0.30≦nS / (nS+nCy)≦0.75 Formula (SCy-1) 0.40≦nS / (nS+nCy)≦0.70 Formula (SCy-2)

[0082] The binder polymer preferably has a structural unit having an acid group, in that the effects of the present invention are more excellent. The acid group includes a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with the carboxy group being preferred. As the structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0083] [ka]

[0084] The binder polymer may have one type of structural unit having an acid group alone, or may have two or more types of structural units having an acid group. When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50 mass%, more preferably 5 to 40 mass%, and even more preferably 10 to 30 mass%, based on the total structural units of the binder polymer, in terms of better effects of the present invention. The content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 20 to 40 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the (meth)acrylic acid-derived structural units in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 20 to 40 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention.

[0085] The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, in that the effects of the present invention are more excellent. The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group. In addition, when the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in a side chain. In this specification, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branching off from the main chain. The ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.

[0086] [ka]

[0087] The binder polymer may have one type of structural unit having a reactive group, or may have two or more types of structural units having a reactive group. When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70 mass%, more preferably 10 to 50 mass%, and even more preferably 20 to 40 mass%, based on the total structural units of the binder polymer, in terms of better effects of the present invention. In addition, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in terms of better effects of the present invention.

[0088] Means for introducing a reactive group into a binder polymer and means for introducing a reactive group into a binder polymer include a method of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic acid anhydride. A preferred example of a method for introducing a reactive group into a binder polymer is to synthesize a polymer having a carboxy group by polymerization, and then react a part of the carboxy group of the obtained polymer with glycidyl (meth)acrylate by a polymer reaction to introduce a (meth)acryloxy group into the polymer. By this method, a binder polymer having a (meth)acryloxy group in the side chain can be obtained. The polymerization reaction is preferably carried out at a temperature of 70 to 100° C., more preferably at a temperature of 80 to 90° C. The polymerization initiator used in the polymerization reaction is preferably an azo-based initiator, more preferably V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The polymerization reaction is preferably carried out at a temperature of 80 to 110° C. In the polymerization reaction, it is preferable to use a catalyst such as an ammonium salt.

[0089] As the binder polymer, the following polymers are preferred in terms of providing better effects for the present invention: The content ratios (a to d) of each of the structural units shown below and the weight average molecular weight Mw can be appropriately changed depending on the purpose.

[0090] [ka] In the above polymer, a: 20 to 60 wt %, b: 10 to 50 wt %, c: 5.0 to 25 wt %, and d: 10 to 50 wt % are preferred.

[0091] [ka] In the above polymer, a: 20 to 60 wt %, b: 10 to 50 wt %, c: 5.0 to 25 wt %, and d: 10 to 50 wt % are preferred.

[0092] [ka] In the above polymer, a: 30 to 65 wt %, b: 1.0 to 20 wt %, c: 5.0 to 25 wt %, and d: 10 to 50 wt % are preferred.

[0093] [ka] In the above polymer, it is preferable that a: 1.0 to 20 wt %, b: 20 to 60 wt %, c: 5.0 to 25 wt %, and d: 10 to 50 wt %.

[0094] The binder polymer may also contain a polymer having a structural unit with 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 is preferably a cyclic carboxylic acid anhydride structure. The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0095] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 in its main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0096] [ka]

[0097] In formula P-1, R A1a represents a substituent, n 1a R A1a may be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, n 1a represents an integer greater than or equal to 0.

[0098] R A1a Examples of the substituent represented by the formula (I) include an alkyl group. Z 1a As the alkylene group, 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 even more preferable. n 1a represents an integer equal to or greater than 0. 1a When represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. n 1a If represents an integer of 2 or more, there are multiple R A1a may be the same or different. In addition, if there are multiple R A1a may be bonded to each other to form a ring, but preferably do not bond to each other to form a ring.

[0099] As a 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, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is even 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.

[0100] Specific examples of structural units having a carboxylic acid anhydride structure are given below, but the structural units having a carboxylic acid anhydride structure are not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0101] [ka]

[0102] [ka]

[0103] The structural unit having a carboxylic acid anhydride structure in the polymer X may be of one type alone, or of two or more types.

[0104] The total content of the structural units having a carboxylic acid anhydride structure relative to all the structural units of the polymer X is preferably from 0 to 60 mol %, more preferably from 5 to 40 mol %, and even more preferably from 10 to 35 mol %.

[0105] The photosensitive composition layer may contain only one type of polymer X, or may contain two or more types. When the photosensitive composition layer contains polymer X, the content of polymer X is preferably 0.1 to 30 mass %, more preferably 0.2 to 20 mass %, even more preferably 0.5 to 20 mass %, and still more preferably 1 to 20 mass %, relative to the total mass of the photosensitive composition layer, in terms of better effects of the present invention.

[0106] The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably from 10,000 to 50,000, and particularly preferably from 15,000 to 30,000, in terms of superior effects of the present invention.

[0107] The acid value of the binder polymer is preferably from 10 to 200 mgKOH / g, more preferably from 60 to 200 mgKOH / g, further preferably from 60 to 150 mgKOH / g, and particularly preferably from 70 to 130 mgKOH / g. The acid value of the binder polymer is a value measured according to the method described in JIS K0070: 1992. From the viewpoint of developability, the dispersity of the binder polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, further preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0108] The photosensitive composition layer may contain only one type of binder polymer, or may contain two or more types of binder polymer. The content of the binder polymer is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and even more preferably from 30 to 70% by mass, based on the total mass of the photosensitive composition layer, in that the effects of the present invention are more excellent.

[0109] <Polymerizable compound> The photosensitive composition layer may contain a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, and the radical polymerizable group is preferable.

[0110] The polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound"). The ethylenically unsaturated group is preferably a (meth)acryloxy group. The ethylenically unsaturated compound in this specification is a compound other than the above-mentioned binder polymer, and preferably has a molecular weight of less than 5,000.

[0111] One preferred embodiment of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M"). Q 2 -R 1 -Q 1 Formula (M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group; R 1 represents a divalent linking group having a chain structure.

[0112] Q in formula (M) 1 and Q 2 From the viewpoint of ease of synthesis, Q 1 and Q 2 are preferably the same group. In addition, Q in formula (M) 1 and Q 2 is preferably an acryloyloxy group from the viewpoint of reactivity. R in formula (M) 1 As the alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is further preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. 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 may be, for example, a branched, cyclic, or straight-chain alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. An alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a straight-chain alkylene group is even more preferred. In addition, the above L 1each 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.

[0113] In addition, Q in compound M 1 and Q 2 The number of atoms in the shortest linking chain between is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12, in terms of superior effects of the present invention. As used herein, "Q 1 and Q 2 The number of atoms in the shortest chain connecting Q 1 R to be connected 1 Q from atoms in 2 R to be connected 1 is the shortest number of atoms that can connect to an atom in

[0114] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, in terms of superior effects of the present invention, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is even more preferred.

[0115] One of the preferred embodiments of the polymerizable compound is an ethylenically unsaturated compound having two or more functionalities. In this specification, the term "di- 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 preferred. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0116] The difunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of the difunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, and 1,4-cyclohexanediol di(meth)acrylate.

[0117] Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and dioxane glycol diacrylate (KAYARAD R-604, manufactured by Nippon Kayaku Co., Ltd.).

[0118] The tri- or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0119] Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0120] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0121] The polymerizable compound also includes a urethane (meth)acrylate compound. Examples of the urethane (meth)acrylate include urethane di(meth)acrylate, such as propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. The urethane (meth)acrylate may also be a trifunctional or higher urethane (meth)acrylate. The lower limit of the number of functional groups is more preferably 6 or more, and even more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0122] One of the preferred embodiments of the polymerizable compound is an ethylenically unsaturated compound having an acid group. Acid groups include phosphate groups, sulfo groups, and carboxy groups. Of these, the acid group is preferably a carboxy group. Examples of the ethylenically unsaturated compound having an acid group include a tri- or tetrafunctional ethylenically unsaturated compound having an acid group [a carboxy group has been introduced into a pentaerythritol tri- or tetraacrylate (PETA) skeleton (acid value: 80 to 120 mg KOH / g)], a penta- or hexafunctional ethylenically unsaturated compound having an acid group (a carboxy group has been introduced into a dipentaerythritol penta- or hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mg KOH / g)], and the like. These trifunctional or higher ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group, if necessary.

[0123] The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, the developability and film strength are further improved. The di- or higher functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of difunctional or higher ethylenically unsaturated compounds having a carboxy group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0124] 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 preferred, and the contents of this publication are incorporated herein by reference.

[0125] Examples of the polymerizable compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters. These may be used alone or in combination of two or more.

[0126] Examples of compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylates having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylates having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylates having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among these, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate are more preferred.

[0127] Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0128] As the polymerizable compound (particularly, an ethylenically unsaturated compound), those containing an ester bond are particularly preferred, in that they provide excellent developability of the photosensitive composition layer after transfer. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but in terms of excellent effects of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred. From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure. Examples of ethylenically unsaturated compounds having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0129] One of the preferred embodiments of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). The polymerizable compound is preferably a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and even more preferably tricyclodecane dimethanol di(meth)acrylate. As the aliphatic hydrocarbon ring structure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure is preferred in terms of achieving superior effects of the present invention.

[0130] The molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, further preferably from 280 to 2,200, and particularly preferably from 300 to 2,200. Among the polymerizable compounds contained in the photosensitive composition layer, the content ratio of polymerizable compounds having a molecular weight of 300 or less is preferably 30 mass % or less, more preferably 25 mass % or less, and even more preferably 20 mass % or less, based on the content of all polymerizable compounds contained in the photosensitive composition layer.

[0131] As one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a difunctional or higher ethylenically unsaturated compound, more preferably contains a trifunctional or higher ethylenically unsaturated compound, and even more preferably contains a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0132] In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and a binder polymer having a structural unit having an aliphatic hydrocarbon ring.

[0133] In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and further preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid modified product of dipentaerythritol pentaacrylate.

[0134] In addition, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0135] In addition, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoints of suppressing development residues and rust prevention, the photosensitive composition layer preferably contains a difunctional ethylenically unsaturated compound (preferably a difunctional (meth)acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound). In the photosensitive composition layer, the mass ratio of the content of the difunctional ethylenically unsaturated compound to the content of the tri- or higher functional ethylenically unsaturated compound is preferably from 10:90 to 90:10, and more preferably from 30:70 to 70:30. The content of the difunctional ethylenically unsaturated compound relative to the total amount of all the ethylenically unsaturated compounds is preferably from 20 to 80 mass %, more preferably from 30 to 70 mass %. The content of the difunctional ethylenically unsaturated compound in the photosensitive composition layer is preferably from 10 to 60% by mass, more preferably from 15 to 40% by mass.

[0136] In one preferred embodiment of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. In addition, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoints of substrate adhesion, suppression of development residue, and rust prevention, the photosensitive composition layer preferably contains a compound M and an ethylenically unsaturated compound having an acid group, more preferably contains a compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, still more preferably contains a compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains a compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound. In addition, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the photosensitive composition layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0137] The photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the di- or higher functional ethylenically unsaturated compound in the above ethylenically unsaturated compound is preferably 60 to 100 mass %, more preferably 80 to 100 mass %, and even more preferably 90 to 100 mass %, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0138] The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more kinds. The content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive composition layer is preferably 1 to 70 mass %, more preferably 5 to 70 mass %, even more preferably 5 to 60 mass %, and particularly preferably 5 to 50 mass %, relative to the total mass of the photosensitive composition layer.

[0139] <Polymerization initiator> The photosensitive composition layer may contain a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter also referred to as an "α-aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as an "N-phenylglycine-based photopolymerization initiator").

[0140] The photopolymerization initiator preferably contains at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based polymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably contains at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

[0141] In addition, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP2011-95716A and paragraphs

[0064] to

[0081] of JP2015-014783A may be used.

