Transfer film, method for manufacturing a laminate, method for manufacturing a circuit wiring

Abstract

The first problem of the present invention is to provide a transfer film which is unlikely to cause a photosensitive composition layer to adhere to a guide roll on contact surfaces between the composition layer and the guide roll during film conveyance, and which further exhibits excellent step conformability for a wide variety of laminating temperatures when thermal lamination is performed on a base material having a step such as a wiring board. In addition, the second problem of the present invention is to provide a manufacturing method for a laminate using the transfer film and a manufacturing method for a circuit wiring.　The transfer film according to the present invention comprises a temporary support and a composition layer arranged on the temporary support. The composition layer includes a photosensitive composition layer. When dynamic viscoelasticity at 25-150°C is measured for the composition layer under the conditions of a frequency of 1 Hz and a rate of temperature rise of 5°C / minute, the transfer film satisfies all the requirements of Expression (1A) to Expression (3A).　Expression (1A): tanδT25≤1.5 Expression (2A): tanδT120≥0.80 Expression (3A): 0.50≤tanδT120 / tanδT80≤10 In Expression (1A) to Expression (3A), tanδT25 represents tanδ at 25°C, tanδT120 represents tanδ at 120°C, and tanδT80 represents tanδ at 80°C.

Description

Technical Field

[0001] The present invention relates to a transfer film, a method for manufacturing a laminate, and a method for manufacturing a circuit wiring.

Background Art

[0002] Since the number of steps for obtaining a predetermined pattern is small, a method is widely used in which a photosensitive composition layer is disposed on an arbitrary substrate using a transfer film, and after exposure through a mask to the photosensitive composition layer, development is performed.

[0003] For example, Patent Document 1 discloses a photosensitive element (transfer film) having a support film and a photosensitive resin composition layer (photosensitive composition layer) provided on the support film.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] When the present inventor examined the transfer film described in Patent Document 1, when the roll-shaped transfer film was unwound and film conveyance was performed in a state where the uncured photosensitive composition layer in the transfer film was in contact with the guide roll, it was found that the photosensitive composition layer might adhere to the guide roll and peeling of the photosensitive composition layer might occur. Furthermore, when the present inventor thermally laminated the transfer film to a substrate having a step such as a wiring board so that the uncured photosensitive composition layer in the transfer film was in contact with the substrate, it was found that bubbles might be mixed between the photosensitive composition layer and the substrate due to insufficient step followability of the transfer film. That is, it was clarified that there is room for further improving the step followability of the transfer film. Incidentally, generally, the higher the lamination temperature, the lower the melt viscosity of the photosensitive composition layer, and the step-following property is improved (that is, the bubbles mixed between the photosensitive composition layer and the substrate are suppressed). However, depending on the type of substrate, increasing the lamination temperature may also cause a problem that the alignment accuracy during exposure cannot be ensured due to thermal expansion. Therefore, from the viewpoint of suppressing the thermal expansion of the substrate and ensuring the alignment accuracy during exposure, it is desirable to set the lamination temperature low. In order to satisfy these requirements, when improving the step-following performance during the thermal lamination of the transfer film, it is also required that the temperature margin of the lamination temperature is wide (that is, the temperature dependence on the lamination temperature is small).

[0006] Therefore, an object of the present invention is to provide a transfer film that is less likely to adhere to a guide roll at the contact surface between the photosensitive composition layer and the guide roll during film conveyance, and further has excellent step-following properties with respect to a wide variety of lamination temperatures when thermally laminated to a substrate having a step such as a wiring board. Another object of the present invention is to provide a method for manufacturing a laminate and a method for manufacturing a circuit wiring using the above transfer film.

