Transfer film, photosensitive material, pattern forming method, method for manufacturing circuit substrate, method for manufacturing touch panel

Abstract

Provided is a transfer film that is excellent in pattern formation and enables formation of a pattern having low moisture permeability. Also provided is a photosensitive material that is excellent in pattern formation. Also provided are a pattern formation method, a method for manufacturing a circuit substrate, and a method for manufacturing a touch panel. The transfer film has a temporary support and a photosensitive layer containing a compound A having an acid group disposed on the temporary support, and the content of the acid group in the photosensitive layer is reduced by irradiation with actinic rays or radiation.

Description

TECHNICAL FIELD

[0001] The present application relates to a transfer film, a photosensitive material, a pattern forming method, a method for manufacturing a circuit substrate, and a method for manufacturing a touch panel. BACKGROUND

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

[0003] Generally, a photosensitive material is used when a patterned layer (hereinafter, also simply referred to as "pattern") is formed, and in particular, since the number of processes for obtaining a desired pattern shape is small, a method using a transfer film having a temporary support and a photosensitive layer formed using a photosensitive material disposed on the temporary support is widely used. As a method of forming a pattern using a transfer film, a method of performing exposure and development of a photosensitive layer transferred from a transfer film to an arbitrary substrate through a mask having a prescribed pattern shape can be cited. A pattern formed on an arbitrary substrate by this method is sometimes provided for use as a protective film (specifically, a protective film (permanent film) for protecting a conductive pattern provided inside the touch panel) in addition to use as an etching resist film, and the like, and low moisture permeability is required.

[0004] As a photosensitive material and a transfer film, for example, in Patent Literature 1, "a photosensitive resin composition containing a binder polymer having a carboxyl group with an acid value of 75 mgKOH / g or more, a photopolymerizable compound, and a photopolymerization initiator on a substrate" and "a photosensitive element provided with a support film and a photosensitive layer composed of the photosensitive resin composition disposed on the support film" are disclosed.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: International Publication No. 2013 / 084886 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] However, in a transfer film, as a basic performance, a performance in which resolution is excellent (hereinafter, also referred to as "pattern forming performance is excellent") is also required.

[0010] As a result of the inventors' research using a photosensitive element (transfer film) described in Patent Document 1 to form a pattern, it was found that low moisture permeability did not meet recent demands. That is, it was confirmed that there was room for a transfer film that was excellent in pattern formation and in which low moisture permeability was improved.

[0011] Furthermore, the inventors' research on the photosensitive layer of the transfer film this time also involved further research on improving the pattern formation of the photosensitive material.

[0012] Therefore, the present application has an object to provide a transfer film that is excellent in pattern formation and in which a pattern with low moisture permeability can be formed.

[0013] Also, the present application has an object to provide a photosensitive material that is excellent in pattern formation.

[0014] Also, the present application has an object to provide a pattern formation method, a method for manufacturing a circuit substrate, and a method for manufacturing a touch panel.

[0015] Means for solving the technical problem

[0016] As a result of the inventors' intensive research to solve the above problem, it was found that the above problem could be solved by the following structure, and thus the present application was completed.

[0017] 〔1〕 A transfer film having a temporary support, a photosensitive layer containing a compound A having an acid group disposed on the temporary support,

[0018] The content of the acid group in the photosensitive layer decreases due to irradiation of actinic rays or radiation.

[0019] 〔2〕 The transfer film according to 〔1〕, wherein

[0020] The photosensitive layer satisfies any of the following requirement (V01) and the following requirement (W01):

[0021] Requirement (V01)

[0022] The photosensitive layer contains the compound A and a compound β having a structure that reduces the amount of the acid group contained in the compound A by exposure.

[0023] Requirement (W01)

[0024] The photosensitive layer contains the compound A, and the compound A further contains a structure that reduces the amount of the acid group by exposure.

[0025] 〔3〕 The transfer film according to 〔2〕, wherein

[0026] In the above requirement (V01), the above compound β is a compound B having a structure capable of accepting an electron from the above acid group included in the above compound A in a photoexcited state,

[0027] In the above requirement (W01), the above structure is a structure capable of accepting an electron from the above acid group in a photoexcited state.

[0028] 〔4〕 The transfer film according to any one of 〔2〕 or 〔3〕, which satisfies the above requirement (V01), and the above compound β is a compound B having a structure capable of accepting an electron from the above acid group included in the above compound A in a photoexcited state,

[0029] In the above photosensitive layer, the total number of the structure capable of accepting the above electron included in the above compound B is 1 mol% or more with respect to the total number of the acid group included in the above compound A.

[0030] 〔5〕 The transfer film according to any one of 〔2〕 to 〔4〕, wherein,

[0031] The above compound β has a molar absorption coefficient ε at 365 nm of 1 x 10 3 (cm·mol / L) -1 or more.

[0032] 〔6〕 The transfer film according to any one of 〔2〕 to 〔5〕, wherein,

[0033] The ratio of the above compound β has a molar absorption coefficient ε at 365 nm to a molar absorption coefficient ε' at 313 nm of the above compound β is 3 or less.

[0034] 〔7〕 The transfer film according to any one of 〔2〕 to 〔6〕, wherein,

[0035] The above compound β has a pKa in a ground state of 2.0 or more.

[0036] 〔8〕 The transfer film according to any one of 〔2〕 to 〔7〕, wherein,

[0037] The above compound β has a pKa in a ground state of 9.0 or more.

[0038] 〔9〕 The transfer film according to any one of 〔2〕 to 〔8〕, wherein,

[0039] The above compound β is an aromatic compound which can have a substituent.

[0040] 〔10〕 The transfer film according to 〔9〕, wherein,

[0041] The above compound β is an aromatic compound which has a substituent.

[0042] 〔11〕 The transfer film according to any one of <1> to <10>, wherein

[0043] The compound A contains a polymer having a weight average molecular weight of 50,000 or less.

[0044] 〔12〕 The transfer film according to any one of <1> to <11>, wherein

[0045] The compound A contains a polymer containing a repeating unit derived from a (meth)acrylic acid.

[0046] 〔13〕 The transfer film according to any one of <1> to <12>, wherein

[0047] The photosensitive layer further contains a polymerizable compound.

[0048] 〔14〕 The transfer film according to any one of <1> to <13>, wherein

[0049] The photosensitive layer further contains a photopolymerization initiator.

[0050] 〔15〕 The transfer film according to any one of <1> to <14>, wherein

[0051] The relative dielectric constant of the photosensitive layer decreases due to irradiation of actinic rays or radiation.

[0052] 〔16〕 The transfer film according to any one of <1> to <15>, wherein

[0053] The transmittance of the photosensitive layer at 365 nm is 65% or more.

[0054] 〔17〕 The transfer film according to any one of <1> to <16>, wherein

[0055] The ratio of the transmittance of the photosensitive layer at 365 nm to the transmittance of the photosensitive layer at 313 nm is 1.5 or more.

[0056] 〔18〕 The transfer film according to any one of <1> to <17>, wherein

[0057] The content of the acid group in the photosensitive layer decreases by 5 mol% or more due to irradiation of actinic rays or radiation.

[0058] <19> A pattern forming method comprising:

[0059] a step of bringing a surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film according to any one of <1> to <18> into contact with a substrate, and laminating the transfer film to the substrate.

[0060] a step of exposing the photosensitive layer to light in a pattern shape;

[0061] a step of developing the photosensitive layer exposed to light using a developer,

[0062] in the case where the developer is an organic solvent-based developer, further comprising a step of exposing a pattern formed by development after the developing step.

[0063] 〔20〕 A pattern forming method comprising, in this order:

[0064] a step of bringing the surface of the photosensitive layer in the transfer film described in any one of 〔1〕 to 〔18〕 on the side opposite to the temporary support body into contact with a substrate, and laminating the transfer film to the substrate;

[0065] a step of exposing the photosensitive layer to light in a pattern shape;

[0066] a step of developing the photosensitive layer exposed to light using an alkali developer to form a patterned photosensitive layer; and

[0067] a step of exposing the patterned photosensitive layer to light.

[0068] 〔21〕 A circuit wiring manufacturing method comprising, in this order:

[0069] a step of bringing the surface of the photosensitive layer in the transfer film described in any one of 〔1〕 to 〔18〕 on the side opposite to the temporary support body into contact with a conductive layer in a substrate having the conductive layer, and laminating the transfer film to the substrate having the conductive layer;

[0070] a step of exposing the photosensitive layer to light in a pattern shape;

[0071] a step of developing the photosensitive layer exposed to light using an alkali developer to form a patterned photosensitive layer;

[0072] a step of exposing the patterned photosensitive layer to light to form an etching resist film; and

[0073] a step of performing an etching treatment on the conductive layer in a region where the etching resist film is not disposed.

[0074] 〔22〕 A touch panel manufacturing method comprising, in this order:

[0075] a step of bringing the surface of the aforementioned photosensitive layer in the transfer film described in any one of the items 〔1〕 to 〔18〕 on the side opposite to the aforementioned temporary support into contact with the aforementioned conductive layer in a substrate having a conductive layer, and joining the aforementioned transfer film to the substrate having the aforementioned conductive layer;

[0076] a step of exposing the aforementioned photosensitive layer to light in a pattern shape;

[0077] a step of developing the exposed aforementioned photosensitive layer using an alkali developer to form a patterned photosensitive layer; and

[0078] a step of exposing the aforementioned patterned photosensitive layer to light to form a protective film or an insulating film of the aforementioned conductive layer.

[0079] 〔23〕 A photosensitive material comprising a photosensitive material of a compound A having a carboxyl group,

[0080] the aforementioned compound A is a polymer containing a repeating unit derived from a (meth)acrylic acid,

[0081] the content of the aforementioned carboxyl group in a photosensitive layer formed from the aforementioned photosensitive material is reduced by irradiation of actinic rays or radiation.

[0082] 〔24〕 The photosensitive material according to 〔23〕, wherein

[0083] the weight average molecular weight of the aforementioned polymer is 50,000 or less.

[0084] 〔25〕 The photosensitive material according to 〔23〕 or 〔24〕, which satisfies any of the following requirement (V02) and the following requirement (W02):

[0085] the requirement (V02): the aforementioned photosensitive material contains the aforementioned compound A and a compound β having a structure that reduces the amount of the aforementioned carboxyl group contained in the aforementioned compound A by exposure;

[0086] the requirement (W02): the aforementioned photosensitive material contains the aforementioned compound A, and the aforementioned compound A contains a structure that reduces the amount of the aforementioned carboxyl group by exposure.

[0087] 〔26〕 The photosensitive material according to 〔25〕, wherein,

[0088] in the aforementioned requirement V02), the aforementioned compound β is a compound B having a structure that can accept an electron from the aforementioned carboxyl group contained in the aforementioned compound A in a photoexcited state,

[0089] in the aforementioned requirement W02), the aforementioned structure is a structure that can accept an electron from the aforementioned carboxyl group in a photoexcited state.

[0090] 〔27〕 The photosensitive material according to any one of 〔25〕 or 〔26〕, which satisfies the above requirement V02), and the above compound β is a compound B having a structure capable of accepting an electron from the above carboxyl group included in the above compound A in a photoexcited state,

[0091] In the above photosensitive material, the total number of the structure capable of accepting the above electron included in the above compound B is 1 mol% or more with respect to the total number of the carboxyl group included in the above compound A.

[0092] 〔28〕 The photosensitive material according to any one of 〔25〕 to 〔27〕, wherein,

[0093] The above compound β has a molar absorption coefficient ε at 365 nm of 1 x 10 3 (cm·mol / L) -1 The following.

[0094] 〔29〕 The photosensitive material according to any one of 〔25〕 to 〔28〕, wherein,

[0095] The ratio of the above compound β has a molar absorption coefficient ε at 365 nm to the above compound β has a molar absorption coefficient ε' at 313 nm is 3 or less.

[0096] 〔30〕 The photosensitive material according to any one of 〔25〕 to 〔29〕, wherein,

[0097] The above compound β has a pKa in a ground state of 2.0 or more.

[0098] 〔31〕 The photosensitive material according to any one of 〔25〕 to 〔30〕, wherein,

[0099] The above compound β has a pKa in a ground state of 9.0 or less.

[0100] 〔32〕 The photosensitive material according to any one of 〔25〕 to 〔31〕, wherein,

[0101] The above compound β is an aromatic compound which can have a substituent.

[0102] 〔33〕 The photosensitive material according to 〔32〕, wherein,

[0103] The above compound β is an aromatic compound which has a substituent.

[0104] 〔34〕 The photosensitive material according to any one of 〔23〕 to 〔33〕, wherein,

[0105] The content of the above carboxyl group in a photosensitive layer formed from the above photosensitive material is reduced by 5 mol% or more due to irradiation of actinic rays or radiation.

[0106] 〔35〕The photosensitive material according to any one of claims 23 to 34, wherein

[0107] The carboxyl group is decarboxylated by irradiation of the actinic rays or the radiation.

[0108] 〔36〕The photosensitive material according to any one of claims 23 to 35, wherein

[0109] The relative dielectric constant of the photosensitive layer formed from the photosensitive material is reduced by irradiation of the actinic rays or the radiation.

[0110] 〔37〕A pattern forming method comprising:

[0111] a step of forming a photosensitive layer on a substrate using the photosensitive material according to any one of claims 23 to 36;

[0112] a step of exposing the photosensitive layer to light in a pattern shape; and

[0113] a step of developing the exposed photosensitive layer using a developer,

[0114] in the case where the developer is an organic solvent-based developer, further comprising a step of exposing a pattern formed by the developing to light after the developing step.

[0115] 〔38〕A pattern forming method comprising, in this order:

[0116] a step of forming a photosensitive layer on a substrate using the photosensitive material according to any one of claims 23 to 36;

[0117] a step of exposing the photosensitive layer to light in a pattern shape;

[0118] a step of developing the exposed photosensitive layer using an alkali developer to form a patterned photosensitive layer; and

[0119] a step of exposing the patterned photosensitive layer to light.

[0120] 〔39〕A circuit wiring manufacturing method comprising, in this order:

[0121] a step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material according to any one of claims 23 to 36;

[0122] a step of exposing the photosensitive layer to light in a pattern shape;

[0123] a step of developing the exposed photosensitive layer using an alkali developer to form a patterned photosensitive layer;

[0124] a step of exposing the patterned photosensitive layer to form an etching resist film; and

[0125] a step of etching the conductive layer in the region where the etching resist film is not disposed.

[0126] 〔40〕 A method for manufacturing a touch panel, comprising, in order:

[0127] a step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material according to any one of 〔23〕 to 〔36〕;

[0128] a step of exposing the photosensitive layer to form a pattern;

[0129] a step of developing the exposed photosensitive layer using an alkali developer to form a patterned photosensitive layer; and

[0130] a step of exposing the patterned photosensitive layer to form a protective film or an insulating film of the conductive layer.

[0131] Effects of the Invention

[0132] According to the present application, it is possible to provide a transfer film which is excellent in pattern formation and in which a pattern having low moisture permeability can be formed.

[0133] Further, according to the present application, it is possible to provide a photosensitive material which is excellent in pattern formation.

[0134] Further, according to the present application, it is possible to provide a pattern formation method, a method for manufacturing a circuit substrate, and a method for manufacturing a touch panel. BRIEF DESCRIPTION OF DRAWINGS

[0135] Figure 1 is a schematic diagram showing an example of a layer structure of a transfer film according to the embodiment. DETAILED DESCRIPTION

[0136] Hereinafter, the present application will be described in detail.

[0137] In the present specification, a numerical range represented by "to" means a range including the lower limit value and the upper limit value recited before and after "to" as the lower limit value and the upper limit value.

[0138] Further, in the numerical range recited in stages in the present specification, the upper limit value or the lower limit value recited in a certain numerical range can be replaced with the upper limit value or the lower limit value of another numerical range recited in stages. Further, in the numerical range recited in the present specification, the upper limit value or the lower limit value recited in a certain numerical range can be replaced with the value shown in the examples.

[0139] Also, the term "step" in the present specification includes a step even when it cannot be clearly distinguished from other steps, as long as the step achieves the intended purpose of the step.

[0140] In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. Thus, for example, a "transparent resin layer" means a resin layer having an average transmittance of visible light having a wavelength of 400 to 700 nm of 80% or more.

[0141] Also, the average transmittance of visible light is a value measured using a spectrophotometer, and for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd. can be used for the measurement.

[0142] In the present specification, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp such as g-rays, h-rays, i-rays, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and an electron beam (EB), and the like. Also, in the present specification, light means actinic rays or radiation.

[0143] In the present specification, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays, X-rays, EUV light, and the like, but also drawing using a particle beam such as an electron beam and an ion beam, unless otherwise specified.

[0144] In the present specification, the content ratio of each structural unit of a polymer is a molar ratio, unless otherwise specified.

[0145] Also, in the present specification, the refractive index is a value measured at a wavelength of 550 nm using an ellipsometer, unless otherwise specified.

[0146] In the present specification, the molecular weight when a polymer has a molecular weight distribution is a weight average molecular weight, unless otherwise specified.

[0147] In the present specification, the weight average molecular weight of a resin is a weight average molecular weight obtained by polystyrene conversion based on gel permeation chromatography (GPC).

[0148] In the present specification, "(meth)acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth)acryloyl" is a concept including both acryloyl and methacryloyl.

[0149] In the present specification, the thickness (film thickness) of a layer is as follows unless otherwise specified: for a thickness of 0.5 μm or more, the average thickness measured using a scanning electron microscope (SEM); and for a thickness of less than 0.5 μm, the average thickness measured using a transmission electron microscope (TEM). The average thickness is obtained by forming a section to be measured using an ultramicrotome, measuring the thickness of any 5 points, and then performing an arithmetic average of the thicknesses.

[0150] [Transfer film]

[0151] The transfer film of the present application has a temporary support and a photosensitive layer containing a compound A having an acid group (hereinafter, also referred to simply as "compound A") disposed on the temporary support.

[0152] As a feature point of the transfer film of the present application, there can be cited the point that the content of the acid group in the photosensitive layer is reduced by irradiation of an actinic ray or a radiation (hereinafter, also referred to as "exposure"). In other words, as a feature point of the transfer film of the present application, there can be cited the point that the photosensitive layer has a mechanism in which the content of the acid group derived from the compound A by exposure is reduced.

[0153] As an example of the photosensitive layer, there can be cited a photosensitive layer (hereinafter, also referred to as "photosensitive layer X") containing a compound A having a carboxyl group and having a mechanism in which the content of the carboxyl group in the layer is reduced by decarboxylation of the carboxyl group by exposure. In addition, the photosensitive layer X will be described later.

[0154] The transfer film of the present application having the above structure exhibits excellent pattern formability with respect to a developing solution (particularly, an alkali developing solution). Furthermore, the pattern formed from the transfer film of the present application has low moisture permeability, and can be preferably used as a protective film (permanent film) for a conductive pattern or the like.

[0155] Although the detailed mechanism of action of the transfer film of the present application is not clear, the present inventors and the like have speculated as follows.

[0156] According to the present research by the present inventors and the like, it is considered that the inclusion of the acid group in the pattern is one of the reasons for the high moisture permeability of the pattern.

[0157] In contrast, the transfer film of the present application makes it possible to form a pattern having low moisture permeability by the photosensitive layer having a mechanism in which the content of the acid group derived from the compound A by exposure is reduced.

[0158] Furthermore, it was also confirmed by the present research by the present inventors and the like that the photosensitive layer having a mechanism in which the content of the acid group derived from the compound A by exposure is reduced has a lower relative dielectric constant after exposure than before exposure.

[0159] In particular, the transfer film of the present application is more suitable for a development method using an alkali developer.

[0160] In order to ensure a good pattern forming ability with respect to an alkali developer, generally, it is necessary to incorporate a component having a high affinity for an alkali developer (for example, a component having an acid group such as an alkali-soluble resin) in the photosensitive layer, for example, as disclosed in Patent Document 1. That is, it is presumed that a component having a high affinity for an alkali developer cannot be avoided in the formed pattern, which becomes a cause of increasing the moisture permeability.

[0161] In contrast, the transfer film of the present application has an excellent pattern forming ability with respect to an alkali developer by the photosensitive layer having a mechanism in which the content of the acid group derived from Compound A due to exposure is reduced, and makes it possible to form a pattern having low moisture permeability.

[0162] Hereinafter, an example of a pattern forming method using a transfer film will be described, and the presumed action mechanism of the transfer film of the present application will be described.

[0163] [Embodiment of the pattern forming method using a transfer film and action mechanism]

[0164] <<<Pattern forming method of Embodiment 1>>>

[0165] The pattern forming method of Embodiment 1 has Steps X1 to X3. In addition, the following Step X2 corresponds to a step in which the content of the acid group derived from Compound A in the photosensitive layer is reduced due to exposure. In the case where the developer of Step X3 is an organic solvent-based developer, Step X4 is further provided after Step X3.

[0166] Step X1: a step of adhering the transfer film to a substrate by contacting the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film to the substrate

[0167] Step X2: a step of exposing (pattern exposure) the photosensitive layer in a pattern shape

[0168] Step X3: a step of developing the photosensitive layer using a developer

[0169] Step X4: a step of further exposing the pattern formed by development after the development step of Step X3

[0170] In the pattern forming method of Embodiment 1, the photosensitive layer of the transfer film is attached to an arbitrary substrate by the process X1 to form a laminate having a substrate and the photosensitive layer disposed on the substrate. Next, if the photosensitive layer of the obtained laminate is subjected to the process X2 (exposure treatment), the content of the acid group decreases in the exposed portion. On the other hand, in the unexposed portion, the content of the acid group is hardly changed. That is, by going through the above process X2, it is possible to produce a difference in solubility to a developing solution (dissolution contrast) between the exposed portion and the unexposed portion of the photosensitive layer. As a result, in the following process X3 (developing process), in the case where the developing solution is an alkali developing solution, the unexposed portion of the photosensitive layer can be dissolved and removed by the alkali developing solution to form a negative pattern. In addition, since the content of the acid group in the exposed portion (residual film) is decreased by the above process X2, the decrease in moisture permeability caused by the residual acid group is suppressed in the formed pattern. On the other hand, in the case where the developing solution of the process X3 is an organic solvent-based developing solution, since the exposed portion of the photosensitive layer is dissolved and removed by the developing solution to form a positive pattern, the process of decreasing the content of the acid group by exposing the above pattern in the following process X4 is performed. The pattern formed by going through the process X4 has the decrease in moisture permeability caused by the residual acid group suppressed.

[0171] That is, the pattern forming method of Embodiment 1 makes it possible to form a low-moisture-permeability pattern in which the content of the acid group is decreased by the photosensitive layer having a mechanism in which the content of the acid group derived from the compound A decreases due to exposure.

[0172] Among them, the pattern forming method of Embodiment 1 is suitable for a developing method using an alkali developing solution. The photosensitive layer having a mechanism in which the content of the acid group derived from the compound A decreases due to exposure has excellent pattern formability to an alkali developing solution, and makes it possible to form a low-moisture-permeability pattern in which the content of the acid group is decreased. Also, in the case where the developing using an alkali developing solution is performed in the pattern forming method of Embodiment 1, it is also preferable that the photosensitive layer further contains a polymerizable compound (a radical polymerizable compound).

[0173] In addition, as the photosensitive layer having a mechanism in which the content of the acid group derived from the compound A decreases due to exposure, for example, the photosensitive layer X described later can be applied.

[0174] Regarding the specific modes of each process of the pattern forming method of Embodiment 1, they are described in the latter part.

[0175] <<<Pattern Forming Method of Embodiment 2>>>

[0176] The pattern formation method of Embodiment 2 successively has the step Y1, the step Y2P, and the step Y3, and further has the step Y2Q (a step of further exposing the exposed photosensitive layer) before the step Y3 or after the step Y3.

[0177] Step Y1: a step of joining the transfer film to the above-mentioned substrate by contacting the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support side with the substrate

[0178] Step Y2P: a step of exposing the photosensitive layer

[0179] Step Y3: a step of developing the photosensitive layer using a developing solution

[0180] As the pattern formation method of Embodiment 2, a mode in which the photosensitive layer can be applied in the case where the photosensitive layer further contains a photopolymerization initiator and a polymerizable compound is equivalent.

[0181] In the pattern formation method of Embodiment 2, in the step Y2P and the step Y2Q, although the exposure treatment is performed, either of the exposure treatments is exposure for reducing the content of the acid group derived from the compound A due to exposure, and either of the exposure treatments is equivalent to exposure for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator. Also, the exposure treatment can be either of the entire surface exposure and the pattern-like exposure (pattern exposure), but either of the exposure treatments is the pattern exposure.

[0182] For example, in the case where the step Y2P is the pattern exposure for reducing the content of the acid group derived from the compound A due to exposure, the developing solution used in the step Y3 can be an alkali developing solution or an organic solvent-based developing solution. In the case where the developing is performed using the organic solvent-based developing solution, the step Y2Q is usually performed after the step Y3. By performing the step Y2Q, in the developed photosensitive layer (pattern), the content of the acid group (preferably, carboxyl group) derived from the compound A is reduced while causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator.

[0183] Also, for example, in the case where the step Y2P is the pattern exposure for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator, the developing solution used in the step Y3 is usually an alkali developing solution. In this case, the step Y2Q can be performed before or after the step Y3, and the step Y2Q performed before the step Y3 is usually the pattern exposure.

[0184] As the pattern forming method of Embodiment 2, it is preferable to have the steps Y1, Y2A, Y3, and Y2B in this order. Further, one of the steps Y2A and Y2B corresponds to an exposure step for reducing the content of the acid group derived from the compound A due to exposure, and the other corresponds to an exposure step for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator.

[0185] Step Y1: a step of adhering the transfer film to the substrate by contacting the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support side with the substrate

[0186] Step Y2A: a step of exposing (pattern exposure) the photosensitive layer in a pattern shape

[0187] Step Y3: a step of forming a patterned photosensitive layer by developing the photosensitive layer using an alkali developer

[0188] Step Y2B: a step of exposing the patterned photosensitive layer

[0189] Hereinafter, the structure and the action mechanism of the pattern forming method of Embodiment 2 will be described, taking as an example the case where the step Y2A is the exposure step for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator, and the step Y2B is the exposure step for reducing the content of the acid group derived from the compound A due to exposure.

[0190] In the pattern forming method of Embodiment 2, the photosensitive layer of the transfer film is adhered to an arbitrary substrate by the step Y1 to form a laminate having the substrate and the photosensitive layer disposed on the substrate. Next, if the exposure step of the step Y2A is performed on the photosensitive layer of the obtained laminate, the polymerization reaction (curing reaction) of the polymerizable compound is performed in the exposed portion, and in the developing step of the step Y3 that follows, the unexposed portion of the photosensitive layer is dissolved and removed by the alkali developer to form a negative pattern-shaped photosensitive layer (cured layer). Further, in the step Y4, the pattern-shaped photosensitive layer obtained in the step Y3 is exposed (preferably, whole-surface exposure) to reduce the content of the acid group in the photosensitive layer.

[0191] That is, in the pattern forming method of Embodiment 2, since the prescribed amount of the acid group is present in the photosensitive layer at the time of performing the alkali developing step of the step Y2A, the photosensitive layer has excellent pattern formability to the alkali developer. Further, in the step Y4, the pattern with low moisture permeability is formed by reducing the content of the acid group in the photosensitive layer. That is, the pattern forming method of Embodiment 2 has excellent pattern formability to the alkali developer by the photosensitive layer having the mechanism of reducing the content of the acid group derived from the compound A due to exposure, and makes it possible to form the pattern with low moisture permeability with reduced content of the acid group.

[0192] In the above embodiment, process Y2A is an exposure process for causing a polymerization reaction of a polymerizable compound based on a photopolymerization initiator, and process Y2B is an exposure process in which the content of an acid group derived from compound A is reduced due to exposure, but the same action mechanism can also be obtained in a manner in which process Y2A and process Y2B are replaced.

[0193] In addition, as the photosensitive layer having a mechanism in which the content of an acid group derived from compound A is reduced due to exposure, for example, the photosensitive layer X described later can be applied, as shown above.

[0194] Regarding the specific manner of each process of the pattern forming method of Embodiment 2, the latter part is described.

[0195] <<<Photosensitive Layer X>>>

[0196] Hereinafter, the photosensitive layer X and the action mechanism thereof are described.

[0197] The photosensitive layer X satisfies any of the following shown requirement (V1-C) and the following shown requirement (W1-C). In addition, the photosensitive layer can be a photosensitive layer that satisfies both the requirement (V1-C) and the requirement (W1-C).

[0198] Requirement (V1-C)

[0199] The photosensitive layer X contains compound A having a carboxyl group and compound B having a structure capable of accepting an electron from the carboxyl group in compound A in a photoexcited state (hereinafter, also referred to as “specific structure S1”).

[0200] Requirement (W1-C)

[0201] The photosensitive layer X contains compound A having a carboxyl group, and the above compound A further contains a structure (specific structure S1) capable of accepting an electron from the carboxyl group in compound A in a photoexcited state.

[0202] The photosensitive layer X is capable of reducing the content of the carboxyl group derived from compound A by exposure through the following shown action mechanism with the specific structure S1 as a starting point.

[0203] The above specific structure S1 increases the electron acceptance if exposed, and an electron is transferred from the carboxyl group possessed by compound A. In addition, the above carboxyl group can become an anion at the time of transferring the electron.