[0142] Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, IGM Resins BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad (registered trademark) 907, IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad (registered trademark) 127, IGM Resins BV], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad (registered trademark) 369, IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad (registered trademark) 1173, IGM Resins BV], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad (registered trademark) 184, IGM Resins BV] BV], 2,2-dimethoxy-1,2-diphenylethan-1-one [product name: Omnirad (registered trademark) 651, IGM Resins B.V Co., Ltd.], oxime ester type [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyl oxime) (trade name: TR-PBG-3 26, Changzhou Strong Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.), APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, Shenzhen UV-ChemTech Ltd.), etc.

[0143] The photopolymerization initiator may be used alone or in combination of two or more. When two or more types are used, it is preferable to use an oxime-based photopolymerization initiator and at least one selected from an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator. When the photosensitive composition layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the photosensitive composition layer, and the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive composition layer.

[0144] <Heterocyclic compounds> The photosensitive composition layer may contain a heterocyclic compound. The heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocycle. Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

[0145] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. Among the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0146] Preferable specific examples of the heterocyclic compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0147] [ka]

[0148] [ka]

[0149] Examples of the tetrazole compound include the following compounds.

[0150] [ka]

[0151] [ka]

[0152] Examples of the thiadiazole compound include the following compounds.

[0153] [ka]

[0154] Examples of the triazine compound include the following compounds.

[0155] [ka]

[0156] Examples of rhodanine compounds include the following compounds.

[0157] [ka]

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

[0159] [ka]

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

[0161] [ka]

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

[0163] [ka]

[0164] [ka]

[0165] Examples of the benzoxazole compound include the following compounds.

[0166] [ka]

[0167] The heterocyclic compounds may be used alone or in combination of two or more. When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0 mass %, more preferably 0.10 to 10.0 mass %, still more preferably 0.30 to 8.0 mass %, and particularly preferably 0.50 to 5.0 mass %, relative to the total mass of the photosensitive composition layer.

[0168] <Aliphatic thiol compounds> The photosensitive composition layer may contain an aliphatic thiol compound. When the photosensitive composition layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with a radical polymerizable compound having an ethylenically unsaturated group, thereby suppressing the cure shrinkage of the film formed and reducing stress.

[0169] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a di- or higher functional aliphatic thiol compound). Among the above, as the aliphatic thiol compound, polyfunctional aliphatic thiol compounds are preferred from the viewpoint of adhesion of the pattern to be formed (particularly adhesion after exposure). In this specification, the term "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also called "mercapto groups") in the molecule.

[0170] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of at least 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and further preferably 150 to 1,000.

[0171] The number of functional groups of the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of adhesion of the formed pattern.

[0172] Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropione), ester), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

[0173] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0174] Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0175] The photosensitive composition layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds.

[0176] When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5 mass% or more, more preferably 5 to 50 mass%, even more preferably 5 to 30 mass%, and particularly preferably 8 to 20 mass%, relative to the total mass of the photosensitive composition layer.

[0177] <Thermal crosslinkable compound> The photosensitive composition layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesion of the obtained uncured film. In this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound but as a thermally crosslinkable compound. Examples of the thermal crosslinking compound include an epoxy compound, an oxetane compound, a methylol compound, and a blocked isocyanate compound. Among these, the blocked isocyanate compound is preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease and its function as a protective film tends to be enhanced. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0178] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably from 90 to 160°C, and more preferably from 100 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of a 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 suitably used. However, the differential scanning calorimeter is not limited to this.

[0179] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, and other compounds having a structure represented by -C(=N-OH)- in the molecule). Among these, as the blocking agent having a dissociation temperature of 90 to 160° C., for example, at least one selected from oxime compounds and pyrazole compounds is preferable from the viewpoint of storage stability.

[0180] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the standpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by converting it into an isocyanurate. Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred in that the dissociation temperature can be set in a preferred range more easily than a compound not having an oxime structure, and development residues can be reduced.

[0181] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radically polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0182] As the blocked isocyanate compound, commercially available products 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, etc. (all manufactured by Showa Denko K.K.), and blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) SBN-70D, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corp.). The blocked isocyanate compound preferably contains a blocked isocyanate compound having an NCO value of 4.5 mmol / g or more (hereinafter, sometimes referred to as the first blocked isocyanate compound) in terms of better effects of the present invention. The NCO value of the first blocked isocyanate compound is preferably 5.0 mmol / g or more, more preferably 5.3 mmol / g or more. The upper limit of the NCO value of the first blocked isocyanate compound is preferably 8.0 mmol / g or less, more preferably 6.0 mmol / g or less, even more preferably less than 5.8 mmol / g, and particularly preferably 5.7 mmol / g or less, in terms of obtaining better effects of the present invention. The NCO value of the blocked isocyanate compound in the present invention means the number of moles of isocyanate groups contained in 1 g of the blocked isocyanate compound, and is a value calculated from the structural formula of the blocked isocyanate compound. The first blocked isocyanate compound preferably has a ring structure in that the effects of the present invention are more excellent. Examples of the ring structure include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocycle, and in that the effects of the present invention are more excellent, an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring are preferred, and an aliphatic hydrocarbon ring is more preferred. Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, and among these, a cyclohexane ring is preferable. Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, with the benzene ring being preferred. A specific example of the heterocyclic ring is an isocyanurate ring. When the first blocked isocyanate compound has a ring structure, in terms of better effects of the present invention, the number of rings is preferably 1 to 2, and more preferably 1. When the first blocked isocyanate compound contains a condensed ring, the number of rings constituting the condensed ring is counted, and for example, the number of rings in a naphthalene ring is counted as 2.

[0183] The number of blocked isocyanate groups in the first blocked isocyanate compound is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2, in terms of excellent strength of the formed pattern and excellent effects of the present invention.

[0184] The first blocked isocyanate compound is preferably a blocked isocyanate compound represented by formula Q, in that the effects of the present invention are more excellent. B 1 -A 1 -L 1 -A 2 -B 2 formula Q

[0185] In formula Q, B 1 and B. 2 each independently represents a blocked isocyanate group. The blocked isocyanate group is not particularly limited, but is preferably a group in which an isocyanate group is blocked with an oxime compound, in that the effects of the present invention are more excellent. Specifically, a group in which an isocyanate group is blocked with methyl ethyl ketoxime (specifically, a group represented by *-NH-C(=O)-ON=C(CH3)-C2H5, where * is A 1 Or A 2 represents the bonding position with.) is more preferred. B 1 and B. 2 are preferably the same group.

[0186] In formula Q, A 1 and A 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, and preferably an alkylene group having 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic, but is preferably linear. The alkylene group has 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 carbon atom, in that the effects of the present invention are more excellent. A 1 and A 2 are preferably the same group.

[0187] In formula Q, L 1 represents a divalent linking group. Specific examples of the divalent linking group include divalent hydrocarbon groups. Specific examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by linking two or more of these groups. The divalent saturated hydrocarbon group may be linear, branched or cyclic, and is preferably cyclic in view of providing better effects for the present invention. The number of carbon atoms in the divalent saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 10, and even more preferably 5 to 8, in view of providing better effects for the present invention. The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and an example of the group is a phenylene group. The divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group). Among these, the divalent linking group is preferably a linear, branched or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a group in which a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms is linked to a linear alkylene group having 1 to 3 carbon atoms, a divalent aromatic hydrocarbon group which may have a substituent, or a group in which a divalent aromatic hydrocarbon group is linked to a linear alkylene group having 1 to 3 carbon atoms, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms or a phenylene group which may have a substituent, still more preferably a cyclohexylene group or a phenylene group which may have a substituent, and particularly preferably a cyclohexylene group.

[0188] The blocked isocyanate compound represented by formula Q is particularly preferably a blocked isocyanate compound represented by formula QA, in that the effects of the present invention are more excellent. B 1a -A 1a -L 1a -A 2a -B 2a QA

[0189] In the QA section, B 1a and B. 2a Each independently represents a blocked isocyanate group. 1a and B. 2a A preferred embodiment of the formula Q is 1 and B. 2 is the same as:

[0190] In the QA, A 1a and A 2a Each of A independently represents a divalent linking group. 1a and A 2a A preferred embodiment of the divalent linking group in formula Q is 1 and A 2 is the same as:

[0191] In the formula QA, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group. L 1a The cyclic divalent saturated hydrocarbon group in preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, further preferably 5 or 6 carbon atoms, and particularly preferably 6 carbon atoms. L 1a A preferred embodiment of the divalent aromatic hydrocarbon group in the formula Q is 1 is the same as: Among them, L 1a is preferably a cyclic divalent saturated hydrocarbon group, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, still more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, particularly preferably a cyclic divalent saturated hydrocarbon group having 5 to 6 carbon atoms, and most preferably a cyclohexylene group. L 1aWhen is a cyclohexylene group, the blocked isocyanate compound represented by the formula QA may be an isomer mixture of cis and trans isomers (hereinafter also referred to as a "cis-trans isomer mixture"). The mass ratio of cis isomer to trans isomer is preferably cis / trans=10 / 90 to 90 / 10, and more preferably cis / trans=40 / 60 to 60 / 40.

[0192] Specific examples of the first blocked isocyanate compound are shown below, but the first blocked isocyanate compound is not limited thereto.

[0193] [ka]

[0194] The thermally crosslinkable compound may be used alone or in combination of two or more kinds. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0195] <Surfactant> The photosensitive composition layer may contain a surfactant. Examples of the surfactant include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0196] Examples of the surfactant include a hydrocarbon surfactant, a fluorine surfactant, and a silicone surfactant. From the viewpoint of improving environmental compatibility, it is preferable that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon surfactant or a silicone surfactant. In addition, the surfactant is preferably a nonionic surfactant. Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, and EXP.MFS-33. 0, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent Examples include 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 U-120E (Unichem Co., Ltd.). Also suitable for use as the fluorosurfactant are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is broken and the fluorine atom volatilizes. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016)), such as Megafac DS-21. 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. Furthermore, as the fluorosurfactant, a block polymer can also be used. In addition, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0197] From the viewpoint of improving environmental compatibility, it is preferable that the fluorosurfactant be a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, and the like. Specific examples include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (all of which are registered trademarks of BASF), Solsperse 20000 (all of which are manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all of which are manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), Paionin D-1105, D-6112, D-6112-W, D-6315 (all of which are manufactured by Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all of which are manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0198] Silicone surfactants include linear polymers consisting of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or ends.

[0199] Specific examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), as well as X-22-4952, X-22-4272, X-2 2-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, K F-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP -125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicones Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (all manufactured by BYK-Chemie).

[0200] The surfactant may be used alone or in combination of two or more kinds. When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably from 0.01 to 3.0 mass %, more preferably from 0.01 to 1.0 mass %, and further preferably from 0.05 to 0.80 mass %, based on the total mass of the photosensitive composition layer.

[0201] <Polymerization inhibitor> The photosensitive composition layer may contain a polymerization inhibitor. The polymerization inhibitor means a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0202] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-tert nitroso compounds or salts thereof, such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds, such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds, such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds, such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among them, in terms of superior effects of the present invention, the polymerization inhibitor is preferably at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound, and more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salt.

[0203] The polymerization inhibitor may be used alone or in combination of two or more kinds. When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.02 to 2.0 mass%, based on the total mass of the photosensitive composition layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.01 to 1.0 mass%, based on the total mass of the polymerizable compounds.

[0204] <Hydrogen donor compound> The photosensitive composition layer may contain a hydrogen donor compound. The hydrogen donor compound has the effect of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

[0205] Examples of hydrogen donor compounds include amines and amino acid compounds.

[0206] Examples of amines include compounds described in MR Sander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), JP-B-020189 / 1969, JP-A-51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure No. 33825. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among these, in terms of obtaining superior effects of the present invention, the amine is preferably at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0207] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred as the amino acid compound in that the effects of the present invention are more excellent.

[0208] Further, examples of hydrogen donor compounds include organometallic compounds (such as tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (such as trithiane) described in JP-A-6-308727.