Means for Solving the Problems

[0007] As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0008] 〔1〕 A transfer film having a temporary support and a composition layer disposed on the temporary support, wherein the composition layer includes a photosensitive composition layer, Regarding the composition layer, when measuring the dynamic viscoelasticity at 25 to 150 ° C. under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C. / min, a transfer film that satisfies all of the requirements of the following formulas (1A) to (3A). Formula (1A) tanδ T25 ≦1.5 Formula (2A) tanδ T120 ≧0.80 Equation (3A): 0.50 ≤ tanδ T120 / tanδ T80 ≤ 10 In the above Equations (1A) to (3A), tanδ T25 represents tanδ at 25°C, tanδ T120 represents tanδ at 120°C, and tanδ T80 represents tanδ at 80°C. 〔2〕 The transfer film according to 〔1〕, which satisfies the requirements of the following Equation (1A’). Equation (1A’) tanδ T25 ≤ 1.2 〔3〕 The transfer film according to 〔1〕 or 〔2〕, which satisfies the requirements of the following Equation (1A’’). Equation (1A’’) tanδ T25 ≤ 1.0 〔4〕 The transfer film according to any one of 〔1〕 to 〔3〕, which satisfies the requirements of the following Equation (3A’). Equation (3A’) 1.0 ≤ tanδ T120 / tanδ T80 ≤ 8.0 〔5〕 The transfer film according to any one of 〔1〕 to 〔4〕, which satisfies the requirements of the following Equation (2A’). Equation (2A’) tanδ T120 ≥ 1.0 〔6〕 The transfer film according to any one of 〔1〕 to 〔5〕, wherein the film thickness of the photosensitive composition layer is 20 μm or less. 〔7〕 The transfer film according to any one of 〔1〕 to 〔6〕, wherein the photosensitive composition layer contains a binder polymer, a photopolymerizable compound, and a photoinitiator. 〔8〕 The transfer film according to any one of 〔1〕 to 〔7〕, which is used for forming a protective film for a touch panel. 〔9〕 A laminating step of laminating the surface of the transfer film according to any one of 〔1〕 to 〔8〕 opposite to the above temporary support in contact with a substrate having a conductive layer, to obtain a substrate with a composition layer having the above substrate, the conductive layer, the composition layer, and the temporary support in this order; An exposure step of pattern-exposing the above composition layer; A developing step of developing the exposed composition layer to form a protective film pattern that protects the conductive layer; Furthermore, between the laminating step and the exposing step, or between the exposing step and the developing step, there is a peeling step of peeling the temporary support from the substrate with the composition layer, and a method for manufacturing a laminate. 〔10〕 The method for manufacturing a laminate according to 〔9〕, wherein the substrate having the conductive layer is a substrate having at least one of an electrode for a touch panel and a wiring for a touch panel. 〔11〕 A laminating step of bringing the surface of the transfer film according to any one of 〔1〕 to 〔8〕 on the side opposite to the temporary support into contact with a substrate having a conductive layer to obtain a substrate with a composition layer having the substrate, the conductive layer, the composition layer, and the temporary support in this order; An exposing step of pattern-exposing the composition layer; A developing step of developing the exposed composition layer to form a resin pattern; An etching step of etching the conductive layer in a region where the resin pattern is not disposed; Furthermore, a method for manufacturing a circuit wiring including a peeling step of peeling a temporary support from the substrate with the composition layer between the laminating step and the exposing step, or between the exposing step and the developing step.

Advantages of the Invention

[0009] According to the present invention, during film conveyance, adhesion of the photosensitive composition layer to the guide roll hardly occurs at the contact surface between the composition layer and the guide roll. Furthermore, when thermally laminated to a base material having a step such as a wiring board, a transfer film having excellent step followability with respect to a wide variety of lamination temperatures can be provided. Also, according to the present invention, a method for manufacturing a laminate and a method for manufacturing a circuit wiring using the transfer film can be provided.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described in detail. In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In this specification, in a numerically defined range described stepwise, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerically defined range described stepwise. Also, in the numerical range described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

[0012] In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved.

[0013] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, and for example, it can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0014] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer, with TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names of Tosoh Corporation) as columns, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of a metal element is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0015] In this specification, “(meth)acryl” is a concept encompassing both acrylic and methacrylic, and “(meth)acryloxy group” is a concept encompassing both acryloxy group and methacryloxy group.

[0016] In this specification, “alkali-soluble” means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0017] In this specification, “water-soluble” means that the solubility in 100 g of water at pH 7.0 with a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, a water-soluble resin is intended to be a resin that satisfies the above solubility conditions.

[0018] In this specification, the "solid content" of a composition means the components that form the composition layer formed using the composition. When the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Also, any liquid component that forms the composition layer is regarded as a solid content as long as it is a component for forming the composition layer.

[0019] [Transfer Film] The transfer film of the present invention has a temporary support and a composition layer disposed on the temporary support, and the composition layer includes a photosensitive composition layer. As a characteristic point of the transfer film of the present invention, for the composition layer, when measuring the dynamic viscoelasticity at 25°C to 150°C under the conditions of a frequency of 1 Hz and a heating rate of 5°C / min, it satisfies all the requirements of the following formulas (1A) to (3A).

[0020] Due to the above configuration, in the transfer film of the present invention, when the film is conveyed, it is difficult for the photosensitive composition layer to adhere to the guide roll at the contact surface between the composition layer and the guide roll. Furthermore, when thermally laminated to a substrate having a step such as a wiring board, it has excellent step followability with respect to a wide variety of lamination temperatures (for example, 80°C, 120°C). That is, the transfer film of the present invention can be thermally laminated at a wide variety of lamination temperatures (for example, 80°C, 120°C) while suppressing the mixing of air bubbles between the photosensitive composition layer and the substrate with respect to a substrate having a step such as a wiring board.