[0204] If the carboxyl group, which can be the anion described above, donates an electron to the specific structure S1, the carboxyl group becomes unstable and is detached as carbon dioxide. If the carboxyl group, which is an acid group, is detached as carbon dioxide, the polarity of this portion decreases. That is, by the action mechanism described above, the photosensitive layer X generates a change in polarity due to detachment of the carboxyl group of the compound A at the exposed portion, and a change in solubility in a developer (solubility in an alkali developer decreases at the exposed portion and solubility in an organic solvent-based developer increases). On the other hand, in the unexposed portion, the solubility in the developer hardly changes. As a result thereof, the photosensitive layer X has excellent pattern formability. Also, in the case where the developer is an alkali developer, formation of a low moisture permeability pattern in which the content of the carboxyl group decreases becomes possible. Furthermore, in the case where the developer is an organic solvent-based developer, formation of a low moisture permeability pattern in which the content of the carboxyl group decreases becomes possible by further performing an exposure process on the pattern after development.

[0205] In addition, regarding the various components of the photosensitive layer X and the formation method, the latter part is described.

[0206] Also, as described later, it is also preferable that the photosensitive layer X contain a polymerizable compound.

[0207] As described above, if the carboxyl group described above donates an electron to the specific structure S1, the carboxyl group becomes unstable and is detached as carbon dioxide. At this time, a radical is generated at the site where the carboxyl group on the compound A is detached as carbon dioxide, and a radical polymerization reaction of the polymerizable compound is caused by this radical. As a result thereof, the pattern formability of the photosensitive layer X after exposure, especially with respect to an alkali developer, is further improved and the film strength is also excellent.

[0208] As described later, it is also preferable that the photosensitive layer X further contain a polymerizable compound and a photopolymerization initiator.

[0209] In the case where the photosensitive layer X contains a photopolymerization initiator, the detachment of the carboxyl group and the polymerization reaction as described above can occur at different times. For example, with respect to the photosensitive layer X, first, a first exposure can be performed at a wavelength or an exposure amount at which detachment of the carboxyl group hardly occurs, and a polymerization reaction of the polymerizable compound based on the photopolymerization initiator is performed to cure it. Then, a second exposure can be performed on the photosensitive layer that has been cured, and detachment of the carboxyl group is caused.

[0210] <<Embodiment of Photosensitive Layer X>>

[0211] Hereinafter, an example of an embodiment of the photosensitive layer X is shown.

[0212] <Photosensitive Layer X of Embodiment X-1-a1-C>

[0213] The photosensitive layer satisfies any of the requirements (V1-C) or (W1-C) and substantially does not contain a polymerizable compound and a photopolymerization initiator.

[0214] The photosensitive layer X of Embodiment X-1-a2-C

[0215] The photosensitive layer satisfies any of the requirements (V1-C) or (W1-C) and substantially does not contain a photopolymerization initiator.

[0216] The photosensitive layer X of Embodiment X-1-a3-C

[0217] The photosensitive layer satisfies any of the requirements (V1-C) or (W1-C) and contains a polymerizable compound and a photopolymerization initiator.

[0218] In addition, in the photosensitive layer X of Embodiment X-1-a1-C, "the photosensitive layer X substantially does not contain a polymerizable compound" means that the content of the polymerizable compound is less than 3% by mass, preferably 0 to 1% by mass, and more preferably 0 to 0.1% by mass, with respect to the total mass of the photosensitive layer X.

[0219] In addition, in the photosensitive layer X of Embodiment X-1-a1-C and Embodiment X-1-a2-C, "the photosensitive layer X substantially does not contain a photopolymerization initiator" means that the content of the photopolymerization initiator is 0.1% by mass or more, preferably 0 to 0.05% by mass, and more preferably 0 to 0.01% by mass, with respect to the total mass of the photosensitive layer X.

[0220] The photosensitive layer X of Embodiment X-1-a1-C and Embodiment X-1-a2-C is preferably applied to the pattern forming method of Embodiment 1 described above. In addition, the photosensitive layer X of Embodiment X-1-a3-C is preferably applied to the pattern forming method of Embodiment 2 described above.

[0221] Structure of transfer film

[0222] Hereinafter, the structure of the transfer film will be described.

[0223] The transfer film of the present application has a temporary support and a photosensitive layer containing a compound A (compound A) having an acid group disposed on the temporary support.

[0224] Figure 1 is a cross-sectional schematic view showing an example of the embodiment of the transfer film of the present application.

[0225] Figure 1 The transfer film 1000 shown in FIG. 12 is a structure in which a temporary support 12, a photosensitive layer 14, and a cover film 16 are laminated.

[0226] Further, although Figure 1 The transfer film 100 shown in FIG. 1 is in a state where the cover film 16 is provided, but the cover film 16 can not be provided.

[0227] Hereinafter, each element constituting the transfer film will be described.

[0228] <<<Temporary Support>>>

[0229] The temporary support is a support that supports the photosensitive layer and can be peeled from the photosensitive layer.

[0230] From the viewpoint that the photosensitive layer can be exposed through the temporary support when the photosensitive layer is subjected to pattern exposure, it is preferable that the temporary support have light transmittance.

[0231] Here, "have light transmittance" means that the transmittance of the main wavelength of light used for exposure (which can be pattern exposure or full-area exposure) is 50% or more. From the viewpoint that the exposure sensitivity is more excellent, the transmittance of the main wavelength of light used for exposure is preferably 60% or more, and more preferably 70% or more. As a method of measuring the transmittance, a method using MCPD Series manufactured by Otsuka Electronics Co., Ltd. can be given.

[0232] As the temporary support, specifically, a glass substrate, a resin film, paper, and the like can be given, and from the viewpoint that strength and flexibility are more excellent, a resin film is preferable. As the resin film, a polyethylene terephthalate film, a triacetyl cellulose film, a polystyrene film, a polycarbonate film, and the like can be given. Among them, a biaxially stretched polyethylene terephthalate film is preferable.

[0233] From the viewpoint of the pattern formation property when the pattern exposure is performed through the temporary support and the transparency of the temporary support, it is preferable that the number of particles, foreign matters, and defects included in the temporary support be small. The number of particles, foreign matters, and defects having a diameter of 2 μm or more is preferably 50 pieces per 10 mm 2 More preferably, 10 pieces per 10 mm 2 Further preferably, 3 pieces per 10 mm 2 Further. The lower limit is not particularly limited, and can be set to 1 piece per 10 mm 2 or more.

[0234] From the viewpoint of further improving the operability, the temporary support preferably has particles having a diameter of 0.5 to 5 μm present at 1 piece per mm 2 or more on the surface on the side opposite to the side where the photosensitive layer is formed. More preferably, the layer described above has particles having a diameter of 0.5 to 5 μm present at 1 to 50 pieces per mm 2 or more on the surface on the side opposite to the side where the photosensitive layer is formed.

[0235] The thickness of the temporary support is not particularly limited, and is preferably 5 to 200 μm, and more preferably 10 to 150 μm, from the viewpoint of easy handling and excellent versatility.

[0236] The thickness of the temporary support can be appropriately selected depending on the material, from the viewpoint of the strength of the support, the flexibility required when the temporary support is attached to the substrate for circuit wiring formation, and the light transmittance required in the initial exposure process, and the like.

[0237] As a preferred form of the temporary support, for example, 0017 to 0018 of Japanese Patent Application Publication No. 2014-085643, 0019 to 0026 of Japanese Patent Application Publication No. 2016-027363, 0041 to 0057 of WO2012 / 081680A1, and 0029 to 0040 of WO2018 / 179370A1 are described, and the contents of these publications are incorporated into the present specification.

[0238] As the temporary support, for example, Cosmo Shine (registered trademark) A4100 manufactured by TOYOBO CO., LTD., Lumirror (registered trademark) 16FB40 manufactured by Toray Industries, Inc., or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by Toray Industries, Inc. can be used.

[0239] Further, as particularly preferred forms of the temporary support, biaxially-stretched polyethylene terephthalate films having a thickness of 16 μm, biaxially-stretched polyethylene terephthalate films having a thickness of 12 μm, and biaxially-stretched polyethylene terephthalate films having a thickness of 9 μm can be given.

[0240] <<<Photosensitive Layer>>>

[0241] The photosensitive layer contains a compound A (compound A) having an acid group, and has a mechanism in which the content of the acid group derived from the compound A decreases due to exposure.

[0242] Further, the reduction rate of the content of the acid group derived from the compound A in the photosensitive layer can be calculated by measuring the amount of the acid group of the photosensitive layer before and after exposure. In measuring the amount of the acid group of the photosensitive layer before exposure, for example, analysis and quantification can be performed by potentiometric titration. Also, in measuring the amount of the acid group of the photosensitive layer after exposure, the amount of the metal ion derived from the hydrogen atom of the acid group can be calculated by substituting the hydrogen atom of the acid group with a metal ion such as lithium, and by analyzing and quantifying the amount of the metal ion by ICP-OES (Inductively coupled plasma optical emission spectrometer).

[0243] Further, the reduction rate of the content of the acid group derived from the compound A in the photosensitive layer can be obtained by measuring the IR (infrared) spectrum of the photosensitive layer before and after exposure, and calculating the reduction rate of the peak derived from the acid group. Further, in the case where the acid group is a carboxyl group, the reduction rate of the content of the carboxyl group can be obtained by calculating the reduction rate of the peak of C=O stretching (1710 cm -1

[0244] The photosensitive layer is preferably a photosensitive layer satisfying any one of the following requirements (V01) and requirements (W01) shown below. Further, the photosensitive layer can be a photosensitive layer satisfying both the requirement (V01) and the requirement (W01).

[0245] Requirement (V01)

[0246] The photosensitive layer contains the compound A having an acid group, and a compound β having a structure in which the amount of the acid group contained in the above-described compound A is reduced due to exposure (hereinafter, also referred to as "specific structure S0").

[0247] Requirement (W01)

[0248] The photosensitive layer contains the compound A having an acid group, and the above-described compound A further contains a structure (specific structure S0) in which the amount of the acid group is reduced by exposure.

[0249] The above-described specific structure S0 refers to a structure that, if exposed, exhibits an action of reducing the amount of the acid group contained in the compound A. As the specific structure S0, a structure that transitions from a ground state to an excited state by exposure, and exhibits an action of reducing the acid group in the compound A in the excited state is preferable. As the specific structure S0, for example, a structure that can be photoexcited to become a photoexcited state, and accept an electron from the acid group contained in the compound A (specific structure S1 described later), and the like can be given.

[0250] Further, an example of an embodiment of the photosensitive layer is shown below. ​

[0251] <the photosensitive layer of embodiment x-1-a1>

[0252] The photosensitive layer satisfies any of the requirements (V01) or (W01), and does not substantially contain a polymerizable compound and a photopolymerization initiator.

[0253] <the photosensitive layer of embodiment x-1-a2>

[0254] The photosensitive layer satisfies any of the requirements (V01) or (W01), and does not substantially contain a photopolymerization initiator.

[0255] <the photosensitive layer of embodiment x-1-a3>

[0256] The photosensitive layer satisfies any of the requirements (V01) or (W01), and contains a polymerizable compound and a photopolymerization initiator.

[0257] In addition, in the photosensitive layer of embodiment X-1-a1, "the photosensitive layer does not substantially contain a polymerizable compound" means that the content of the polymerizable compound is less than 3% by mass, preferably 0 to 1% by mass, and more preferably 0 to 0.1% by mass, with respect to the total mass of the photosensitive layer.

[0258] In addition, in the photosensitive layer of embodiment X-1-a1 and embodiment X-1-a2, "the photosensitive layer does not substantially contain a photopolymerization initiator" means that the content of the photopolymerization initiator is 0.1% by mass or more, preferably 0 to 0.05% by mass, and more preferably 0 to 0.01% by mass, with respect to the total mass of the photosensitive layer.

[0259] The photosensitive layer of embodiment X-1-a1 and embodiment X-1-a2 is preferably applied to the pattern forming method of embodiment 1 described above. In addition, the photosensitive layer of embodiment X-1-a3 is preferably applied to the pattern forming method of embodiment 2 described above.

[0260] As the above requirement (V01), the following requirement (V1) is preferable, and as the above requirement (W01), the following requirement (W1) is preferable. That is, in the above requirement (V01), the above compound β is preferably a compound B having a structure capable of accepting an electron from an acid group included in the compound A in a photoexcited state. In addition, in the above requirement (W01), the above structure is preferably a structure capable of accepting an electron from an acid group included in the compound A in a photoexcited state.

[0261] Requirement (V1): The photosensitive layer contains a compound A having an acid group and a compound B having a structure (specific structure S1) capable of accepting an electron from the above acid group included in the above compound A in a photoexcited state.

[0262] Requirement (W1): The photosensitive layer contains a compound A having an acid group, and the above compound A further contains a structure (specific structure S1) capable of accepting an electron from the above acid group in a photoexcited state.

[0263] As the photosensitive layer, more preferably, one satisfying any of the above requirement (V1-C) and requirement (W1-C). In addition, requirement (V1-C) corresponds to the case where the acid group in requirement (V1) is a carboxyl group, and requirement (W1-C) corresponds to the case where the acid group in requirement (W1) is a carboxyl group.

[0264] Further, as the embodiment of the photosensitive layer, more preferably, one of the above embodiment X-1-a1-C to embodiment X-1-a3-C. In addition, embodiment X-1-a1-C to embodiment X-1-a3-C correspond to the case where requirement (V01) and requirement (W01) in embodiment X-1-a1 to embodiment X-1-a3 are requirement (V1-C) and requirement (W1-C), respectively.

[0265] In addition, as the mechanism of the reduction in the content of the acid group derived from the compound A due to exposure, it is not limited to the method based on decarboxylation described later, and a publicly known method capable of reducing the content of the acid group derived from the compound A can be appropriately selected.

[0266] <<Various Components>>

[0267] <Compound A having an acid group>

[0268] The photosensitive layer contains a compound A having an acid group (compound A).

[0269] As the acid group contained in the compound A, a proton dissociation group having a pKa of 12 or less is preferable. As the acid group, specifically, a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, a sulfimide group, and the like can be mentioned, and a carboxyl group is preferable.

[0270] As the compound A, it can be a low molecular compound, or a high molecular compound (hereinafter, also referred to as "polymer"), and a polymer is preferable.

[0271] In the case where the compound A is a low molecular compound, as the molecular weight of the compound A, less than 5,000 is preferable, 2,000 or less is more preferable, 1,000 or less is further preferable, 500 or less is particularly preferable, and 400 or less is most preferable.

[0272] In the case where the compound A is a polymer, the lower limit value of the weight average molecular weight of the compound A is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more from the viewpoint of excellent formability of the photosensitive layer (in other words, excellent film formation properties for forming the photosensitive layer). There is no particular limitation on the upper limit value, and the upper limit value is preferably 50,000 or less from the viewpoint of more excellent adhesion (laminating adhesion) at the time of attachment to an arbitrary substrate (at the time of transfer).

[0273] In addition, in the case where the compound A is a polymer, the above polymer is an alkali-soluble resin.

[0274] In the present application, "alkali-solubility" means that the dissolution rate is 0.01 μm / sec or more, which is obtained by the following method.

[0275] A propylene glycol monomethyl ether acetate solution having a concentration of 25 mass% of the target compound (for example, a resin) was applied to a glass substrate, and then, heated with a 100°C oven for 3 minutes, thereby forming a coating film (thickness: 2.0 μm) of the above target compound. The dissolution rate (μm / sec) of the above coating film was obtained by immersing the above coating film in a 1 mass% sodium carbonate aqueous solution (liquid temperature: 30°C).

[0276] In addition, in the case where the target compound is not dissolved in propylene glycol monomethyl ether acetate, the target compound was dissolved in an organic solvent (for example, tetrahydrofuran, toluene, or ethanol) having a boiling point of less than 200°C other than propylene glycol monomethyl ether acetate.

[0277] In addition, in the case where the compound A is a polymer, the acid value of the compound A as a polymer is preferably 60 to 300 mgKOH / g, more preferably 60 to 275 mgKOH / g, and further preferably 75 to 250 mgKOH / g from the viewpoint of developability.

[0278] In the present specification, the acid value of a resin is a value measured by a titration method prescribed in JIS K0070 (1992).

[0279] The compound A preferably also contains a structure (specific structure S0) in which the amount of an acid group contained in the compound A is reduced by exposure. In addition, hereinafter, the compound A not containing the specific structure S0 is referred to as "compound Aa", and the compound A containing the specific structure S0 is referred to as "compound Ab". In addition, the compound Ab is preferably a polymer.

[0280] The fact that the compound A does not contain the specific structure S0 means that the compound A contains substantially no specific structure S0, for example, the content of the specific structure S0 in the compound Aa is less than 1 mass% with respect to the total mass of the compound Aa, preferably 0 to 0.5 mass%, and more preferably 0 to 0.05 mass%.

[0281] The content of the specific structure S0 in the compound Ab is preferably 1 mass% or more, more preferably 1 to 50 mass%, and further more preferably 5 to 40 mass% with respect to the total mass of the compound Ab.

[0282] In the case where the compound A contains the compound Ab, the content of the compound Ab is preferably 5 to 100 mass% with respect to the total mass of the compound A.

[0283] The specific structure S0 means a structure that, if exposed to light, shows an action of reducing the amount of the acid group contained in the compound A. As the specific structure S0, a structure that transitions from a ground state to an excited state by exposure to light and shows an action of reducing the acid group in the compound A in the excited state is preferable.

[0284] As the specific structure S0 possessed by the compound A, a structure that can accept an electron from the acid group contained in the compound A in a photo-excited state (specific structure S1) can be given.

[0285] As such a specific structure S1, a heteroaromatic ring can be given.

[0286] The above heteroaromatic ring can be a monocyclic ring or a polycyclic ring, and is preferably a polycyclic ring. The polycyclic heteroaromatic ring is formed by fusing a plurality of (for example, 2 to 5) aromatic ring structures, and at least one of the above plurality of aromatic ring structures has a heteroatom as a ring member atom.

[0287] The heteroaromatic ring has one or more heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) as a ring member atom, and preferably has one to four. Also, the heteroaromatic ring preferably has one or more (for example, one to four) nitrogen atoms as a ring member atom.

[0288] The above heteroaromatic ring preferably has 5 to 15 ring member atoms.

[0289] As the above heteroaromatic ring, for example, a monocyclic heteroaromatic ring such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; a 2-ring fused heteroaromatic ring such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and a 3-ring fused heteroaromatic ring such as an acridine ring, a phenanthridine ring, a phenanthroline ring, and a phenazine ring can be given.

[0290] The above heteroaromatic ring can have one or more (e.g., 1 to 5) substituents, and as the substituents, there can be mentioned alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, arylcarbonyl groups, carbamoyl groups, hydroxyl groups, cyano groups, and nitro groups. Also, in the case where the above aromatic ring has two or more substituents, the substituents can be bonded to each other to form a non-aromatic ring.

[0291] Also, it is preferable that the above heteroaromatic ring be directly bonded to a carbonyl group.

[0292] It is also preferable that the above heteroaromatic ring be bonded to an imide group to form a heteroaromatic imide group. Also, the imide group in the heteroaromatic imide group can form an imide ring together with the heteroaromatic ring, or can not form an imide ring.

[0293] Also, in the compound A, in the case where a plurality of aromatic rings (e.g., 2 to 5 aromatic rings) form a series of aromatic ring structures bonded by a structural bond selected from a single bond, a carbonyl group, and a multiple bond (e.g., a vinylene group which can have a substituent, -C≡C-, -N=N-, etc.), and one or more of the plurality of aromatic rings constituting the series of aromatic ring structures is the above heteroaromatic ring, the entire series of aromatic ring structures is regarded as one specific structure S1.

[0294] Also, part or all of the acid groups possessed by the compound A can be anionized in the photosensitive layer, or can not be anionized, and an acid group can include both an anionized acid group and a non-anionized acid group. That is, the compound A can be anionized in the photosensitive layer, or can not be anionized.

[0295] As the compound A, from the viewpoint of more excellent pattern-forming ability of the photosensitive layer and the viewpoint of more excellent film-forming ability, a compound having a carboxyl group is preferable.

[0296] As the compound having a carboxyl group, a monomer containing a carboxyl group (hereinafter, also referred to as "monomer containing a carboxyl group") or a polymer containing a carboxyl group (hereinafter, also referred to as "polymer containing a carboxyl group") is preferable, and from the viewpoint of more excellent pattern-forming ability of the photosensitive layer and the viewpoint of more excellent film-forming ability, a polymer containing a carboxyl group is more preferable.

[0297] Also, part or all of the carboxyl groups (-COOH) possessed by the monomer containing a carboxyl group and the polymer containing a carboxyl group can be anionized in the photosensitive layer, or can not be anionized, and a carboxyl group can include both an anionized carboxyl group (-COO - ) and a non-anionized carboxyl group.

[0298] That is, the carboxyl group-containing monomer can be anionized in the photosensitive layer or can not be anionized, and an anionized carboxyl group-containing monomer and a non-anionized carboxyl group-containing monomer can be included at the same time.

[0299] That is, the carboxyl group-containing polymer can be anionized in the photosensitive layer or can not be anionized, and an anionized carboxyl group-containing polymer and a non-anionized carboxyl group-containing polymer can be included at the same time.

[0300] As described above, the compound A containing a carboxyl group can include the specific structure S0 (preferably the specific structure S1). In other words, the carboxyl group-containing monomer and the carboxyl group-containing polymer can include the specific structure S0 (preferably the specific structure S1). In the case where the compound A containing a carboxyl group includes the specific structure S0 (preferably the specific structure S1), the carboxyl group-containing polymer including the specific structure S0 (preferably the specific structure S1) is preferred, and the carboxyl group-containing polymer including the specific structure S1 is more preferred.

[0301] In the photosensitive layer, as a lower limit value of the content of the compound A, 1% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, more further preferably 45% by mass or more, and particularly preferably 50% by mass or more, relative to the total mass of the photosensitive layer is preferred. As an upper limit value of the content of the compound A, 100% by mass or less, more preferably 99% by mass or less, further preferably 97% by mass or less, particularly preferably 93% by mass or less, more particularly preferably 85% by mass or less, and most preferably 75% by mass or less, relative to the total mass of the photosensitive layer is preferred. In addition, in the case where the photosensitive layer satisfies the requirement (W01), as an upper limit value of the content of the compound A, 99% by mass or less, relative to the total mass of the photosensitive layer is preferred.

[0302] The compound A can be used alone or two or more kinds can be used.

[0303] (carboxyl group-containing monomer)

[0304] As the carboxyl group-containing monomer, a polymerizable compound containing a carboxyl group and containing one or more (for example, 1 to 15) ethylenically unsaturated groups is included.

[0305] As the ethylenically unsaturated group, for example, (meth)acryloyl group, vinyl group, and styryl group can be mentioned, and (meth)acryloyl group is preferred.

[0306] As the carboxyl group-containing monomer, from the viewpoint of more excellent film formability, a 2 or more functional monomer containing a carboxyl group is preferred. In addition, the 2 or more functional monomer refers to a polymerizable compound having two or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule.

[0307] The monomer containing a carboxyl group can further have an acid group other than a carboxyl group as an acid group. As the acid group other than a carboxyl group, for example, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group can be given.

[0308] The 2 or more functional monomer containing a carboxyl group is not particularly limited and can be appropriately selected from publicly known compounds.

[0309] As the 2 or more functional monomer containing a carboxyl group, for example, 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.), and the like can be given.

[0310] Also, as the 2 or more functional monomer containing a carboxyl group, for example, a 3 to 4 functional polymerizable compound having a carboxyl group (a compound in which a carboxyl group is introduced into a pentaerythritol tri- and tetraacrylate [PETA] skeleton (acid value = 80 to 120 mgKOH / g)) and a 5 to 6 functional polymerizable compound containing a carboxyl group (a compound in which a carboxyl group is introduced into a dipentaerythritol penta- and hexa(meth)acrylate [DPHA] skeleton (acid value = 25 to 70 mgKOH / g)), and the like can be given. In addition, in the case where the 3 or more functional monomer containing the above carboxyl group is used, from the viewpoint that the film formability is more excellent, it is also preferable that the 2 or more functional monomer containing a carboxyl group is used at the same time.

[0311] As the 2 or more functional monomer containing a carboxyl group, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 can also be given. The content of this publication is incorporated into the present specification.

[0312] (Polymer containing a carboxyl group)

[0313] Generally, the polymer containing a carboxyl group is an alkali-soluble resin. In addition, the definition and the measurement method of the alkali solubility are as already described.

[0314] The polymer containing a carboxyl group can further have an acid group other than a carboxyl group as an acid group. As the acid group other than a carboxyl group, for example, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group can be given.

[0315] From the viewpoint of development properties, the acid value of the polymer containing a carboxyl group is preferably 60 to 300 mgKOH / g, more preferably 60 to 275 mgKOH / g, and further preferably 75 to 250 mgKOH / g.

[0316] <Repeat unit having a carboxyl group>

[0317] The polymer containing a carboxyl group preferably has a repeating unit having a carboxyl group.

[0318] As the repeating unit having a carboxyl group, for example, a repeating unit represented by the following general formula (A) can be given.

[0319] [Chemical Formula 1]

[0320]

[0321] In the general formula (A), R A1 represents a hydrogen atom, a halogen atom, or an alkyl group.

[0322] The above alkyl group can be linear or branched. The number of carbon atoms of the above alkyl group is preferably 1 to 5, more preferably 1.

[0323] In the general formula (A), A 1 represents a single bond or a divalent linking group.

[0324] As the above divalent linking group, for example, -CO-, -O-, -S-, -SO-, -SO2-, -NR N -(R N is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), a hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group such as a phenylene group, and the like), and a linking group in which a plurality of these are linked.

[0325] As the monomer that becomes the source of the repeating unit having a carboxyl group, for example, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid can be given. Among them, from the viewpoint of more excellent patterning properties, (meth)acrylic acid is preferred. That is, the repeating unit having a carboxyl group is preferably a repeating unit derived from (meth)acrylic acid.

[0326] In the polymer containing a carboxyl group, the content of the repeating unit having a carboxyl group is preferably 5 to 100 mol%, more preferably 10 to 65 mol%, and further preferably 15 to 45 mol% with respect to all the repeating units of the polymer containing a carboxyl group.

[0327] Also, in the polymer containing a carboxyl group, the content of the repeating unit having a carboxyl group is preferably 1 to 100 mass%, more preferably 5 to 70 mass%, and further preferably 12 to 50 mass% with respect to all the repeating units of the polymer containing a carboxyl group.

[0328] The repeating unit having a carboxyl group can be used alone or two or more kinds can be used.

[0329] Repeating Unit Having a Polymerizable Group

[0330] The polymer containing a carboxyl group preferably has, in addition to the above-mentioned repeating unit, a repeating unit having a polymerizable group.

[0331] As the polymerizable group, for example, an olefinically unsaturated group (e.g., a (meth)acryloyl group, a vinyl group, a styryl group, and the like) and a cyclic ether group (e.g., an epoxy group, an oxetanyl group, and the like) can be given, and an olefinically unsaturated group is preferred, and a (meth)acryloyl group is more preferred.

[0332] As the repeating unit having a polymerizable group, for example, a repeating unit represented by the following general formula (B) can be given.

[0333] [Chemical Formula 2]

[0334]

[0335] In the general formula (B), X B1 and X B2 independently represent -O- or -NR N -.

[0336] R N represents a hydrogen atom or an alkyl group. The above-mentioned alkyl group can be linear or branched, and the number of carbon atoms is preferably from 1 to 5.

[0337] L represents an alkylene group or an arylene group. The above-mentioned alkylene group can be linear or branched, and the number of carbon atoms is preferably from 1 to 5. The above-mentioned arylene group can be monocyclic or polycyclic, and the number of carbon atoms is preferably from 6 to 15. The above-mentioned alkylene group and arylene group can have a substituent, and as the above-mentioned substituent, for example, a hydroxyl group is preferred.

[0338] R B1 and R B2 independently represent a hydrogen atom or an alkyl group. The above-mentioned alkyl group can be linear or branched. The number of carbon atoms of the above-mentioned alkyl group is preferably from 1 to 5, and more preferably 1.

[0339] In the polymer containing a carboxyl group, the content of the repeating unit having a polymerizable group is preferably from 3 to 60 mol%, more preferably from 5 to 40 mol%, and further preferably from 10 to 30 mol%, relative to all the repeating units of the polymer containing a carboxyl group.

[0340] In the polymer containing a carboxyl group, the content of the repeating unit having a polymerizable group is preferably from 1 to 70 mass%, more preferably from 5 to 50 mass%, and further preferably from 12 to 45 mass%, relative to all the repeating units of the polymer containing a carboxyl group.

[0341] The repeating unit having a polymerizable group can be used singly or two or more kinds can be used.

[0342] Repeating unit having specific structure S0

[0343] The carboxyl group-containing polymer preferably has, in addition to the repeating unit described above, a repeating unit having a specific structure S0 (preferably, specific structure S1).

[0344] The specific structure S0 and the specific structure S1 are as described above.

[0345] In the repeating unit having the specific structure S0 (preferably, specific structure S1), the specific structure S0 (preferably, specific structure S1) can be present in the main chain or in the side chain, and is preferably present in the side chain. In the case where the specific structure S0 (preferably, specific structure S1) is present in the side chain, the specific structure S0 (preferably, specific structure S1) is bonded to the main chain of the polymer via a single bond or a linking group.