[0209] The hydrogen donor compounds may be used alone or in combination of two or more kinds. When the photosensitive composition layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01 to 10.0 mass %, more preferably 0.01 to 8.0 mass %, and even more preferably 0.03 to 5.0 mass %, relative to the total mass of the photosensitive composition layer, from the viewpoint of improving the curing rate through a balance between the polymerization growth rate and chain transfer.

[0210] <Impurities, etc.> The photosensitive composition layer may contain a certain amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halide ions (chloride ions, bromide ions, iodide ions), sodium ions, and potassium ions are easily mixed in as impurities, so it is preferable to set the content to the following.

[0211] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, based on mass. The content of impurities in the photosensitive composition layer can be 1 ppb or more, or 0.1 ppm or more, based on mass. A specific example of the content of impurities in the photosensitive composition layer is an embodiment in which all of the above impurities are 0.6 ppm, based on mass.

[0212] Methods for keeping the amount of impurities within the above range include selecting raw materials for the photosensitive composition layer that contain a small amount of impurities, preventing impurities from being mixed in during the formation of the photosensitive composition layer, and removing them by washing. By such methods, the amount of impurities can be kept within the above range.

[0213] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0214] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably low. The content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit can be 10 ppb or more, and can be 100 ppb or more, by mass. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. They can also be quantified by known measurement methods.

[0215] The water content in the photosensitive composition layer is preferably from 0.01 to 1.0% by mass, and more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0216] <Residual monomer> The photosensitive composition layer may contain residual monomers of each of the structural units of the alkali-soluble resin described above. From the viewpoints of patterning property and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, based on the total mass of the alkali-soluble resin. Although there is no particular lower limit, it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning property and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm or less, based on the total mass of the photosensitive composition layer. Although there is no particular lower limit, it is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

[0217] The amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range. The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

[0218] <Other ingredients> The photosensitive composition layer may contain components other than those described above (hereinafter, also referred to as "other components"). Examples of the other components include particles (e.g., metal oxide particles), colorants, and antioxidants. Examples of the other components include other additives described in paragraphs

[0058] to

[0071] of JP-A-2000-310706.

[0219] (particle) The particles are preferably metal oxide particles. The metals in the metal oxide particles include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle size of the particles is, for example, preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and taking the arithmetic mean of the measurement results. If the particle shape is not spherical, the longest side is used as the particle size.

[0220] When the photosensitive composition layer contains particles, it may contain only one type of particles having different metal species, sizes, etc., or may contain two or more types of particles. The photosensitive composition layer does not contain particles, or, if the photosensitive composition layer contains particles, the particle content is preferably more than 0 mass% and not more than 35 mass%, relative to the total mass of the photosensitive composition layer; more preferably, the photosensitive composition layer does not contain particles, or the particle content is more than 0 mass% and not more than 10 mass%, relative to the total mass of the photosensitive composition; even more preferably, the photosensitive composition layer does not contain particles, or the particle content is more than 0 mass% and not more than 5 mass%, relative to the total mass of the photosensitive composition layer; even more preferably, the photosensitive composition layer does not contain particles, or the particle content is more than 0 mass% and not more than 1 mass%, relative to the total mass of the photosensitive composition layer; and particularly preferably, the photosensitive composition layer does not contain particles.

[0221] (Coloring agent) The photosensitive composition layer may contain a small amount of a colorant (pigment, dye, etc.). However, from the standpoint of transparency, for example, it is preferable that the photosensitive composition layer does not substantially contain a colorant. When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1 mass %, more preferably less than 0.1 mass %, based on the total mass of the photosensitive composition layer.

[0222] (Antioxidants) Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among these, 3-pyrazolidones are preferred as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferred, in terms of the superior effect of the present invention.

[0223] When the photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 1% by mass or less.

[0224] <Thickness of Photosensitive Composition Layer> The thickness of the photosensitive composition layer is not particularly limited, but is often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less, in terms of superior effects of the present invention. The lower limit is preferably 0.60 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more, in terms of superior strength of the film obtained by curing the photosensitive composition layer. The thickness of the photosensitive composition layer can be calculated, for example, as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0225] <Refractive Index of Photosensitive Composition Layer> The refractive index of the photosensitive composition layer is preferably from 1.41 to 1.59, and more preferably from 1.47 to 1.56.

[0226] <Color of Photosensitive Composition Layer> The photosensitive composition layer is preferably achromatic. Specifically, the total reflection (incident angle 8°, light source: D-65 (2° visual field)) is preferably achromatic in the CIE1976 (L*, a*, b*) color space. * The value is preferably 10 to 90, * The value is preferably -1.0 to 1.0, and b * The value is preferably between -1.0 and 1.0.

[0227] The pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) is preferably achromatic. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is the L of the pattern in the CIE1976 (L*, a*, b*) color space. * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably between -1.0 and 1.0.

[0228] <Transmittance of Photosensitive Composition Layer> The visible light transmittance per 1.0 μm of film thickness of the photosensitive composition layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more. As the visible light transmittance, it is preferable that the average transmittance at a wavelength of 400 to 800 nm, the minimum transmittance at a wavelength of 400 to 800 nm, and the transmittance at a wavelength of 400 nm all satisfy the above. Preferable values ​​of the transmittance include, for example, 87%, 92%, and 98%. The same applies to the transmittance per 1 μm of film thickness of the cured film of the photosensitive composition layer.

[0229] <Moisture Permeability of Photosensitive Composition Layer> The moisture permeability of the pattern (cured film of the photosensitive composition layer) obtained by curing the photosensitive composition layer at a film thickness of 40 μm is set to 500 g / m from the viewpoints of rust prevention of the electrodes or wiring and reliability of the device. 2 / 24hr or less is preferable, and 300g / m 2 / 24hr or less is more preferable, and 100g / m 2 It is more preferable that the time is 24 hours or less. The moisture permeability was measured by exposing the photosensitive composition layer to i-rays at a dose of 300 mJ / cm 2 After exposure to light at 40° C., the photosensitive composition layer is post-baked at 145° C. for 30 minutes to cure the photosensitive composition layer, and the moisture permeability is measured on the cured film. The moisture permeability is measured according to the cup method of JIS Z0208. It is preferable that the moisture permeability is as above under any of the test conditions of temperature 40° C. / humidity 90%, temperature 65° C. / humidity 90%, and temperature 80° C. / humidity 95%. A specific preferable value is, for example, 80 g / m 2 / 24hr, 150g / m 2 / 24hr, 220g / m 2 / 24hr, etc.

[0230] <Dissolution rate of photosensitive composition layer> The dissolution rate of the photosensitive composition layer in a 1.0% aqueous solution of sodium carbonate is preferably 0.01 μm / sec or more, more preferably 0.10 μm / sec or more, and more preferably 0.20 μm / sec or more, from the viewpoint of suppressing residues during development. From the viewpoint of the edge shape of the pattern, it is preferably 5.0 μm / sec or less, more preferably 4.0 μm / sec or less, and even more preferably 3.0 μm / sec or less. Specific preferred values ​​include, for example, 1.8 μm / sec, 1.0 μm / sec, and 0.7 μm / sec. The dissolution rate of the photosensitive composition layer in a 1.0 mass% aqueous solution of sodium carbonate per unit time is measured as follows. The photosensitive composition layer (thickness in the range of 1.0 to 10 μm) formed on the glass substrate and from which the solvent has been sufficiently removed is shower-developed at 25° C. using a 1.0% by mass aqueous solution of sodium carbonate until the photosensitive composition layer is completely dissolved (however, the maximum time is 2 minutes). The thickness of the photosensitive composition layer is calculated by dividing the thickness by the time required for the photosensitive composition layer to be completely dissolved. If the photosensitive composition layer is not completely dissolved within 2 minutes, the thickness is calculated in the same manner from the amount of change in thickness up to that point. The dissolution rate of the cured film of the photosensitive composition layer (within the range of film thickness 1.0 to 10 μm) in a 1.0% aqueous solution of sodium carbonate is preferably 3.0 μm / sec or less, more preferably 2.0 μm / sec or less, further preferably 1.0 μm / sec or less, and most preferably 0.2 μm / sec or less. The cured film of the photosensitive composition layer is formed by exposing the photosensitive composition layer to i-rays at an exposure dose of 300 mJ / cm. 2 The film is obtained by exposure at 1000 nm. Specific preferred values ​​include, for example, 0.8 μm / sec, 0.2 μm / sec, and 0.001 μm / sec. Development is performed using a 1 / 4MIN JJX030PP shower nozzle manufactured by Ikeuchi Co., Ltd., with a shower spray pressure of 0.08 MPa. Under the above conditions, the shower flow rate per unit time is 1,800 mL / min.

[0231] <Swelling ratio of photosensitive composition layer> From the viewpoint of improving pattern formability, the swelling ratio of the photosensitive composition layer after exposure to a 1.0 mass % aqueous sodium carbonate solution is preferably 100% or less, more preferably 50% or less, and even more preferably 30% or less. The swelling ratio of the photosensitive composition layer after exposure to a 1.0 mass % aqueous sodium carbonate solution is measured as follows. A photosensitive resin layer (thickness in the range of 1.0 to 10 μm) formed on a glass substrate and from which the solvent has been sufficiently removed is exposed to 500 mJ / cm2 (measured with i-line) from an ultra-high pressure mercury lamp. The glass substrate is immersed in a 1.0 mass % sodium carbonate aqueous solution at 25°C, and the film thickness is measured after 30 seconds. The rate at which the film thickness after immersion has increased relative to the film thickness before immersion is calculated. Specific preferred values ​​include, for example, 4%, 13%, and 25%.

[0232] <Foreign matter in the photosensitive composition layer> From the viewpoint of pattern forming, the number of foreign matters having a diameter of 1.0 μm or more in the photosensitive composition layer is set to 10 / mm 2 It is preferable that the number of pieces is less than 5 / mm 2 It is more preferable that the number of foreign particles is equal to or less than 0. The number of foreign particles is measured as follows. From the normal direction of the surface of the photosensitive composition layer, any 5 regions (1 mm x 1 mm) on the surface of the photosensitive composition layer are visually observed using an optical microscope, and the number of foreign particles having a diameter of 1.0 μm or more in each region is counted, and the arithmetic average of these is calculated as the number of foreign particles. A specific preferred numerical value is, for example, 0 particles / mm 2 , 1 piece / mm 2 , 4 pieces / mm 2 , 8 pieces / mm 2 etc. can be mentioned.

[0233] <Haze of Dissolved Material in Photosensitive Composition Layer> From the viewpoint of preventing the generation of aggregates during development, 1.0 cm of 1.0 mass % sodium carbonate in 1.0 liter of 30°C aqueous solution was used. 3The haze of the solution obtained by dissolving the photosensitive resin layer is preferably 60% or less, more preferably 30% or less, even more preferably 10% or less, and most preferably 1% or less. The haze is measured as follows. First, a 1.0% by mass aqueous solution of sodium carbonate is prepared, and the liquid temperature is adjusted to 30°C. 1.0 cm3 of sodium carbonate is added to 1.0 L of the aqueous solution of sodium carbonate. 3 The photosensitive resin layer is placed in the solution. The solution is stirred at 30°C for 4 hours, taking care not to introduce air bubbles. After stirring, the haze of the solution in which the photosensitive resin layer has been dissolved is measured. The haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) with a liquid measurement unit and a dedicated liquid measurement cell with an optical path length of 20 mm. Specific preferred values ​​include, for example, 0.4%, 1.0%, 9%, and 24%.

[0234] <Viscosity of Photosensitive Composition Layer> The photosensitive composition layer has a melt viscosity of 1.0×10 3 ~1.0×10 6 Pa s is preferred, and 5.0×10 3 ~8.0×10 5 It is more preferable that the melt viscosity at 60°C is 1.0×10 Pa·s. 3 If the viscosity is 1.0×10 Pa·s or more, the flowability during lamination is not too high, and contamination of the heat roll of the laminator is unlikely to occur. 6 When the viscosity is less than Pa·s, the film has excellent conformability when laminated with a substrate, air bubbles are less likely to be trapped between the film and the substrate, and the film has excellent adhesion to the substrate. The melt viscosity of the photosensitive composition layer can be measured using a melt viscosity measuring device such as a Rheometer VAR-1000 (manufactured by Rheological Co., Ltd.) or a Vibron DD-III (manufactured by Toyo Baldwin Co., Ltd.).