[0021] Note that, as described later, the transfer film only needs to contain at least one composition layer, and may contain other composition layers other than the photosensitive composition layer. Further, when the transfer film contains two or more composition layers, the composition layer disposed at the position farthest from the temporary support may be other than the photosensitive composition layer. In other words, in the transfer film of the present invention, the aspect in which the composition layer is other than the photosensitive composition layer is not limited. Usually, when the transfer film contains two or more composition layers, the composition layer disposed on the side opposite to the temporary support side of the photosensitive composition layer is often thinner than the photosensitive composition layer. Therefore, even when there is another composition layer on the side opposite to the temporary support side of the photosensitive composition layer, at the contact surface between the composition layer and the guide roll during film conveyance, the physical properties of the photosensitive composition layer have a greater influence than those of the other composition layer that directly contacts the guide roll. Actually, components derived from the photosensitive composition layer are observed in the deposits on the guide roll during conveyance.

[0022] In the following, when the film is conveyed, the fact that the adhesion of the photosensitive composition layer to the guide roll is less likely to occur at the contact surface between the composition layer and the guide roll, and / or when heat-laminating to a substrate having a step such as a wiring board, having better step-following properties for a wide variety of lamination temperatures, may be referred to as "the effects of the present invention are more excellent".

[0023] Tanδ (loss tangent) is represented by the ratio of the storage elastic modulus G' to the loss elastic modulus G" (G" / G'), and is an index representing the ratio of the elastic property to the viscous property of the polymer material. The higher the value of tanδ, the stronger the viscous property, and the lower the value of tanδ, the lower the elastic property. Now, the present inventor has found that there is a correlation between the above-described problem to be solved and the value of tanδ of the composition layer of the transfer film. That is, it has been found that the above problem can be solved by adjusting the value of tanδ of the composition layer of the transfer film to a predetermined condition. The mechanism of action of the transfer film of the present invention is not clear, but is presumed as follows. The higher the value of tanδ, the better the wetting (adhesiveness) of the composition layer to the guide roll at the contact surface between the composition layer and the guide roll during film conveyance, and since the composition layer is also easily deformed by a weak force, soiling of the guide roll (adhesion of the photosensitive composition layer in the composition layer to the guide roll) is likely to occur. When the composition layer of the transfer film satisfies the requirements of formula (1A), soiling of the guide roll can be suppressed. Furthermore, when the composition layer of the transfer film satisfies the requirements of formula (2A) and formula (3A), when the transfer film is laminated by thermal lamination so that the composition layer is in contact with the substrate with respect to a substrate having a step such as wiring, the adhesiveness of the composition layer is appropriate, and air bubbles are less likely to be mixed between the composition layer and the substrate. Furthermore, since the temperature margin of the lamination temperature with step following property correlates well with the temperature dependence of tanδ, tanδ can be an index of the temperature margin of the lamination temperature. That is, when the composition layer of the transfer film satisfies the requirements of formula (3A), it has excellent step following property with respect to a wide variety of lamination temperatures.

[0024] In the measurement of tanδ of the composition layer of the transfer film, the following measurement samples are used. Hereinafter, the method for producing the measurement samples will be described. First, when the transfer film has a protective film on the composition layer, the protective film is peeled off from the transfer film. The film obtained by peeling off the protective film is folded so that the surfaces of the composition layers exposed by peeling off the protective film face each other, and the surfaces of the composition layers are bonded together to produce a laminate 1 of a temporary support / composition layer (two-layer laminate) / temporary support. Next, one of the temporary supports in the laminate 1 is peeled off. Then, the laminate 1 from which the temporary support has been peeled off is folded so that the composition layers (two-layer laminate) exposed by peeling off the temporary support face each other, and the composition layers (two-layer laminate) are bonded together to produce a laminate 2 of a temporary support / composition layer (four-layer laminate) / temporary support. Further, one of the temporary supports in the laminate 2 is peeled off. Then, the laminate 2 from which the temporary support has been peeled off is folded so that the composition layers (four-layer laminate) exposed by peeling off the temporary support face each other, and the composition layers (four-layer laminate) are bonded together to produce a laminate 3 of a temporary support / composition layer (eight-layer laminate) / temporary support. By repeating the bonding of the composition layers in the same procedure, a laminate N of a temporary support / composition layer of a predetermined thickness / temporary support is produced. Then, by removing the temporary support from the laminate N, a measurement sample composed of a composition layer of a predetermined thickness is produced. Note that the thickness of the composition layer serving as the measurement sample can be selected to be a thickness suitable for the dynamic viscoelasticity measurement device to be used (usually 0.1 to 1.0 mm). For example, when measuring tanδ using a rheometer DHR-2 (manufactured by TA Instruments Japan), the thickness may be set to 0.5 mm, which is the Gap of the Peltier plate.

[0025] Hereinafter, the transfer film of the present invention will be described. The transfer film of the present invention has a temporary support and a composition layer disposed on the temporary support, and the composition layer includes a photosensitive composition layer. The composition layer is not particularly limited as long as it includes a photosensitive composition layer. The photosensitive composition layer may be a negative-type photosensitive composition layer or a chemically amplified photosensitive composition layer, but a negative-type photosensitive composition layer is preferred. Further, the composition layer may have a single-layer structure or a structure of two or more layers. When the composition layer includes other composition layers than the photosensitive composition layer, examples of the other composition layers include a thermoplastic resin layer, an intermediate layer, and a refractive index adjustment layer. Further, the transfer film may have a structure having a protective film on the composition layer.