[0346] The repeating unit having the specific structure S0 (preferably, specific structure S1) is, for example, a repeating unit based on a monomer having a heteroaromatic ring (specifically, a (meth)acrylate monomer having a vinyl heteroaromatic ring and a heteroaromatic ring such as a vinylpyridine and a vinyl(iso)quinoline, and the like).

[0347] Hereinafter, specific examples of the repeating unit having the specific structure S0 (preferably, specific structure S1) will be shown, but are not limited thereto.

[0348] [Chemical Formula 3]

[0349]

[0350] In the case where the carboxyl group-containing polymer has the repeating unit having the specific structure S0 (preferably, specific structure S1), the content thereof is preferably 3 to 75 mol%, more preferably 5 to 60 mol%, and further preferably 10 to 50 mol% with respect to all of the repeating units of the carboxyl group-containing polymer.

[0351] In the case where the carboxyl group-containing polymer has the repeating unit having the specific structure S0 (preferably, specific structure S1), the content thereof is preferably 1 to 75 mass%, more preferably 3 to 60 mass%, and further preferably 5 to 30 mass% with respect to all of the repeating units of the carboxyl group-containing polymer.

[0352] The repeating unit having the specific structure S0 (preferably, specific structure S1) can be used alone or two or more kinds thereof can be used.

[0353] Repeating unit having aromatic ring

[0354] The polymer containing a carboxyl group preferably has, in addition to the above-mentioned repeating unit, a repeating unit having an aromatic ring (preferably an aromatic hydrocarbon ring). For example, a (meth)acrylate-based repeating unit having an aromatic ring and a repeating unit based on styrene and a polymerizable styrene derivative can be given.

[0355] As the (meth)acrylate having an aromatic ring, a benzyl (meth)acrylate, a phenethyl (meth)acrylate, a phenoxyethyl (meth)acrylate, and the like can be given.

[0356] As the styrene and the polymerizable styrene derivative, a methylstyrene, a vinyltoluene, a t-butoxy styrene, an acetoxy styrene, a 4-vinylbenzoic acid, a styrene dimer, a styrene trimer, and the like can be given.

[0357] As the repeating unit having an aromatic ring, for example, a repeating unit represented by the following general formula (C) is also preferable.

[0358] [Chemical Formula 4]

[0359]

[0360] In the general formula (C), R C1 represents a hydrogen atom, a halogen atom, or an alkyl group. The above-mentioned alkyl group can be linear or branched. The number of carbon atoms of the above-mentioned alkyl group is preferably 1 to 5, more preferably 1.

[0361] Ar C represents a phenyl group or a naphthyl group. The above-mentioned phenyl group and naphthyl group can have one or more substituents, and as the above-mentioned substituents, for example, an alkyl group, an alkoxy group, an aryl group, a halogen atom, and a hydroxyl group can be given.

[0362] Hereinafter, a repeating unit having an aromatic ring will be exemplified.

[0363] [Chemical Formula 5]

[0364]

[0365] As the repeating unit having an aromatic ring, the following structure is preferable.

[0366] [Chemical Formula 6]

[0367]

[0368] In the polymer containing a carboxyl group, the content of the repeating unit having an aromatic ring is preferably 5 to 80 mol%, more preferably 15 to 75 mol%, and further preferably 30 to 70 mol% with respect to all the repeating units of the polymer containing a carboxyl group.

[0369] The content of the repeating unit having an alicyclic structure in the carboxyl group-containing polymer is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, and further preferably 10 to 55 mol% relative to all of the repeating units of the carboxyl group-containing polymer.

[0370] The repeating unit having an alicyclic structure can be used singly or two or more kinds can be used.

[0371] Repeating unit having alicyclic structure

[0372] The carboxyl group-containing polymer preferably has a repeating unit having an alicyclic structure in addition to the above-described repeating units. The alicyclic structure can be a monocyclic ring or a polycyclic ring.

[0373] As the alicyclic structure, for example, a dicyclopentyl ring structure, a dicyclopentenyl ring structure, an isobornyl ring structure, an adamantyl ring structure, and a cyclohexyl ring structure can be given.

[0374] As the monomer derived from the repeating unit having an alicyclic structure, for example, a dicyclopentyl (meth)acrylate, a dicyclopentenyl (meth)acrylate, an isobornyl (meth)acrylate, an adamantyl (meth)acrylate, and a cyclohexyl (meth)acrylate can be given.

[0375] The content of the repeating unit having an alicyclic structure in the carboxyl group-containing polymer is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, and further preferably 10 to 55 mol% relative to all of the repeating units of the carboxyl group-containing polymer.

[0376] The content of the repeating unit having an alicyclic structure in the carboxyl group-containing polymer is preferably 3 to 90 mass%, more preferably 5 to 70 mass%, and further preferably 25 to 60 mass% relative to all of the repeating units of the carboxyl group-containing polymer.

[0377] The repeating unit having an alicyclic structure can be used singly or two or more kinds can be used.

[0378] Other repeating unit

[0379] The carboxyl group-containing polymer can have other repeating units in addition to the above-described repeating units.

[0380] As the monomer that becomes the source of the above-described other repeating unit, an alkyl (meth)acrylate can be given, and as the alkyl group, an alkyl group having a chain structure can be given. The chain structure can be a straight chain structure or a branched chain structure. The alkyl group can have a substituent such as a hydroxyl group. As the number of carbon atoms of the alkyl group, 1 to 50, and more preferably 1 to 10 can be given. As a specific example, a methyl (meth)acrylate can be given.

[0381] In polymers containing carboxyl groups, the content of other repeating units relative to all repeating units in the polymer containing carboxyl groups is preferably 1 to 70 mol%, more preferably 2 to 50 mol%, and even more preferably 3 to 20 mol%.

[0382] In the polymer containing carboxyl groups, the content of other repeating units relative to all repeating units of the polymer containing carboxyl groups is preferably 1 to 70% by mass, more preferably 2 to 50% by mass, and even more preferably 5 to 35% by mass.

[0383] Other repeating units can be used individually or in two or more ways.

[0384] The weight-average molecular weight of the polymer containing carboxyl groups is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and most preferably 11,000 to 49,000.

[0385] The content of the carboxyl-containing polymer in compound A is preferably 75 to 100% by mass relative to the total content of compound A, more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.

[0386] The content of the carboxyl-containing monomer in compound A is preferably 0 to 25% by mass relative to the total content of compound A, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass.

[0387] In the photosensitive layer of embodiment X-1-a1, the content of compound A relative to the total mass of the photosensitive layer is preferably 40 to 98% by mass, more preferably 50 to 96% by mass, and even more preferably 60 to 93% by mass.

[0388] In the photosensitive layer of embodiment X-1-a2, the content of compound A is preferably 30 to 85% by mass relative to the total mass of the photosensitive layer, more preferably 45 to 75% by mass.

[0389] In the photosensitive layer of embodiment X-1-a3, the content of compound A is preferably 30 to 85% by mass relative to the total mass of the photosensitive layer, more preferably 45 to 75% by mass.

[0390] <Compound β>

[0391] The photosensitive layer preferably contains compound β.

[0392] Compound β is a compound having a structure (specific structure S0) that reduces the amount of acid groups contained in compound A through exposure. Specific structure S0 has already been described.

[0393] The specific structure S0 possessed by the compound β can be an overall structure constituting the entirety of the compound β, or a partial structure constituting a part of the compound β.

[0394] The compound β can be a high molecular compound or a low molecular compound, and is preferably a low molecular compound.

[0395] The molecular weight of the compound β as a low molecular compound is preferably less than 5,000, more preferably less than 1,000, further preferably 65 to 300, and particularly preferably 75 to 250.

[0396] As the specific structure S0, a structure capable of accepting an electron from the acid group contained in the compound A in a photoexcited state (specific structure S1) is preferable. That is, as the compound β, a compound B capable of accepting an electron from the acid group contained in the compound A in a photoexcited state (specific structure S1) is preferable.

[0397] Hereinafter, the compound β (preferably, the compound B) will be described.

[0398] The compound β (preferably, the compound B) is preferably an aromatic compound from the viewpoint of more excellent pattern-forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower.

[0399] The aromatic compound refers to a compound having one or more aromatic rings.

[0400] The aromatic ring can exist only one in the compound β (preferably, the compound B), or can exist a plurality of. In the case where a plurality of exists, for example, the above-described aromatic ring can exist in a side chain of a resin or the like.

[0401] In the compound β (preferably, the compound B), the aromatic ring can serve as a structure capable of accepting an electron from the acid group contained in the compound A in the above-described photoexcited state (specific structure S1). The above-described aromatic ring can be an overall structure constituting the entirety of the compound β (preferably, the compound B), or a partial structure constituting a part of the compound β (preferably, the compound B).

[0402] The above-described aromatic ring can be a monocyclic ring or a polycyclic ring, and is preferably a polycyclic ring. The polycyclic aromatic ring is, for example, an aromatic ring in which a plurality of (for example, 2 to 5) aromatic ring structures are fused, and preferably at least one of the above-described plurality of aromatic ring structures has a hetero atom as a ring member atom.

[0403] The above-described aromatic ring can be a heteroaromatic ring, and is preferably a heteroaromatic ring having one or more (for example, 1 to 4) hetero atoms (nitrogen atom, oxygen atom, sulfur atom, or the like) as a ring member atom, and more preferably a heteroaromatic ring having one or more (for example, 1 to 4) nitrogen atoms as a ring member atom.

[0404] The number of ring member atoms of the aromatic ring is preferably 5 to 15.

[0405] It is preferable that the compound β (preferably, the compound B) be a compound having, as a ring member atom, an aromatic ring having a 6-membered ring with a nitrogen atom.

[0406] As the aromatic ring, for example, there can be mentioned a monocyclic aromatic ring such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; a 2-ring condensed aromatic ring such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and a 3-ring condensed aromatic ring such as an acridine ring, a phenanthridine ring, a phenanthroline ring, and a phenoxazine ring.

[0407] The aromatic ring can have one or more (for example, 1 to 5) substituents, and as the substituent, there can be mentioned an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, an amino group, and a nitro group. Further, in the case where the aromatic ring has two or more substituents, the substituents can be bonded to each other to form a non-aromatic ring.

[0408] Further, it is also preferable that the aromatic ring be directly bonded to a carbonyl group to form an aromatic carbonyl group in the compound β (preferably, the compound B). It is also preferable that the aromatic rings be bonded to each other via a carbonyl group.

[0409] It is also preferable that the aromatic ring be bonded to an imide group to form an aromatic imide group in the compound β (preferably, the compound B). Further, the imide group in the aromatic imide group can form an imide ring together with the aromatic ring, or can not form an imide ring.

[0410] Further, in the case where a plurality of aromatic rings (for example, 2 to 5 aromatic rings) form a series of aromatic ring structures bonded by a structural bond selected from a single bond, a carbonyl group, and a multiple bond (for example, a vinylene group, -C≡C-, -N=N-, and the like, which can have a substituent), the entire series of the aromatic ring structures is regarded as one specific structure S1.

[0411] Further, it is preferable that one or more of the plurality of aromatic rings constituting the series of the aromatic ring structures be the above-described heteroaromatic ring.

[0412] From the viewpoint of more excellent pattern-forming ability and / or the viewpoint of lower moisture permeability of the formed pattern, the compound β (preferably, the compound B) is preferably a compound satisfying one or more (for example, 1 to 4) of the following requirements (1) to (4). Among them, it is preferable that at least the requirement (2) be satisfied, and it is preferable that the heteroatom possessed as the heteroaromatic ring be at least a nitrogen atom.

[0413] (1) An aromatic ring having a polycyclic ring.

[0414] (2) A heteroaromatic ring.

[0415] (3) has an aromatic carbonyl group.

[0416] (4) has an aromatic imide group.

[0417] As specific examples of the compound β (preferably, the compound B), there can be mentioned monocyclic aromatic compounds such as pyridine and pyridine derivatives, pyrazine and pyrazine derivatives, pyrimidine and pyrimidine derivatives, and triazine and triazine derivatives; 2-ring fused compounds forming an aromatic ring such as quinoline and quinoline derivatives, isoquinoline and isoquinoline derivatives, quinoxaline and quinoxaline derivatives, and quinazoline and quinazoline derivatives; and 3-rings or more fused compounds forming an aromatic ring such as acridine and acridine derivatives, phenanthridine and phenanthridine derivatives, phenanthroline and phenanthroline derivatives, and phenoxazine and phenoxazine derivatives.

[0418] Among them, the compound β (preferably, the compound B) is preferably one or more selected from the group consisting of pyridine and pyridine derivatives, quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives, more preferably one or more selected from the group consisting of quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives, and further preferably one or more selected from the group consisting of isoquinoline and isoquinoline derivatives.

[0419] These compounds and derivatives thereof can further have a substituent, and as the above-mentioned substituent, it is preferable that it is an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, an amino group, or a nitro group, more preferable that it is an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, or a nitro group, further preferable that it is an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, or a nitro group, and particularly preferable that it is an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms).

[0420] Further, from the viewpoint of more excellent pattern-forming ability and / or the viewpoint of making the moisture permeability of the formed pattern lower, the compound β (preferably, the compound B) is preferably an aromatic compound having a substituent (a compound having a substituent at a structure atom of an aromatic ring included in the compound β (preferably, the compound B)), more preferably a compound satisfying one or more (for example, 1 to 4) of the above-mentioned requirements (1) to (4) and further having a substituent.

[0421] As the position of the substituent, for example, in the case where the compound β (preferably, the compound B) is a quinoline and a quinoline derivative, from the viewpoint that the pattern forming ability is more excellent and / or the moisture permeability of the formed pattern becomes lower, it is preferable that the substituent is present at a position of at least 2 and 4 on the quinoline ring. Also, for example, in the case where the compound β (preferably, the compound B) is an isoquinoline and an isoquinoline derivative, from the viewpoint that the pattern forming ability is more excellent and / or the moisture permeability of the formed pattern becomes lower, it is preferable that the substituent is present at a position of at least 1 on the isoquinoline ring. In addition, as the substituent, an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms) is preferable.

[0422] In the case where the compound β (preferably, the compound B) is a polymer, the specific structure S0 (preferably, the specific structure S1) can be a polymer which is bonded to the main chain of the polymer via a single bond or a linking group.

[0423] The compound β (preferably, the compound B) which becomes a polymer is obtained, for example, by polymerizing a monomer having a heteroaromatic ring (specifically, a (meth)acrylate monomer having a vinyl heteroaromatic ring and / or the specific structure S0 (preferably, the specific structure S1, more preferably, a heteroaromatic ring)). Copolymerization with other monomers can be performed as needed.

[0424] From the viewpoint that the pattern forming ability is more excellent and / or the moisture permeability of the formed pattern becomes lower, the molar absorption coefficient (molar absorption coefficient ε) of the compound β (preferably, the compound B) for light having a wavelength of 365 nm is, for example, 1 x 10 3 (cm·mol / L) -1 Hereinafter, it is preferable that the molar absorption coefficient is 1 x 10 3 (cm·mol / L) -1 Hereinafter, it is more preferable that the molar absorption coefficient is less than 5 x 10 2 (cm·mol / L) -1 Hereinafter, it is further preferable that the molar absorption coefficient is 1 x 10 2 (cm·mol / L) -1 Hereinafter. The lower limit of the molar absorption coefficient ε is not particularly limited, and is, for example, more than 0 (cm·mol / L) -1 .

[0425] In the case where the photosensitive layer is exposed through a temporary support (preferably, a PET film), the molar absorption coefficient ε of the compound β (preferably, the compound B) within the above range is particularly advantageous.

[0426] That is, in the case where the acid group of the compound A having an acid group is a carboxyl group, since the molar absorption coefficient ε is moderately low, even if exposure is performed through the temporary support, the generation of bubbles due to decarboxylation can be controlled, and thus the deterioration of the pattern shape can be prevented.

[0427] Further, in the case where the photosensitive layer is used for the production of a protective film (permanent film), by setting the molar absorption coefficient ε of the compound β (preferably, the compound B) to the above range, the coloring of the film can be suppressed.

[0428] As the compound having such a molar absorption coefficient ε, the monocyclic aromatic compound or the aromatic compound in which the aromatic ring is formed by the condensation of 2 rings is preferable, and pyridine or a pyridine derivative, quinoline or a quinoline derivative, or isoquinoline or an isoquinoline derivative is preferable.

[0429] Further, from the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower, the ratio of the molar absorption coefficient of the compound β (preferably, the compound B) at 365 nm (molar absorption coefficient ε) to the molar absorption coefficient of the compound β (preferably, the compound B) at 313 nm (molar absorption coefficient ε') (i.e., the ratio represented by molar absorption coefficient ε / molar absorption coefficient ε') is preferably 3 or less, more preferably 2 or less, and further preferably less than 1. There is no particular limitation on the lower limit value, and for example, it is 0.01 or more.

[0430] In addition, the molar absorption coefficient of the compound β (preferably, the compound B) for light of wavelength 365 nm (molar absorption coefficient ε) and the molar absorption coefficient for light of wavelength 313 nm (molar absorption coefficient ε') are the molar absorption coefficients determined by dissolving the compound β (preferably, the compound B) in acetonitrile. In the case where the compound β (preferably, the compound B) is not dissolved in acetonitrile, the solvent in which the compound β (preferably, the compound B) is dissolved can be appropriately changed.

[0431] As specific examples of the compound β (preferably, the compound B), 5,6,7,8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, 1-phenylisoquinoline, 1-n-butylisoquinoline, 1-n-butyl-4-methylisoquinoline, 1-methylisoquinoline, 2,4,5,7-tetramethylquinoline, 2-methyl-4-methoxyquinoline, 2,4-dimethylquinoline, phenanthridine, 9-methylacridine, 9-phenylacridine, pyridine, isoquinoline, quinoline, acridine, 4-aminopyridine, and 2-chloropyridine, and the like can be given.

[0432] As a lower limit value of the pKa of the compound β (preferably, the compound B) in the ground state, it is preferably 0.5 or more, more preferably 2.0 or more from the viewpoint of more excellent pattern-forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower. Also, as an upper limit value of the pKa of the compound β (preferably, the compound B) in the ground state, it is preferably 10.0 or less, more preferably 9.0 or less from the viewpoint of more excellent pattern-forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower. The upper limit value of the pKa of the compound β (preferably, the compound B) in the ground state is more preferably smaller from the viewpoint of more excellent pattern-forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower, and is further preferably 8.0 or less, particularly preferably 7.0 or less. Note that the pKa of the compound β (preferably, the compound B) in the ground state means the pKa of the compound β (preferably, the compound B) in an unexcited state, and can be obtained by acid titration. Also, in the case where the compound β (preferably, the compound B) is a nitrogen-containing aromatic compound, the pKa of the compound β (preferably, the compound B) in the ground state means the pKa of the conjugate acid of the compound β (preferably, the compound B) in the ground state.

[0433] Also, in the case where the photosensitive layer is formed by coating, the molecular weight of the compound β (preferably, the compound B) is preferably 120 or more, more preferably 130 or more, further preferably 180 or more from the viewpoint that the compound β (preferably, the compound B) is less likely to be volatilized from the coating process and the residual rate in the photosensitive layer is more excellent (and further from the viewpoint of more excellent pattern-forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower). Note that there is no particular limitation on the upper limit value of the molecular weight of the compound β (preferably, the compound B), and it is, for example, 50,000 or less.

[0434] Also, in the case where the compound β (preferably, the compound B) is a compound (for example, a nitrogen-containing aromatic compound) that exhibits a cationic state, as the energy level of the HOMO (highest occupied molecular orbital) of the compound β (preferably, the compound B) in the cationic state, it is preferably -8.5 eV or less, more preferably -7.8 eV or less from the viewpoint of more excellent pattern-forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower. Note that there is no particular limitation on the lower limit value, and it is more preferably -13.6 eV or more.

[0435] In the present specification, the energy level of HOMO (HOMO in the 1st excited state) of compound β (preferably, compound B) in the cation state is calculated by a quantum chemistry calculation program Gaussian09 (Gaussian 09, Revision A.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009).

[0436] As a calculation method, a time-dependent density functional method using B3LYP in a functional and 6-31+G(d,p) in a basis function was used. Also, in order to promote solvent effect, a PCM method based on parameters of chloroform set in Gaussian09 was used. With this method, a structure optimization calculation of the 1st excited state was performed to find a structure having the minimum energy, and the energy of HOMO at the structure was calculated.

[0437] Hereinafter, with respect to a representative example of the compound β (preferably, the compound B), the HOMO energy level (eV) in the cationic state thereof is shown. In addition, the molecular weight is also shown.

[0438] [Table 1]

[0439] Table 1

[0440]

[0441] From the viewpoint of more excellent pattern-forming ability and / or the viewpoint of lower moisture permeability of the formed pattern, the content of the compound β (preferably, the compound B) in the photosensitive layer is preferably 0.1 to 50 mass% with respect to the total mass of the photosensitive layer.

[0442] In the photosensitive layer of Embodiment X-1-a1, the content of the compound β (preferably, the compound B) is preferably 2.0 to 40 mass%, more preferably 4 to 35 mass%, and further preferably 8 to 30 mass% with respect to the total mass of the photosensitive layer.

[0443] In the photosensitive layer of Embodiment X-1-a2, the content of the compound β (preferably, the compound B) is preferably 0.5 to 20 mass%, and more preferably 1.0 to 10 mass% with respect to the total mass of the photosensitive layer.

[0444] In the photosensitive layer of Embodiment X-1-a3, the content of the compound β (preferably, the compound B) is preferably 0.3 to 20 mass%, and more preferably 0.5 to 8 mass% with respect to the total mass of the photosensitive layer.

[0445] The compound β (preferably, the compound B) can be used singly or two or more kinds thereof can be used.

[0446] In the case where the compound β is the compound B, from the viewpoint of more excellent pattern-forming ability and / or the viewpoint of lower moisture permeability of the formed pattern, the total number of the structures capable of accepting electrons (specific structure S1) possessed by the compound B in the photosensitive layer is preferably 1 mol% or more, more preferably 3 mol% or more, further preferably 5 mol% or more, particularly preferably 10 mol% or more, and most preferably 20 mol% or more with respect to the total number of the acid groups (preferably, carboxyl groups) possessed by the compound A.

[0447] The upper limit of the total number of structures capable of accepting electrons (specific structure S1) possessed by the compound B is not particularly limited, and is preferably 200 mol% or less, more preferably 100 mol% or less, and further preferably 80 mol% or less, relative to the total number of acid groups (preferably carboxyl groups) possessed by the compound A, from the viewpoint of the film quality of the obtained film.

[0448] <Polymerizable compound>

[0449] The photosensitive layer also preferably contains a polymerizable compound. In addition, the polymerizable compound is a different component from the compound A having an acid group, and does not contain an acid group.

[0450] The polymerizable compound is preferably a different component from the compound A, for example, preferably a compound having a molecular weight (weight average molecular weight in the case of having a molecular weight distribution) of less than 5,000, and also preferably a polymerizable monomer.

[0451] The polymerizable compound is a polymerizable compound having 1 or more (for example, 1 to 15) ethylenically unsaturated groups in one molecule.

[0452] The polymerizable compound is preferably a polymerizable compound containing 2 or more functions.

[0453] The polymerizable compound having 2 or more functions refers to a polymerizable compound having 2 or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule.

[0454] As the ethylenically unsaturated group, for example, (meth)acryloyl group, vinyl group, and styryl group can be given, and (meth)acryloyl group is preferred.

[0455] As the polymerizable compound, (meth)acrylate is preferred.

[0456] The photosensitive layer preferably contains a polymerizable compound having 2 functions (preferably (meth)acrylate having 2 functions) and a polymerizable compound having 3 or more functions (preferably (meth)acrylate having 3 or more functions).

[0457] As the polymerizable compound having 2 functions, there is no particular limitation, and it can be appropriately selected from publicly known compounds.

[0458] As the polymerizable compound having 2 functions, for example, tricyclodecanedimethylol diacrylate, tricyclodecanedimethylol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate can be given.

[0459] As the 2-functional polymerizable compound, more specifically, for example, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like can be given.

[0460] As the 3 or more functional polymerizable compound, there is no particular limitation, and it can be appropriately selected from publicly known compounds.

[0461] As the 3 or more functional polymerizable compound, for example, 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 glycerol tri(meth)acrylate skeleton (meth)acrylate compounds, and the like can be given.

[0462] Here, "(tri / tetra / penta / hexa) (meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra) (meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0463] Further, as the polymerizable compound, for example, caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., and the like), alkylene oxide-modified compounds of (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., and the like), and ethoxylated glyceryl triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., and the like) can be given.

[0464] As the polymerizable compound, urethane (meth) acrylates (preferably 3 or more functional urethane (meth) acrylates) can also be mentioned. The lower limit of the number of functional groups is more preferably 6 or more, and further preferably 8 or more. The upper limit of the number of functional groups is, for example, 20 or less.

[0465] As the 3 or more functional urethane (meth) acrylates, for example, 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO., LTD.): UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.): AH-600 (trade name) manufactured by KYOEISHA CHEMICAL Co., LTD.: UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.), and the like can be mentioned.

[0466] The weight average molecular weight (Mw) of the polymerizable compound that can be contained in the photosensitive layer is preferably 200 to 3000, more preferably 250 to 2600, and further preferably 280 to 2200.

[0467] In the case where the photosensitive layer contains a polymerizable compound, the molecular weight of the polymerizable compound having the smallest molecular weight among all the polymerizable compounds contained in the photosensitive layer is preferably 250 or more, and more preferably 280 or more.

[0468] In the case where the photosensitive layer contains a polymerizable compound, the content thereof with respect to the total mass of the photosensitive layer is preferably 3 to 70% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 55% by mass.

[0469] In the case where the photosensitive layer contains a polymerizable compound and a carboxyl group-containing polymer, the mass ratio of the polymerizable compound to the carboxyl group-containing polymer (mass of the polymerizable compound / mass of the carboxyl group-containing polymer) is preferably 0.2 to 2.0, and more preferably 0.4 to 0.9.

[0470] The polymerizable compound can be used alone or two or more kinds thereof can be used.

[0471] Further, in the case where the photosensitive layer contains a 2-functional polymerizable compound and a 3 or more functional polymerizable compound, the content of the 2-functional polymerizable compound with respect to all the polymerizable compounds contained in the photosensitive layer is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and further preferably 30 to 80% by mass.

[0472] Also, in this case, the content of the polyfunctional or more polymerizable compound is preferably 10 to 90 mass%, more preferably 15 to 80 mass%, and further preferably 20 to 70 mass% with respect to all of the polymerizable compounds contained in the photosensitive layer.

[0473] Also, in the case where the photosensitive layer contains a polymerizable compound of 2 or more functions, the photosensitive layer can further contain a monofunctional polymerizable compound.

[0474] Also, in the case where the photosensitive layer contains a polymerizable compound of 2 or more functions, the polymerizable compound of 2 or more functions is preferably a main component among the polymerizable compounds that the photosensitive layer can contain.

[0475] Specifically, in the case where the photosensitive layer contains a polymerizable compound of 2 or more functions, the content of the polymerizable compound of 2 or more functions is preferably 60 to 100 mass%, more preferably 80 to 100 mass%, and further preferably 90 to 100 mass% with respect to the total content of the polymerizable compounds contained in the photosensitive layer.

[0476] <Photopolymerization initiator>

[0477] The photosensitive layer also preferably contains a photopolymerization initiator.

[0478] The photopolymerization initiator can be a photoradical polymerization initiator, a photocationic polymerization initiator, or a photanionic polymerization initiator, and is preferably a photoradical polymerization initiator.

[0479] There is no particular limitation on the photopolymerization initiator, and a publicly known photopolymerization initiator can be used.

[0480] As the photopolymerization initiator, one or more selected from the group consisting of oxime ester compounds (photopolymerization initiators having an oxime ester structure) and aminophenylacetophenone compounds (photopolymerization initiators having an aminophenylacetophenone structure) is preferred, and a compound containing both of them is more preferred. In the case where a compound containing both of them is used, the content of the oxime ester compound is preferably 5 to 90 mass%, and more preferably 15 to 50 mass% with respect to the total content of both compounds. Other photopolymerization initiators can be further used at the same time, and examples thereof include hydroxyphenylacetophenone compounds, acylphosphine oxide compounds, and bis-triphenyl imidazole compounds.

[0481] Also, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-095716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-014783 can be used.

[0482] As specific examples of the photopolymerization initiator, the following photopolymerization initiators can be exemplified.

[0483] As the oxime ester compound, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)] (trade name: IRGACURE OXE-01, manufactured by BASF Corporation, IRGACURE series), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF Corporation), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF Corporation), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF Corporation and trade name: Lunar6, manufactured by DKSH Japan K.K.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 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 Tronly New Electronic 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, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) can be given.

[0484] As the aminophenylacetone compound, for example, 2-(dimethylamino)-2-[(4- methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad series are manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthio- phenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), API-307 (1-(diphenyl- 4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.) can be mentioned.

[0485] As other photopolymerization initiators, for example, 2-hydroxy-1-{4-[4-(2-hydroxy- 2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy- cyclohexyl-phenyl ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenyl- ethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819) can be mentioned.