[0235] <<Protective film>> The transfer film has a protective film (cover film). As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Furthermore, as the protective film, a resin film made of the same material as the above-mentioned temporary support may be used. Among these, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0236] The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, further preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of being relatively inexpensive.

[0237] In addition, the number of fish eyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 It is preferable that: "Fish eyes" are foreign matter, unmelted material, and oxidized deterioration products of the material that become trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0238] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The following is even more preferred: This makes it possible to suppress defects caused by the transfer of unevenness due to particles contained in the protective film to the photosensitive composition layer or the conductive layer.

[0239] From the viewpoint of providing winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, while it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. In order to suppress defects during transfer, the surface roughness Ra of the protective film on the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, and is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0240] <<Relationship between temporary support, photosensitive composition layer and protective film>> In the first embodiment of the transfer film, it is also preferred that the breaking elongation of the cured film obtained by curing the photosensitive composition layer at 120°C is 15% or more, the arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive composition layer is 50 nm or less, and the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive composition layer is 150 nm or less.

[0241] In addition, it is preferable that the transfer film satisfies the following formula (1). X×Y<1500 Formula (1) Here, in formula (1), X represents the breaking elongation value (%) of the cured film obtained by curing the photosensitive composition layer at 120°C, and Y represents the arithmetic mean roughness Ra value (nm) of the surface of the temporary support on the photosensitive composition layer side. The above X x Y is more preferably 750 or less. Specific values ​​of the above X include 18%, 25%, 30%, and 35%, etc. Specific values ​​of the above X x Y include 4 nm, 8 nm, 15 nm, and 30 nm, etc. Specific values ​​of the above X x Y include 150, 200, 300, 360, and 900, etc.

[0242] It is preferred that the breaking elongation at 120°C of the cured film obtained by curing the photosensitive composition layer is at least two times larger than the breaking elongation at 23°C. The breaking elongation was measured by irradiating a 20 μm-thick photosensitive composition layer with an ultra-high pressure mercury lamp at 120 mJ / cm 2 After curing by exposure, it is irradiated with 400mJ / cm 2 high pressure mercury lamp. 2 The cured film is then subjected to additional exposure at 150° C. and heated at 145° C. for 30 minutes, and then subjected to a tensile test.

[0243] In addition, it is also preferable that the transfer film satisfies the following formula (2). Y≦Z Equation (2) Here, in formula (2), Y represents the value of the arithmetic mean roughness Ra (nm) of the surface of the temporary support facing the photosensitive composition layer, and Z represents the value of the arithmetic mean roughness Ra (nm) of the surface of the protective film facing the photosensitive composition layer.

[0244] <<Refractive index adjustment layer>> The transfer film may have a refractive index adjusting layer. The refractive index adjusting layer may be a known refractive index adjusting layer. Examples of materials contained in the refractive index adjusting layer include binder polymers, polymerizable compounds, metal salts, and particles. The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a complex of a metal salt and a resin.

[0245] Examples of the binder polymer and the polymerizable compound include the binder polymer and the polymerizable compound described above in the section "Photosensitive composition layer."

[0246] Examples of particles include metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metal in the metal oxide particles includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0247] The average primary particle size of the particles is, for example, preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and taking the arithmetic mean of the measurement results. If the particle shape is not spherical, the longest side is used as the particle size.

[0248] Specifically, the metal oxide particles are preferably at least one selected from the group consisting of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof. Among these, the metal oxide particles are more preferably at least one type selected from the group consisting of zirconium oxide particles and titanium oxide particles, for example, from the viewpoint of ease of adjusting the refractive index.

[0249] Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined 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 Industries, Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0250] The particles may be used alone or in combination of two or more kinds. The content of the particles in the refractive index adjusting layer is preferably from 1 to 95% by mass, more preferably from 20 to 90% by mass, and further preferably from 40 to 85% by mass, based on the total mass of the refractive index adjusting layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and further preferably 40 to 85 mass %, based on the total mass of the refractive index adjusting layer.

[0251] The refractive index of the refractive index adjusting layer is preferably higher than the refractive index of the photosensitive composition layer. The refractive index of the refractive index-adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, even more 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 even more preferably 1.78 or less.

[0252] The thickness of the refractive index adjusting layer is preferably from 50 to 500 nm, more preferably from 55 to 110 nm, and further preferably from 60 to 100 nm. The thickness of the refractive index adjusting layer is calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0253] <<Manufacturing method of transfer film according to the first embodiment>> The method for producing the transfer film of the first embodiment is not particularly limited, and any known method can be used. Examples of a manufacturing method for the transfer film 30 include a method including the steps of applying a photosensitive composition to the surface of the temporary support 32 to form a coating film, and then drying the coating film to form the photosensitive composition layer 34, applying a composition for forming a refractive index adjusting layer to the surface of the photosensitive composition layer 34 to form a coating film, and then drying the coating film to form the refractive index adjusting layer 36, and pressing a protective film 40 onto the refractive index adjusting layer 36. By the above steps, the transfer film 30 including the temporary support 32, the photosensitive composition layer 34, the refractive index adjusting layer 36, and the protective film 40 can be manufactured. After the transfer film 30 is manufactured by the above-mentioned manufacturing method, the rolled body of the present invention is obtained by winding up the transfer film 30. The rolled body of the present invention can be provided in its original form to the lamination step with a substrate in a roll-to-roll system described later.

[0254] The method for producing the transfer film 30 may include forming the refractive index matching layer 36 on the protective film 40 and then forming the photosensitive composition layer 34 on the surface of the refractive index matching layer 36. In addition, the manufacturing method of the above-mentioned transfer film 30 may be a method in which a photosensitive composition layer 34 is formed on a temporary support 32, a refractive index adjustment layer 36 is separately formed on a protective film 40, and the photosensitive composition layer 34 and the refractive index adjustment layer 36 are bonded together to form the transfer film 30.

[0255] <Photosensitive composition and method for forming photosensitive composition layer> From the viewpoints of excellent productivity and ease of forming the above-mentioned photosensitive composition layer, it is preferable that the photosensitive composition layer in the transfer film is formed by a coating method using a photosensitive composition containing the above-mentioned components constituting the photosensitive composition layer (e.g., binder polymer, polymerizable compound, polymerization initiator, etc.) and a solvent. Specifically, the method for producing the transfer film of the first embodiment is preferably a method in which a photosensitive composition is applied onto a temporary support to form a coating film, and the coating film is dried at a predetermined temperature to form a photosensitive composition layer.

[0256] The solvent that can be contained in the photosensitive composition is preferably an organic solvent, such as methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0257] Furthermore, as the solvent, an organic solvent having a boiling point of 180 to 250° C. (high boiling point solvent) can also be used, if necessary.

[0258] The solvent may be used alone or in combination of two or more kinds. The total solid content of the photosensitive composition is preferably from 5 to 80 mass %, more preferably from 5 to 40 mass %, and even more preferably from 5 to 30 mass %, based on the total mass of the photosensitive composition. That is, the content of the solvent in the photosensitive composition is preferably from 20 to 95% by mass, more preferably from 60 to 95% by mass, and further preferably from 70 to 95% by mass, based on the total mass of the photosensitive composition.

[0259] The viscosity of the photosensitive composition at 25°C is, for example, preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s, from the viewpoint of coatability. The viscosity is measured using a viscometer. As the viscometer, for example, a viscometer manufactured by Toki Sangyo Co., Ltd. (product name: VISCOMETER TV-22) can be suitably used. However, the viscometer is not limited to the above-mentioned viscometer.

[0260] The surface tension of the photosensitive composition at 25°C is, for example, preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m, from the viewpoint of coatability. The surface tension is measured using a surface tensiometer. As the surface tensiometer, for example, a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (product name: Automatic Surface Tensiometer CBVP-Z) can be suitably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0261] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0262] As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred. In this specification, "drying" means removing at least a part of the solvent contained in the composition. Examples of the drying method include natural drying, heat drying, and reduced pressure drying. The above methods can be applied alone or in combination. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. Although there is no particular upper limit, the drying time is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0263] <Composition for forming refractive index adjusting layer and method for forming refractive index adjusting layer> The composition for forming the refractive index adjusting layer preferably contains various components forming the refractive index adjusting layer described above and a solvent. Note that, in the composition for forming the refractive index adjusting layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjusting layer described above. The solvent is not particularly limited as long as it is capable of dissolving or dispersing the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably from 50 to 2,500 parts by mass, more preferably from 50 to 1,900 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0264] The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0265] <How to apply protective film> Moreover, the transfer film of the first embodiment can be produced by bonding the protective film to the refractive index adjusting layer. The method for bonding the protective film to the refractive index adjusting layer is not particularly limited, and any known method can be used. Examples of a device for bonding the protective film to the refractive index adjusting layer include known laminators such as a vacuum laminator and an autocut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and capable of applying pressure and heat.

[0266] <How to cut the transfer film> The transfer film can be cut to adjust the width and length depending on the size of the substrate to be laminated. As a method for cutting the transfer film, for example, various slitting processes are used, such as shear cutting, razor cutting, score cutting, heat cutting, water jet cutting, and ultrasonic cutting, and shear cutting is preferred. When a shear cut is applied, it is preferable that the angle of the upper blade is small in order to make it possible to reduce the absolute values ​​of the positions X and Y. Furthermore, by setting the clearance between the upper blade and the lower blade (the horizontal distance between the upper blade and the lower blade) to a certain level or less, the protective film end is less likely to recede from the temporary support end, and positions X and Y can be made smaller. On the other hand, by setting the clearance between the upper blade and the lower blade to a certain level or more, the life of the upper blade and the lower blade can be extended. The amount of overlap between the upper blade and the lower blade (the amount of vertical overlap between the upper blade and the lower blade) can be selected as appropriate. When applying a shear cut, the acute-angled blade may be placed on either the temporary support side or the protective film side, but is preferably placed on the temporary support side in order to easily prevent peeling of the temporary support during slitting. For the slit processing method, reference can be made to the methods described in paragraphs

[0061] to

[0063] of JP 2017-211643 A, paragraph

[0054] of JP 2017-177713 A, and paragraphs

[0070] to

[0071] and

[0090] to

[0095] of JP 2016-061959 A, etc.

[0267] After slitting, the transfer film is wound up to obtain the roll of the present invention. The tension during winding is appropriately set within the range of, for example, 0.1 to 10 kg / 10 cm.

[0268] [Transfer film according to the second embodiment] An example of the transfer film according to the second embodiment will be described below. The transfer film 50 shown in FIG. 7 has a temporary support 52, a thermoplastic resin layer 54, an intermediate layer 56, a composition layer 60 including a photosensitive composition layer 58, and a protective film 62, in this order. 7 has a form in which a thermoplastic resin layer 54 and an intermediate layer 56 are arranged, but the thermoplastic resin layer 54 may not be arranged, and the intermediate layer 56 may not be arranged. In terms of obtaining superior effects of the present invention, it is preferable that the composition layer has at least one of an intermediate layer and a thermoplastic resin layer between the temporary support and the photosensitive composition layer. Each element constituting the transfer film will be described below. In the transfer film of the second embodiment, the temporary support 52 and the protective film 62 can be the same as the temporary support 32 and the protective film 40 of the first embodiment described above, and the preferred aspects are also the same, so their description will be omitted.

[0269] <<Photosensitive composition layer>> The transfer film has a photosensitive composition layer. In display devices (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.) equipped with a touch panel such as a capacitance-type input device, an electrode pattern corresponding to a sensor of a visual recognition section, a conductive layer pattern such as wiring of a peripheral wiring section and an extraction wiring section, etc. are provided inside the touch panel. In general, a method is widely adopted for forming a patterned layer, in which a negative photosensitive composition layer (photosensitive layer) is provided on a substrate using a transfer film or the like, the photosensitive layer is exposed to light through a mask having a desired pattern, and then the layer is developed. Therefore, the photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.