[0026] Further, in the transfer film of the present invention, when measuring the dynamic viscoelasticity of the composition layer at 25°C to 150°C under the conditions of a frequency of 1 Hz and a temperature increase rate of 5°C / min, all of the requirements of formulas (1A) to (3A) are satisfied.

[0027] Formula (1A) tanδ T25 ≤1.5 Formula (2A) tanδ T120 ≥0.80 Formula (3A) 0.50 ≤ tanδ T120 / tanδ T80 ≤10 In the following formulas (1A) to (3A), tanδ T25 represents tanδ at 25°C (tanδ of the composition layer at 25°C), tanδ T120 represents tanδ at 120°C (tanδ of the composition layer at 120°C), and tanδ T80 represents tanδ at 80°C (tanδ of the composition layer at 80°C).

[0028] Among them, in terms of more excellent effects of the present invention, it is preferable to satisfy the requirement of the following formula (1A'), and it is more preferable to satisfy the requirement of the following formula (1A''). Formula (1A') tanδ T25 ≤1.2 Formula (1A'') tanδ T25 ≤1.0 Note that the lower limit of the above tanδ T25 is not particularly limited, but in terms of more excellent effects of the present invention, 0.20 or more is preferable.

[0029] Further, in terms of more excellent effects of the present invention, it is preferable to satisfy the requirement of the following formula (2A'). Formula (2A') tan δ T120 ≧1.0 In addition, the above tan δ T120 The upper limit is not particularly limited, but is preferably 12 or less in terms of obtaining better effects of the present invention.

[0030] In order to obtain better effects of the present invention, it is preferable that the requirement of the following formula (3A') is satisfied. Formula (3A') 1.0≦tanδ T120 / tanδ T80 <=8.0

[0031] An example of the embodiment of the transfer film of the present invention is shown below, but the present invention is not limited thereto. (1) "Temporary support / photosensitive composition layer / refractive index adjusting layer / protective film" (2) "Temporary support / photosensitive composition layer / protective film" (3) "Temporary support / intermediate layer / photosensitive composition layer / protective film" (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film" In each of the above-mentioned configurations, the photosensitive composition layer is preferably a negative photosensitive composition layer, and is also preferably a colored resin layer. The transfer film of the present invention may be used as a transfer film for a wiring protective film, as described below, or as a transfer film for an etching resist. When the transfer film is used as a wiring protection film, the transfer film preferably has the above-mentioned configuration (1) or (2), and when the transfer film is used as an etching resist, the transfer film preferably has the above-mentioned configuration (2) to (4).

[0032] In the case where the composition layer of the transfer film further has another composition layer on the side opposite the temporary support side of the photosensitive composition layer, the total thickness of the other layers disposed on the side opposite the temporary support side of the photosensitive composition layer is preferably 0.1 to 30% and more preferably 0.1 to 20% of the thickness of the photosensitive composition layer.

[0033] Hereinafter, an example of a specific embodiment will be given to describe the transfer film of the present invention. Note that the transfer film of the following first embodiment has a configuration that can be preferably used for a transfer film for a wiring protection film, and the transfer film of the following second embodiment has a configuration that can be preferably used for a transfer film for an etching resist.

[0034] 〔Transfer Film of the First Embodiment〕 Hereinafter, an example of an embodiment of the transfer film of the first embodiment will be described. The transfer film 10 shown in FIG. 1 has a temporary support 1, a composition layer 2 including a photosensitive composition layer 3 and a refractive index adjustment layer 5, and a protective film 7 in this order. Further, the composition layer 2 satisfies all the requirements of the above-described formulas (1A) to (3A). Note that the transfer film 10 shown in FIG. 1 is in a form in which the protective film 7 is disposed, but the protective film 7 may not be disposed. Further, the transfer film 10 shown in FIG. 1 is in a form in which the refractive index adjustment layer 5 is disposed, but the refractive index adjustment layer 5 may not be disposed. Hereinafter, each element constituting the transfer film will be described.

[0035] <<Temporary Support>> The transfer film has a temporary support. The temporary support is a member that supports the composition layer and is finally removed by a peeling process.

[0036] The temporary support may have a single-layer structure or a multilayer structure. The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film having flexibility and not undergoing significant deformation, shrinkage, or elongation under pressure or under pressure and heating is preferred. Examples of the film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a triacetate cellulose film, a polystyrene film, a polyimide film, and a polycarbonate film. Among them, as the temporary support, a polyethylene terephthalate film is preferred. In addition, the film used as the temporary support preferably has no deformation such as wrinkles and no damage such as scratches.