[0486] In the case where the photosensitive layer contains a photopolymerization initiator, the content thereof is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass, relative to the total mass of the photosensitive layer.

[0487] The photopolymerization initiator can be used singly or two or more kinds thereof can be used.

[0488] <Surfactant>

[0489] The photosensitive layer can contain a surfactant.

[0490] As the surfactant, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be mentioned, and nonionic surfactants are preferred.

[0491] As the nonionic surfactant, for example, polyoxyethylene higher alkyl ether, polyoxyethylene higher alkyl phenyl ether, polyoxyethylene glycol higher fatty acid diester, silicone-based surfactants, and fluorine-based surfactants can be mentioned.

[0492] As the surfactant, for example, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640 can also be used.

[0493] Further, as the surfactant, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of Japanese Laid-Open Patent Publication No. 2009-237362 can also be used.

[0494] As commercially available products of the fluorine-based surfactant, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorad FC 430, 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.), Poly Fox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Tnc.), FTERGENT 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by ENEOS Corporation), and the like can be mentioned.

[0495] Further, as the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and the functional group portion containing the fluorine atom is cleaved and the fluorine atom is volatilized when heat is applied, can be preferably used. As such a fluorine-based surfactant, MEGAFACE DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nihon Keizai Shimbun (February 23, 2016)) can be exemplified, for example, MEGAFACE DS-21 can be exemplified.

[0496] Further, as the fluorine-based surfactant, a polymer of an ethylene ether compound containing a fluorine atom having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic ethylene ether compound is also preferably used.

[0497] Further, as the fluorine-based surfactant, a block polymer can also be used.

[0498] Further, as the fluorine-based surfactant, a fluorine-containing high molecular compound containing a constitutional unit derived from a (meth)acrylate compound having a fluorine atom and a constitutional unit derived from a (meth)acrylate compound having 2 or more (preferably 5 or more) alkylene oxide groups (preferably ethylene oxide, propylene oxide) can be preferably used.

[0499] Further, as the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in a side chain can also be used. MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation), and the like can be exemplified.

[0500] As the fluorine-based surfactant, from the viewpoint of improving environmental adaptability, a surfactant derived from a substitute material for a compound having a linear perfluoroalkyl group having 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) is preferred.

[0501] As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates of these (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF Corporation), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF Corporation), Solsperse 20000 (all manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), OLFINE 1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Co., Ltd.), and the like can be given.

[0502] As the silicone-based surfactant, a straight-chain polymer composed of a siloxane bond and a modified siloxane polymer obtained by introducing an organic group into a side chain or a terminal can be given.

[0503] As specific examples of the surfactant, 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.), and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (all manufactured by BYK Chemie GmbH), and the like can be given.

[0504] The content of the surfactant is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, and further preferably 0.005 to 3% by mass, with respect to the total mass of the photosensitive layer.

[0505] The surfactant can be used alone or two or more kinds can be used.

[0506] <Other additives>

[0507] The photosensitive layer can contain other additives as needed.

[0508] As the other additives, for example, plasticizers, sensitizers, heterocyclic compounds, and alkoxy silane compounds, and the like can be given.

[0509] As the plasticizers, sensitizers, heterocyclic compounds, and alkoxy silane compounds, for example, the compounds described in paragraphs 0097 to 0119 of International Publication No. 2018 / 179640 can be given.

[0510] In the case where the photosensitive layer is formed by a photosensitive material containing a solvent, the solvent is sometimes left, but it is preferable that the photosensitive layer does not contain the solvent.

[0511] The content of the solvent in the photosensitive layer is preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.1% by mass or less, relative to the total mass of the photosensitive layer.

[0512] Further, the photosensitive layer can further contain, as other additives, known additives such as rust-preventive agents, metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, coloring agents, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickening agents, crosslinking agents, and organic or inorganic suspending agents.

[0513] Regarding the preferable modes of these components, the contents of 0165 to 0184 of Japanese Patent Application Publication No. 2014-085643 are respectively incorporated into the present specification.

[0514] The photosensitive layer can contain impurities.

[0515] As the impurities, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and these ions can be mentioned. Among them, since halide ions, sodium ions, and potassium ions are easily mixed as impurities, it is particularly preferable to set the contents to the following.

[0516] The content of the impurities in the photosensitive layer is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and further preferably 2 ppm by mass or less, relative to the total mass of the photosensitive layer. The content of the impurities in the photosensitive layer can be set to 1 ppb by mass, or can be 0.1 ppm by mass or more.

[0517] As a method of setting the impurities within the above range, for example, a method of selecting a material having a small content of impurities as a raw material of the photosensitive material, a method of preventing the mixing of impurities at the time of forming the photosensitive material, and a method of cleaning and removing the impurities can be mentioned. By such a method, the impurity content can be set within the above range.

[0518] For example, the impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0519] Also, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably small. As the content of these compounds in the photosensitive layer, each is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and further preferably 4 mass ppm or less, with respect to the total mass of the photosensitive layer.

[0520] The lower limit of the above content can be set to 10 mass ppb or more, or 100 mass ppb or more, with respect to the total mass of the photosensitive layer. The content of these compounds can be suppressed by the same method as that for the above-mentioned impurities of metals. Also, quantification can be performed by a known measurement method.

[0521] From the viewpoint of improving the patterning properties, the content of water in the photosensitive layer is preferably 0.01 to 1.0 mass%, and more preferably 0.05 to 0.5 mass%, with respect to the total mass of the photosensitive layer.

[0522] <Average thickness of photosensitive layer>

[0523] The average thickness of the photosensitive layer is preferably 0.5 to 20 μm. If the average thickness of the photosensitive layer is 20 μm or less, the resolution of the pattern is more excellent, and if the average thickness of the photosensitive layer is 0.5 μm or more, it is preferable from the viewpoint of the straightness of the pattern. The average thickness of the photosensitive layer is more preferably 0.8 to 15 μm, and further preferably 1.0 to 10 μm. Specific examples of the average thickness of the photosensitive layer include 3.0 μm, 5.0 μm, and 8.0 μm.

[0524] <Method for forming photosensitive layer>

[0525] The photosensitive layer can be formed by preparing a photosensitive material containing components used for the formation of the photosensitive layer and a solvent, and performing coating and drying. Each component can also be previously dissolved in a solvent as a solution, and the obtained solutions can be mixed at a predetermined ratio to prepare a composition. The composition prepared in the above manner is preferably filtered, for example, using a filter having a pore size of 0.2 to 30 μm.

[0526] The photosensitive layer can be formed by coating the photosensitive material on a temporary support or a cover film, and performing drying.

[0527] The coating method is not particularly limited, and known methods such as slit coating, spin coating, curtain coating, and inkjet coating can be used.

[0528] Also, in the case where other layers described later are formed on the temporary support or the cover film, the photosensitive layer can be formed on the above other layers.

[0529] The transmittance of the photosensitive layer at 365 nm is preferably 20% or more, more preferably 65% or more, and further preferably 90% or more, from the viewpoint of more excellent pattern-forming ability and / or lower moisture permeability of the formed pattern. There is no particular limitation on the upper limit value, and it is 100% or less.

[0530] The ratio of the transmittance of the photosensitive layer at 365 nm to the transmittance of the photosensitive layer at 313 nm (the ratio represented by the transmittance of the photosensitive layer at 365 nm / the transmittance of the photosensitive layer at 313 nm) is preferably 1 or more, and more preferably 1.5 or more, from the viewpoint of more excellent pattern-forming ability and / or lower moisture permeability of the formed pattern. There is no particular limitation on the upper limit value, and it is, for example, 1000 or less.

[0531] The acid group possessed by the compound A in the photosensitive layer is preferably a carboxyl group. Furthermore, the photosensitive layer is preferably a photosensitive layer in which the content of the carboxyl group in the photosensitive layer is reduced at a reduction rate of 5 mol% or more due to irradiation of actinic rays or radiation. As such a photosensitive layer, more preferably, the photosensitive layer satisfies any of the above requirements (V1-C) and (W1-C).

[0532] Further, as the embodiment of the photosensitive layer, more preferably, the photosensitive layer of the above-described embodiment X-1-a1-C to embodiment X-1-a3-C.

[0533] The visible light transmittance per 1.0 μm film thickness of the photosensitive layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.

[0534] As the visible light transmittance, the average transmittance at wavelengths of 400 nm to 800 nm, the minimum value of the transmittance at wavelengths of 400 nm to 800 nm, and the transmittance at a wavelength of 400 nm are preferably each satisfied with the above-described conditions.

[0535] As the preferable value of the visible light transmittance per 1.0 μm film thickness of the photosensitive layer, for example, 87%, 92%, 98%, and the like can be given.

[0536] From the viewpoint of residue inhibition at the time of development, the dissolution speed of the photosensitive layer in a 1.0 mass% sodium carbonate aqueous solution 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 the edge shape of the pattern, it is preferably 5.0 μm / sec or less. As a specific preferable value, for example, 1.8 μm / sec, 1.0 μm / sec, 0.7 μm / sec, and the like can be given.

[0537] The dissolution rate per unit time of the photosensitive layer with respect to 1.0 mass% sodium carbonate aqueous solution was determined as follows.

[0538] A photosensitive layer (film thickness in the range of 1.0 to 10 μm) formed on a glass substrate from which the solvent was sufficiently removed was subjected to spray development using 1.0 mass% sodium carbonate aqueous solution at 25°C until the photosensitive layer was completely dissolved (wherein 2 minutes was set as the maximum).

[0539] The dissolution rate was obtained by dividing the film thickness of the photosensitive layer by the time required until the photosensitive layer was completely dissolved. In addition, in the case where the dissolution was not complete within 2 minutes, the dissolution rate was calculated in the same manner from the amount of change in the film thickness until that time.

[0540] In the development, a spray nozzle of 1 / 4 MINJJ X030PP manufactured by H. IKEUCHI & CO., LTD. was used, and the spray application pressure of the spray was set to 0.08 MPa. At the above conditions, the spray flow rate per unit time was set to 1,800 mL / min.

[0541] From the viewpoint of pattern formability, the number of foreign matters having a diameter of 1.0 μm or more in the photosensitive layer is preferably 10 / mm 2 More preferably, the number is 5 / mm 2 or less.

[0542] The number of foreign matters was determined as follows.

[0543] The number of foreign matters having a diameter of 1.0 μm or more in each of the regions was determined by visually observing any 5 regions (1 mm x 1 mm) on the surface of the photosensitive layer from the normal direction of the surface of the photosensitive layer using an optical microscope, and the numbers were arithmetically averaged to calculate the number of foreign matters.

[0544] As a specific preferable number, for example, 0 / mm 2 , 1 / mm 2 , 4 / mm 2 , 8 / mm 2 , etc. can be given.

[0545] From the viewpoint of suppressing the generation of agglomerates at the time of development, the haze of a solution obtained by dissolving 1.0 em 3 of the photosensitive layer in 1.0 liter of 1.0 mass% sodium carbonate aqueous solution at 30°C is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and most preferably 1% or less.

[0546] The haze was determined as follows.

[0547] First, a 1.0 mass% sodium carbonate aqueous solution was prepared, and the liquid temperature was adjusted to 30°C. 1.0 cm 3 of the photosensitive layer was added to 1.0 L of the sodium carbonate aqueous solution. While taking care not to mix in air bubbles, the mixture was stirred at 30°C for 4 hours. After the stirring, the haze of the solution in which the photosensitive resin layer was dissolved was measured. A haze meter (product name "NDH4000", manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd.) was used, and a liquid measurement cell and a liquid measurement special cell with an optical path length of 20 mm were used to measure the haze.

[0548] As a specific preferable value, for example, 0.4%, 1.0%, 9%, 24%, and the like can be given.

[0549] <Photosensitive material>

[0550] The photosensitive material preferably contains components used for the formation of the photosensitive layer and a solvent. By mixing the components and the solvent, adjusting the viscosity, and performing coating and drying, the photosensitive layer can be preferably formed.

[0551] (Component used for the formation of the photosensitive layer)

[0552] Regarding the components used for the formation of the photosensitive layer, as already described. The preferable range of the content of each component in the photosensitive material is the same as the preferable range obtained by replacing "the content of each component in the photosensitive layer (mass%)" described above with "the content of each component in the total solid components of the photosensitive material (mass%)". In addition, the solid components of the photosensitive material refer to the components other than the solvent in the photosensitive material. Thus, for example, the description "in the photosensitive layer, the content of Compound A is preferably 25 mass% or more with respect to the total mass of the photosensitive layer" is replaced with "in the photosensitive material, the content of Compound A is preferably 25 mass% or more with respect to the total solid components of the photosensitive material". In addition, the solid components refer to all components other than the solvent of the photosensitive material. Also, even if the photosensitive material is in a liquid state, the components other than the solvent are regarded as solid components.

[0553] (Solvent)

[0554] As the solvent, a generally used solvent can be used without particular limitation.

[0555] As the solvent, an organic solvent is preferable.

[0556] As the organic solvent, for example, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, 2-propanol, and mixed solvents of these can be given.

[0557] As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is preferred.

[0558] In the case where the photosensitive material contains a solvent, the solid content of the photosensitive material is preferably 5 to 80 mass%, more preferably 8 to 40 mass%, and further preferably 10 to 30 mass%. That is, in the case where the photosensitive material contains a solvent, the content of the solvent is preferably 20 to 95 mass%, more preferably 60 to 95 mass%, and further preferably 70 to 95 mass% with respect to the total mass of the photosensitive material.

[0559] The solvent can be used singly or two or more kinds can be used.

[0560] In the case where the photosensitive material contains a solvent, the viscosity (25°C) of the photosensitive material is preferably 1 to 50 mPa-s, more preferably 2 to 40 mPa-s, and further preferably 3 to 30 mPa-s from the viewpoint of coatability.

[0561] The viscosity is measured, for example, using a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO., LTD.).

[0562] In the case where the photosensitive material contains a solvent, the surface tension (25°C) of the photosensitive material is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and further preferably 15 to 40 mN / m from the viewpoint of coatability.

[0563] The surface tension is measured, for example, using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., LTD.).

[0564] As the solvent, Solvents described in paragraphs 0054 and 0055 of U.S. Application Publication No. 2005 / 282073, the content of which is incorporated into the present specification, can also be used.

[0565] Further, as the solvent, an organic solvent (high-boiling-point solvent) having a boiling point of 180 to 250°C can also be used as necessary.

[0566] <<< Other Layer >>>

[0567] Further, in the case where the high-refractive layer and / or other layer described later is formed on the temporary support or the cover film, the photosensitive layer can be formed on the above high-refractive layer and / or other layer.

[0568] <<high refractive index layer>>

[0569] The transfer film is also preferably further provided with a high refractive index layer.

[0570] The high refractive index layer is preferably disposed adjacent to the photosensitive layer, and is also preferably disposed on the side opposite to the temporary support when viewed from the photosensitive layer.

[0571] The high refractive index layer is not particularly limited except that the refractive index at a wavelength of 550 nm is 1.50 or more.

[0572] The refractive index of the high refractive index layer is preferably 1.55 or more, and more preferably 1.60 or more.

[0573] The upper limit of the refractive index of the high refractive index layer is not particularly limited, and is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.

[0574] Also, the refractive index of the high refractive index layer is preferably higher than the refractive index of the photosensitive layer.

[0575] The high refractive index layer can have photocurability (i.e., photosensitivity), can have thermocurability, or can have both photocurability and thermocurability.

[0576] The high refractive index layer having photosensitivity has the advantage that the photosensitive layer and the high refractive index layer transferred onto the substrate can be patterned together by one photolithography after transfer.

[0577] The high refractive index layer is preferably provided with alkali solubility (e.g., solubility in a weakly alkaline aqueous solution).

[0578] Also, the high refractive index layer is preferably a transparent layer.

[0579] The film thickness of the high refractive index layer is preferably 500 nm or less, more preferably 110 nm or less, and further preferably 100 nm or less.

[0580] Also, the film thickness of the high refractive index layer is preferably 20 nm or more, more preferably 55 nm or more, further preferably 60 nm or more, and particularly preferably 70 nm or more.

[0581] The high refractive index layer sometimes forms a laminate together with the transparent electrode pattern (preferably an ITO pattern) and the photosensitive layer by being interposed between the transparent electrode pattern and the photosensitive layer after transfer. In this case, by reducing the refractive index difference between the transparent electrode pattern and the high refractive index layer and the refractive index difference between the high refractive index layer and the photosensitive layer, light reflection is further reduced. Thus, the concealability of the transparent electrode pattern is further improved.

[0582] For example, in the case where the transparent electrode pattern, the high refractive index layer, and the photosensitive layer are sequentially stacked, the transparent electrode pattern is not easily recognized when viewed from the transparent electrode pattern side.

[0583] The refractive index of the high refractive index layer is preferably adjusted according to the refractive index of the transparent electrode pattern.

[0584] For example, in the case where the transparent electrode pattern is formed using an oxide of In and Sn (ITO), in the case where the refractive index of the transparent electrode pattern is in the range of 1.8 to 2.0, the refractive index of the high refractive index layer is preferably 1.60 or greater. The upper limit of the refractive index of the high refractive index layer at this time is not particularly limited, and is preferably 2.1 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.

[0585] For example, in the case where the transparent electrode pattern is formed using an oxide of In and Zn (IZO; Indium Zinc Oxide), in the case where the refractive index of the transparent electrode pattern exceeds 2.0, the refractive index of the high refractive index layer is preferably 1.70 or greater and 1.85 or less.

[0586] The method of controlling the refractive index of the high refractive index layer is not particularly limited, and examples include a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, and a method of using a composite of a metal salt and a resin.

[0587] The kind of the metal oxide particles or the metal particles is not particularly limited, and publicly known metal oxide particles or metal particles can be used. In the metal of the metal oxide particles or the metal particles, a semi-metal such as B, Si, Ge, As, Sb, and Te is also included.

[0588] For example, from the viewpoint of transparency, the average primary particle diameter of the particles (metal oxide particles or metal particles) is preferably 1 to 200 nm, and more preferably 3 to 80 nm.

[0589] The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and performing an arithmetic average of the measurement results. In the case where the shape of the particles is not spherical, the longest side is used as the particle diameter.

[0590] As the metal oxide particles, specifically, zirconium oxide particles (Zr02particles), Nb205particles, titanium oxide particles (Ti02particles), and silicon dioxide particles (Si02particles) are preferred, and at least one selected from among these composite particles is also preferred.

[0591] Among these, as the metal oxide particles, for example, from the viewpoint of easily adjusting the refractive index of the high refractive index layer to 1.6 or more, it is more preferable that at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles.

[0592] In the case where the high refractive index layer contains the metal oxide particles, the high refractive index layer can contain only one kind of metal oxide particles, or can contain two or more kinds.

[0593] From the viewpoint of being able to make the concealability of the concealed object such as the electrode pattern good, and effectively improving the visibility of the concealed object, the content of the particles (metal oxide particles or metal particles) is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 40 to 85% by mass, with respect to the total mass of the high refractive index layer.

[0594] In the case where titanium oxide particles are used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 40 to 85% by mass, with respect to the total mass of the high refractive index layer.

[0595] As the commercially available product of the metal oxide particles, there can be mentioned calcined zirconium oxide particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), calcined zirconium oxide particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK NanoTek Corporation, 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.).

[0596] The high refractive index layer preferably contains one or more selected from the group consisting of inorganic particles (metal oxide particles or metal particles) having a refractive index of 1.50 or more (more preferably 1.55 or more, and further preferably 1.60 or more), a resin having a refractive index of 1.50 or more (more preferably 1.55 or more, and further preferably 1.60 or more), and a polymerizable compound having a refractive index of 1.50 or more (more preferably 1.55 or more, and further preferably 1.60 or more).

[0597] If this mode is adopted, it is easy to adjust the refractive index of the high-refractive layer to 1.50 or more (more preferably 1.55 or more, and particularly preferably 1.60 or more).

[0598] Further, the high-refractive layer preferably contains a binder polymer, a polymerizable monomer, and particles.

[0599] As to the components of the high-refractive layer, the components of the curable transparent resin layer described in paragraphs 0019 to 0040 and 0144 to 0150 of Japanese Patent Application Publication No. 2014-108541, the components of the transparent layer described in paragraphs 0024 to 0035 and 0110 to 0112 of Japanese Patent Application Publication No. 2014-010814, the components of the composition having an ammonium salt described in paragraphs 0034 to 0056 of International Publication No. 2016 / 009980, and the like can be referred to.

[0600] Further, the high-refractive layer preferably contains a metal oxidation inhibitor.

[0601] The metal oxidation inhibitor is a compound (except for compound β) that can perform surface treatment on a member (for example, a conductive member formed on a substrate) that directly contacts the high-refractive layer.

[0602] In the case where the high-refractive layer contains a metal oxidation inhibitor, when the high-refractive layer is transferred onto a substrate (i.e., a transfer target), it is possible to perform surface treatment on a member (for example, a conductive member formed on a substrate) that directly contacts the high-refractive layer. This surface treatment imparts a metal oxidation inhibition function (protective property) to the member that directly contacts the high-refractive layer.

[0603] The metal oxidation inhibitor is preferably a compound having an aromatic ring having a 5-membered ring including a nitrogen atom as a ring member atom. The compound having an aromatic ring having a 5-membered ring including a nitrogen atom as a ring member atom can have a substituent.

[0604] The metal oxidation inhibitor is preferably a compound having an aromatic ring having a 5-membered ring including a nitrogen atom as a ring member atom.

[0605] As the aromatic ring including a nitrogen atom, an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, or a fused ring of any one of these and another aromatic ring is preferable, and an imidazole ring, a triazole ring, a tetrazole ring, or a fused ring of any one of these and another aromatic ring is more preferable.

[0606] The "other aromatic ring" that forms the fused ring can be a monocyclic ring or a heterocyclic ring, but is preferably a monocyclic ring, and more preferably a benzene ring or a naphthalene ring, and further preferably a benzene ring.

[0607] As the metal oxidation inhibitor, imidazole, benzimidazole, tetrazole, 5-amino-lH-tetrazole, mercaptothiadiazole, or benzotriazole is preferred, and imidazole, benzimidazole, 5-amino-lH-tetrazole, or benzotriazole is more preferred.

[0608] As the metal oxidation inhibitor, a commercially available product can be used, and as the commercially available product, for example, BT120 manufactured by JOHOKU CHEMICAL CO., LTD. containing benzotriazole can be preferably used.

[0609] In the case where the high refractive index layer contains the metal oxidation inhibitor, the content of the metal oxidation inhibitor is preferably 0.1 to 20 mass% with respect to the total solid components of the high refractive index layer, more preferably 0.5 to 10 mass%, and further preferably 1 to 5 mass%.

[0610] The high refractive index layer can contain other components than the above components.

[0611] As the other components that the high refractive index layer can contain, the same components as the other components that the photosensitive layer can contain can be given.

[0612] The high refractive index layer also preferably contains a surfactant.

[0613] The method of forming the high refractive index layer is not particularly limited.

[0614] As the method of forming the high refractive index layer, for example, a method of forming the high refractive index layer by applying a high refractive index layer-forming composition containing an aqueous solvent to the above photosensitive layer formed on a temporary support and drying as necessary can be given.

[0615] The high refractive index layer-forming composition can contain each component of the above high refractive index layer.

[0616] The high refractive index layer-forming composition contains, for example, a binder polymer, a polymerizable monomer, a particle, and an aqueous solvent.

[0617] Also, as the high refractive index layer-forming composition, a composition having an ammonium salt described in paragraphs 0034 to 0056 of International Publication No. 2016 / 009980 is also preferred.

[0618] The photosensitive layer and the high refractive index layer are preferably colorless. Specifically, in the CIE1976 (L * , a * , b * ) color space of the total reflection (incident angle 8°, light source: D-65 (2° field of view)), the L * value is preferably 10 to 90, the a * value is preferably -1.0 to 1.0, and the b *The value is preferably -1.0 to 1.0.

[0619] <cover film>

[0620] The transfer film of the present application can further have a cover film on the side opposite to the temporary support, when viewed from the photosensitive layer.

[0621] In the case where the transfer film of the present application has a high refractive index layer, the cover film is preferably disposed on the side opposite to the temporary support (i.e., the side opposite to the photosensitive layer), when viewed from the high refractive index layer. In this case, the transfer film is, for example, a laminate in the order of "temporary support / photosensitive layer / high refractive index layer / cover film".

[0622] As for the cover film, the number of fish eyes having a diameter of 80 μm or more contained in the cover film is preferably 5 / m 2 Hereinafter, the "fish eye" refers to a foreign matter, an undissolved substance, and / or an oxidized deteriorated substance of a material, which is incorporated into a film when the film is manufactured by a method such as heat melting, kneading, extrusion, and / or biaxial stretching of the material, and casting.

[0623] The number of particles having a diameter of 3 μm or more contained in the cover film is preferably 30 / mm 2 More preferably, it is 10 / mm 2 Further preferably, it is 5 / mm 2 Hereinafter, the "fish eye" refers to a foreign matter, an undissolved substance, and / or an oxidized deteriorated substance of a material, which is incorporated into a film when the film is manufactured by a method such as heat melting, kneading, extrusion, and / or biaxial stretching of the material, and casting.

[0624] The arithmetic average roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. When Ra is within these ranges, for example, in the case where the transfer film is in a long strip shape, the winding property at the time of winding the transfer film can be made good.

[0625] Furthermore, from the viewpoint of suppressing defects at the time of transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

[0626] As the cover film, for example, polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film can be given.

[0627] As the cover film, for example, the films described in paragraphs 0083 to 0087 and 0093 of Japanese Patent Application Publication No. 2006-259138 can be used.

[0628] As the cover film, for example, Alfan (registered trademark) FG-201 manufactured by Oji F-Tex Co., Ltd., Alfan (registered trademark) E-201F manufactured by Oji F-Tex Co., Ltd., Cerapeel (registered trademark) 25WZ manufactured by TORAY ADVANCED FILM CO., LTD., or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by TORAY INDUSTRIES, INC. can be used.

[0629] <<Other layer>>

[0630] The transfer film can include other layers (hereinafter, also referred to as "other layers") in addition to the above-described layers. As the other layers, for example, an intermediate layer, a thermoplastic resin layer, and the like can be cited, and a publicly known layer can be appropriately used.

[0631] Regarding the preferable mode of the thermoplastic resin layer, 0189 to 0193 of Japanese Patent Application Publication No. 2014-085643, and regarding the preferable mode of the other layers in addition to the above-described layers, 0194 to 0196 of Japanese Patent Application Publication No. 2014-085643 are respectively described, and the contents of the publication are incorporated into the present specification.

[0632] <<<Manufacturing method of transfer film>>>

[0633] The manufacturing method of the transfer film is not particularly limited, and a publicly known manufacturing method can be applied.

[0634] As the manufacturing method of the transfer film, it is preferable to include a step of forming a photosensitive layer by applying a photosensitive material including a solvent on a temporary support and drying it, and it is more preferable to include a step of further disposing a cover film on the photosensitive layer after the step of forming the photosensitive layer.

[0635] Further, after the step of forming the photosensitive layer, a step of forming a high refractive layer by applying a high refractive layer-forming composition and drying it can be further included. In this case, after the step of forming the high refractive layer, it is more preferable to further include a step of disposing a cover film on the high refractive layer.

[0636] [Pattern forming method]

[0637] As the pattern forming method of the present application, as long as it is a pattern forming method using the above-described transfer film, there is no particular limitation, and it is preferably a pattern forming method sequentially including a step of forming a photosensitive layer on a substrate, a step of performing pattern exposure on the above-described photosensitive layer, and a step of developing (alkaline development or organic solvent development) the exposed photosensitive layer. In addition, in the case of the above-described development being organic solvent development, it is preferable to include a step of further exposing the pattern obtained.

[0638] As a specific embodiment of the pattern forming method of the present application, the pattern forming methods of Embodiment 1 and Embodiment 2 can be cited.

[0639] Hereinafter, each step of the pattern forming methods of Embodiment 1 and Embodiment 2 will be described in detail.

[0640] 〔Pattern forming method of Embodiment 1〕

[0641] The pattern forming method of Embodiment 1 has steps X1 to X3. In addition, the following step X2 corresponds to a step in which the content of acid groups derived from the compound A in the photosensitive layer is reduced due to exposure. In the case where the developing solution of step X3 is an organic solvent-based developing solution, step X4 is further provided after step X3.

[0642] Step X1: a step of adhering the transfer film to the substrate by contacting the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film with the substrate

[0643] Step X2: a step of performing pattern exposure on the photosensitive layer

[0644] Step X3: a step of developing the photosensitive layer using a developing solution

[0645] Step X4: a step of further exposing the pattern formed by development after the developing step of step X3

[0646] In the case where an alkaline developing solution is used as the developing solution of step X3, it is preferable that the above-described photosensitive layer be the photosensitive layer of Embodiment X-1-a1 or Embodiment X-1-a2. In the case where an organic solvent-based developing solution is used as the developing solution of step X3, it is preferable that the above-described photosensitive layer be the photosensitive material of Embodiment X-1-a1.

[0647] The pattern forming method of Embodiment 1 is preferably applied to a transfer film including the photosensitive layer of Embodiment X-1-a1 or Embodiment X-1-a2.

[0648] <<<Step X1>>>

[0649] The pattern forming method of Embodiment 1 has a process of joining the transfer film to the substrate by bringing the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support side into contact with the substrate.