[0270] When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a resin, a polymerizable compound, and a polymerization initiator.In addition, when the photosensitive composition layer is a negative photosensitive composition layer, it is also preferable that the resin contains an alkali-soluble resin (such as polymer A, which is an alkali-soluble resin) as a part or all of the resin, as described later. That is, in one embodiment, the photosensitive composition layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Such a photosensitive composition layer (negative photosensitive composition layer) preferably contains, based on the total mass of the photosensitive composition layer, 10 to 90 mass % of resin, 5 to 70 mass % of polymerizable compound, and 0.01 to 20 mass % of polymerization initiator. Each component will be described in turn below.

[0271] <Polymer A (resin)> When the photosensitive composition layer is a negative photosensitive composition layer, the resin contained in the photosensitive composition layer is particularly referred to as polymer A. Resin A is not particularly limited, but examples thereof include (meth)acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and acid-modified epoxy acrylate resin obtained by reaction of epoxy acrylate resin with acid anhydride.

[0272] Resin A is preferably a (meth)acrylic resin. In this specification, (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from a (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on the total structural units of the (meth)acrylic resin. Resin A is also preferably a polymer having a structural unit derived from a (meth)acrylic compound and a structural unit derived from a styrene compound. The polymer A is preferably an alkali-soluble resin. The acid value of polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g, from the viewpoint of suppressing swelling of the negative photosensitive composition layer by a developer and thereby achieving better resolution. The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more.

[0273] The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample. The acid value can be calculated, for example, from the average content of acid groups in a compound. The acid value of the polymer A may be adjusted by changing the type of structural unit constituting the polymer A and the content of the structural unit containing an acid group.

[0274] The weight average molecular weight of polymer A is preferably 5,000 to 500,000. The weight average molecular weight is preferably 500,000 or less from the viewpoint of improving resolution and developability, more preferably 100,000 or less, and even more preferably 60,000 or less. On the other hand, a weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of the development aggregates and the properties of the unexposed film such as edge fuse property and cut chip property when the negative photosensitive resin laminate is formed. 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 of tendency of the negative photosensitive composition layer to protrude from the edge of the roll when the negative photosensitive resin laminate is wound into a roll. The cut chip property refers to the degree of tendency of chips to fly off when the unexposed film is cut with a cutter. If the chips adhere to the top surface of the negative photosensitive resin laminate, they will be transferred to a mask in a subsequent exposure process, causing defective products. The dispersity of polymer A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, further preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0. In this specification, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight), and the weight average molecular weight and the number average molecular weight are values ​​measured using gel permeation chromatography.

[0275] In the negative photosensitive composition layer, from the viewpoint of suppressing line width thickening and deterioration of resolution caused by deviation of the focal position during exposure, it is preferable that the polymer A contains a structural unit based on a monomer having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the structural units based on the monomer having an aromatic hydrocarbon group is preferably 20% by mass or more, and more preferably 30% by mass or more, based on the total mass of the polymer A. There is no particular upper limit, but it is preferably 95% by mass or less, and more preferably 85% by mass or less. When multiple types of polymer A are included, it is preferable that the average content of the structural units based on the monomer having an aromatic hydrocarbon group falls within the above range.

[0276] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is styrene, the content of structural units based on styrene is preferably 20 to 70 mass%, more preferably 25 to 65 mass%, further preferably 30 to 60 mass%, and particularly preferably 30 to 55 mass%, relative to the total mass of polymer A. When the photosensitive resin layer contains multiple types of polymer A, the content of structural units derived from monomers having an aromatic hydrocarbon group is determined as a weight average value.

[0277] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, with a substituted or unsubstituted benzyl group being preferred.

[0278] An example of the monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0279] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth)acrylate, the content of the structural unit based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, further preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of the polymer A.

[0280] The polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one type of first monomer described below and / or at least one type of second monomer described below.

[0281] Polymer A that does not contain a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described later, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described later.

[0282] The first monomer is a monomer having a carboxyl 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, and maleic acid half ester. Among these, (meth)acrylic acid is preferred. The content of the constitutional units based on the first monomer in polymer A is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and even more preferably from 15 to 30 mass %, based on the total mass of polymer A. A content of 5% by mass or more is preferable from the viewpoints of achieving good developability, controlling edge fusing properties, etc. A content of 50% by mass or less is preferable from the viewpoints of high resolution and foot shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

[0283] The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred. The content of the constitutional units based on the second monomer in polymer A is preferably from 5 to 60 mass %, more preferably from 15 to 50 mass %, and even more preferably from 17 to 45 mass %, based on the total mass of polymer A.

[0284] When the polymer A contains a constituent unit based on a monomer having an aralkyl group and / or a constituent unit based on a monomer of styrene, it is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure. For example, a copolymer containing a constituent unit based on methacrylic acid, a constituent unit based on benzyl methacrylate, and a constituent unit based on styrene, a copolymer containing a constituent unit based on methacrylic acid, a constituent unit based on methyl methacrylate, a constituent unit based on benzyl methacrylate, and a constituent unit based on styrene, etc. are preferable. In one embodiment, polymer A is preferably a polymer containing 25 to 55 mass% of structural units based on a monomer having an aromatic hydrocarbon group, 20 to 35 mass% of structural units based on a first monomer, and 15 to 45 mass% of structural units based on a second monomer. In another embodiment, polymer A is preferably a polymer containing 70 to 90 mass% of structural units based on a monomer having an aromatic hydrocarbon group, and 10 to 25 mass% of structural units based on the first monomer.

[0285] The polymer A may have a linear structure, a branched structure, or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain, or a monomer containing a group having an alicyclic structure in the side chain, it is possible to introduce a branched structure or an alicyclic structure into the side chain of polymer A. The group having an alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred. Specific examples of monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group, as well as (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-2-(meth)acrylate, 2 ... Examples of such acrylates include 1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is more preferred.

[0286] The polymer A may be used alone or in combination of two or more. When two or more kinds are used, it is preferable to mix two kinds of polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group, or to mix a polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group with a polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of the polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of the polymer A.

[0287] The synthesis of polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0288] The glass transition temperature Tg of the polymer A is preferably 30 to 135°C. By using the polymer A having a Tg of 135°C or less, it is possible to suppress line width thickening and deterioration of resolution when the focal position is shifted during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. In addition, it is preferable to use the polymer A having a Tg of 30°C or more from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40°C or more, further preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0289] The negative photosensitive composition layer may contain, as the polymer A, a resin other than those mentioned above. Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols. As the polymer A, an alkali-soluble resin may be used, which will be described later in the description of the thermoplastic resin layer.

[0290] The content of polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the negative photosensitive composition layer. It is preferable to set the content of polymer A to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to set the content of polymer A to 10% by mass or more from the viewpoint of improving edge fuse resistance.

[0291] <Polymerizable compound> When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a polymerizable compound having a polymerizable group. In this specification, the term "polymerizable compound" refers to a compound that is polymerized by the action of a polymerization initiator described later and is different from the polymer A described above.

[0292] The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group such as an epoxy group and an oxetane group. As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

[0293] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the negative photosensitive composition layer is superior. From the viewpoint of obtaining superior resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0294] In order to obtain a better balance between the photosensitivity, resolution, and peelability of the negative photosensitive composition layer, it is preferable for the composition to contain a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and it is more preferable for the composition to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. The content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more, relative to the total mass of the negative photosensitive composition layer, from the viewpoint of excellent peelability. The upper limit is not particularly limited, and may be 100% by mass. That is, all of the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Moreover, the ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group.

[0295] (Polymerizable compound B1) The negative photosensitive composition layer also preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The aromatic ring of the polymerizable compound B1 can be, for example, aromatic hydrocarbon ring such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocycle such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof, preferably aromatic hydrocarbon ring, more preferably benzene ring.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.

[0296] The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive composition layer due to a developer. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0297] An example of the polymerizable compound B1 having a bisphenol structure is 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 may be directly bonded to the two polymerizable groups, or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy or propyleneoxy, more preferably ethyleneoxy. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP2016-224162A, the contents of which are incorporated herein by reference.

[0298] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of suitable ethoxylated (10) bisphenol A diacrylate include 2,2-bis(4-(methacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0299] As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0300] [ka]

[0301] In the general formula (B1), R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer of 1 to 39, and n1+n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 represents an integer of 0 to 30. The arrangement of the structural units -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

[0302] The polymerizable compound B1 may be used alone or in combination of two or more kinds. The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive composition layer from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which photosensitive resin oozes out from the edge of a transfer member).

[0303] The mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% or more, more preferably 50% or more, even more preferably 55% or more, and particularly preferably 60% or more, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100% or less, preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, and particularly preferably 85% or less.

[0304] The negative photosensitive composition 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, the compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), the bifunctional ethylenically unsaturated compound without aromatic ring, and the trifunctional or higher ethylenically unsaturated compound can be mentioned.

[0305] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0306] Examples of difunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0307] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified versions of these. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compounds is preferably (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compounds)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

[0308] Examples of alkylene oxide modified trifunctional or higher ethylenically unsaturated compounds include caprolactone modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0309] Also, as the polymerizable compound, a polymerizable compound having an acid group (such as a carboxy group) may be used. The acid group may form an acid anhydride group. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). As the polymerizable compound having an acid group, for example, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.

[0310] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 10 to 70% by mass, more preferably from 15 to 70% by mass, and further preferably from 20 to 70% by mass, based on the total mass of the negative photosensitive composition layer.

[0311] The molecular weight (weight average molecular weight when the polymerizable compound has a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0312] <Polymerization initiator> When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer also preferably contains a polymerization initiator. The polymerization initiator is selected depending on the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0313] The negative photosensitive composition layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to active light such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and any 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 preferred.

[0314] 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, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0315] From the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution, the negative photosensitive composition layer preferably contains at least one photoradical polymerization initiator selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Derivatives of 2,4,5-triarylimidazole dimers 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-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0316] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783 may be used.

[0317] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0318] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins), BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade 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, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester photoinitiator (trade name: Lunar 6, DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Strong Electronic New Materials Co., Ltd.), Examples of suitable oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

[0319] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. As the photocationic polymerization initiator, a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferred, but the chemical structure is not limited. In addition, even if a photocationic polymerization initiator is not directly sensitive to actinic rays having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it responds to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. 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 a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of the pKa is not particularly set, but is preferably, for example, -10.0 or more.

[0320] The photocationic polymerization initiator includes 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, as well as quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP2014-085643A may be used.

[0321] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A may be used. As oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 may be used.

[0322] The negative photosensitive composition 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.

[0323] The polymerization initiator may be used alone or in combination of two or more kinds. The content of the polymerization initiator (preferably photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the negative photosensitive composition layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the negative photosensitive composition layer.

[0324] <Dye> From the viewpoints of visibility of exposed and unexposed parts, pattern visibility after development, and resolution, the photosensitive composition layer preferably contains a dye (also called "dye N") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes depending on an acid, a base, or a radical. When dye N is contained, the adhesion with adjacent layers (for example, a water-soluble resin layer) is improved, and the resolution is more excellent, although the detailed mechanism is unknown.

[0325] In this specification, the dye's "maximum absorption wavelength changes due to an acid, a base, or a radical" may mean any of the following: a dye in a colored state is decolorized by an acid, a base, or a radical; a dye in a decolorized state is colored by an acid, a base, or a radical; and a dye in a colored state is changed to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state by exposure, or may be a compound that changes from a colored state to a decolored state by exposure. In this case, the dye may be a dye whose colored or decolored state changes when an acid, base, or radical is generated and acts in the photosensitive composition layer by exposure, or a dye whose colored or decolored state changes when the state (e.g., pH) in the photosensitive composition layer changes due to an acid, base, or radical. Alternatively, the dye may be a dye whose colored or decolored state changes when it is directly stimulated by an acid, base, or radical without exposure.