[0037] From the viewpoint that pattern exposure can be performed through the temporary support, the temporary support preferably has high transparency. The transmittance at 365 nm is preferably 60% or more, and more preferably 70% or more. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. The number of fine particles, foreign substances, and defects having a diameter of 1 μm or more in the temporary support is 50 pieces / 10 mm 2 or less is preferred, 10 pieces / 10 mm 2 or less is more preferred, 3 pieces / 10 mm 2 or less is even more preferred, and 0 pieces / 10 mm 2 is particularly preferred.

[0038] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 150 μm, and even more preferably 10 to 50 μm from the viewpoints of ease of handling and versatility. The thickness of the temporary support is calculated as the average value of any five points measured by cross-sectional observation using SEM (Scanning Electron Microscope).

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

[0040] Preferred forms of the temporary support include, for example, paragraphs

[0017] to

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

[0019] to

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

[0041] ~

[0057] of WO 2012 / 081680, and paragraphs

[0029] to

[0040] of WO 2018 / 179370, the contents of these publications being incorporated herein by reference.

[0041] In terms of imparting handleability, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. Also, the film thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0042] <<Photosensitive Composition Layer>> The transfer film has a photosensitive composition layer. After transferring the photosensitive composition layer onto the transfer target and performing exposure and development, a pattern can be formed on the transfer target. As the photosensitive composition layer, a negative type is preferred. The negative type photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer decreases upon exposure. When the photosensitive composition layer is a negative type photosensitive composition layer, the formed pattern corresponds to a cured layer.

[0043] Hereinafter, the components that can be contained in the photosensitive composition layer will be described in detail.

[0044] <Binder Polymer> The photosensitive composition layer may contain a binder polymer. Examples of the binder polymer include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide-epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, epoxy acrylate resins obtained by the reaction of an epoxy resin and (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of an epoxy acrylate resin and an acid anhydride.

[0045] One preferred embodiment of the binder polymer is a (meth)acrylic resin, which is excellent in alkali developability and film-forming properties. In the present specification, the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more based on all the structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of a structural unit derived from a (meth)acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth)acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth)acrylic compound is 100% by mass or less based on all the structural units of the (meth)acrylic resin.

[0046] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile. Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl ester is preferred. Examples of the (meth)acrylamide include acrylamides such as diacetone acrylamide.

[0047] Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters having a linear or branched alkyl group with 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate; (meth)acrylic acid alkyl esters having a cyclic alkyl group with 6 to 12 carbon atoms, such as hexyl (meth)acrylate and heptyl (meth)acrylate. A preferred embodiment of the (meth)acrylic acid ester includes (meth)acrylic acid alkyl esters having a linear or branched alkyl group with 1 to 4 carbon atoms, and among them, methyl (meth)acrylate or ethyl (meth)acrylate is preferred. Another preferred embodiment of the (meth)acrylic acid ester includes (meth)acrylic acid alkyl esters having a cyclic alkyl group with 6 to 12 carbon atoms, and among them, hexyl (meth)acrylate and dicyclopentanyl (meth)acrylate are preferred. The cyclic alkyl group may be monocyclic or polycyclic.

[0048] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer forming the above-mentioned structural unit is not particularly limited as long as it is a compound other than (meth)acrylic compounds copolymerizable with (meth)acrylic compounds. For example, styrene compounds which may have a substituent at the α-position or on the aromatic ring such as styrene, vinyltoluene, and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid can be mentioned. These polymerizable monomers may be used alone or in combination of two or more. Furthermore, the (meth)acrylic resin may have a reactive group as described later.

[0049] Also, from the viewpoint of making the alkali developability better, the (meth)acrylic resin preferably has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Among them, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0050] The content of the structural unit having an acid group (preferably the structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more with respect to the total mass of the (meth)acrylic resin in terms of excellent developability. Also, the upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less in terms of excellent alkali resistance.

[0051] Also, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester. The content of the structural unit derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 90% by mass based on all the structural units of the (meth)acrylic resin.

[0052] Moreover, the (meth)acrylic resin preferably has a reactive group, and more preferably has a structural unit having a reactive group. As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the (meth)acrylic resin has an ethylenically unsaturated group, the (meth)acrylic resin preferably has a structural unit having an ethylenically unsaturated group in the side chain. In this specification, the "main chain" represents the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the "side chain" represents an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable. Examples of the structural unit having a reactive group include, but are not limited to, those shown below.

[0053]

Chemical formula

[0054] The (meth)acrylic resin may have one kind of the structural unit having a reactive group alone or two or more kinds thereof. When the (meth)acrylic resin has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass based on all the structural units of the (meth)acrylic resin from the viewpoint of more excellent effects of the present invention.