[0650] <substrate>

[0651] There is no particular limitation on the substrate, and for example, a glass substrate, a silicon substrate, and a resin substrate, and a substrate having a conductive layer can be given. As the substrate included in the substrate having a conductive layer, a glass substrate, a silicon substrate, and a resin substrate can be given.

[0652] The above-mentioned substrate is preferably transparent.

[0653] The above-mentioned substrate preferably has a refractive index of 1.50 to 1.52.

[0654] The above-mentioned substrate can be composed of a light-transmissive substrate such as a glass substrate, and for example, a strengthened glass typified by Gorilla Glass of Corning Incorporated Co., Ltd. or the like can be used. Also, as the material included in the above-mentioned substrate, the material described in Japanese Patent Application Publication No. 2010-086684, Japanese Patent Application Publication No. 2010-152809, and Japanese Patent Application Publication No. 2010-257492 is preferably used.

[0655] In the case where the above-mentioned substrate includes a resin substrate, it is more preferable to use a resin film having small optical distortion and / or high transparency as the resin substrate. As a specific raw material, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and a cyclic olefin polymer, or the like can be given.

[0656] As the substrate included in the substrate having a conductive layer, a resin substrate is preferable from the viewpoint of roll-to-roll production, and a resin film is more preferable.

[0657] As the conductive layer, any conductive layer used in general circuit wiring or touch panel wiring can be given.

[0658] As the conductive layer, from the viewpoints of conductivity and fine line formability, one or more layers selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer is preferable, a metal layer is more preferable, and a copper layer or a silver layer is further preferable.

[0659] Also, the conductive layer in the substrate having a conductive layer can be one layer, or two or more layers.

[0660] In the case where the substrate having a conductive layer includes two or more conductive layers, each conductive layer is preferably a conductive layer of a different material from each other.

[0661] As the material of the conductive layer, a metal single body and a conductive metal oxide, etc. can be given.

[0662] As the metal single body, Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, Au, etc. can be given.

[0663] As the conductive metal oxide, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), SiO2, etc. can be given. In addition, "conductive" means that the volume resistivity is less than 1 x 10 6 Ωcm, and preferably, the volume resistivity is less than 1 x 10 4 Ωcm.

[0664] In the case where the conductive layer in the substrate having the conductive layer is two or more layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide.

[0665] As the conductive layer, it is preferable that the electrode pattern of the sensor corresponding to the visual recognition portion in the electrostatic capacitance type touch panel or the wiring of the peripheral lead-out portion.

[0666] Further, the conductive layer is preferably a transparent layer.

[0667] <<Sequence of Step X1>>

[0668] Step X1 is preferably a lamination step using pressure by a roll, etc. and heating.

[0669] At the time of lamination, a publicly known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator can be used.

[0670] Step X1 is preferably performed by a roll-to-roll method, and thus, the substrate to which the transfer film is laminated is preferably a resin film or a resin film having a conductive layer.

[0671] Hereinafter, the roll-to-roll method will be described.

[0672] The roll-to-roll method means that a substrate capable of being wound and unwound is used as the substrate, and includes a step of unwinding the substrate (also referred to as "unwinding step") before any step included in the pattern forming method of the present application, and a step of winding the substrate (also referred to as "winding step") after any step, and the method is performed while the substrate is transported, at least any step (preferably, all steps or all steps except the heating step) is performed.

[0673] As the unwinding method in the unwinding step and the winding method in the winding step, there is no particular limitation as long as a publicly known method is used in the manufacturing method in which the roll-to-roll method is applied.

[0674] <<Process X2>>

[0675] The pattern forming method of Embodiment 1 includes a process (Process X2) of subjecting the photosensitive layer to pattern exposure after the above Process X1. Process X2 corresponds to a process in which the content of the acid group derived from Compound A in the photosensitive layer is reduced due to exposure. More specifically, it is preferable to subject the photosensitive layer to pattern exposure using light of a wavelength that excites the specific structure S0 (preferably, specific structure S1) in Compound β (preferably, Compound B) (when the requirement (V01) is satisfied) and the specific structure S0 (preferably, specific structure S1) in Compound A (when the requirement (W01) is satisfied) in the photosensitive layer.

[0676] In the exposure process, the detailed configuration and the specific size of the pattern are not particularly limited.

[0677] For example, in the case where the pattern forming method of Embodiment 1 is applied to the manufacture of circuit wiring, from the viewpoint of improving the display quality of a display device (for example, a touch panel) that has an input device having circuit wiring manufactured by the pattern forming method of Embodiment 1, and from the viewpoint of being able to reduce the area occupied by lead-out wiring as much as possible, at least a part of the pattern (particularly, a part corresponding to a part of the electrode pattern and the lead-out wiring of the touch panel) is preferably a fine line of 100 μm or less, and more preferably a fine line of 70 μm or less.

[0678] As the light source used for exposure, any light source that emits light in a wavelength region capable of reducing the content of the acid group derived from Compound A in the photosensitive layer (light of a wavelength that excites the specific structure S0 (preferably, specific structure S1) in Compound β (preferably, Compound B) (when the requirement (V01) is satisfied) and the specific structure S0 (preferably, specific structure S1) in Compound A (when the requirement (W01) is satisfied) in the photosensitive layer) can be appropriately selected. Specifically, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an LED (Light Emitting Diode), and the like can be given.

[0679] As the exposure amount, 10 to 10,000 mJ / cm2 2 , and more preferably 50 to 3,000 mJ / cm2 2 .

[0680] In the process X2, the pattern exposure can be performed after the temporary support is peeled from the photosensitive layer, or the pattern exposure can be performed through the temporary support before the temporary support is peeled, and then the temporary support is peeled. In order to prevent the mask from being contaminated by the contact of the photosensitive layer with the mask, and to avoid the influence on the exposure caused by the foreign matter attached to the mask, it is preferable that the pattern exposure is performed without peeling the temporary support. In addition, the pattern exposure can be exposure through the mask, or direct exposure using laser or the like.

[0681] In addition, before the process X3 described later, the temporary support is peeled from the photosensitive layer.

[0682] <<Process X3>>

[0683] The pattern forming method of the embodiment 1 includes, after the process X2 described above, a process (process X3+) of developing the photosensitive layer subjected to the pattern exposure using a developing solution (alkaline developing solution or organic solvent-based developing solution).

[0684] The photosensitive layer subjected to the process X2 has the content of the acid group in the photosensitive layer of the exposed portion reduced, and has the difference in the solubility in the developing solution (dissolution contrast) between the exposed portion and the unexposed portion generated. By forming the dissolution contrast in the photosensitive layer, the pattern can be formed in the process X3. In addition, in the case where the developing solution of the process X3 described above is the alkaline developing solution, the unexposed portion is removed by implementing the process X3 described above to form a negative pattern. On the other hand, in the case where the developing solution of the process X3 described above is the organic solvent-based developing solution, the exposed portion is removed by implementing the process X3 described above to form a positive pattern. The positive pattern obtained needs to be subjected to the treatment in which the content of the acid group derived from the compound A is reduced by the process X4 described later.

[0685] (alkaline developing solution)

[0686] As the alkaline developing solution, there is no particular limitation as long as the unexposed portion of the photosensitive resin layer can be removed, and for example, a known developing solution described in Japanese Patent Application Laid-Open No. 5-072724 or the like can be used.

[0687] As the alkaline developing solution, for example, an aqueous alkali solution-based developing solution containing a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L (liter) is preferable.

[0688] Further, the alkaline developing solution can further contain a water-soluble organic solvent and a surfactant or the like. As the alkaline developing solution, for example, the developing solution described in paragraph 0194 of International Publication No. 2015 / 093271 is preferable.

[0689] (organic solvent-based developing solution)

[0690] As the organic solvent-based developing solution, there is no particular limitation as long as the exposed portion of the photosensitive resin layer can be removed, and for example, a developing solution containing a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, a hydrocarbon-based solvent, or the like can be used.

[0691] In the organic solvent-based developing solution, the organic solvent can be mixed with a plurality of types, or can be used by mixing with an organic solvent other than the above or water. Among them, in order to sufficiently exert the effects of the present application, the water content rate of the entire organic solvent-based developing solution is preferably less than 10% by mass, and more preferably substantially free from moisture. The concentration of the organic solvent (total in the case of mixing a plurality of types) in the organic solvent-based developing solution is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. In addition, as an upper limit value, for example, it is 100% by mass or less.

[0692] As the developing method, there is no particular limitation, and it can be any one of spin immersion developing, spray developing, spin developing, and dip coating developing, or the like. Among them, in the case of describing the spray developing, the developing solution can be blown to the photosensitive resin layer after exposure by spraying, and thus the unnecessary portion can be removed. Also, after the developing, a cleaning agent or the like is preferably blown by spraying, and the developing residue is removed while being wiped with a brush or the like. As the liquid temperature of the developing solution, it is preferably 20 to 40°C.

[0693] The pattern forming method of Embodiment 1 can further have a baking step after heating treatment of the pattern including the photosensitive layer obtained by developing.

[0694] The post-baking is preferably performed in an environment of 8.1 to 121.6 kPa, and more preferably in an environment of 50.66 kPa or more. On the other hand, it is more preferably performed in an environment of 111.46 kPa or less, and further preferably in an environment of 101.3 kPa or less.

[0695] The temperature of the post-baking is preferably 80 to 250°C, more preferably 110 to 170°C, and further preferably 130 to 150°C.

[0696] The time of the post-baking is preferably 1 to 60 minutes, more preferably 2 to 50 minutes, and further preferably 5 to 40 minutes.

[0697] The post-baking can be performed in an air environment, or can be performed in a nitrogen-substituted environment.

[0698] <<Process X4>>

[0699] In the case where the developing solution of the above-mentioned process X3 is an organic solvent-based developing solution, process X4 is performed on the positive pattern obtained. Process X4 is a process equivalent to exposing the positive pattern obtained in process X3 and reducing the content of the acid group derived from compound A. More specifically, it is preferable to perform pattern exposure on the photosensitive layer using light of a wavelength that excites the specific structure S0 (preferably, specific structure S1) in compound β (preferably, compound B) in the photosensitive layer (when requirement (V01) is satisfied) and the specific structure S0 (preferably, specific structure S1) in compound A (when requirement (W01) is satisfied).

[0700] As the light source used for exposure and the exposure amount, the same as the light source and the exposure amount described in process X1 is preferable, and the same as the preferable mode is also preferable.

[0701] [Pattern forming method of embodiment 2]

[0702] The pattern forming method of embodiment 2 successively has process Y1, process Y2P, and process Y3, and further has process Y2Q (a process of further exposing the exposed photosensitive layer in process Y2P) between process Y2P and process Y3 or after process Y3.

[0703] Process Y1: a process of joining the transfer film to the above-mentioned substrate by contacting the surface of the side opposite to the temporary support side of the photosensitive layer in the transfer film to the substrate

[0704] Process Y2P: a process of exposing the photosensitive layer

[0705] Process Y3: a process of developing the photosensitive layer using a developing solution

[0706] As the pattern forming method of embodiment 2, as described above, a mode in which the photosensitive layer can be applied in the case where it further contains a photopolymerization initiator and a polymerizable compound is equivalent. Therefore, the pattern forming method of embodiment 2 is preferably applied to a transfer film containing the photosensitive layer of the above-mentioned embodiment X-1-a3.

[0707] Hereinafter, the pattern forming method of embodiment 2 is described, and regarding process Y1 and process Y3, the same as process X1 and process X3, respectively, and the description is omitted.

[0708] In addition, process Y3 can be performed at least after process Y2P, and process Y3 can be performed between process Y2P and process Y2Q.

[0709] Further, the pattern forming method of Embodiment 2 can further have a post-baking step after heating the pattern of the photosensitive layer obtained by development after the step Y3. As for the post-baking step, the same method as the post-baking step that the pattern forming method of Embodiment 1 can have can be employed. In the case where the step Y3 is performed between the step Y2P and the step Y2Q, the post-baking step can be performed before the step Y2Q or after the step Y2Q as long as it is performed after the step Y3.

[0710] <<Step Y2P, Step Y2Q>>

[0711] The pattern forming method of Embodiment 2 includes a step of exposing the photosensitive layer subjected to the step Y1 (step Y2P) and a step of further exposing the exposed photosensitive layer (step Y2Q).

[0712] Either one of the exposure processes (step Y2P and step Y2Q) is mainly exposure for reducing the content of the acid group derived from the compound A due to exposure, and the other of the exposure processes (step Y2P and step Y2Q) corresponds to exposure mainly for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator. Also, the exposure processes (step Y2P and step Y2Q) can each be either one of the full-area exposure and the pattern exposure, but either one of the exposure processes is the pattern exposure.

[0713] For example, in the case where the step Y2P is the pattern exposure for reducing the content of the acid group derived from the compound A due to exposure, the developing solution used in the step Y3 can be the alkali developing solution or the organic solvent-based developing solution. In the case where the developing is performed using the organic solvent-based developing solution, the step Y2Q is usually performed after the step Y3, and in the developed photosensitive layer (pattern), the content of the acid group (preferably, carboxyl group) derived from the compound A is reduced while causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator.

[0714] Also, for example, in the case where the step Y2P is the pattern exposure for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator, the developing solution used in the step Y3 is usually the alkali developing solution. In this case, the step Y2Q can be performed before or after the step Y3, and the step Y2Q performed before the step Y3 is usually the pattern exposure.

[0715] In the process Y2P and the process Y2Q, as a light source used for exposure, a light source of a wavelength capable of reducing the content of the acid group derived from the compound A in the photosensitive layer (a light of a wavelength that excites the specific structure S0 (preferably the specific structure S1) in the compound β (preferably the compound B) in the photosensitive layer (when the requirement (V01) is satisfied) and the specific structure S0 (preferably the specific structure S1) in the compound A (when the requirement (W01) is satisfied)) or a light of a wavelength capable of causing a reaction of a polymerizable compound based on a photopolymerization initiator in the photosensitive layer (a light of a wavelength that excites the photopolymerization initiator. For example, 254 nm, 313 nm, 365 nm, 405 nm, and the like) can be appropriately selected. Specifically, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode) and the like can be mentioned.

[0716] In the exposure for reducing the content of the acid group derived from the compound A in the photosensitive layer, as an exposure amount, 10 to 10000 mJ / cm 2 , more preferably 50 to 3000 mJ / cm 2 .

[0717] In the exposure for causing a reaction of a polymerizable compound based on a photopolymerization initiator in the photosensitive layer, as an exposure amount, 5 to 200 mJ / cm 2 , more preferably 10 to 150 mJ / cm 2 .

[0718] In the process Y2P and the process Y2Q, the pattern exposure can be performed after the temporary support is peeled from the photosensitive layer, or the pattern exposure can be performed through the temporary support before the temporary support is peeled, and then the temporary support is peeled. In order to prevent contamination of the mask caused by contact of the photosensitive layer with the mask, and to avoid the influence on exposure caused by foreign matter attached to the mask, it is preferable that the pattern exposure is performed without peeling the temporary support. In addition, the pattern exposure can be exposure through the mask, or direct exposure using a laser or the like.

[0719] In the exposure process, the detailed configuration and the specific size of the pattern are not particularly limited.

[0720] For example, in the case where the pattern forming method of Embodiment 2 is applied to the manufacture of a circuit wiring, at least a part of the pattern (particularly, a part corresponding to a part of the electrode pattern and the lead-out wiring of the touch panel) is preferably a fine line of 100 μm or less, more preferably a fine line of 70 μm or less, from the viewpoint of improving the display quality of a display device (for example, a touch panel) provided with an input device having a circuit wiring manufactured by the pattern forming method of Embodiment 2, and from the viewpoint of being able to minimize the area occupied by the lead-out wiring.

[0721] <Preferred Embodiment>

[0722] As the pattern forming method of Embodiment 2, it is preferable to have, in order, the step Y1, the step Y2A, the step Y3, and the step Y2B. In addition, one of the step Y2A and the step Y2B corresponds to an exposure step for reducing the content of the acid group derived from the compound A due to exposure, and the other corresponds to an exposure step for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator.

[0723] Step Y1: a step of joining the transfer film to the above-mentioned substrate by contacting the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film with the substrate

[0724] Step Y2A: a step of performing pattern exposure on the photosensitive layer

[0725] Step Y3: a step of forming a patterned photosensitive layer by developing the photosensitive layer using an alkali developer

[0726] Step Y2B: a step of exposing the patterned photosensitive layer

[0727] The above-mentioned step Y2A is preferably an exposure step for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator, and the above-mentioned step Y2B is preferably an exposure step for reducing the content of the acid group derived from the compound A due to exposure.

[0728] [Arbitrary Steps that the Pattern Forming Method of Embodiment 1 and Embodiment 2 May Have]

[0729] The pattern forming method of Embodiment 1 and Embodiment 2 can include an arbitrary step (other step) other than the above-mentioned. For example, the following steps can be cited, but are not limited to these steps.

[0730] [Cover Film Peeling Step]

[0731] In the case where the transfer film has a cover film, the above-mentioned pattern forming method preferably includes a step of peeling the cover film of the above-mentioned transfer film (hereinafter, also referred to as "cover film peeling step"). The method of peeling the cover film is not particularly limited, and a publicly known method can be applied.

[0732] <Process of reducing the visible light reflectance>

[0733] In the case where the substrate is a substrate having a conductive layer, the above-described pattern forming method can further include a process of performing a treatment of reducing the visible light reflectance of the conductive layer. In addition, in the case where the above-described substrate is a substrate having a plurality of conductive layers, the treatment of reducing the visible light reflectance can be performed on a part of the conductive layers, or can be performed on all of the conductive layers.

[0734] As the treatment of reducing the visible light reflectance, an oxidation treatment can be given. For example, by performing an oxidation treatment on copper to become copper oxide to make it black, the visible light reflectance of the conductive layer can be reduced.

[0735] Regarding the preferable mode of the treatment of reducing the visible light reflectance, 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and 0041, 0042, 0048, and 0058 of Japanese Patent Application Publication No. 2013-206315 are incorporated into the present specification.

[0736] <Etching process>

[0737] In the case where the substrate is a substrate having a conductive layer, the above-described pattern forming method preferably includes a process (etching process) of performing an etching treatment on the conductive layer in a region where the etching resist film is not disposed, using the pattern formed by the process X3 (or the process X4) and the process Y3 as the etching resist film.

[0738] As the method of the etching treatment, the method based on wet etching described in 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155 and the publicly known method based on dry etching such as plasma etching can be applied.

[0739] For example, as the method of the etching treatment, a wet etching method of generally performed by dipping in an etching solution can be given. The etching solution used in the wet etching can be appropriately selected from an acidic type or an alkaline type etching solution according to the object of the etching.

[0740] As the acidic type etching solution, an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt such as ferric chloride, ammonium fluoride, or potassium permanganate, and the like can be given. The acidic component can use a component in which a plurality of acidic components are combined.

[0741] As the etching solution of the alkaline type, an aqueous solution of an alkali component alone such as sodium hydroxide, potassium hydroxide, ammonia, a salt of an organic amine such as tetramethylammonium hydroxide, and a mixed aqueous solution of an alkali component and a salt such as potassium permanganate are exemplified. The alkali component can use a component in which a plurality of alkali components are combined.

[0742] The temperature of the etching solution is not particularly limited, and is preferably 45°C or lower. In the method for manufacturing a circuit pattern of the present application, the pattern formed by the process X3 (or the process X4) and the process Y3, which is used as the etching resist film, preferably exhibits particularly excellent resistance to the acidic and alkaline etching solutions in the temperature range of 45°C or lower. By the above structure, peeling of the etching resist film in the etching process can be prevented, and the portion where the etching resist film is not present can be selectively etched.

[0743] After the etching process, in order to prevent contamination of the process line, a cleaning process of cleaning the substrate subjected to the etching treatment and a drying process of drying the cleaned substrate can be performed as necessary.

[0744] <<Other Embodiments>>

[0745] As for the above pattern forming method, it is also preferable to use substrates each having a plurality of conductive layers on both surfaces, and to form patterns on the conductive layers formed on both surfaces successively or simultaneously.

[0746] By this structure, it is possible to form a first conductive pattern on one surface of the substrate, and to form a second conductive pattern on the other surface. It is also preferable to form from both sides of the substrate in a roll-to-roll manner.

[0747] [Pattern]

[0748] The pattern formed by the pattern forming method of Embodiment 1 and Embodiment 2 has a reduced content of acid groups, and thus has reduced polarity, moisture permeability, and relative dielectric constant.

[0749] The content of the acid groups in the above pattern is preferably reduced by 5 mol% or more, more preferably by 10 mol% or more, still more preferably by 20 mol% or more, further preferably by 31 mol% or more, particularly preferably by 40 mol% or more, particularly more preferably by 51 mol% or more, and most preferably by 71 mol% or more, relative to the content of the acid groups in the photosensitive layer formed in the process X1 or the process Y1. There is no particular limitation on the upper limit value, and it is, for example, 100 mol% or less.

[0750] The moisture permeability of the above pattern is preferably reduced by 5% or more, more preferably by 10% or more, and further preferably by 20% or more, relative to the moisture permeability of the photosensitive layer formed in the process X1 or the process Y1. There is no particular limitation on the upper limit value, and it is, for example, 100% or less.

[0751] The relative dielectric constant of the above pattern is preferably reduced by 5% or more, more preferably by 10% or more, and further preferably by 15% or more, relative to the relative dielectric constant of the photosensitive layer formed in the process Xl or the process Yl. In addition, there is no particular limitation on the upper limit value, and it is, for example, 100% or less.

[0752] The average thickness of the pattern formed by the above pattern forming method is preferably 0.5 to 20 μm. The average thickness of the pattern is more preferably 0.8 to 15 μm, and further preferably 1.0 to 10 μm.

[0753] The pattern formed by the above pattern forming method is preferably colorless.

[0754] Specifically, the total reflection (incident angle 8°, light source: D-65 (2° field of view)) in the CIE 1976 (L * , a * , b * ) color space is preferably 10 to 90 for the L * value of the pattern, -1.0 to 1.0 for the a * value of the pattern, and -1.0 to 1.0 for the b * value of the pattern.

[0755] There is no particular limitation on the use of the pattern formed by the above pattern forming method, and it can be used as various protective films or insulating films.

[0756] Specifically, the use as a protective film (permanent film) for protecting a conductive pattern, the use as an interlayer insulating film between conductive patterns, and the use as an etching resist film during the manufacture of a circuit wiring, and the like can be given. The above pattern is excellent in low moisture permeability, and among them, the use as a protective film (permanent film) for protecting a conductive pattern or an interlayer insulating film between conductive patterns is preferred.

[0757] In addition, the above pattern can be used, for example, as a protective film (permanent film) for protecting a conductive pattern such as an electrode pattern, a peripheral wiring portion, and a lead-out wiring portion of a sensor corresponding to a visually recognizable portion provided inside a touch panel, or as an interlayer insulating film between conductive patterns.

[0758] [Method for manufacturing circuit wiring]

[0759] The manufacturing method of the circuit wiring of the present application is not particularly limited as long as the manufacturing method of the circuit wiring using the transfer film described above is used, but preferably includes, in order, a process (adhesion process) of adhering the transfer film to a substrate having a conductive layer with the surface of the photosensitive layer on the transfer film opposite to the temporary support side being in contact with the conductive layer of the substrate having a conductive layer, a process (first exposure process) of performing pattern exposure on the photosensitive layer of the adhered transfer film, a process (alkali development process) of forming a patterned photosensitive layer by developing the exposed photosensitive layer using an alkali developer, a process (second exposure process) of forming an etching resist film by exposing the patterned photosensitive layer, and a process (etching treatment process) of performing etching treatment on the conductive layer in the region of the transfer film where the etching resist film is not disposed.

[0760] In the manufacturing method of the circuit wiring of the present application, the adhesion process, the first exposure process, the alkali development process, and the second exposure process can be performed in the same order as the processes Y1, Y2A, Y3, and Y2B of the pattern forming method of Embodiment 2 described above. Also, the substrate having a conductive layer used in the manufacturing method of the circuit wiring of the present application is the same as the substrate having a conductive layer used in the process X1 described above. Also, the manufacturing method of the circuit wiring of the present application can have other processes in addition to the processes described above. As the other processes, the same processes as any of the processes that the pattern forming methods of Embodiments 1 and 2 can have can be cited.

[0761] The manufacturing method of the circuit wiring of the present application also preferably has the five processes of the adhesion process, the first exposure process, the development process, the second exposure process, and the etching process as one group, and is repeated multiple times.

[0762] The film used as the etching resist film can also be used as a protective film (permanent film) of the formed circuit wiring.

[0763] [Manufacturing method of touch panel]

[0764] The manufacturing method of the touch panel of the present application is not particularly limited as long as it is a manufacturing method of a touch panel using the above-described transfer film, but preferably includes, in order, a step (adhesion step) of contacting the surface of the side opposite to the temporary support side of the photosensitive layer in the above-described transfer film with the conductive layer in the substrate having the conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring), a step (first exposure step) of pattern-exposing the photosensitive layer in the adhered transfer film, a step (alkali development step) of developing the exposed photosensitive layer using an alkali developer to form a patterned photosensitive layer, and a step (second exposure step) of exposing the patterned photosensitive layer to form a protective film or an insulating film of the conductive layer.

[0765] The protective film formed by the second exposure step has a function as a film that protects the surface of the conductive layer. Also, the insulating film has a function as an interlayer insulating film between the conductive layers. In addition, in the case where the second exposure step is a step of forming an insulating film of the conductive layer, the manufacturing method of the touch panel of the present application preferably further has a step of forming a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring) on the insulating film formed by the second exposure step.

[0766] In the manufacturing method of the touch panel of the present application, the adhesion step, the first exposure step, the alkali development step, and the second exposure step can be performed in the same order as the steps Y1, Y2A, Y3, and Y2B of the pattern formation method of Embodiment 2 described above. Also, the substrate having the conductive layer used in the manufacturing method of the touch panel of the present application is the same as the substrate having the conductive layer used in the above-described step X1. As other steps, the same steps as any of the steps that the pattern formation methods of Embodiments 1 and 2 can have can be cited.

[0767] As the manufacturing method of the touch panel of the present application, a structure other than the above-described modes can be referred to a publicly known manufacturing method of a touch panel.

[0768] The touch panel manufactured by the manufacturing method of the touch panel of the present application preferably has a transparent substrate, an electrode, and a protective layer (protective film).

[0769] As the detection method in the above-described touch panel, any of publicly known methods such as a resistive film method, an electrostatic capacitance method, an ultrasonic wave method, an electromagnetic induction method, and an optical method can be used. Among them, the electrostatic capacitance method is preferable.

[0770] As the touch panel type, there can be mentioned the so-called in-cell type (for example, the structures described in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open (kokai) No. 2012-517051), the so-called on-cell type (for example, the structure described in FIG. 19 of Japanese Patent Application Laid-Open No. 2013-168125, the structures described in FIGS. 1, 2, and 3 of Japanese Patent Application Laid-Open No. 2012-089102 Figure 1 , the OGS (One Glass Solution) type, the TOL (Touch-on-Lens) type (for example, the structure described in FIG. 2 of Japanese Patent Application Laid-Open No. 2013-054727), other structures (for example, the structure described in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871), and various on-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, G1F, and the like).

[0771] [Photosensitive material according to other embodiments, and transfer film, pattern forming method, circuit substrate manufacturing method, and touch panel manufacturing method using the same]

[0772] The present application still further relates to a photosensitive material excellent in pattern formation (hereinafter, also referred to as "photosensitive material of the present application").

[0773] Hereinafter, the photosensitive material of the present application, and the transfer film, pattern forming method, circuit substrate manufacturing method, and touch panel manufacturing method using the same will be described.

[0774] [Photosensitive material]

[0775] As a feature point of the photosensitive material of the present application, there can be mentioned a photosensitive material containing a compound A having a carboxyl group (hereinafter, also referred to as "compound A").

[0776] (1) The above compound A contains a polymer containing a repeating unit derived from a (meth)acrylic acid.

[0777] (2) The content of the above carboxyl group in a photosensitive layer formed from the above photosensitive material due to irradiation of actinic rays or radiation is reduced. In other words, the content of the carboxyl group derived from the compound A in the photosensitive layer formed from the above photosensitive material is reduced due to irradiation (exposure) of actinic rays or radiation.

[0778] The photosensitive material of the present application is excellent in pattern formation by the above structure. Specifically, it is excellent in resolution and excellent in film reduction inhibition.

[0779] Further, it was confirmed by the present inventors' research that the photosensitive layer formed from the above photosensitive material has a reduced content of carboxyl groups derived from Compound A due to exposure, and thus has a reduced relative dielectric constant after exposure as compared to before exposure.

[0780] As a method in which the photosensitive material of the present application exhibits the mechanism of (2), for example, a method in which a photosensitive material satisfying the following requirement (V02) or requirement (W02) is provided can be given.

[0781] Requirement (V02): The photosensitive material contains Compound A having a carboxyl group and Compound β having a structure (specific structure S0) in which the amount of the carboxyl group contained in Compound A is reduced by exposure.

[0782] Requirement (W02): The photosensitive material contains Compound A having a carboxyl group, and Compound A contains a structure (specific structure S0) in which the amount of the carboxyl group is reduced by exposure.