[0326] Among these, from the viewpoints of visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. When the photosensitive composition layer is a negative type photosensitive composition layer, the negative type photosensitive composition layer preferably contains, from the viewpoints of visibility of exposed and non-exposed areas and resolution, both a dye whose maximum absorption wavelength changes due to radicals as dye N, and a photoradical polymerization initiator. From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0327] An example of the color-developing mechanism of dye N is a mode in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to the radical, acid, or base generated from the photoradical polymerization initiator, the photocationic photopolymerization initiator, or the photobase generator.

[0328] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength of 550 nm or more in a wavelength range of 400 to 780 nm upon color development, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm when it develops color, or may have two or more maximum absorption wavelengths. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0329] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimal (maximum absorption wavelength).

[0330] Examples of the dye that develops or loses color upon exposure to light include leuco compounds. Examples of dyes that disappear upon exposure to light 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 exposed and non-exposed areas.

[0331] Preferred examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluoran skeleton (fluoran dyes), leuco compounds having a diarylmethane skeleton (diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0332] From the viewpoint of visibility of the exposed and non-exposed parts, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, the sultine ring, or the sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby changing the leuco compound to a ring-closed state to cause discoloration, or changing the leuco compound to a ring-open state to cause color development. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which is colored by opening the lactone ring, the sultine ring, or the sultone ring with a radical or an acid, and more preferably a compound having a lactone ring, which is colored by opening the lactone ring with a radical or an acid.

[0333] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the pigments N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya 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.), and Examples of the oil-soluble pigments include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0334] Specific examples of the leuco compound among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-(N-cyclohexyl-N-methylamino)fluoran, and the like. -methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)- 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0335] From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals. Dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalenesulfonate.

[0336] The dye N may be used alone or in combination of two or more kinds. From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 to 10 mass %, even more preferably 0.1 to 5 mass %, and particularly preferably 0.1 to 1 mass %, relative to the total mass of the photosensitive composition layer.

[0337] The content of dye N means the content of dye when all of dye N contained in the total mass of the photosensitive composition layer is in a color-developing state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example. Prepare solutions by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. Add the photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Co., Ltd.) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals and make all the dyes colored. Then, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) in an air atmosphere, and create a calibration curve. Next, the absorbance of the solution in which all the dyes have been colored is measured in the same manner as above, except that the photosensitive composition layer 3g is dissolved in methyl ethyl ketone instead of the dye. The content of the dye contained in the photosensitive composition layer is calculated based on the calibration curve from the absorbance of the solution containing the obtained photosensitive composition layer. The photosensitive composition layer 3g is the same as the total solid content 3g in the photosensitive resin composition.

[0338] <Thermal crosslinkable compound> When the photosensitive composition layer is a negative photosensitive composition layer, it is preferable to include a thermal crosslinking compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Note that, in this specification, the thermal crosslinking compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound but as a thermal crosslinking compound. Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesion of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound or the like has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when a film obtained by curing a negative type photosensitive composition layer is used as a protective film. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0339] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably from 100 to 160°C, and more preferably from 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of a 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 suitably used. However, the differential scanning calorimeter is not limited to this.

[0340] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.

[0341] The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by converting it into an isocyanurate. Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred from the viewpoints that the dissociation temperature can be set in a preferred range more easily than a compound not having an oxime structure, and that development residues can be reduced.

[0342] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radically polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0343] As the blocked isocyanate compound, commercially available products 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, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). In addition, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0344] [ka]

[0345] The thermally crosslinkable compounds may be used alone or in combination of two or more. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0346] <Other additives> The photosensitive composition layer may contain known additives, if necessary, in addition to the above components. Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazoles), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants. Each of the additives may be used alone or in combination of two or more.

[0347] The photosensitive composition layer may contain a radical polymerization inhibitor. The radical polymerization inhibitor may be, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Other radical polymerization inhibitors may include naphthylamine, cuprous chloride, N-nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition layer, it is preferable to use N-nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor. The preferred content of the radical polymerization inhibitor is the same as in the first embodiment.

[0348] The photosensitive composition layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.The sensitizer can be, for example, a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone compound, a thioxanthone compound, an acridone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound (for example, 1,2,4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.

[0349] The sensitizers may be used alone or in combination of two or more. When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoints of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, relative to the total mass of the photosensitive composition layer.

[0350] The photosensitive composition layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs 0097-0103 and 0111-0118 of WO 2018 / 179640.

[0351] The photosensitive composition layer may include benzotriazoles or carboxybenzotriazoles. Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, 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, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of carboxybenzotriazoles that can be used include commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name).

[0352] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3 mass %, more preferably 0.05 to 1 mass %, based on the total mass of the photosensitive composition layer. When the content is 0.01 mass % or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the content is 3 mass % or less, the sensitivity can be maintained and decolorization of the dye can be further suppressed.

[0353] The photosensitive composition layer preferably contains a surfactant. Examples of the surfactant include the same surfactants as those in the first embodiment, and preferred embodiments are also the same.

[0354] The photosensitive composition layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid amplifiers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents. Additives contained in the photosensitive composition layer are described in paragraphs

[0165] to

[0184] of JP2014-085643A, the contents of which are incorporated herein by reference.

[0355] The thickness of the photosensitive composition layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, further preferably 0.5 to 20 μm, particularly preferably 2.0 to 10 μm, and most preferably 0.5 to 8 μm, which can improve the developability of the photosensitive composition layer and the resolution.

[0356] From the viewpoint of obtaining superior adhesion, the transmittance of the photosensitive composition layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. Although there is no particular upper limit, it is preferably 99.9% or less.

[0357] <Impurities, etc.> The photosensitive composition layer may contain a certain amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so it is preferable to set the contents to the following values.

[0358] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, by mass.

[0359] Methods for keeping the amount of impurities within the above range include selecting raw materials for the composition that contain a small amount of impurities, preventing impurities from being mixed in during the preparation of the photosensitive composition layer, and removing the impurities by washing. By such methods, the amount of impurities can be kept within the above range. Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0360] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably small. The content of these compounds relative to the total mass of the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit, based on mass, can be 10 ppb or more, and can be 100 ppb or more, based on the total mass of the photosensitive composition layer. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Also, they can be quantified by known measurement methods.

[0361] The water content in the photosensitive composition layer is preferably from 0.01 to 1.0 mass %, and more preferably from 0.05 to 0.5 mass %, from the viewpoint of improving reliability and lamination properties.

[0362] <Pigments> The photosensitive composition layer may be a colored resin layer containing a pigment. In some cases, in order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc. is attached to the liquid crystal display window. A colored resin layer can be used to form such a light-shielding layer. The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. Among them, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0363] As the black pigment, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as long as the effect of the present invention is not impaired. Among them, from the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium carbide, iron oxide, titanium oxide, and graphite, and carbon black is particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a part of the surface of which is coated with a resin is preferred.

[0364] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably from 0.001 to 0.1 μm, more preferably from 0.01 to 0.08 μm, in terms of number average particle size. Here, the particle size refers to the diameter of a circle whose area is equal to the area of ​​a pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope, and the number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the particle sizes of the 100 particles thus calculated.

[0365] As a pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used. Specifically, among the white pigments, the inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide, and even more preferably titanium oxide. As the inorganic pigment, rutile or anatase titanium oxide is more preferable, and rutile titanium oxide is particularly preferable. The surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be treated with two or more of these, which suppresses the catalytic activity of titanium oxide and improves heat resistance and light fading resistance. From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

[0366] In addition, when the photosensitive composition layer is a colored resin layer, it is also preferable that the photosensitive composition layer further contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability. When the chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of better dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI 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 Fast Blue (CI Pigment Red 146 ... Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Of these, CI Pigment Red 177 is preferred.

[0367] When the photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3 mass% and not more than 40 mass%, more preferably more than 3 mass% and not more than 35 mass%, even more preferably more than 5 mass% and not more than 35 mass%, and particularly preferably 10 mass% or more and not more than 35 mass%, relative to the total mass of the photosensitive composition layer.

[0368] When the photosensitive composition layer contains pigments other than the black pigment (white pigment and chromatic pigments), the content of the pigments other than the black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass, relative to the black pigment.

[0369] In addition, when the photosensitive composition layer contains a black pigment and is formed from a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion may be prepared by adding a mixture of a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant may be used. The vehicle refers to the medium portion in which the pigment is dispersed when the pigment dispersion is prepared, and is liquid, and includes a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0370] Examples of dispersants include urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, their modifications, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and their salts. Oil-based dispersants include water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters. The form of the dispersant may be selected from the items described in paragraphs

[0021] to

[0065] of JP 2021-012355 A.

[0371] A preferred dispersant is, for example, a basic polymer type dispersant. A preferred basic polymer type dispersant is, for example, a polymer containing a nitrogen atom. The nitrogen atom may be contained in the main chain of the polymer, in the side chain of the polymer, or in the main chain and the side chain of the polymer. In particular, the basic polymer type dispersant is preferably a polymer containing a nitrogen atom in the side chain. Since the surface of carbon black is generally acidic, when carbon black is used as a pigment, a basic polymer type dispersant is particularly preferred as the dispersant.

[0372] Examples of the polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in the side chain) include a polymer containing at least one type of atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group. For example, a polymer containing a quaternary ammonium base is preferred. The atomic group is preferably introduced into the side chain of the polymer. For example, a polymer containing at least one type of atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group in the side chain is preferred, and a polymer containing a quaternary ammonium base in the side chain is more preferred. Examples of the counter ion of the quaternary ammonium cation in the quaternary ammonium base include a carboxylate ion. Examples of the carboxylate ion include an aliphatic carboxylate ion and an aromatic carboxylate ion.

[0373] The polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in the side chain) is preferably a polymer containing a structural unit derived from styrene and a structural unit derived from a maleimide derivative, and more preferably a copolymer of styrene and a maleimide derivative. The maleimide derivative has a structure in which at least one hydrogen atom of the maleimide is replaced by a substituent. For example, the maleimide derivative includes a maleimide derivative containing at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group. The maleimide derivative is preferably a maleimide derivative containing a quaternary ammonium base.

[0374] The dispersant may be a commercially available dispersant, for example, BYK-2012 (BYK Japan Co., Ltd.).

[0375] In addition to the pigment, the composition may contain a dispersing aid (also called a pigment dispersing aid). The dispersing aid may be selected from known dispersing aids. Examples of the dispersing aid include compounds having an organic dye residue. Examples of the organic dye include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, and the like. The compound having an organic dye residue may have an acidic substituent, a basic substituent, or a neutral substituent. Examples of the acidic substituent include a sulfo group, a carboxy group, and a phosphoric acid group. Examples of the basic substituent include a sulfonamide group and an amino group. Examples of the neutral substituent include a phenyl group and a phthalimidoalkyl group. The embodiment of the dispersion aid may be selected from the items described in paragraphs

[0067] to

[0084] of JP2021-012355A.

[0376] A preferred dispersing aid is, for example, a compound having a phthalocyanine residue. Specifically, the dispersing aid is preferably a phthalocyanine pigment derivative having an acidic substituent or a salt thereof, more preferably a phthalocyanine pigment derivative having at least one acidic substituent selected from the group consisting of a sulfo group, a carboxy group, and a phosphoric acid group or a salt thereof, and even more preferably a phthalocyanine pigment derivative having a sulfo group or a salt thereof. Phthalocyanine pigment derivatives are described, for example, in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A. These publications are incorporated herein by reference.

[0377] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details of dispersing machines and fine pulverization, see the description in "Encyclopedia of Pigments" (written by Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0378] The thickness, refractive index, color, transmittance, foreign matter, haze of the dissolved material, viscosity, and the like of the photosensitive composition layer can be appropriately adjusted within the same ranges as those of the transfer film of the first embodiment.

[0379] <<Relationship between temporary support, photosensitive composition layer and protective film>> In the second embodiment as well, it is preferable that the relationships among the temporary support, the photosensitive composition layer, and the protective film described in the first embodiment are satisfied.