[0055] As a preferable embodiment of the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid alkyl ester is preferable. As another preferred embodiment of the (meth)acrylic resin, there may be mentioned a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate. As another preferred embodiment of the (meth)acrylic resin, there may be mentioned a resin having a structural unit derived from (meth)acrylic acid, a structural unit derived from an alkyl (meth)acrylate, and a structural unit having a reactive group. As another preferred embodiment of the (meth)acrylic resin, there may be mentioned an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate. As another preferred embodiment of the (meth)acrylic resin, there may be mentioned a resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from cyclohexyl methacrylate, and a structural unit having a reactive group.

[0056] Further, from the viewpoint of more excellent effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate. From the viewpoint of more excellent effects of the present invention, the total content of the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on all the structural units of the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, preferably 80% by mass or less.

[0057] Further, from the viewpoint of more excellent effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from alkyl acrylates. From the viewpoint of more excellent effects of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylates is preferably 60 / 40 to 80 / 20 by mass ratio with respect to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylates.

[0058] The (meth)acrylic resin preferably has an ester group at the terminal in terms of excellent developability of the photosensitive composition layer after transfer. Note that the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. The (meth)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0059] Another preferred embodiment of the binder polymer includes an alkali-soluble resin. The binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more, for example, from the viewpoint of developability. Further, the binder polymer is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin), for example, from the viewpoint of easily forming a strong film by thermally crosslinking with a crosslinking component by heating, and even more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth)acrylic resin). When the binder polymer is a resin having a carboxy group, for example, by adding a thermally crosslinkable compound such as a blocked isocyanate compound and performing thermal crosslinking, the three-dimensional crosslink density can be increased. Further, when the carboxy group of the resin having a carboxy group is anhydrified and hydrophobized, the wet heat resistance can be improved.

[0060] The carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph

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

[0033] to

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

[0061] Another preferred embodiment of the binder polymer includes a styrene-acrylic copolymer. In the present specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound. The total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer. Further, the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5 to 80% by mass, based on all the structural units of the copolymer. Further, the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20 to 95% by mass, based on all the structural units of the copolymer.

[0062] From the viewpoint of more excellent effects of the present invention, the binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure. Examples of the monomer that forms a structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth)acrylate. Among them, styrene compounds are preferred, and styrene is more preferred. Further, from the viewpoint of more excellent effects of the present invention, the binder polymer more preferably has a structural unit (structural unit derived from styrene) represented by the following formula (S).

[0063]

Chemical formula

[0064] When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass with respect to all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention. Further, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 60 mol% with respect to all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention. Furthermore, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol% with respect to all the structural units of the binder polymer, from the viewpoint of more excellent effects of the present invention. In the present specification, when the content of the "structural unit" is defined by a molar ratio, the above "structural unit" shall be synonymous with the "monomer unit". Further, in the present specification, the above "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0065] The binder polymer preferably has an aliphatic hydrocarbon ring structure from the viewpoint of more excellent effects of the present invention. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. Among them, the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

[0066] Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isobornyl ring. Among them, from the viewpoint of more excellent effects of the present invention, a ring in which two or more aliphatic hydrocarbon rings are fused is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 decane ring) is more preferable. Examples of the monomer that forms the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Further, the binder polymer more preferably has a structural unit represented by the following formula (Cy) from the viewpoint of more excellent effects of the present invention, and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0067]

Chemical formula

[0068] In formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0069] R M in formula (Cy) is preferably a methyl group. R CyFrom the viewpoint of more excellent effects of the present invention, it is preferably a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms. Further, R in the formula (Cy) Cy In terms of more excellent effects of the present invention, the aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isobornyl ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure. Furthermore, R in the formula (Cy) Cy In terms of more excellent effects of the present invention, the aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, and more preferably a ring in which 2 to 4 aliphatic hydrocarbon rings are fused. Furthermore, R in the formula (Cy) Cy From the viewpoint of more excellent effects of the present invention, it is preferably a group in which the oxygen atom of -C(=O)O- in the formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and still more preferably a dicyclopentanyl group.

[0070] The binder polymer may have one kind or two or more kinds of structural units having an aliphatic hydrocarbon ring structure. When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass based on all the structural units of the binder polymer from the viewpoint of more excellent effects of the present invention. In addition, from the viewpoint of more excellent effects of the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer. Furthermore, from the viewpoint of more excellent effects of the present invention, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

[0071] When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects of the present invention, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass based on all the structural units of the binder polymer. In addition, from the viewpoint of more excellent effects of the present invention, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% based on all the structural units of the binder polymer. Furthermore, from the viewpoint of more excellent effects of the present invention, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% based on all the structural units of the binder polymer. In addition, from the viewpoint of more excellent effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and still more preferably satisfy the following formula (SCy-2). 0.2 ≦ nS / (nS + nCy) ≦ 0.8 Formula (SCy) 0.30 ≦ nS / (nS + nCy) ≦ 0.75 (Equation (SCy - 1)) 0.40 ≦ nS / (nS + nCy) ≦ 0.70 (Equation (SCy - 2))

[0072] From the viewpoint of more excellent effects of the present invention, the binder polymer preferably has a structural unit having an acid group. Examples of the above acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable. As the structural unit having the above acid group, the structural unit derived from (meth) acrylic acid shown below is preferable, and the structural unit derived from methacrylic acid is more preferable.