[0783] The specific structure S0 in the above requirement (V02) and requirement (W02) has the same meaning as the specific structure S0 in the above requirement (V01) and requirement (W01) of the transfer film.

[0784] As the above requirement (V02), the following requirement (V2) is preferable, and as the above requirement (W02), the following requirement (W2) is preferable. That is, in the above requirement (V02), the above Compound β is preferably a compound B having a structure capable of accepting an electron from the carboxyl group contained in Compound A in a photoexcited state. Further, in the above requirement (W02), the above structure is preferably a structure capable of accepting an electron from the carboxyl group contained in Compound A in a photoexcited state.

[0785] In addition, the specific structure S1 in the above requirement (V2) and requirement (W2) has the same meaning as the specific structure S1 in the above requirement (V1) and requirement (W1) of the transfer film.

[0786] Requirement (V2): The photosensitive material contains Compound A having a carboxyl group and Compound B having a structure (specific structure S1) capable of accepting an electron from the carboxyl group contained in the above Compound A in a photoexcited state, and the above Compound A contains a polymer containing a repeating unit derived from a (meth)acrylic acid.

[0787] Requirement (W2): The above photosensitive material contains Compound A having a carboxyl group, and the above Compound A contains a repeating unit derived from a (meth)acrylic acid and a structure (specific structure S1) capable of accepting an electron from the above carboxyl group in a photoexcited state.

[0788] The photosensitive layer formed from the photosensitive material described above is capable of reducing the content of carboxyl groups derived from the compound A by exposure through the action mechanism using the specific structure SO as a starting point.

[0789] Hereinafter, the inference mechanism capable of reducing the content of carboxyl groups derived from the compound A by exposure will be described taking the specific structure S1 as an example.

[0790] The specific structure described above, if exposed, increases the electron acceptance and accepts an electron from the carboxyl group possessed by the compound A. In addition, the carboxyl group can become an anion at the time of transferring the electron.

[0791] If the carboxyl group that can become the anion transfers an electron to the specific structure S1, the carboxyl group becomes unstable and is detached as carbon dioxide. If the carboxyl group as an acid group is detached as carbon dioxide, the polarity of the portion decreases. That is, through the action mechanism, the photosensitive layer generates a change in polarity due to the detachment of the carboxyl group of the compound A at the exposed portion, and a change in solubility in the developer (the solubility in the alkali developer decreases at the exposed portion and the solubility in the organic solvent-based developer increases). On the other hand, in the unexposed portion, the solubility in the developer hardly changes. As a result thereof, the photosensitive layer has excellent pattern formability. Furthermore, in the case where the developer is an alkali developer, the formation of a low moisture permeability pattern in which the content of the carboxyl group is reduced becomes possible. In addition, in the case where the developer is an organic solvent-based developer, the formation of a low moisture permeability pattern in which the content of the carboxyl group is reduced becomes possible by further performing exposure treatment on the pattern after development.

[0792] Furthermore, as described later, the photosensitive material preferably also contains a polymerizable compound.

[0793] As described above, if the carboxyl group transfers an electron to the specific structure S1, the carboxyl group becomes unstable and is detached as carbon dioxide. At this time, a radical is generated at the site where the carboxyl group on the compound A is detached as carbon dioxide, and a radical polymerization reaction of the polymerizable compound is caused by this radical. As a result thereof, the photosensitive layer formed from the photosensitive material has more excellent pattern formability particularly to an alkali developer, and the film strength of the pattern formed is also excellent.

[0794] As described later, the photosensitive material preferably further contains a polymerizable compound and a photopolymerization initiator.

[0795] In the case where the photosensitive material contains a photopolymerization initiator, decarboxylation and polymerization reactions as described above can occur at different times. For example, with respect to a photosensitive layer formed from the photosensitive material, first, a first exposure can be performed at a wavelength or exposure amount at which decarboxylation hardly occurs, and a polymerization reaction of a polymerizable compound based on the photopolymerization initiator is performed to cure it. Then, a second exposure can be performed on the cured photosensitive layer, and decarboxylation is caused to occur.

[0796] Hereinafter, as an example, polyacrylic acid as Compound A and quinoline as Compound B are cited, and the inference mechanism of the decarboxylation process (an inference mechanism capable of reducing the content of carboxyl groups derived from Compound A by exposure, with a specific structure S1 as a starting point) is described in detail.

[0797] As shown in the following drawing, the carboxyl group of polyacrylic acid forms a hydrogen bond in coexistence with the nitrogen atom of quinoline. If quinoline is exposed, the electron acceptance increases, and an electron is transferred from the carboxyl group possessed by polyacrylic acid (Step 1: photoexcitation). If the carboxyl group possessed by polyacrylic acid transfers an electron to quinoline, it becomes unstable and is decarboxylated as carbon dioxide (Step 2: decarboxylation reaction). If the above decarboxylation reaction proceeds, a radical is generated at the residue of polyacrylic acid, and a radical reaction proceeds. A radical reaction can occur between the residues of polyacrylic acid, between the residue of polyacrylic acid and a polymerizable compound (monomer (M)) optionally contained, and between hydrogen atoms in the atmosphere (Step 3: polarity conversion, crosslinking, and polymerization reaction). Furthermore, after the radical reaction is completed, Compound B is regenerated and can again contribute to the decarboxylation process of Compound A (Step 4: regeneration of Compound B (catalyst)).

[0798] [Chemical Formula 7]

[0799]

[0800] In particular, from the viewpoint of having more excellent pattern-forming ability in an alkali developer, the content of carboxyl groups derived from Compound A in the photosensitive layer formed from the photosensitive material is preferably reduced at a rate of 5 mol% or more, more preferably at a rate of 10 mol% or more, still more preferably at a rate of 20 mol% or more, further preferably at a rate of 31 mol% or more, particularly preferably at a rate of 40 mol% or more, more particularly preferably at a rate of 51 mol% or more, and most preferably at a rate of 71 mol% or more, due to exposure. In addition, there is no particular limitation on the upper limit value, and it is, for example, 100 mol% or less.

[0801] In addition, the reduction rate of the content of the carboxyl group derived from the compound A in the photosensitive layer can be calculated by measuring the amount of the carboxyl group in the photosensitive layer before and after exposure. In measuring the amount of the carboxyl group in the photosensitive layer before exposure, analysis and quantification can be performed by, for example, potentiometric titration. In measuring the amount of the carboxyl group in the photosensitive layer after exposure, the amount of the carboxyl group can be calculated by substituting the hydrogen atom of the carboxyl group with a metal ion such as lithium, and by analyzing and quantifying the amount of the metal ion by ICP-OES (Inductively coupled plasma optical emission spectrometer).

[0802] Also, the reduction rate of the content of the acid group derived from the photosensitive layer can be obtained by measuring the IR (infrared) spectrum of the photosensitive layer before and after exposure, and calculating the reduction rate of the peak derived from the acid group.

[0803] <<Embodiment of photosensitive material>>

[0804] Hereinafter, an example of an embodiment of the photosensitive material will be shown.

[0805] <Photosensitive material of embodiment Y-1-a1>

[0806] A photosensitive material satisfying any of the requirements (V02) or (W02), and substantially not containing a polymerizable compound and a photopolymerization initiator.

[0807] <Photosensitive material of embodiment Y-1-a2>

[0808] A photosensitive material satisfying any of the requirements (V02) or (W02), and substantially not containing a photopolymerization initiator.

[0809] <Photosensitive material of embodiment Y-1-a3>

[0810] A photosensitive material satisfying any of the requirements (V02) or (W02), and containing a polymerizable compound and a photopolymerization initiator.

[0811] In addition, in the photosensitive material of embodiment Y-1-a1, "the photosensitive material substantially does not contain a polymerizable compound" means that the content of the polymerizable compound is less than 3% by mass, preferably 0 to 1% by mass, and more preferably 0 to 0.1% by mass, with respect to the total solid content of the photosensitive material.

[0812] Further, in the photosensitive material of Embodiment Y-1-a1 and Embodiment Y-1-a2, "the photosensitive material substantially contains no photopolymerization initiator" means that the content of the photopolymerization initiator is less than 0.1% by mass, preferably 0 to 0.05% by mass, and more preferably 0 to 0.01% by mass, with respect to the total solid content of the photosensitive material.

[0813] Further, as described above, the solid content refers to all components other than the solvent of the photosensitive material.

[0814] The photosensitive material of Embodiment Y-1-a1 and Embodiment Y-1-a2 is preferably applied to the pattern forming method of Embodiment 1' described later. Further, the photosensitive material of Embodiment Y-1-a3 is preferably applied to the pattern forming method of Embodiment 2' described later.

[0815] Further, in Embodiment Y-1-a1 to Embodiment Y-1-a3, the requirement (V02) and the requirement (W02) are each preferably the requirement (V2) and the requirement (W2) described above.

[0816] Hereinafter, the photosensitive material of the present application will be described.

[0817] <<<Various Components>>>

[0818] <<Compound A Having an Acid Group>>

[0819] The photosensitive material of the present application contains a compound A having a carboxyl group.

[0820] As the compound A having a carboxyl group, the same compound as the "compound having a carboxyl group" contained in the photosensitive layer of the transfer film of the present application described above can be given.

[0821] In the photosensitive material of the present application, the compound A having a carboxyl group contains a polymer containing a repeating unit derived from a (meth)acrylic acid (hereinafter, also referred to as "polymer Al").

[0822] Generally, the polymer Al is an alkali-soluble resin.

[0823] Further, the definition and the measurement method of the "alkali-solubility" have been described.

[0824] The polymer Al can further have an acid group other than the carboxyl group. As the acid group other than the carboxyl group, for example, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group can be given.

[0825] From the viewpoint of development properties, the acid value of the polymer Al is preferably 60 to 300 mgKOH / g, more preferably 60 to 275 mgKOH / g, and further preferably 75 to 250 mgKOH / g.

[0826] In the polymer A1, the content of the repeating unit derived from the (meth)acrylic acid is preferably 5 to 100 mol%, more preferably 10 to 65 mol%, and further preferably 15 to 45 mol% with respect to all the repeating units of the polymer A1.

[0827] The polymer A1 can include other repeating units in addition to the repeating unit derived from the (meth)acrylic acid.

[0828] As the other repeating units, for example, the repeating units that can be included in the "carboxyl group-containing polymer" that the compound A having an acid group included in the photosensitive layer in the transfer film of the present application can include, in addition to the "repeating unit derived from the (meth)acrylic acid", can include the repeating unit including the specific structure S0 (preferably the specific structure S1), the repeating unit having a polymerizable group, the repeating unit having an aromatic ring, the repeating unit having an alicyclic structure, and other repeating units.

[0829] The preferable range of each of the repeating units in the polymer A1 is as follows.

[0830] In the case where the polymer A1 contains the repeating unit including the specific structure S0 (preferably the specific structure S1), the content thereof is preferably 3 to 75 mol%, more preferably 5 to 60 mol%, and further preferably 10 to 50 mol% with respect to all the repeating units of the polymer A1.

[0831] In the case where the polymer A1 has the repeating unit having the specific structure S0 (preferably the specific structure S1), the content thereof is preferably 1 to 75 mass%, more preferably 3 to 60 mass%, and further preferably 5 to 30 mass% with respect to all the repeating units of the polymer A1.

[0832] The repeating unit including the specific structure S0 (preferably the specific structure S1) can be used alone or two or more kinds thereof can be used.

[0833] In the polymer A1, the content of the repeating unit having a polymerizable group is preferably 3 to 60 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 30 mol% with respect to all the repeating units of the polymer A1.

[0834] In the polymer A1, the content of the repeating unit having a polymerizable group is preferably 1 to 70 mass%, more preferably 5 to 50 mass%, and further preferably 12 to 45 mass% with respect to all the repeating units of the polymer A1.

[0835] The repeating unit having a polymerizable group can be used alone or two or more kinds thereof can be used.

[0836] The content of the repeating unit having an aromatic ring in the polymer A1 is preferably 5 to 80 mol%, more preferably 15 to 75 mol%, and further preferably 30 to 70 mol% with respect to all the repeating units of the polymer A1.

[0837] The content of the repeating unit having an aromatic ring in the polymer A1 is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and further preferably 30 to 70 mass% with respect to all the repeating units of the polymer A1.

[0838] The repeating unit having an aromatic ring can be used singly or two or more kinds thereof can be used.

[0839] The content of the repeating unit having an alicyclic structure in the polymer A1 is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, and further preferably 10 to 55 mol% with respect to all the repeating units of the polymer A1.

[0840] The content of the repeating unit having an alicyclic structure in the polymer A1 is preferably 3 to 90 mass%, more preferably 5 to 70 mass%, and further preferably 25 to 60 mass% with respect to all the repeating units of the polymer A1.

[0841] The repeating unit having an alicyclic structure can be used singly or two or more kinds thereof can be used.

[0842] The content of the other repeating unit in the polymer A1 is preferably 1 to 70 mol%, more preferably 2 to 50 mol%, and further preferably 3 to 20 mol% with respect to all the repeating units of the polymer A1.

[0843] The content of the other repeating unit in the polymer A1 is preferably 1 to 70 mass%, more preferably 2 to 50 mass%, and further preferably 5 to 35 mass% with respect to all the repeating units of the polymer A1.

[0844] The other repeating unit can be used singly or two or more kinds thereof can be used.

[0845] As the lower limit value of the weight average molecular weight of the polymer A1, it is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more from the viewpoint that the formability of the photosensitive layer is excellent (in other words, the film formation performance for forming the photosensitive layer is excellent). As the upper limit value, there is no particular limitation, and it is preferably 50,000 or less from the viewpoint that the adhesion (laminating adhesion) at the time of being attached to an arbitrary substrate (at the time of transfer) is more excellent.

[0846] As a preferable range of the weight average molecular weight of the polymer A1, it is preferable to be from 5,000 to 200,000, more preferable to be from 10,000 to 100,000, and most preferable to be from 11,000 to 49,000.

[0847] In the photosensitive material of the present application, the content of the compound A is more preferably 25% by mass or more, further preferably 30% by mass or more, still further preferably 45% by mass or more, and particularly preferably 50% by mass or more, with respect to the total solid content of the photosensitive material. As an upper limit of the content of the compound A, it is preferable to be 100% by mass or less, more preferable to be 99% by mass or less, further preferable to be 97% by mass or less, particularly preferable to be 93% by mass or less, more particularly preferable to be 85% by mass or less, and most preferable to be 75% by mass or less, with respect to the total solid content of the photosensitive material. In addition, in the case where the photosensitive material satisfies the requirement (W02), as an upper limit of the content of the compound A, it is preferable to be 99% by mass or less, with respect to the total solid content of the photosensitive material.

[0848] The compound A can be used singly or two or more kinds thereof can be used.

[0849] In the photosensitive material of the embodiment Y-1-a1, the content of the compound A is preferably from 40 to 98% by mass, more preferably from 50 to 96% by mass, and more preferably from 60 to 93% by mass, with respect to the total solid content of the photosensitive material.

[0850] In the photosensitive material of the embodiment Y-1-a2, the content of the compound A is preferably from 30 to 85% by mass, and more preferably from 45 to 75% by mass, with respect to the total solid content of the photosensitive material.

[0851] In the photosensitive material of the embodiment Y-1-a3, the content of the compound A is preferably from 30 to 85% by mass, and more preferably from 45 to 75% by mass, with respect to the total solid content of the photosensitive material.

[0852] <<Compound β>>

[0853] The photosensitive material preferably contains the compound β.

[0854] As the compound β, the same as the compound β that the photosensitive layer of the transfer film of the present application described above can contain, and the preferable modes thereof are also the same.

[0855] From the viewpoint of more excellent pattern formation ability, in the photosensitive material, the content of the compound β (preferably the compound B) is preferably from 0.1 to 50% by mass, with respect to the total solid content of the photosensitive material.

[0856] In the photosensitive material of Embodiment Y-1-a1, the content of the compound β (preferably, the compound B) is, for example, 0.2 to 45% by mass, preferably 2.0 to 40% by mass, more preferably 4 to 35% by mass, and further preferably 8 to 30% by mass, with respect to the total solid content of the photosensitive material.

[0857] In the photosensitive material of Embodiment Y-1-a2, the content of the compound β (preferably, the compound B) is preferably 0.5 to 20% by mass, and more preferably 1.0 to 10% by mass, with respect to the total solid content of the photosensitive material.

[0858] In the photosensitive material of Embodiment Y-1-a3, the content of the compound β (preferably, the compound B) is preferably 0.3 to 20% by mass, and more preferably 0.5 to 8% by mass, with respect to the total solid content of the photosensitive material.

[0859] The compound ββ (preferably, the compound B) can be used singly or two or more kinds can be used.

[0860] In the case where the compound β is the compound B, the total number of the structures capable of accepting electrons (specific structure S1) possessed by the compound B is preferably 1% by mole or more, more preferably 3% by mole or more, further preferably 5% by mole or more, and particularly preferably 10% by mole or more, and most preferably 20% by mole or more, with respect to the total number of the carboxyl groups possessed by the compound A, from the viewpoint of more excellent pattern formation ability.

[0861] The upper limit of the total number of the structures capable of accepting electrons (specific structure S1) possessed by the compound B is not particularly limited, and is preferably 200% by mole or less, more preferably 100% by mole or less, and further preferably 80% by mole or less, with respect to the total number of the carboxyl groups possessed by the compound A, from the viewpoint of the film quality of the obtained film.

[0862] <<Polymerizable Compound>>

[0863] The photosensitive material preferably contains a polymerizable compound.

[0864] As the polymerizable compound, the same as the polymerizable compound that the photosensitive layer in the transfer film of the present application described above can contain is preferable, and the same preferred modes are also preferable. In addition, the polymerizable compound is a component different from the compound A having a carboxyl group, and does not contain a carboxyl group.

[0865] In the case where the photosensitive material contains a polymerizable compound, the content thereof is preferably 3 to 70% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 55% by mass, with respect to the total solid content of the photosensitive material.

[0866] In the case where the photosensitive material contains the polymerizable compound, the mass ratio of the polymerizable compound to the polymer Al (mass of the polymerizable compound / mass of the polymer Al) is preferably 0.2 to 2.0, more preferably 0.4 to 0.9.

[0867] The polymerizable compound can be used singly or two or more kinds can be used.

[0868] In the case where the photosensitive material contains the 2-functional polymerizable compound and the 3 or more functional polymerizable compound, the content of the 2-functional polymerizable compound is preferably 10 to 90 mass%, more preferably 20 to 85 mass%, further preferably 30 to 80 mass% with respect to all the polymerizable compounds contained in the photosensitive material.

[0869] In this case, the content of the 3 or more functional polymerizable compound is preferably 10 to 90 mass%, more preferably 15 to 80 mass%, further preferably 20 to 70 mass% with respect to all the polymerizable compounds contained in the photosensitive material.

[0870] In the case where the photosensitive material contains the 2 or more functional polymerizable compound, the photosensitive material can further contain the monofunctional polymerizable compound.

[0871] In the case where the photosensitive material contains the 2 or more functional polymerizable compound, it is preferable that the 2 or more functional polymerizable compound be the main component among the polymerizable compounds that can be contained in the photosensitive material.

[0872] Specifically, in the case where the photosensitive material contains the 2 or more functional polymerizable compound, the content of the 2 or more functional polymerizable compound is preferably 60 to 100 mass%, more preferably 80 to 100 mass%, further preferably 90 to 100 mass% with respect to the total content of the polymerizable compounds contained in the photosensitive material.

[0873] <Photopolymerization Initiator>

[0874] The photosensitive material preferably contains the photopolymerization initiator.

[0875] As the photopolymerization initiator, the same as the photopolymerization initiator that can be contained in the photosensitive layer of the transfer film of the present application described above is preferable, and the same as the preferable mode is also preferable.

[0876] In the case where the photosensitive material contains the photopolymerization initiator, the content thereof is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, particularly preferably 1 to 5 mass% with respect to the total solid content of the photosensitive material. The photopolymerization initiator can be used singly or two or more kinds can be used.

[0877] <Surfactant>

[0878] The photosensitive material can contain a surfactant.

[0879] As the surfactant, the same surfactant as that which the photosensitive layer in the transfer film of the present application described above can contain, and the same preferable mode are preferable.

[0880] The content of the surfactant is preferably 0.0001 to 10 mass% with respect to the total solid content of the photosensitive material, more preferably 0.001 to 5 mass%, and further preferably 0.005 to 3 mass%. One kind of surfactant can be used alone, or two or more kinds of surfactants can be used.

[0881] <<Solvent>>

[0882] The photosensitive material of the present application can contain a solvent from the viewpoint of forming the photosensitive layer by coating.

[0883] As the solvent, a generally used solvent can be used without particular limitation.

[0884] As the solvent, an organic solvent is preferable.

[0885] As the organic solvent, for example, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-acetyl propyl), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, 2-propanol, and a mixed solvent of these can be mentioned.

[0886] As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is preferable.

[0887] In the case where the photosensitive material of the present application contains a solvent, the content of the solvent with respect to the total mass of the photosensitive material is preferably 20 to 95 mass%, more preferably 60 to 95 mass%, and 70 to 95 mass%. Further, in the case where the photosensitive material of the present application contains a solvent, one kind of solvent can be used alone, or two or more kinds of solvents can be used.

[0888] In the case where the photosensitive material of the present application contains a solvent, the viscosity (25°C) of the photosensitive material is preferably 1 to 50 mPa-s, more preferably 2 to 40 mPa-s, and further preferably 3 to 30 mPa-s from the viewpoint of coatability.

[0889] The viscosity was measured using a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO., LTD.), for example.

[0890] In the case where the photosensitive material of the present application contains a solvent, the surface tension (25°C) of the photosensitive material is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and further preferably 15 to 40 mN / m, from the viewpoint of coatability.

[0891] The surface tension was measured using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., LTD.), for example.

[0892] As the solvent, Solvents described in paragraphs 0054 and 0055 of U.S. Application Publication No. 2005 / 282073, the content of which is incorporated into the present specification, can also be used.

[0893] Further, as the solvent, an organic solvent (high-boiling-point solvent) having a boiling point of 180 to 250°C can also be used as needed.

[0894] In addition, in the case where the photosensitive material of the present application is used to form the photosensitive layer (layer formed using the photosensitive material) in the transfer film described later, the photosensitive material as the photosensitive layer preferably substantially does not contain a solvent. Substantially not containing a solvent means that the content of the solvent is less than 1% by mass with respect to the total mass of the photosensitive material, and is preferably 0 to 0.5% by mass, and more preferably 0 to 0.001% by mass.

[0895] <<Other additives>>

[0896] The photosensitive material can contain other additives as needed.

[0897] As the other additives, the same preferences as the other additives that can be contained in the photosensitive layer of the transfer film of the present application described above apply.

[0898] [Photosensitive layer]

[0899] The photosensitive material of the present application can be used as a photosensitive layer (e.g., photosensitive layer of a transfer film) when forming various patterns. Hereinafter, the manner in which the photosensitive material of the present application is used as a photosensitive layer will be described.

[0900] <<Method for forming photosensitive layer>>

[0901] The photosensitive layer can be formed by preparing a photosensitive material containing components used for the formation of the photosensitive layer and a solvent, and performing coating and drying. The components can also be separately dissolved in a solvent in advance as a solution, and then the obtained solutions can be mixed at a prescribed ratio to prepare a composition. The composition prepared in the above manner is preferably filtered, for example, using a filter having a pore size of 0.2 to 30 μm.

[0902] The photosensitive layer can be formed by coating the photosensitive material on a temporary support or a cover film, and performing drying.

[0903] As the coating method, there is no particular limitation, and known methods such as slit coating, spin coating, curtain coating, and inkjet coating can be given.

[0904] Also, in the case where other layers described later are formed on the temporary support or the cover film, the photosensitive layer can be formed on the above other layers.

[0905] As the average thickness of the photosensitive layer, 0.5 to 20 μm is preferable. If the average thickness of the photosensitive layer is 20 μm or less, the resolution of the pattern is more excellent, and if the average thickness of the photosensitive layer is 0.5 μm or more, it is preferable from the viewpoint of the straightness of the pattern. As the average thickness of the photosensitive layer, 0.8 to 15 μm is more preferable, and 1.0 to 10 μm is further preferable. As a specific example of the average thickness of the photosensitive layer, 3.0 μm, 5.0 μm, and 8.0 μm can be given.

[0906] The photosensitive layer is preferably colorless. Specifically, in the CIE1976 (L * , a * , b * ) color space of the total reflection (incident angle 8°, light source: D-65 (2° field of view)), the L * value is preferably 10 to 90, the a * value is preferably -1.0 to 1.0, and the b * value is preferably -1.0 to 1.0.

[0907] 〔Transfer Film〕

[0908] The photosensitive material of the present application can be preferably applied to the photosensitive layer of a transfer film.

[0909] In addition, the structure of the transfer film is as described above. By forming the photosensitive layer in the above transfer film using the photosensitive material of the present application, a transfer film having excellent pattern formability can be obtained. In addition, the manufacturing method of the transfer film is also the same as the above method.

[0910] 〔Pattern Forming Method〕

[0911] As the pattern forming method of the present application, as long as the pattern forming method using the above-mentioned photosensitive material is used, there is no particular limitation, and it is preferable to sequentially include a step of forming a photosensitive layer on a substrate, a step of performing pattern exposure on the above-mentioned photosensitive layer, and a step of developing (alkaline development or organic solvent development) the exposed above-mentioned photosensitive layer. In addition, in the case of the above-mentioned development being organic solvent development, it is preferable to include a step of further exposing the obtained pattern.

[0912] As a specific embodiment of the pattern forming method of the present application, the pattern forming methods of Embodiment 1' and Embodiment 2' described below can be cited.

[0913] <<<Pattern forming method of Embodiment 1'>>

[0914] The pattern forming method of Embodiment 1' has Steps X1' to X3'. In addition, the following Step X2' corresponds to a step in which the content of the carboxyl group derived from the compound A in the photosensitive layer is reduced due to exposure. In the case where the developing solution of Step X3' is an organic solvent-based developing solution, Step X4' is further included after Step X3'.

[0915] Step X1': a step of forming a photosensitive layer on a substrate using a photosensitive material

[0916] Step X2': a step of performing pattern exposure on the photosensitive layer

[0917] Step X3': a step of developing the pattern-exposed photosensitive layer using a developing solution

[0918] Step X4': a step of further exposing the pattern formed by development after the developing step of Step X3'

[0919] In the case where an alkaline developing solution is used as the developing solution of Step X3, it is preferable that the above-mentioned photosensitive layer is the photosensitive layer of Embodiment X-1-a1 and Embodiment X-1-a2. In the case where an organic solvent-based developing solution is used as the developing solution of Step X3, it is preferable that the above-mentioned photosensitive layer is the photosensitive material of Embodiment X-1-a1.

[0920] The pattern forming method of Embodiment 1' is preferably applied to the photosensitive materials of Embodiment Y-1-a1 and Embodiment Y-1-a2 described above.

[0921] Regarding the specific order and preferable modes of the pattern forming method of Embodiment 1', the same as the pattern forming method of Embodiment 1 except for Step X1' is cited.

[0922] The process X1' can be performed by the method described in the above method for forming a photosensitive layer. Also, it can be provided that a transfer film containing a photosensitive layer formed from the photosensitive material of the present application is prepared in advance, and the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film is brought into contact with the substrate to adhere the above transfer film to the substrate. In addition, in the case where the process X1' is an adhering process using a transfer film, the specific order and preferred mode thereof are the same as those of the process X1 of the pattern forming method of Embodiment 1.

[0923] <<<Pattern forming method of Embodiment 2'>>>

[0924] The pattern forming method of Embodiment 2 has, in order, a process Y1', a process Y2P', and a process Y3', and further has a process Y2Q' (a process of further exposing the exposed photosensitive layer in the process Y2P') before the process Y3' or after the process Y3'.

[0925] Process Y1': a process of adhering a transfer film to a substrate by bringing the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film into contact with the above substrate

[0926] Process Y2P': a process of exposing a photosensitive layer

[0927] Process Y3': a process of developing a photosensitive layer using a developing solution

[0928] The pattern forming method of Embodiment 2' is preferably applied to a transfer film containing the photosensitive resin layer of the above Embodiment Y-1-a3.

[0929] In addition, the specific order and preferred mode of the pattern forming method of Embodiment 2' are the same as those of the pattern forming method of Embodiment 2 except for the process Y1'. That is, the process Y2P' is the same as the process Y2P, the process Y2Q' is the same as the process Y2Q, and the process Y3' is the same as the process Y3.

[0930] The process Y1' can be performed by the method described in the above method for forming a photosensitive layer. Also, it can be provided that a transfer film containing a photosensitive layer formed from the photosensitive material of the present application is prepared in advance, and the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film is brought into contact with the substrate to adhere the above transfer film to the substrate. In addition, in the case where the process Y1' is an adhering process using a transfer film, the specific order and preferred mode thereof are the same as those of the process Y1 of the pattern forming method of Embodiment 2.

[0931] <<Preferred mode>>

[0932] As the pattern forming method of Embodiment 2', it is preferable to have, in order, the step Y1', the step Y2A', the step Y3', and the step Y2B'. In addition, one of the step Y2A' and the step Y2B' corresponds to an exposure step for reducing the content of the carboxyl group derived from the compound A due to exposure, and the other corresponds to an exposure step for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator.