[0380] <<Middle layer>> The transfer film may have an intermediate layer. In the transfer film 50, the intermediate layer 56 is present between the thermoplastic resin layer 54 and the photosensitive composition layer 58, thereby suppressing mixing of components that may occur during the coating and formation of the thermoplastic resin layer 54 and the photosensitive composition layer 58 and during storage after coating and formation. As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used. In addition, as the intermediate layer, an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-072724, can also be used. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and productivity is improved, which is preferable. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred. Hereinafter, each component that may be contained in the water-soluble resin layer (intermediate layer) will be described.

[0381] The water-soluble resin layer (intermediate layer) contains a resin. The resin includes a water-soluble resin as a part or the whole. Examples of resins that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. In addition, as the water-soluble resin, a copolymer of (meth)acrylic acid / vinyl compound can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / allyl (meth)acrylate is preferable, and a copolymer of methacrylic acid / allyl methacrylate is more preferable. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol %) of each is, for example, preferably from 90 / 10 to 20 / 80, and more preferably from 80 / 20 to 30 / 70.

[0382] The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more, and the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersity (Mw / Mn) of the water-soluble resin is preferably 1-10, and more preferably 1-5.

[0383] In order to further improve the interlayer mixing suppression ability of the water-soluble resin layer (intermediate layer), it is preferable that the resin in the water-soluble resin layer (intermediate layer) is different from the resin contained in the layer disposed on one side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other side of the water-soluble resin layer (intermediate layer). For example, when the photosensitive composition layer 58 contains a polymer A and the thermoplastic resin layer 54 contains a thermoplastic resin (alkali-soluble resin), it is preferable that the resin of the water-soluble resin layer (intermediate layer) 56 is different from the polymer A and the thermoplastic resin (alkali-soluble resin).

[0384] The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in order to further improve the oxygen barrier property and the ability to inhibit interlayer mixing.

[0385] The water-soluble resin may be used alone or in combination of two or more kinds. The content of the water-soluble resin is not particularly limited, but from the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppression ability, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the water-soluble resin layer (intermediate layer).The upper limit is not particularly limited, but for example, it is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less. The intermediate layer may contain known additives such as a surfactant, if necessary.

[0386] The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property is not reduced, and the interlayer mixing suppression ability is excellent. Furthermore, the increase in the time required to remove the water-soluble resin layer (intermediate layer) during development can also be suppressed.

[0387] Furthermore, when the transfer film of the second embodiment has an intermediate layer, it is also preferable that the adhesion between the layers satisfies the following relationship. Adhesion relationship 1: The adhesion between the intermediate layer and the photosensitive composition layer is greater than the adhesion between the photosensitive composition layer and the protective film. Adhesion relationship 2: The adhesion between the temporary support and the intermediate layer is greater than the adhesion between the photosensitive composition layer and the protective film. When the above adhesion relationships 1 and 2 are satisfied, peeling occurs at the interface between the photosensitive composition layer and the protective film when the protective film is peeled off from the transfer film, making the film suitable for use as a transfer film.

[0388] It is also preferable that the adhesive strength of the intermediate layer satisfies the following relationship: Adhesion relationship 3: The adhesion between the intermediate layer and the photosensitive composition layer is greater than the adhesion between the temporary support and the intermediate layer. When the above-mentioned adhesion relationship 3 is satisfied, peeling occurs between the temporary support and the intermediate layer in the temporary support peeling step described later in detail, and the intermediate layer is likely to remain on the photosensitive composition layer side. As a result, the intermediate layer is likely to function as an oxygen barrier layer, etc.

[0389] <<Thermoplastic resin layer>> The transfer film may have a thermoplastic resin layer. The thermoplastic resin layer is usually disposed between the temporary support and the photosensitive composition layer. By providing the transfer film with the thermoplastic resin layer, the conformability to the substrate during the bonding process between the transfer film and the substrate is improved, and the inclusion of air bubbles between the substrate and the transfer film can be suppressed. As a result, the adhesion between the thermoplastic resin layer and the adjacent layer (e.g., the temporary support) can be ensured.

[0390] The thermoplastic resin layer includes a resin. The resin includes a thermoplastic resin as a part or the whole. That is, in one embodiment, the thermoplastic resin layer preferably includes a thermoplastic resin as a resin.

[0391] <Alkali-soluble resin (thermoplastic resin)> The thermoplastic resin is preferably an alkali-soluble resin. Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0392] As the alkali-soluble resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin is preferred. Here, the acrylic resin means a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. The acrylic resin preferably contains structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides in a total content of 50 mass% or more relative to the total mass of the acrylic resin. In particular, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester is preferably 30 to 100 mass %, and more preferably 50 to 100 mass %, based on the total mass of the acrylic resin.

[0393] The alkali-soluble resin is preferably a polymer having an acid group. Acid groups include carboxy groups, sulfo groups, phosphoric acid groups, and phosphonic acid groups, with the carboxy groups being preferred. From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more 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 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0394] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and may be appropriately selected from known resins. Examples of the alkali-soluble resin include a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162. The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and even more preferably from 12 to 30 mass %, based on the total mass of the acrylic resin. As the alkali-soluble resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred.

[0395] The alkali-soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples of the reactive group include ethylenically unsaturated groups, polycondensable groups such as hydroxyl groups and carboxyl groups, and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0396] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 50,000.

[0397] The alkali-soluble resin may be used alone or in combination of two or more kinds. From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10 to 99 mass %, more preferably 20 to 90 mass %, even more preferably 40 to 80 mass %, and particularly preferably 50 to 75 mass %, relative to the total mass of the thermoplastic resin layer.

[0398] <Dye> The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm when colored and whose maximum absorption wavelength changes due to an acid, a base, or a radical. A preferred embodiment of dye B is the same as the preferred embodiment of dye N described above, except for the points described below.

[0399] From the viewpoints of visibility of exposed and unexposed areas and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in the presence of an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in the presence of an acid. From the viewpoints of visibility and resolution of exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye B whose maximum absorption wavelength changes in response to acid, and a compound that generates acid when exposed to light, as described below.

[0400] The dye B may be used alone or in combination of two or more kinds. From the viewpoint of visibility of exposed and non-exposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 to 6 mass%, even more preferably 0.2 to 5 mass%, and particularly preferably 0.25 to 3.0 mass%, relative to the total mass of the thermoplastic resin layer.

[0401] Here, the content of dye B means the content of dye when all of dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example. Prepare solutions by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. Add the photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Co., Ltd.) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals and make all the dyes colored. Then, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) in an air atmosphere, and create a calibration curve. Next, the absorbance of the solution in which all the dye has been colored is measured in the same manner as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. The amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve from the absorbance of the solution containing the thermoplastic resin layer obtained. The thermoplastic resin layer 3g is the same as the 3g of the solid content of the composition.

[0402] <Compounds that generate acids, bases, or radicals when exposed to light> The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical when exposed to light (also simply referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base, or a radical upon exposure to actinic rays such as ultraviolet light and visible light. As the compound C, a known photoacid generator, photobase generator, or photoradical polymerization initiator (photoradical generator) can be used.

[0403] (Photoacid generator) From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator. Examples of the photoacid generator include the above-mentioned cationic photopolymerization initiators that may be contained in the negative photosensitive composition layer, and preferred embodiments are the same except for the points described below.

[0404] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and from the viewpoints of sensitivity, resolution, and adhesion, it is more preferable that the photoacid generator contains an oxime sulfonate compound. As the photoacid generator, a photoacid generator having the following structure is also preferred.

[0405] [ka]

[0406] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator. As the photoradical polymerization initiator, the above-mentioned photoradical polymerization initiator that may be contained in the negative photosensitive composition layer can be mentioned, and the preferred embodiments are also the same.

[0407] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator. The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- 1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(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.

[0408] The compound C may be used alone or in combination of two or more. The content of compound C is preferably from 0.1 to 10 mass %, more preferably from 0.5 to 5 mass %, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of exposed and non-exposed areas.

[0409] <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 when it is an oligomer or polymer and has a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0410] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound contained in the negative photosensitive composition layer. In the transfer film, when the thermoplastic resin layer and the negative photosensitive composition layer are laminated in direct contact with each other, it is preferable that both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound. This is because the thermoplastic resin layer and the negative photosensitive composition layer each contain the same (meth)acrylate compound, which suppresses component diffusion between layers and improves storage stability.

[0411] 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 area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and an adjacent layer. In addition, as the (meth)acrylate compound used as a plasticizer, from the viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred. Furthermore, 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 preferred.

[0412] The plasticizers may be used alone or in combination of two or more. From the viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1 to 70 mass %, more preferably 10 to 60 mass %, and even more preferably 20 to 50 mass %, relative to the total mass of the thermoplastic resin layer.

[0413] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that may be contained in the negative photosensitive composition layer described above.

[0414] The sensitizers may be used alone or in combination of two or more. The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoints of improving sensitivity to the light source and visibility of exposed and non-exposed areas, it is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, relative to the total mass of the thermoplastic resin layer.

[0415] <Additives, etc.> In addition to the above components, the thermoplastic resin layer may contain known additives such as a surfactant, if necessary. In addition, the thermoplastic resin layer is described in paragraphs

[0189] to

[0193] of JP2014-085643A, the contents of which are incorporated herein by reference.

[0416] The thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion with adjacent layers, it is preferably 0.1 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more.The upper limit is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

[0417] <<Manufacturing method of transfer film according to the second embodiment>> The method for producing the transfer film of the second embodiment is not particularly limited, and any known method can be used. Examples of a method for manufacturing the transfer film 50 include a method including the steps of applying a thermoplastic resin composition to the surface of the temporary support 52 to form a coating film, and then drying the coating film to form the thermoplastic resin layer 54; applying a water-soluble resin composition to the surface of the thermoplastic resin layer 54 to form a coating film, and then drying the coating film to form the intermediate layer 56; applying a photosensitive composition to the surface of the intermediate layer 56 to form a coating film, and then drying the coating film to form the photosensitive composition layer 58; and pressing a protective film 62 onto the photosensitive composition layer 58. By the above-mentioned manufacturing method, the transfer film 50 including the temporary support 52, the thermoplastic resin layer 54, the intermediate layer 56, the photosensitive composition layer 58, and the protective film 62 can be manufactured. After the transfer film 50 is manufactured by the above manufacturing method, a transfer film in a roll form may be produced and stored by winding up the transfer film 50. The transfer film in a roll form can be provided as it is to the lamination step with a substrate in a roll-to-roll system described later.

[0418] In addition, the manufacturing method of the above-mentioned transfer film 50 may be a method in which a photosensitive composition layer 58 and an intermediate layer 56 are formed on a protective film 62, and then a thermoplastic resin layer 54 is formed on the surface of the intermediate layer 56.

[0419] <Photosensitive composition and method for forming photosensitive composition layer> From the viewpoints of excellent productivity and ease of forming the above-mentioned photosensitive composition layer, it is desirable to form the photosensitive composition by a coating method using a photosensitive composition containing the components constituting the above-mentioned photosensitive composition layer (e.g., a binder polymer, a polymerizable compound, a polymerization initiator, etc.) and a solvent. Specifically, a preferred method for producing the transfer film of the second embodiment is a method in which a photosensitive composition is applied onto an intermediate layer to form a coating film, and this coating film is then dried at a predetermined temperature to form a photosensitive composition layer.

[0420] The photosensitive composition preferably contains various components forming the photosensitive composition layer described above and a solvent. Note that, in the photosensitive composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive composition layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used.Specific examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0421] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents, and cyclic ether solvents is even more preferred.