[0073] [Chemical formula]

[0074] The binder polymer may have one kind of structural unit having an acid group alone or two or more kinds thereof. When the binder polymer has a structural unit having an acid group, from the viewpoint of more excellent effects of the present invention, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to all the structural units of the binder polymer. Further, from the viewpoint of more excellent effects of the present invention, the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% with respect to all the structural units of the binder polymer. Furthermore, from the viewpoint of more excellent effects of the present invention, the content of the structural unit derived from (meth) acrylic acid in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% with respect to all the structural units of the binder polymer.

[0075] From the viewpoint of more excellent effects of the present invention, the binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group. As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. Further, when the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain. In the present specification, the "main chain" represents the relatively longest bonding chain in the molecule of the high molecular compound constituting the resin, and the "side chain" represents an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable. As an example of the structural unit having a reactive group, those shown below are mentioned, but are not limited thereto.

[0076]

Chemical formula

[0077] The binder polymer may have one kind of structural unit having a reactive group alone or two or more kinds thereof. When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, still more preferably 20 to 40% by mass, based on all the structural units of the binder polymer, from the viewpoint that the effects of the present invention are more excellent. Further, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 50 mol%, based on all the structural units of the binder polymer, from the viewpoint that the effects of the present invention are more excellent.

[0078] As a means for introducing a reactive group into the binder polymer, there is mentioned a method of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride. As a preferred example of a means for introducing a reactive group into a binder polymer, after synthesizing a polymer having a carboxy group by a polymerization reaction, glycidyl (meth) acrylate is reacted with a part of the carboxy groups of the obtained polymer by a polymer reaction to introduce a (meth) acryloxy group into the polymer. By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained. The above polymerization reaction is preferably carried out under temperature conditions of 70 to 100°C, more preferably under temperature conditions of 80 to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fuji Film Wako Pure Chemical Corporation is more preferable. The above polymer reaction is preferably carried out under temperature conditions of 80 to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0079] As the binder polymer, from the viewpoint of more excellent effects of the present invention, the following polymers are preferable. The content ratios (a to d) of each structural unit shown below, the weight average molecular weight Mw, etc. can be appropriately changed according to the purpose.

[0080]

Chemical formula

[0081]

Chemical formula

[0082] Further, the binder polymer may contain a polymer having a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as "polymer X"). The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure. As the ring of the cyclic carboxylic anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is even more preferable.

[0083] The structural unit having a carboxylic anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from the compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0084]

Chemical formula

[0085] In formula P-1, R A1a represents a substituent, and n 1a number of R A1a may be the same or different, and Z 1a represents a divalent group that forms a ring containing -C(=O)-O-C(=O)-, and n 1a represents an integer of 0 or more.

[0086] Examples of the substituent represented by R A1a include, for example, an alkyl group. Z 1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms. n 1a represents an integer of 0 or more. When Z 1a represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. n 1a When represents an integer of 2 or more, a plurality of R A1a may be the same or different. Also, a plurality of R A1a may be bonded to each other to form a ring, but it is preferably not bonded to each other to form a ring.

[0087] As the structural unit having a carboxylic anhydride structure, a structural unit derived from an unsaturated carboxylic anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic anhydride is more preferable, a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride is still more preferable, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.

[0088] Hereinafter, specific examples of the structural unit having a carboxylic anhydride structure will be given, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or a CF 3 group, and Me represents a methyl group.

[0089] [Chemical formula]

[0090] [Chemical formula]

[0091] The structural unit having a carboxylic anhydride structure in polymer X may be a single type or two or more types.

[0092] The total content of the structural unit having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 35 mol% based on all the structural units of polymer X.

[0093] The photosensitive composition layer may contain only one type of polymer X or may contain two or more types. When the photosensitive composition layer contains polymer X, from the viewpoint of more excellent effects of the present invention, the content of polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 20% by mass, and still more preferably 1.0 to 20% by mass based on the total mass of the photosensitive composition layer.

[0094] The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 100,000, and particularly preferably 15,000 to 80,000 from the viewpoint of more excellent effects of the present invention.

[0095] The acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 mg to 200 mgKOH / g, still more preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 110 mgKOH / g. The acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992.

[0096] The photosensitive composition layer may contain only one kind of binder polymer or may contain two or more kinds. The content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of more excellent effects of the present invention.

[0097] <Polymerizable compound> The photosensitive composition layer may contain a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, and a radical polymerizable group is preferred.

[0098] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as "ethylenically unsaturated compound"). As the ethylenically unsaturated group, a (meth)acryloxy group is preferred. The ethylenically unsaturated compound in the present specification is a compound other than the above binder polymer, and preferably has a molecular weight of less than 5,000.