[0933] Step Y1': a step of forming a photosensitive layer on a substrate using a photosensitive material

[0934] Step Y2A': a step of performing pattern exposure on the photosensitive layer

[0935] Step Y3': a step of forming a patterned photosensitive layer by developing the photosensitive layer using an alkali developer

[0936] Step Y2B': a step of performing exposure on the patterned photosensitive layer

[0937] The step Y2A' is preferably an exposure step for causing the polymerization reaction of the polymerizable compound based on the photopolymerization initiator, and the step Y2B' is preferably an exposure step for reducing the content of the carboxyl group derived from the compound A due to exposure.

[0938] 〔Arbitrary steps that the pattern forming method of Embodiment 1' and Embodiment 2' can have〕

[0939] The pattern forming method of Embodiment 1' and Embodiment 2' can include an arbitrary step (other step) other than the above. As the arbitrary step, the preferable mode is the same as the arbitrary step that the pattern forming method of Embodiment 1 and Embodiment 2 can have.

[0940] 〔Pattern〕

[0941] The pattern formed by the pattern forming method of Embodiment 1' and Embodiment 2' has a reduced content of carboxyl group, and thus has reduced polarity, moisture permeability, and relative dielectric constant.

[0942] The physical properties and uses of the pattern formed by the pattern forming method of Embodiment 1' and Embodiment 2' are the same as the physical properties and uses of the pattern formed by the pattern forming method of Embodiment 1 and Embodiment 2, and the preferable mode is the same.

[0943] 〔Method for manufacturing circuit wiring〕

[0944] The manufacturing method of the circuit wiring of the present application is not particularly limited as long as the manufacturing method of the circuit wiring using the above-mentioned photosensitive material is used, and preferably sequentially includes a step of forming a photosensitive layer on a substrate having a conductive layer using the above-mentioned photosensitive material (photosensitive layer forming step), a step of performing pattern exposure on the photosensitive layer (first exposure step), a step of forming a patterned photosensitive layer by developing the exposed photosensitive layer using an alkali developer (alkali development step), a step of forming an etching resist film by exposing the patterned photosensitive layer (second exposure step), and a step of performing etching treatment on the above-mentioned conductive layer in a region where the etching resist film is not disposed (etching treatment step).

[0945] In the manufacturing method of the circuit wiring of the present application, the photosensitive layer forming step can be performed by the same sequence as the step X1 of the pattern forming method of the above-mentioned embodiment 1'. Also, the first exposure step, the alkali development step, and the second exposure step can each be performed by the same sequence as the steps Y1, Y2A, Y3, and Y2B of the pattern forming method of the above-mentioned embodiment 2. Also, the substrate having a conductive layer used in the manufacturing method of the circuit wiring of the present application is the same as the substrate having a conductive layer used in the above-mentioned step X1. Also, the manufacturing method of the circuit wiring of the present application can have other steps in addition to the above-mentioned steps. As the other steps, the same steps as any of the steps that the pattern forming method of the embodiment 1 and the embodiment 2 can have can be cited.

[0946] The manufacturing method of the circuit wiring of the present application also preferably has the above-mentioned photosensitive layer forming step, the above-mentioned first exposure step, the above-mentioned development step, the above-mentioned second exposure step, and the above-mentioned etching step as one group, and is repeated multiple times. The film used as the etching resist film can also be used as a protective film (permanent film) of the formed circuit wiring.

[0947] [Manufacturing method of touch panel]

[0948] The manufacturing method of the touch panel of the present application is not particularly limited as long as the manufacturing method of the touch panel using the above-mentioned photosensitive material is used, and preferably sequentially includes a step of forming a photosensitive layer on a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring) in a substrate having a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring) using the above-mentioned photosensitive material (photosensitive layer forming step), a step of performing pattern exposure on the photosensitive layer (first exposure step), a step of forming a patterned photosensitive layer by developing the exposed photosensitive layer using an alkali developer (alkali development step), and a step of forming a protective film or an insulating film of the conductive layer by exposing the patterned photosensitive layer (second exposure step).

[0949] The protective film formed by the second exposure process has a function as a film that protects the surface of the conductive layer. Also, the insulating film has a function as an interlayer insulating film between the conductive layers. In the case where the second exposure process is a process of forming the insulating film of the conductive layer, the manufacturing method of the touch panel of the present application preferably further has a process of forming a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring) on the insulating film formed by the second exposure process.

[0950] In the manufacturing method of the touch panel of the present application, the photosensitive layer forming process can be performed by the same sequence as the process X1 of the pattern forming method of Embodiment 1'. Also, the first exposure process, the alkali development process, and the second exposure process can each be performed by the same sequence as the processes Y1, Y2A, Y3, and Y2B of the pattern forming method of Embodiment 2. Also, the substrate having a conductive layer used in the manufacturing method of the touch panel of the present application is the same as the substrate having a conductive layer used in the above process X1. As other processes, the same processes as any of the processes that the pattern forming methods of Embodiments 1 and 2 can have can be cited.

[0951] As the manufacturing method of the touch panel of the present application, a structure other than the above-described modes can be referred to a publicly known manufacturing method of a touch panel.

[0952] The touch panel manufactured by the manufacturing method of the touch panel of the present application preferably has a transparent substrate, an electrode, and a protective layer (protective film).

[0953] As the detection method in the above-described touch panel, any of publicly known methods such as a resistive film method, an electrostatic capacity method, an ultrasonic wave method, an electromagnetic induction method, and an optical method can be used. Among them, the electrostatic capacity method is preferable.

[0954] As the touch panel type, a so-called in-cell type (for example, the structures described in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Publication No. 2012-517051), a so-called on-cell type (for example, the structure described in FIG. 19 of Japanese Patent Application Publication No. 2013-168125, the structures described in FIGS. 5 and 6 of Japanese Patent Application Publication No. 2012-89102), an OGS (One Glass Solution) type, a TOL (Touch-on-Lens) type (for example, the structure described in FIG. 2 of Japanese Patent Application Publication No. 2013-54727), other structures (for example, the structure described in FIG. 6 of Japanese Patent Application Publication No. 2013-164871), and various on-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, G1F, and the like) can be cited. Figure 1 ​

[0955] Examples

[0956] Hereinafter, the present application will be further explained by citing examples. The materials, amounts, ratios, processing contents, processing sequences, and the like shown in the following examples can be appropriately changed as long as the purpose of the present application is not deviated. Therefore, the scope of the present application is not limited to the specific examples shown below. In addition, "parts" and "%" are based on mass unless otherwise specified.

[0957] In addition, in the following examples, the weight average molecular weight of the resin is the weight average molecular weight calculated based on polystyrene by gel permeation chromatography (GPC).

[0958] In the following examples, H03-L31 manufactured by EYE GRAPHICS CO., LTD. was used as a high-pressure mercury lamp unless otherwise specified. The above high-pressure mercury lamp has a wavelength of 365 nm as a main wavelength and has strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm. In addition, USH-2004MB manufactured by USHIO INC. was used as an ultrahigh-pressure mercury lamp unless otherwise specified. The above ultrahigh-pressure mercury lamp has strong line spectra at 313 nm, 365 nm, 405 nm, and 436 nm.

[0959] [Example 1]

[0960] [Preparation of photosensitive materials]

[0961] As the compound A having a carboxyl group, a styrene / acrylic acid copolymer (acid value: 200, Mw: 8500, manufactured by TOAGOSEI CO., LTD., ARUFON UC3910 (trade name)) and the compound β shown in Table 2 were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the blending amount described in Table 2 shown in the latter part, and the solid content concentration of the finally obtained photosensitive material was made to be 25 mass%, thereby obtaining a mixed solution. In the above mixed solution, MEGAFACE F551 (fluorine-containing nonionic surfactant manufactured by DIC Corporation) was added as a surfactant so as to be a concentration of 100 mass ppm with respect to the total solid content of the photosensitive material, thereby preparing the photosensitive material of each example or comparative example.

[0962] In addition, the blending amount (mass parts) shown in the table is the solid content amount of each component.

[0963] [Physical property evaluation of compound β]

[0964] (Measurement of pKa of compound β in the ground state)

[0965] The pKa of the compound β in the ground state was measured using an automatic titrator manufactured by HIRANUMA Co., Ltd. and by the following method. In addition, in the case where the compound β is a nitrogen-containing aromatic compound, the pKa of the compound β in the ground state indicates the pKa of the conjugate acid of the compound β.

[0966] 0.1 g of the compound β was dissolved in 20 ml of methanol, and 20 ml of ultrapure water was added thereto. This was titrated using a 0.1 N-HCL aqueous solution, and the pH at the point of time at which the titration amount required until the equivalent point was halved was set as the pKa (pKa of the compound β in the ground state).

[0967] (Measurement and evaluation of ε365 and ε365 / ε313)

[0968] The molar absorption coefficient of the compound β at 365 nm ((cm'mol / L -1 , "ε365") and the molar absorption coefficient at 313 nm ((cm'mol / L -1 , "ε313") were found, and the value of ε365 divided by ε313 (ε365 / ε313) was found.

[0969] The ε365 and ε313 of the compound β are the molar absorption coefficients found by dissolving the compound β in acetonitrile. In the case where the compound β is not dissolved in acetonitrile, the solvent in which the compound β is dissolved can be appropriately changed.

[0970] <Evaluation of the photosensitive material>

[0971] (Production of the photosensitive layer)

[0972] The photosensitive material of each of the examples and comparative examples was spin-coated on a silicon wafer, and then the obtained coated film was dried at 80°C using a hot plate, to obtain a photosensitive layer having a film thickness of 5 μm.

[0973] The obtained photosensitive layer was evaluated in the following manner.

[0974] (Evaluation of carboxyl consumption rate (IR measurement))

[0975] The obtained photosensitive layer was subjected to full-face exposure using a high-pressure mercury lamp. The cumulative exposure amount measured by an illuminance meter at 365 nm was 1000 mJ / cm 2 . In addition, the light emitted from the above high-pressure mercury lamp had a wavelength of 365 nm as the main wavelength, and had strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0976] The IR spectrum of the photosensitive layer was measured before and after exposure, and the peak value of the C=0 stretch of the carboxyl group (1710 cm-1 The carboxyl consumption rate (mol%) was calculated from the reduction rate of the peak value of the carboxyl group.

[0977] The higher the carboxyl consumption rate, the more the decarboxylation reaction proceeds.

[0978] The results are shown in Table 2 (see the column of "Carboxyl consumption rate (mol%) [IR measurement]"). Table 2

[0979] (Carboxyl consumption rate evaluation (ashing measurement))

[0980] The carboxyl consumption rate was measured by the following procedure.

[0981] • Measurement of the amount of carboxyl group in the photosensitive layer after exposure (measurement of the amount of carboxyl group after exposure)

[0982] The photosensitive layer obtained in the above section was exposed by the following exposure conditions.

[0983] "Exposure conditions"

[0984] The obtained photosensitive layer was subjected to full-face exposure using a high-pressure mercury lamp. The cumulative exposure amount measured by an illuminometer at 365 nm was 1000 mJ / cm 2 In addition, the light emitted from the above high-pressure mercury lamp has a wavelength of 365 nm as the main wavelength, and has strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0985] Next, the photosensitive layer after exposure was scraped off by about 20 mg, and after freezing and pulverizing, NMP (N-methyl-2-pyrrolidone) 150 μL was added, and then stirred in a lithium carbonate (Li2CO3) aqueous solution (1.2 g / 100 mL. After dissolving lithium carbonate in ultrapure water, it was filtered to obtain) for 6 days.

[0986] After the stirring was completed, the particles were settled by ultracentrifugation (140,000 rpm x 30 min), and after the supernatant was replaced with ultrapure water (the replacement was repeated 5 times), the obtained precipitate was dried and solidified to be an analysis sample (the sample was prepared in n = 2). The analysis sample was analyzed by ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.).

[0987] In addition, the above ICP-OES measurement was performed by the following procedure.

[0988] About 1.5 mg to 2 mg (n = 3) of the above analysis sample was weighed, and after 5 mL of a 60% HNO3 aqueous solution was added, MW iron fluorine dragon ashing (microwave sample decomposition device Ultra WAVE max: 260°C) was performed.

[0989] After ashing, ultrapure water was added to 50 mL, and the amount of Li was quantified using ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.) and an absolute calibration curve method.

[0990] • Measurement of the amount of carboxyl groups in the photosensitive material before exposure (measurement of the amount of carboxyl groups before exposure)

[0991] The amount of carboxyl groups in the photosensitive material of each of the examples and comparative examples used in forming the above-described photosensitive layer was measured in the following order.

[0992] The photosensitive material 1 g was dissolved in tetrahydrofuran 63 ml, and ultrapure water 12 ml was added thereto. Subsequently, an automatic titration device manufactured by HIRANUMA Co., Ltd. was used, and the obtained solution was titrated with a 0.1 N NaOH aqueous solution. The amount of carboxyl groups obtained by titration was converted into a solid content concentration, and the amount of carboxyl groups in the photosensitive material was calculated.

[0993] • Calculation of the decarboxylation rate

[0994] Based on the results of the measurement of the amount of carboxyl groups before and after exposure, the decarboxylation rate was calculated by the following formula.

[0995] Decarboxylation rate (%) : {(amount of carboxyl groups before exposure - amount of carboxyl groups after exposure) / amount of carboxyl groups before exposure} x 100 (%)

[0996] Based on the obtained values, evaluation was performed by the following evaluation criteria.

[0997] In the case of the above-described method, there is a detection limit. When the carboxyl content is 1.05 mmol / g or less, it is possible to replace 90% or more of Li. In regions other than this, a calibration curve was prepared using a crosslinked polymer of which the acid value was known, and calculation was performed.

[0998] • Evaluation criteria

[0999] A decarboxylation rate of 71 mole% or more

[1000] B decarboxylation rate of 50 mole% or more and less than 71 mole%

[1001] C decarboxylation rate of 31 mole% or more and less than 50 mole%

[1002] D decarboxylation rate of 5 mole% or more and less than 31 mole%

[1003] E decarboxylation rate of less than 5 mole%

[1004] The results are shown in Table 2 (refer to the column of "Carboxyl consumption rate (ashing measurement)".).

[1005] (Patterning Evaluation 1)

[1006] The obtained photosensitive layer was exposed using a high-pressure mercury lamp through any one of the following (1) to (3) masks. The cumulative exposure amount measured by an illuminometer at 365 nm was 1000 mJ / cm 2 .

[1007] (1) Mask with a line size = 25 μm and line : space = 1 : 1

[1008] (2) Mask with a line size = 50 μm and line : space = 1 : 1

[1009] (3) Mask with a line size = 250 μm and line : space = 1 : 1

[1010] After the exposed photosensitive layer was dip-developed with a 1 mass% aqueous sodium carbonate solution for 30 seconds, it was rinsed with pure water for 20 seconds and dried to obtain a pattern (line-and-space pattern).

[1011] The line-and-space pattern with a line width and a space width of 25 μm, 50 μm, or 250 μm, which was produced in this way, was observed and evaluated in the following manner.

[1012] A: The line-and-space pattern was resolved (the photosensitive layer of the space portion was removed), and the film of the pattern was not reduced.

[1013] B: The line-and-space pattern was resolved, but the film of the pattern was slightly reduced

[1014] C: The line-and-space pattern was resolved, but the film of the pattern was greatly reduced

[1015] D: The line-and-space pattern was not resolved (the photosensitive layer of the space portion remained or the pattern was completely dissolved and disappeared)

[1016] (Relative Dielectric Constant Evaluation 1)

[1017] A photosensitive layer with a thickness of 8 μm was produced by spin-coating a photosensitive material on an aluminum substrate with a thickness of 0.1 mm and then drying the obtained coating film at 80°C using a hot plate.

[1018] The obtained photosensitive layer was subjected to whole-surface exposure using a high-pressure mercury lamp. The cumulative exposure amount measured by an illuminometer at 365 nm was 1000 mJ / cm 2 .

[1019] As for the exposed photosensitive layer, using LCR meter 4284A and Dielectric test fixture 16451B manufactured by Agilent Technologies, Inc., the relative dielectric constant at 1 kHz was measured in an environment of 23°C, 50% RH.

[1020] The relative dielectric constant of the exposed photosensitive layer formed using the photosensitive material of Comparative Example 1A was set to 100%, and in comparison therewith, the reduction rate of the relative dielectric constant of the exposed photosensitive layer formed using the photosensitive material of each of the examples was calculated, and evaluated in accordance with the following criteria.

[1021] The greater the value of the reduction rate, the lower the relative dielectric constant compared to Comparative Example 1A, and the more effective as an insulating film.

[1022] A: reduction rate of 15% or more

[1023] B: reduction rate of 10% or more and less than 15%

[1024] C: reduction rate of 5% or more and less than 10%

[1025] D: reduction rate of less than 5%

[1026] (Pre- and post-exposure relative dielectric constant evaluation 1)

[1027] The exposed photosensitive layer was produced in the same manner as in the above (relative dielectric constant evaluation 1). At this time, the relative dielectric constant of each photosensitive layer was measured before and after exposure in the same manner as in the above (relative dielectric constant evaluation 1).

[1028] The relative dielectric constant of each photosensitive layer before exposure was set to 100%, and the amount by which the dielectric constant of each photosensitive layer was reduced due to exposure was calculated, and evaluated in accordance with the following criteria.

[1029] It was possible to judge that the greater the reduction rate, the more the reduction in the dielectric constant based on the decarboxylation reaction caused by exposure was performed.

[1030] A: reduction rate of 15% or more

[1031] B: reduction rate of 10% or more and less than 15%

[1032] C: reduction rate of 5% or more and less than 10%

[1033] D: reduction rate of less than 5%

[1034] <Evaluation of transfer film>

[1035] (Production of transfer film)

[1036] On a polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16KS40 (16QS62)) having a thickness of 16 μm (temporary support), the photosensitive material of each example or comparative example was coated using a slit nozzle so as to have a dry thickness of 5 μm, and dried at 100°C for 2 minutes to form a photosensitive layer.

[1037] On the obtained photosensitive layer, a polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16KS40 (16QS62)) having a thickness of 16 μm (cover film) was pressure-bonded to produce a transfer film of Example 1.

[1038] (Carboxyl consumption rate evaluation (IR measurement))

[1039] The photosensitive layer of the transfer film was transferred onto the surface of a silicon wafer by peeling the cover film from the above-produced transfer film and laminating it to the silicon wafer. The lamination conditions were set to be a temperature of the substrate for a touch panel of 40°C, a rubber roll temperature (i.e., lamination temperature) of 110°C, a line pressure of 3 N / cm, and a conveyance speed of 2 m / minute.

[1040] The photosensitive layer after transfer was exposed by the following exposure conditions.

[1041] "Exposure conditions"

[1042] After peeling the temporary support, the photosensitive layer was subjected to full-face exposure using a high-pressure mercury lamp. The cumulative exposure amount measured by a 365 nm luxmeter was 1000 mJ / cm 2 . In addition, the light emitted from the above high-pressure mercury lamp had a wavelength of 365 nm as the main wavelength, and had strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[1043] The IR spectrum of the photosensitive layer was measured before and after exposure, and the carboxyl consumption rate (mole %) was calculated from the reduction rate of the peak value of the C=0 stretching of the carboxyl group (1710 cm -1 ).

[1044] The higher the carboxyl consumption rate, the more the decarboxylation reaction proceeded.

[1045] The results are shown in Table 1 (refer to the column of "Carboxyl consumption rate (mole %) (IR measurement)".

[1046] (Carboxyl consumption rate evaluation (ashing measurement))

[1047] The photosensitive layer of the transfer film was peeled off from the glass substrate, and laminated to a glass (Eagle XG manufactured by Corning Incorporated Co., Ltd.) 10 x 10 cm 2 The photosensitive layer of the transfer film was peeled off from the glass substrate, and laminated to a glass (Eagle XG manufactured by Corning Incorporated Co., Ltd.) 10 x 10 cm

[1048] • Measurement of the amount of carboxyl groups in the photosensitive layer after exposure (measurement of the amount of carboxyl groups after exposure)

[1049] The photosensitive layer after transfer was exposed by the following exposure conditions.

[1050] Exposure conditions

[1051] After peeling off the temporary support, the photosensitive layer was subjected to full-face exposure using a high-pressure mercury lamp. The cumulative exposure amount measured by a 365 nm luxmeter was 1000 mJ / cm 2 In addition, the light emitted from the above high-pressure mercury lamp has a wavelength of 365 nm as the main wavelength, and has strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[1052] Next, about 20 mg of the photosensitive layer after exposure was scraped off, and after freezing and pulverizing it, 150 μL of NMP (N-methyl-2-pyrrolidone) was added, and then it was stirred in an aqueous lithium carbonate (Li2CO3) solution (1.2 g / 100 mL. After dissolving lithium carbonate in ultrapure water, it was filtered to obtain.) for 6 days.

[1053] After the stirring was completed, the particles were settled by ultracentrifugation (140,000 rpm x 30 min), and after replacing the supernatant with ultrapure water (repeated 5 times), the obtained precipitate was dried and solidified as an analysis sample (samples were prepared with n = 2). The analysis sample was analyzed by ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.).

[1054] In addition, the above ICP-OES measurement was performed by the following sequence.

[1055] About 1.5 mg to 2 mg of the above analysis sample (n = 3) was weighed, and after adding 5 mL of a 60% aqueous HNO3 solution, MW iron fluorine dragon ashing (microwave sample decomposition device Ultra WAVE max: 260°C) was performed.

[1056] After ashing, ultrapure water was added to 50 mL, and the amount of Li was quantified using ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.) and an absolute calibration curve method.

[1057] • Measurement of the amount of carboxyl groups in the photosensitive layer before exposure (measurement of the amount of carboxyl groups before exposure)

[1058] The amount of carboxyl groups in the photosensitive layer of each of the examples and comparative examples was measured in the following order.

[1059] One gram of the photosensitive layer before exposure was scraped off and dissolved in 63 ml of tetrahydrofuran, and 12 ml of ultrapure water was added thereto. Next, an automatic titration device manufactured by HIRANUMA Co., Ltd. was used, and the obtained solution was titrated with a 0.1 N NaOH aqueous solution. The amount of carboxyl groups obtained by titration was converted into a solid content concentration, and the amount of carboxyl groups in the photosensitive layer was calculated.

[1060] • Calculation of the decarboxylation rate

[1061] Based on the results of the measurement of the amount of carboxyl groups before and after exposure described above, the decarboxylation rate was calculated by the following formula.

[1062] Decarboxylation rate (%) : {(amount of carboxyl groups before exposure - amount of carboxyl groups after exposure) / amount of carboxyl groups before exposure} x 100 (%)

[1063] Based on the obtained values, evaluation was performed by the following evaluation criteria.

[1064] In the case of the above method, there is a detection limit. When the carboxyl group content is 1.05 mmol / g or less, 90% or more of Li can be replaced. In other regions, a calibration curve was prepared using a crosslinked polymer of which the acid value was known, and calculation was performed.

[1065] • Evaluation criteria

[1066] A decarboxylation rate of 71 mol% or more

[1067] B decarboxylation rate of 50 mol% or more and less than 71 mol%

[1068] C decarboxylation rate of 31 mol% or more and less than 50 mol%

[1069] D decarboxylation rate of 5 mol% or more and less than 31 mol%

[1070] E decarboxylation rate of less than 5 mol%

[1071] The results are shown in Table 2 (refer to the column of "Carboxyl group consumption rate [ashing measurement]").

[1072] The results are shown in Table 2 (refer to the column of "Carboxyl group consumption rate [ashing measurement]").

[1072] (365 nm transmittance)

[1073] The 365 nm transmittance of the photosensitive layer was measured using a UV- visible spectrophotometer UV1800 manufactured by SHIMADZU CORPORATION, and evaluation was performed based on the following evaluation criteria.

[1074] A transmittance of 90% or more

[1075] B transmittance of 65% or more and less than 90%

[1076] C transmittance of 20% or more and less than 65%

[1077] D transmittance of less than 20%

[1078] (365 nm transmittance / 313 nm transmittance)

[1079] The 365 nm transmittance and the 313 nm transmittance of the photosensitive layer were measured using a UV-visible spectrophotometer UV1800 manufactured by SHIMADZU CORPORATION, and the value calculated by dividing the 365 nm transmittance by the 313 nm transmittance was evaluated as follows.

[1080] A 1.5 or more

[1081] B 1 or more and less than 1.5

[1082] C less than 1

[1083] (Lamination suitability evaluation)

[1084] A laminate having a "temporary support / photosensitive layer / copper foil / substrate (PET film)" stacked structure was obtained by peeling the cover film from the transfer film produced above and laminating the photosensitive layer of the transfer film to a PET film (substrate for touch panel) on which a copper foil was laminated (GEOMATEC Co., Ltd.). The conditions for lamination were set to a temperature of the substrate for touch panel of 40°C, a rubber roll temperature (i.e., lamination temperature) of 110°C, a line pressure of 3 N / cm, and a conveyance speed of 2 m / minute. In addition, the copper foil was a film that assumes wiring for a touch panel.

[1085] The photosensitive layer was visually evaluated for the area that was bubble-free and adhered to the copper foil, the proportion (%) of the adhered area was calculated based on the following formula, and evaluation was performed according to the following criteria. It can be considered that the greater the proportion (%) of the adhered area, the more excellent the lamination suitability.

[1086] Proportion (%) of adhered area = area to which the photosensitive layer adhered ÷ area of the laminated transfer film x 100

[1087] A: The ratio (%) of the area of adhesion is 95% or more

[1088] B: The ratio (%) of the area of adhesion is less than 95%

[1089] (Patterning Evaluation 2)

[1090] Next, the temporary support was peeled from the above-described laminate, and the exposed photosensitive layer was exposed using a high-pressure mercury lamp. At the time of exposure, exposure was performed through any of the following (1) to (3). The cumulative exposure amount measured with a 365 nm lux meter was 1000 mJ / cm 2 .

[1091] (1) Mask with a line size = 25 μm and line: space = 1 : 1

[1092] (2) Mask with a line size = 50 μm and line: space = 1 : 1

[1093] (3) Mask with a line size = 250 μm and line: space = 1 : 1

[1094] Next, the exposed photosensitive layer was developed for 40 seconds using a 1 mass% sodium carbonate aqueous solution (liquid temperature: 32°C) as a developing solution. After development, the pattern (line and space pattern) was obtained by rinsing with pure water for 20 seconds and further blowing air to remove moisture.

[1095] The line and space patterns with a line width and space width of 25 μm, 50 μm, or 250 μm, which were produced in this way, were evaluated in the same manner as in the above-described (Patterning Evaluation 1).

[1096] (Relative Dielectric Constant Evaluation 2)

[1097] The cover film was peeled from the above-described produced transfer film, and was laminated onto an aluminum substrate with a thickness of 0.1 mm under the same conditions as in the above-described (Laminating Suitability Evaluation), to obtain a laminate having a "temporary support / photosensitive layer / aluminum substrate" laminate structure. Next, the temporary support was peeled from the laminate. The exposed photosensitive layer was subjected to full-face exposure using a high-pressure mercury lamp. The cumulative exposure amount measured with a 365 nm lux meter was 1000 mJ / cm 2 .

[1098] With respect to the photosensitive layer after exposure, an LCR meter 4284A and a Dielectric test fixture 16451B manufactured by Agilent Technologies, Inc. were used, and the relative dielectric constant at 1 kHz was measured in an environment of 23°C, 50% RH.

[1099] The relative dielectric constant of the photosensitive layer after exposure using the photosensitive material of Comparative Example 1A was set to 100%, and the reduction rate of the relative dielectric constant of the photosensitive layer after exposure using the photosensitive material of each of the examples was calculated, and evaluated according to the following criteria.

[1100] The greater the value of the reduction rate, the lower the relative dielectric constant compared to Comparative Example 1A, and the more effective as an insulating film.

[1101] A: reduction rate of 15% or more

[1102] B: reduction rate of 10% or more and less than 15%

[1103] C: reduction rate of 5% or more and less than 10%

[1104] D: reduction rate of less than 5%

[1105] (Evaluation 2 of the relative dielectric constant before and after exposure)

[1106] The photosensitive layer after exposure was produced in the same manner as in the above (Evaluation 2 of the relative dielectric constant). At this time, the relative dielectric constant of each photosensitive layer was measured in the same manner as in the above (Evaluation 2 of the relative dielectric constant) before and after exposure.

[1107] The relative dielectric constant of each photosensitive layer before exposure was set to 100%, and the amount by which the dielectric constant of each photosensitive layer was reduced due to exposure was calculated, and evaluated according to the following criteria.

[1108] It was possible to judge that the greater the reduction rate, the more the reduction in the dielectric constant based on the decarboxylation reaction caused by exposure.

[1109] A: reduction rate of 15% or more

[1110] B: reduction rate of 10% or more and less than 15%

[1111] C: reduction rate of 5% or more and less than 10%

[1112] D: reduction rate of less than 5%

[1113] (Evaluation of the moisture permeability (WVTR))

[1114] Preparation of a sample for moisture permeability measurement

[1115] On a polyethylene terephthalate (PET) film (temporary support) having a thickness of 75 μm, each of the photosensitive materials of the examples or comparative examples was coated using a slit-shaped nozzle, and then dried to form a photosensitive layer having a thickness of 8 μm, and a transfer film for sample preparation was obtained.