[0422] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of JP-A-2018-177889 may be used, the contents of which are incorporated herein by reference. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1,200 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0423] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0424] The method for drying the coating of the photosensitive composition is preferably drying by heating or drying under reduced pressure. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher. The upper limit is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. Although there is no particular upper limit, the drying time is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0425] <Composition for forming thermoplastic resin layer and method for forming thermoplastic resin layer> The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and any known method can be used. For example, the thermoplastic resin layer can be formed by applying a composition for forming a thermoplastic resin layer on the temporary support and drying it as necessary. The thermoplastic resin layer forming composition preferably contains various components forming the above-mentioned thermoplastic resin layer and a solvent. In the thermoplastic resin layer forming composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the above-mentioned thermoplastic resin layer. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used. Examples of the solvent include the same solvents contained in the photosensitive composition described below, and the preferred embodiments are also the same. The content of the solvent is preferably from 50 to 1,900 parts by mass, and more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0426] 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-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0427] <Water-soluble resin composition and method for forming intermediate layer (water-soluble resin layer)> The water-soluble resin composition preferably contains various components forming the intermediate layer (water-soluble resin layer) described above and a solvent. In the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the water-soluble resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably from 50 to 2,500 parts by mass, more preferably from 50 to 1,900 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0428] The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0429] <How to apply protective film> Furthermore, a protective film is attached to the photosensitive composition layer to produce the transfer film of the second embodiment. The method for attaching the protective film to the photosensitive composition layer is not particularly limited, and any known method can be used. Examples of a device for laminating the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an autocut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and capable of applying pressure and heat. <How to cut the transfer film> The transfer film can be cut to adjust the width and length depending on the size of the substrate to be laminated. As a method for cutting the transfer film, for example, various slitting processes are used. The slitting processes are as described for the transfer film in the first embodiment. After the slitting process, the transfer film is wound up to form the roll of the present invention.

[0430] [Uses of transfer film] The transfer film constituting the roll of the present invention can be applied to various uses. For example, it can be applied to an electrode protective film, an insulating film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an anti-reflection film, an etching resist, and a plating member. More specific examples include a protective film or insulating film for a touch panel electrode, a protective film or insulating film for a printed wiring board, a protective film or insulating film for a TFT substrate, a color filter, an overcoat film for a color filter, an etching resist and a plating resist for wiring formation, and the like. [Method of manufacturing a laminate having a conductive pattern] The above-mentioned wound body can be used to manufacture a laminate having a conductor pattern. The method for manufacturing the laminate having a conductor pattern is not particularly limited as long as it is a method using the above-mentioned wound body, but the following manufacturing method is preferred as the manufacturing method for the laminate having a conductor pattern of the present invention. an unwinding step of unwinding a transfer film from a roll of the transfer film (the roll of the present invention) having a support, a composition layer, and a protective film in this order, the composition layer including a photosensitive composition layer; a peeling step of peeling the protective film from the transfer film to expose the surface of the composition layer; a lamination step of laminating the transfer film and a substrate having a conductive layer such that the exposed surface of the composition layer is in contact with the conductive layer of the substrate having a conductive layer on its surface; an exposure step of exposing a photosensitive composition layer contained in the composition layer; a developing step of performing a development treatment on the exposed photosensitive composition layer to form a resist pattern; one of an etching process for performing an etching process on the conductive layer in an area where the resist pattern is not disposed, and a plating process for performing a plating process on the conductive layer; a resist pattern stripping step of stripping the resist pattern; In the case where a plating treatment step is further included, a removal step of removing the conductive layer exposed by the resist pattern peeling step to form a conductive pattern on the substrate is included in the method for producing a laminate having a conductive pattern, A method for producing a laminate having a conductive pattern, further comprising a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step.

[0431] A specific procedure for the method of manufacturing a laminate having a conductor pattern will now be described. Also, steps that may be included in the method for producing a laminate having the above-mentioned preferred conductor pattern will be described.

[0432] [Unwinding process] The unwinding step is a step of unwinding the transfer film from the roll of the present invention. The unwinding method can be a known method, and the unwinding step may be performed by a roll-to-roll method.

[0433] [Peeling process] The peeling step is a step of peeling the protective film from the transfer film. When the peeling step is carried out, the surface of the photosensitive composition layer of the transfer film is exposed. The method for peeling off the protective film is not particularly limited, and can be a known method. For example, the protective film can be peeled off while being wound into a roll.

[0434] [Lamination process] The lamination step is a step of laminating the transfer film and a substrate having a conductive layer such that the exposed surface of the photosensitive composition layer is in contact with the conductive layer of the substrate having a conductive layer on its surface. When the lamination step is carried out, a laminate (substrate with a photosensitive composition layer) having the substrate, the conductive layer, the photosensitive composition layer, and the temporary support in this order is obtained.

[0435] The substrate having a conductive layer has a conductive layer on a substrate, and may have an optional layer formed thereon, i.e., the substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0436] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the substrate is described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference. The material of the resin substrate is preferably a cycloolefin polymer or a polyimide, and the thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm.

[0437] From the viewpoints of electrical conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Furthermore, only one conductive layer may be disposed on the substrate, or two or more conductive layers may be disposed on the substrate. When two or more conductive layers are disposed, it is preferable that the conductive layers are made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph

[0141] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0438] The conductive layer may be a transparent conductive layer capable of forming a transparent electrode through a process described later. The transparent conductive layer is preferably composed of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), a metal mesh, or a metal thin wire such as a metal nanowire. Examples of the thin metal wires include thin wires of silver, copper, etc. Among them, conductive silver materials such as silver mesh and silver nanowires are preferred.

[0439] The thickness of the conductive layer is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more, and is preferably 10 μm or less, more preferably 2 μm or less.

[0440] In the lamination, it is preferable to apply pressure so that the conductive layer and the surface of the photosensitive composition layer are in contact with each other. The method of pressure bonding is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferable to place the surface of the photosensitive composition layer on a substrate having a conductive portion, and apply pressure and heat with a roll or the like. For lamination, a known laminator such as a vacuum laminator or an autocut laminator can be used. The lamination temperature is not particularly limited, but is preferably from 70 to 130°C, for example.

[0441] [Exposure process] The exposure step is a step of pattern-exposing the photosensitive composition layer contained in the composition layer. By carrying out an exposure step and a development step described below, a resist pattern that protects at least a part of the conductive layer is formed on the conductive layer on the substrate. Here, the term "pattern exposure" refers to a form of exposure in a pattern, that is, exposure in a form in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and may be appropriately adjusted. The photosensitive composition layer may be exposed from the side opposite to the substrate, or from the substrate side of the photosensitive composition layer.

[0442] The light source for the pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range (e.g., 365 nm or 405 nm) that can at least cure the photosensitive composition layer. Among them, the dominant wavelength of the exposure light for the pattern exposure is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity.

[0443] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose is 5 to 200 mJ / cm 2 is preferable, and 10 to 200 mJ / cm 2 is more preferred.

[0444] Preferred embodiments of the light source, exposure dose, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0445] [Temporary support peeling step] The temporary support peeling step is a step of peeling off the temporary support from the substrate with the photosensitive composition layer between the laminating step and the exposure step, or between the exposure step and the development step described below. The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP2010-072589A can be used.

[0446] [Development process] The development step is a step of developing the exposed photosensitive composition layer to form a resist pattern. The photosensitive composition layer can be developed using a developer. The developer is preferably an alkaline aqueous solution. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0447] Examples of the development method include paddle development, shower development, spin development, and dip development.

[0448] In the present specification, examples of the developing solution that can be suitably used include the developing solution described in paragraph

[0194] of WO 2015 / 093271, and examples of the developing method that can be suitably used include the developing method described in paragraph

[0195] of WO 2015 / 093271.

[0449] After the development, it is also preferable to carry out a rinsing treatment for removing the developer remaining on the conductive layer-formed substrate before proceeding to the next step. Water or the like can be used for the rinsing treatment. After the development and / or rinsing process, a drying process may be carried out to remove excess liquid from the substrate with the conductive layer.

[0450] [Etching process] In the above manufacturing method, either an etching step or a plating step, which will be described later, is carried out. In the etching step, an etching process is performed on the conductive layer in the area where the resist pattern is not disposed. By the etching process, a conductor pattern corresponding to the pattern of the resist pattern is formed. As the etching method, known methods can be applied, and examples thereof include the method described in paragraphs

[0209] to

[0210] of JP2017-120435A, the method described in paragraphs

[0048] to

[0054] of JP2010-152155A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.

[0451] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched. Examples of the acidic etching solution include an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an aqueous solution of a mixture of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of a plurality of acidic components. Examples of the alkaline etching solution include an aqueous solution of an alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), and an aqueous solution of a mixture of an alkaline component and a salt (e.g., potassium permanganate). The alkaline component may be a combination of a plurality of alkaline components.

[0452] [Plating process] The plating step is a step of plating the conductive layer in the area where the resist pattern is not disposed. Examples of plating methods include electrolytic plating and electroless plating, with electrolytic plating being preferred from the standpoint of productivity. When the plating step is carried out, a plating layer having a pattern shape similar to that of the area where the resist pattern is not disposed (openings of the resist pattern) is obtained on the substrate with the conductive layer. When a plating step is carried out, the conductive layer is preferably a metal layer.

[0453] Examples of the metal contained in the plating layer include known metals. Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals. In particular, the plating layer preferably contains copper or an alloy thereof, since the conductive pattern has better electrical conductivity. Also...

Claims

1. A roll of a transfer film having a temporary support, a composition layer, and a protective film in this order, the composition layer comprises a photosensitive composition layer, The transfer film unwound from the roll is subjected to the following cross-sectional observation at five different locations at intervals of 8 cm along the longitudinal direction of the transfer film, and the minimum and maximum values ​​of five positions X and five positions Y obtained in each cross-sectional observation are all within the range of −40 to 40 μm. Cross-sectional observation: The transfer film unwound from the roll was cut along the width direction of the transfer film, and one of the two exposed cross sections was observed from the normal direction of the one cross section. In the exposed cross section, the position of one end located on the outermost side of the temporary support in the width direction of the transfer film is defined as a first position, the position of one end located on the outermost side of the protective film in the width direction of the transfer film and on the same side as the first position is defined as a second position, and the position of the second position is defined as position X when a position on the outer side along the width direction of the transfer film from the first position as a reference is expressed as a positive value in the width direction of the transfer film, In the exposed cross-section, the position of the other end that is located at the outermost position of the temporary support in the width direction of the transfer film is defined as a third position, and the position of the other end that is located at the outermost position of the protective film in the width direction of the transfer film and is on the same side as the third position is defined as a fourth position, and the position of the fourth position is defined as position Y when the position along the width direction of the transfer film that is outer than the third position relative to the third position is expressed as a positive value.

2. The wound body according to claim 1, wherein the minimum value is within a range of 0.1 to 40 μm.

3. 2. The roll according to claim 1, wherein the photosensitive composition layer has a thickness of 2 to 20 μm.

4. The roll according to claim 1 , wherein the composition layer has at least one of an intermediate layer and a thermoplastic resin layer between the temporary support and the photosensitive composition layer.

5. The wound body according to claim 4, wherein the intermediate layer has a thickness of 0.1 to 10 μm.

6. The wound body according to claim 4, wherein the thermoplastic resin layer has a thickness of 0.1 to 10 μm.

7. An unwinding step of unwinding the transfer film from the roll according to any one of claims 1 to 6; a peeling step of peeling the protective film from the transfer film to expose a surface of the composition layer; a bonding step of bonding the transfer film to a substrate having a conductive layer such that an exposed surface of the composition layer is in contact with the conductive layer of the substrate; an exposure step of exposing the photosensitive composition layer contained in the composition layer; a development step of performing a development treatment on the exposed photosensitive composition layer to form a resin pattern, The method for producing a laminate having a resin pattern further comprises a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step.

8. An unwinding step of unwinding the transfer film from the roll according to any one of claims 1 to 6; a peeling step of peeling the protective film from the transfer film to expose a surface of the composition layer; a bonding step of bonding the transfer film to a substrate having a conductive layer such that an exposed surface of the composition layer is in contact with the conductive layer of the substrate; an exposure step of exposing the photosensitive composition layer contained in the composition layer; a developing step of performing a development treatment on the exposed photosensitive composition layer to form a resist pattern; one of an etching process for performing an etching process on the conductive layer in an area where the resist pattern is not disposed, and a plating process for performing a plating process on the conductive layer in an area where the resist pattern is not disposed; a resist pattern stripping step of stripping the resist pattern; In the case where the plating treatment step is further included, a removal step of removing the conductive layer exposed by the resist pattern peeling step to form a conductive pattern on the substrate, The method for producing a laminate having a conductor pattern further comprises a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step.

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