[1116] Next, a sample was prepared by laminating the transfer film to a PTFE (polytetrafluoroethylene resin) Membrane filter FP-100-100 manufactured by Sumitomo Electric Industries, Ltd. to form a laminate A having a layer structure of "temporary support / photoreceptive layer having a thickness of 8 μm / membrane filter". The laminating conditions were set to a membrane filter temperature of 40°C, a laminating roll temperature of 110°C, a line pressure of 3 N / cm, and a conveyance speed of 2 m / min.

[1117] Next, the temporary support was peeled from the laminate A.

[1118] A sample was further prepared by laminating the transfer film in the same manner to the photoreceptive layer of the laminate A, and the temporary support was peeled from the obtained laminate 4 times to form a laminate B having a layer structure of "photoreceptive layer having a total film thickness of 40 μm / membrane filter".

[1119] The photoreceptive layer of the obtained laminate B was subjected to full-face exposure using a high-pressure mercury lamp. The cumulative exposure amount measured with a 365 nm lux meter was 1000 mJ / cm 2 .

[1120] In this manner, a moisture permeability test sample having a layer structure of "exposed photoreceptive layer having a total film thickness of 40 μm / membrane filter" was obtained.

[1121] Measurement of moisture permeability (WVTR)

[1122] Using the moisture permeability test sample, a measurement of moisture permeability based on the cup method was performed in accordance with JIS-Z-0208 (1976). Details will be described below.

[1123] First, a circular sample having a diameter of 70 mm was cut out from the moisture permeability test sample. Next, 20 g of dried calcium chloride was put in a measuring cup, and then covered with the above circular sample to prepare a capped measuring cup.

[1124] The capped measuring cup was left in a constant temperature and humidity chamber at 65°C and 90% RH for 24 hours. From the change in the mass of the capped measuring cup before and after the above leaving, the moisture permeability (WVTR) of the circular sample was calculated (unit: g / (m 2 day).

[1125] The above measurement was performed 3 times, and the average of the WVTRs in the 3 measurements was calculated.

[1126] The moisture permeability was evaluated based on the reduction rate (%) of the WVTR of each of the examples when the WVTR of Comparative Example 1A was taken as 100%. In addition, the greater the value of the reduction rate, the lower the moisture permeability compared to Comparative Example 1A, and it is preferable as a protective film. In the following evaluation criteria, A or B is preferable, and A is more preferable.

[1127] In addition, in the above-described measurement, the WVTR of the circular test sample having the layered structure of the "exposed photosensitive layer / film filter with a total film thickness of 40 μm" was measured in the above-described manner. However, since the WVTR of the film filter is extremely high compared to the WVTR of the exposed photosensitive layer, in the above-described measurement, it substantially means that the WVTR of the exposed photosensitive layer itself was measured.

[1128] A: The reduction rate of the WVTR is 20% or more

[1129] B: The reduction rate of the WVTR is more than 10% and less than 20%

[1130] C: The reduction rate of the WVTR is more than 7.5% and less than 10%

[1131] D: The reduction rate of the WVTR is more than 5% and less than 7.5%

[1132] E: The reduction rate of the WVTR is less than 5%

[1133] <Results>

[1134] The kind and the amount of the compound A and the compound β in the photosensitive material of each of the examples and the comparative examples in Example 1, and the results of the test are shown in the following Table 2.

[1135] The "amount" column in the table indicates the amount (mass parts) of the "compound A having an acid group (compound A)" and the "compound β" added to the photosensitive material. In addition, the above-described amount (mass parts) is the amount of the "compound A having an acid group" and the "compound β" itself (solid content) added to the photosensitive material.

[1136] The "molar ratio of compound A to carboxyl group (mole %)" column in the table indicates the proportion (mole %) of the total number of the structures (specific structure SI) that the compound β in the photosensitive material has and that can accept an electron from the acid group of the compound A in a photoexcited state, with respect to the total number of the carboxyl groups that the compound A has.

[1137] The "ε365" column indicates the molar absorption coefficient of the compound β with respect to light of a wavelength of 365 nm in acetonitrile ((cm·mol / L) -1 ).

[1138] The column of "ε365 / ε313" represents a value obtained by dividing the molar absorption coefficient ((cm.mol / L) of compound β with respect to light of wavelength 365 nm) by the molar absorption coefficient ((cm.mol / L) of compound β with respect to light of wavelength 313 nm). In addition, the molar absorption coefficients are all values in acetonitrile. -1 -1 The column of "365 nm transmittance" represents the transmittance of the photosensitive layer with respect to light of wavelength 365 nm.

[1139] The column of "365 nm transmittance" represents the transmittance of the photosensitive layer with respect to light of wavelength 365 nm.

[1140] The column of "365 nm transmittance / 313 nm transmittance" represents a value obtained by dividing the transmittance of the photosensitive layer with respect to light of wavelength 365 nm by the transmittance of the photosensitive layer with respect to light of wavelength 313 nm.

[1141] [Table 2]

[1142]

[1143] [Table 3]

[1144]

[1145] It was confirmed from the results shown in the above tables that the problems of the present application can be solved by using the transfer film of the present application.

[1146] Further, it was confirmed that in the photosensitive layer in the transfer film of the present application, when the total number of the specific structure S1 possessed by compound β is 3 mol% or more (preferably 5 mol% or more, more preferably 10 mol% or more) with respect to the total number of the acid groups possessed by compound A, the pattern formation is more excellent, and the relative dielectric constant of the formed pattern is lower (comparison of the results of Reference Examples 1-4, 1-8, 1-9, 1-10, 1-11, etc.).

[1147] Further, it was confirmed that in the photosensitive layer in the transfer film of the present application, when compound β is a compound in which the molar absorption coefficient with respect to light of wavelength 365 nm is 1 x 10 3 -1 (cm.mol / L) 2 -1 (cm.mol / L) -1 Further, it was confirmed that in the photosensitive layer in the transfer film of the present application, when compound β is a compound in which the molar absorption coefficient with respect to light of wavelength 365 nm is 1 x 10

[1148] Further, it was confirmed that in the photosensitive layer in the transfer film of the present application, when compound β is a compound in which the molar absorption coefficient with respect to light of wavelength 365 nm is 1 x 10 -1 ​) Molar absorption coefficient ((cm.mol / L) with respect to light of wavelength 313 nm -1 ) In the case of a compound having a ratio of 3 or less, the pattern formation is more excellent (see the comparison of the results of Reference Examples 1-1 to 1-7, etc.).

[1149] [Example 2]

[1150] Preparation of photosensitive material and evaluation thereof

[1151] The materials described in the following Table 3 were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the blending amounts described in Table 3, and the solid content concentration of the finally obtained photosensitive material was made to be 25 mass%, whereby the photosensitive materials were prepared.

[1152] With respect to the obtained photosensitive materials of Example 2 (the photosensitive materials of Examples 2-1 to 2-8), the results of the carboxyl consumption rate (mole%) were confirmed by IR measurement as in Example 1, and it was found that the carboxyl consumption rate was 20 mole% or more in each of them.

[1153] Also, with respect to the photosensitive materials of each of the examples or comparative examples of Example 2 obtained, the carboxyl consumption rate, the pattern formation of the photosensitive material, the relative dielectric constant and the change in the relative dielectric constant before and after exposure, and the lamination suitability, the pattern formation, the relative dielectric constant, the change in the relative dielectric constant before and after exposure, and the moisture permeability of the transfer film were evaluated as in Example 1. Also, as in Example 1, with respect to the photosensitive layer in the transfer film, the carboxyl consumption rate, the transmittance with respect to light of 365 nm, and the ratio of the transmittance with respect to light of 365 nm to the transmittance with respect to light of 313 nm were also evaluated. Also, as in Example 1, the physical properties of ε365 / ε313 of the compound β included in the photosensitive material and the photosensitive layer were evaluated.

[1154] Among them, the reference for the evaluation of the relative dielectric constant of the photosensitive material and the reduction rate in the evaluation of the relative dielectric constant and the moisture permeability of the transfer film was the relative dielectric constant or the moisture permeability of Comparative Example 2A.

[1155] The results of the blending and the test of the solid components of the photosensitive materials of each of the examples or comparative examples of Example 2 are shown in the following Table 3.

[1156] In the table, the value described in the column of "solid content blend" indicates the content (mass parts) of each solid component included in the photosensitive material of each example or comparative example. In addition, the value in parentheses in the compound β indicates the proportion (mole %) of the total number of the structures (specific structure S1) possessed by the compound β, which are capable of accepting an electron from the structure (specific structure S1) possessed by the compound A, with respect to the total number of the carboxyl groups possessed by the compound A (compound A), in the photosensitive material.

[1157] In addition, the value (ε365) in parentheses described in the name of the component of the compound β indicates the molar absorption coefficient ((cm·mol / L) -1 ) of the compound β with respect to light of wavelength 365 nm in acetonitrile.

[1158] In addition, the value (pKa in the ground state) in parentheses described in the name of the component of the compound β indicates the pKa in the ground state of the compound β. The measurement method is as described above.

[1159] In addition, the column of "ε365 / ε313" in the evaluation of the photosensitive material and the evaluation of the transfer film indicates the value obtained by dividing the molar absorption coefficient ((cm·mol / L) -1 ) of the compound β with respect to light of wavelength 365 nm by the molar absorption coefficient ((cm·mol / L) -1 ) of the compound β with respect to light of wavelength 313 nm. In addition, the molar absorption coefficients are each a value in acetonitrile.

[1160] In addition, the column of "365 nm transmittance" in the evaluation of the transfer film indicates the transmittance of the photosensitive layer with respect to light of wavelength 365 nm.

[1161] In addition, the column of "365 nm transmittance / 313 nm transmittance" in the evaluation of the transfer film indicates the value obtained by dividing the transmittance of the photosensitive layer with respect to light of wavelength 365 nm by the transmittance of the photosensitive layer with respect to light of wavelength 313 nm.

[1162] [Table 4]

[1163]

[1164] UC3910: ARUFON UC3910 (manufactured by TOAGOSEI CO., LTD.)

[1165] DPHA: dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1166] A-NOD-N: 1,9-nonanediol diacrylate (manufactured by Shin Nakamura Chemical Industry Co., LTD. as A-NOD-N)

[1167] DTMPT: ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd. as KAYARAD T-1420(T))

[1168] A-DCP: dicyclopentanediol dimethanol diacrylate (manufactured by Shin Nakamura Chemical Industry Co., LTD. as A-DCP)

[1169] TMPT: trimethylolpropane triacrylate (manufactured by Shin Nakamura Chemical Industry Co., LTD. as A-TMPT)

[1170] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[1171] It was confirmed from the results of the above table that the problem of the present application could be solved by the transfer film of the present application even in the case where the photosensitive material contains a polymerizable compound.

[1172] Further, it was confirmed that the conditions in which the effect of the present application was more excellent were the same as the tendency confirmed with respect to the Example 1 system.

[1173] [Example 3 system]

[1174] [Preparation of photosensitive material and evaluation thereof]

[1175] The materials described in the 4th table shown in the latter part were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the blending amount described in the 4th table, and the solid content concentration of the photosensitive material finally obtained was made to be 25 mass%, whereby the photosensitive material was prepared.

[1176] In addition, in the preparation of the photosensitive material, as the "synthesis method of resin A" and "synthesis method of resin B", a solution of resin A or a solution of resin B obtained by the method described later was used, and resin A or resin B was introduced into the photosensitive material.

[1177] As to the photosensitive materials of the obtained Example 3 series (the photosensitive materials of Examples 3-1 to 3-12), the results of the carboxyl group consumption rate (mole%) were confirmed by IR measurement in the same manner as shown in the carboxyl group consumption rate evaluation (IR measurement) in the Example 1 series, and it was found that the carboxyl group consumption rate was 20 mole% or more in each of the photosensitive materials.

[1178] Further, the following test was also performed: before exposure of 1000 mJ / cm2using the high-pressure mercury lamp in the carboxyl group consumption rate evaluation (IR measurement) shown in the Example 1 series, exposure of 100 mJ / cm2using an ultrahigh-pressure mercury lamp was performed, and then exposure of 1000 mJ / cm2using the high-pressure mercury lamp was performed. Even in the case where exposure of 100 mJ / cm2was performed in this manner in advance, when any of the photosensitive materials of the Example 3 series (the photosensitive materials of Examples 3-1 to 3-12) was used, the carboxyl group consumption rate before and after exposure of 1000 mJ / cm2became 20 mole% or more. 2 2 2 2 2

[1179] Further, as to the photosensitive materials of each of the examples or comparative examples of the Example 3 series, the carboxyl group consumption rate, the relative dielectric constant of the photosensitive material and the change in the relative dielectric constant before and after exposure, and the lamination suitability, the relative dielectric constant, the change in the relative dielectric constant before and after exposure, and the moisture permeability of the transfer film were evaluated in the same manner as shown in the Example 1 series. Further, in the same manner as shown in the Example 1 series, as to the photosensitive layer in the transfer film, the carboxyl group consumption rate, the transmittance of light with respect to 365 nm, and the ratio of the transmittance of light with respect to 365 nm to the transmittance of light with respect to 313 nm were also evaluated. Further, in the same manner as shown in the Example 1 series, the physical properties of ε365 / ε313of the compound β included in the photosensitive material and the photosensitive layer were evaluated.

[1180] Among them, the reference of the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and the moisture permeability of the transfer film was set to the relative dielectric constant or the moisture permeability of Comparative Example 3A.

[1181] As to the photosensitive materials of each of the examples or comparative examples of the Example 3 series, the evaluation was performed in the same manner as the Example 1 series except that the pattern formation, the pattern formation method was changed as follows.

[1182] The photosensitive materials of each of the examples or comparative examples were spin-coated on a silicon wafer, and then the obtained coated film was dried at 80°C with a hot plate to obtain a photosensitive layer having a film thickness of 5 μm.

[1183] ​​​​​The photosensitive layer obtained was exposed through the same mask as in Example 1 using an ultrahigh pressure mercury lamp. The cumulative exposure amount measured by a 365 nm lux meter was 100 mJ / cm 2 .

[1184] Next, the photosensitive layer exposed to the pattern was developed for 40 seconds using a 1 mass% sodium carbonate aqueous solution (liquid temperature: 32°C) as a developer. After development, the pattern was obtained by rinsing with pure water for 20 seconds and further blowing air to remove moisture.

[1185] The pattern obtained was exposed to the whole surface using a high pressure mercury lamp. The cumulative exposure amount measured by a 365 nm lux meter was 1000 mJ / cm 2 .

[1186] As to the transfer film of each example or comparative example in Example 3, evaluation was performed in the same manner as in Example 1 except that the pattern formation and pattern formation method were changed as follows.

[1187] By peeling the cover film from the prepared transfer film and laminating to a COP film (substrate for touch panel) on which a copper foil was laminated, the photosensitive layer of the transfer film was transferred onto the surface of the copper foil to obtain a laminate having a "temporary support / photosensitive layer / copper foil / substrate (COP film)" laminated structure. The conditions for lamination were set as follows: temperature of the substrate for touch panel 40°C, rubber roll temperature (i.e., lamination temperature) 110°C, line pressure 3 N / cm, and conveyance speed 2 m / minute. The copper foil is a film that assumes wiring of a touch panel.

[1188] As a result, the lamination was good.

[1189] Next, the photosensitive layer of the above laminate was exposed to a pattern through the temporary support using a proximity exposure machine (Hitachi High-Tech Corporation.) having an ultrahigh pressure mercury lamp, and setting the distance between the exposure mask surface and the surface of the temporary support to 125 μm, and using the ultrahigh pressure mercury lamp at an exposure amount of 100 mJ / cm 2 (i-ray).

[1190] The mask was a mask having the same line and space pattern as in Example 1.

[1191] After exposure, the temporary support was peeled from the laminate.

[1192] Next, the photosensitive layer of the laminate from which the temporary support was peeled was developed for 40 seconds using a 1 mass% sodium carbonate aqueous solution (liquid temperature: 32°C) as a developer. After development, the pattern was obtained by rinsing with pure water for 20 seconds and blowing air to remove moisture.

[1193] The obtained pattern was subjected to full-area exposure using a high-pressure mercury lamp. The cumulative exposure amount measured with a 365 nm lux meter was 1000 mJ / cm 2 .

[1194] <Relative dielectric constant evaluation under twice exposure conditions>

[1195] In the Example 3 series, evaluation of the relative dielectric constant under twice exposure conditions was also performed. In addition, the evaluation of the relative dielectric constant under once exposure conditions refers to the evaluation of the relative dielectric constant under the same conditions as those shown in the above (relative dielectric constant evaluation 2) in the Example 1 series.

[1196] As for the photosensitive material of the Example 3 series, a transfer film was produced in the same manner as shown in (production of transfer film) in the Example 1 series. The cover film was peeled off from the obtained transfer film, and the transfer film was laminated under the same conditions as those shown in the above (laminating suitability evaluation) on an aluminum substrate having a thickness of 0.1 mm, to obtain a laminate having a "temporary support / photosensitive layer / aluminum substrate" stacked structure.

[1197] On the above laminate, as the first exposure, the photosensitive layer was subjected to full-area exposure using an ultra-high-pressure mercury lamp through the temporary support. In the first exposure, the cumulative exposure amount measured with a 365 nm lux meter was 100 mJ / cm 2 . In addition, since the first exposure was exposure through the temporary support (polyethylene terephthalate), light having a wavelength of 320 nm or less was mostly shielded. Therefore, it is considered that a substance having a large molar absorption coefficient with respect to light having a wavelength of 365 nm (for example, 1 x 10 3 (cm·mol / L) -1 or more) preferentially participates in the reaction.

[1198] Then, the temporary support was peeled off from the above laminate, and as the second exposure, the photosensitive layer was subjected to full-area exposure using a high-pressure mercury lamp. In the second exposure, the cumulative exposure amount measured with a 365 nm lux meter was 1000 mJ / cm 2 .

[1199] As for the photosensitive layer exposed in this manner, the relative dielectric constant was measured in the same manner as shown in the above (relative dielectric constant evaluation 2) in the Example 1 series.

[1200] Here, as a reference of the relative dielectric constant, the relative dielectric constant of Comparative Example 3A under twice exposure conditions was set.

[1201] The compounding of the solid components of the photosensitive material of each of the examples or comparative examples in the Example 3 series and the results of the tests are shown in the following Table 4.

[1202] In Table 4, the same description as in Table 3 indicates the same meaning as the description made with respect to Table 3.

[1203] [Table 5]

[1204]

[1205] Resin A: Resin of the following structure (acid value: 94.5 mgKOH / g)

[1206] [Chemical Formula 8]

[1207]

[1208] Method for synthesizing Resin A

[1209] Propylene glycol monomethyl ether 200 g and propylene glycol monomethyl ether acetate 50 g were added to a flask, and heated to 90°C under a nitrogen stream. To this liquid, a solution in which cyclohexylmethyl methacrylate 192.9 g, methyl methacrylate 4.6 g, methacrylic acid 89.3 g were dissolved in propylene glycol monomethyl ether acetate 60 g, and a solution in which polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) 9.2 g was dissolved in propylene glycol monomethyl ether acetate 114.8 g were simultaneously added dropwise over 3 hours. After the completion of the dropwise addition, a solution in which 2 g of V-601 was dissolved in propylene glycol monomethyl ether acetate 10 g was added 3 times at intervals of 1 hour. Then, it was further reacted for 3 hours. Dilution was performed with propylene glycol monomethyl ether acetate 168.7 g. The reaction liquid was warmed to 100°C under an air stream, and tetraethylammonium bromide 1.5 g, p-methoxyphenol 0.67 g were added. To this, glycidyl methacrylate (BLEMMER GH manufactured by NOF CORPORATION) 63.4 g was added dropwise over 20 minutes. It was reacted at 100°C for 6 hours to obtain a solution of Resin A. The solid content concentration of the obtained solution was 36.2%. The weight average molecular weight in GPC was 27000, the dispersity was 2.9, and the acid value of the polymer was 94.5 mgKOH / g. The amount of residual monomers determined using gas chromatography analysis was less than 0.1 mass% with respect to the polymer solid content in any monomer.

[1210] Resin B: Resin of the following structure (acid value: 94.5 mgKOH / g)

[1211] [Chemical Formula 9]

[1212]

[1213] Method for synthesizing Resin B

[1214] Propylene glycol monomethyl ether 82.4 g was put into a flask and heated to 90°C under a stream of nitrogen. In this liquid, a solution of styrene 38.4 g, dicyclopentyl methacrylate 30.1 g, methacrylic acid 34.0 g dissolved in propylene glycol monomethyl ether 20 g and a solution of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) 5.4 g dissolved in propylene glycol monomethyl ether acetate 43.6 g were simultaneously added dropwise over 3 hours. After the completion of the dropwise addition, 0.75 g of V...

Claims

1. A transfer film having a temporary support and a photosensitive layer disposed on the temporary support, comprising a compound A having an acid group. The content of the acid groups in the photosensitive layer decreases due to irradiation by photochemical rays or radiation. The photosensitive layer satisfies the following requirement V01: Requirement V01 The photosensitive layer comprises compound A and compound β having a structure that reduces the amount of the acid groups contained in compound A through exposure. In requirement V01, compound β is compound B having a structure capable of accepting electrons from the acid group contained in compound A in a photoexcited state. In the photosensitive layer, the total number of electron-accepting structures contained in compound B is at least 5 mol% relative to the total number of acid groups contained in compound A. The molar absorptivity ε of the compound β at 365 nm is 1×10⁻⁶. 3 (cm·mol / L) -1 the following, The compound β is an aromatic compound that optionally has substituents. The compound β has a heteroaromatic ring, and the compound β has at least a nitrogen atom as a heteroatom present in the heteroaromatic ring. In the photosensitive layer, the content of compound A is 45% by mass or more relative to the total mass of the photosensitive layer. Compound A contains a polymer comprising repeating units derived from (meth)acrylic acid.

2. The transfer film according to claim 1, wherein, The ratio of the molar absorptivity ε of compound β at 365 nm to the molar absorptivity ε' of compound β at 313 nm is less than 3.

3. The transfer film according to claim 1, wherein, The compound β has a pKa of 2.0 or higher and 9.0 or lower in the ground state.

4. The transfer film according to any one of claims 1 to 3, wherein, Compound A comprises polymers with a weight-average molecular weight of less than 50,000.

5. The transfer film according to any one of claims 1 to 3, wherein, The photosensitive layer further comprises a polymeric compound.

6. The transfer film according to any one of claims 1 to 3, wherein, The photosensitive layer further comprises a photopolymerization initiator.

7. The transfer film according to any one of claims 1 to 3, wherein, The relative permittivity of the photosensitive layer decreases due to irradiation by photochemical rays or radiation.

8. The transfer film according to any one of claims 1 to 3, wherein, The photosensitive layer has a transmittance of over 65% at 365nm.

9. The transfer film according to any one of claims 1 to 3, wherein, The ratio of the transmittance of the photosensitive layer at 365 nm to the transmittance of the photosensitive layer at 313 nm is 1.5 or higher.

10. The transfer film according to any one of claims 1 to 3, wherein, The content of the acid groups in the photosensitive layer decreases by a rate of 5 mol% or more due to irradiation by photochemical rays or radiation.

11. The transfer film according to any one of claims 1 to 3, wherein, In the photosensitive layer, the total number of structures in compound B that are capable of accepting electrons is 10 mol% or more and 200 mol% or less relative to the total number of acid groups in compound A.

12. The transfer film according to any one of claims 1 to 3, wherein, In the photosensitive layer, the content of compound β is 8% to 30% by mass relative to the total mass of the photosensitive layer.

13. A method for forming a pattern, comprising: The process of bringing the surface of the photosensitive layer in the transfer film according to any one of claims 1 to 12, opposite to the temporary support side, into contact with the substrate, thereby bonding the transfer film to the substrate; The process of exposing the photosensitive layer to form a pattern; and The process of developing the exposed photosensitive layer using a developing solution. If the developer is an organic solvent-based developer, the process further includes a step of exposing the pattern formed by development after the development step.

14. A method for forming a pattern, comprising, in sequence: The process of bringing the surface of the photosensitive layer in the transfer film according to any one of claims 1 to 12, opposite to the temporary support side, into contact with the substrate, thereby bonding the transfer film to the substrate; The process of exposing the photosensitive layer into a pattern; The process of developing the exposed photosensitive layer with an alkaline developing solution to form a patterned photosensitive layer; and The process of exposing the patterned photosensitive layer.

15. A method for manufacturing circuit wiring, comprising the following steps: A process of bringing the surface of the photosensitive layer in the transfer film according to any one of claims 1 to 12, opposite to the temporary support side, into contact with the conductive layer in the substrate having the conductive layer, thereby bonding the transfer film to the substrate having the conductive layer. The process of exposing the photosensitive layer into a pattern; The process of developing the exposed photosensitive layer with an alkaline developing solution to form a patterned photosensitive layer; The process of exposing the patterned photosensitive layer to form an etch resist film; and The process of etching the conductive layer in areas where the etch resist film is not disposed.

16. A method for manufacturing a touch panel, comprising the following steps: A process of bringing the surface of the photosensitive layer in the transfer film according to any one of claims 1 to 12, opposite to the temporary support side, into contact with the conductive layer in the substrate having the conductive layer, thereby bonding the transfer film to the substrate having the conductive layer. The process of exposing the photosensitive layer into a pattern; The process of developing the exposed photosensitive layer with an alkaline developing solution to form a patterned photosensitive layer; and The process of exposing the patterned photosensitive layer to form a protective film or insulating film for the conductive layer.

17. A photosensitive material comprising a compound A having a carboxyl group, Compound A contains a polymer comprising repeating units derived from (meth)acrylic acid. The content of carboxyl groups in the photosensitive layer formed from the photosensitive material decreases due to irradiation by photochemical rays or radiation. The photosensitive material satisfies the following requirement V02: Requirement V02: The photosensitive material comprises the compound A and a compound β having a structure that reduces the amount of the carboxyl groups contained in the compound A upon exposure. In requirement V02, compound β is compound B having a structure capable of accepting electrons from the carboxyl group contained in compound A in a photoexcited state. In the photosensitive material, the total number of electron-accepting structures contained in compound B is at least 5 mol% relative to the total number of carboxyl groups contained in compound A. The molar absorptivity ε of the compound β at 365 nm is 1×10⁻⁶. 3 (cm·mol / L) -1 the following, The compound β is an aromatic compound that optionally has substituents. The compound β has a heteroaromatic ring, and the compound β has at least a nitrogen atom as a heteroatom present in the heteroaromatic ring. In the photosensitive material, the content of compound A is 45% by mass or more relative to the total solid content of the photosensitive material.

18. The photosensitive material according to claim 17, wherein, The polymer has a weight-average molecular weight of less than 50,000.

19. The photosensitive material according to claim 17, wherein, The ratio of the molar absorptivity ε of compound β at 365 nm to the molar absorptivity ε' of compound β at 313 nm is less than 3.

20. The photosensitive material according to claim 17, wherein, The compound β has a pKa of 2.0 or higher and 9.0 or lower in the ground state.

21. The photosensitive material according to any one of claims 17 to 20, wherein, The content of the carboxyl groups in the photosensitive layer formed from the photosensitive material decreases by a rate of 5 mol% or more due to irradiation by photochemical rays or radiation.

22. The photosensitive material according to any one of claims 17 to 20, wherein, The carboxyl group is decarboxylated due to irradiation by photochemical rays or radiation.

23. The photosensitive material according to any one of claims 17 to 20, wherein, The relative permittivity of the photosensitive layer formed from the photosensitive material decreases due to irradiation by photochemical rays or radiation.

24. The photosensitive material according to any one of claims 17 to 20, wherein, In the photosensitive material, the total number of structures in compound B that can accept electrons is 10 mol% or more and 200 mol% or less relative to the total number of acid groups in compound A.

25. The photosensitive material according to any one of claims 17 to 20, wherein, In the photosensitive material, the content of compound β is 8% to 30% by mass relative to the total mass of the photosensitive material.

26. A method for forming a pattern, comprising: The process of forming a photosensitive layer on a substrate using the photosensitive material according to any one of claims 17 to 25; The process of exposing the photosensitive layer to form a pattern; and The process of developing the exposed photosensitive layer using a developing solution. If the developer is an organic solvent-based developer, the process further includes a step of exposing the pattern formed by development after the development step.

27. A method for forming a pattern, comprising, in sequence: The process of forming a photosensitive layer on a substrate using the photosensitive material according to any one of claims 17 to 25; The process of exposing the photosensitive layer into a pattern; The process of developing the exposed photosensitive layer with an alkaline developing solution to form a patterned photosensitive layer; and The process of exposing the patterned photosensitive layer.

28. A method for manufacturing circuit wiring, comprising the following steps: The process of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material according to any one of claims 17 to 25; The process of exposing the photosensitive layer into a pattern; The process of developing the exposed photosensitive layer with an alkaline developing solution to form a patterned photosensitive layer; The process of exposing the patterned photosensitive layer to form an etch resist film; and The process of etching the conductive layer in areas where the etch resist film is not disposed.

29. A method for manufacturing a touch panel, comprising the following steps: The process of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material according to any one of claims 17 to 25; The process of exposing the photosensitive layer into a pattern; The process of developing the exposed photosensitive layer with an alkaline developing solution to form a patterned photosensitive layer; and The process of exposing the patterned photosensitive layer to form a protective film or insulating film for the conductive layer.

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