[0099] As one of the preferred embodiments of the coincidence compound, a compound represented by the following formula (M) (simply referred to as "compound M") can be mentioned. Q 2 -R 1 -Q 1 Formula (M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.

[0100] Q in formula (M) 1 and Q 2 are preferably the same group from the viewpoint of ease of synthesis. 1 and Q 2 are preferably the same group. Also, Q in formula (M) 1 and Q 2 are preferably acryloyloxy groups from the viewpoint of reactivity. As R in formula (M) 1 , from the viewpoint that the effects of the present invention are more excellent, an alkylene group, an alkyleneoxyalkylene group (-L 1 -O-L 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferable, a hydrocarbon group having 2 to 20 carbon atoms, or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is still more preferable, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferable. The above hydrocarbon group only needs to have a chain structure at least partially, and the part other than the above chain structure is not particularly limited. For example, it may be any of a branched chain, a cyclic structure, or a linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, and combinations thereof. A group obtained by combining an alkylene group or two or more alkylene groups and one or more arylene groups is preferable, an alkylene group is more preferable, and a linear alkylene group is still more preferable. Note that the above L 1Each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

[0101] Also, Q in compound M 1 and Q 2 The number of atoms in the shortest linking chain connecting between them is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, and particularly preferably 8 to 12 from the viewpoint of more excellent effects of the present invention. In this specification, "the number of atoms in the shortest linking chain connecting between Q 1 and Q 2 " means the shortest number of atoms connecting from the atom in R 1 linked to Q 1 to the atom in R 2 linked to Q 1 .

[0102] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, from the viewpoint of more excellent effects of the present invention, it is preferably at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. More preferably, it is at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, and 1,10 - decanediol di(meth)acrylate. Even more preferably, it is at least one compound selected from the group consisting of 1,9 - nonanediol di(meth)acrylate and 1,10 - decanediol di(meth)acrylate.

[0103] Further, as one of the preferred embodiments of the polymerizable compound, a polyfunctional ethylenically unsaturated compound having two or more functional groups can be mentioned. In the present specification, the "polyfunctional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0104] There is no particular limitation on the bifunctional ethylenically unsaturated compound, and it can be appropriately selected from known compounds. Examples of the bifunctional ethylenically unsaturated compound other than the above compound M include tricyclodecane dimethanol di(meth)acrylate.

[0105] Examples of commercially available difunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0106] There are no particular restrictions on the ethylenically unsaturated compounds having three or more functional groups, and they can be appropriately selected from known compounds. Examples of the ethylenically unsaturated compounds having three or more functional groups include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0107] Here, “(tri / tetra / penta / hexa)(meth)acrylate” is a concept encompassing tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra)(meth)acrylate” is a concept encompassing tri(meth)acrylate and tetra(meth)acrylate.

[0108] Examples of the polymerizable compound include caprolactone-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., etc.), and ethoxylated glycerol triacrylate (such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0109] Examples of the polymerizable compound also include urethane (meth)acrylate compounds. Examples of urethane (meth)acrylate include urethane di(meth)acrylate, such as propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. In addition, examples of urethane (meth)acrylate also include urethane (meth)acrylate having 3 or more functional groups. The lower limit of the number of functional groups is more preferably 6 or more, and even more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of urethane (meth)acrylate having 3 or more functional groups include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0110] One preferred embodiment of the polymerizable compound includes ethylenically unsaturated compounds having an acid group. Examples of the acid group include a phosphate group, a sulfo group, and a carboxy group. Among these, as the acid group, a carboxy group is preferred. Examples of the ethylenically unsaturated compound having an acid group include 3- to 4-functional ethylenically unsaturated compounds having an acid group [compounds in which a carboxy group is introduced into a pentaerythritol tri- and tetraacrylate (PETA) skeleton (acid value: 80 to 120 mgKOH / g)], 5- to 6-functional ethylenically unsaturated compounds having an acid group [compounds in which a carboxy group is introduced into a dipentaerythritol penta- and hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mgKOH / g)], and the like. These ethylenically unsaturated compounds having 3 or more functional groups with an acid group may be used in combination with a 2-functional ethylenically unsaturated compound having an acid group as needed.

[0111] As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of ethylenically unsaturated compounds having 2 or more functional groups with a carboxy group and carboxylic acid anhydrides thereof is preferable. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of ethylenically unsaturated compounds having 2 or more functional groups with a carboxy group and carboxylic acid anhydrides thereof, the developability and film strength are further enhanced. The ethylenically unsaturated compound having 2 or more functional groups with a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of the ethylenically unsaturated compound having 2 or more functional groups with a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0112] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

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

[0113] In addition, as the ethylenically unsaturated compound having an acid group, ethylene oxide-modified dimethacrylate phosphate (KAYAMER PM-21, manufactured by Nippon Kayaku Co., Ltd.), which is an ethylenically unsaturated compound having a phosphate group, can also be used.

[0114] Examples of the overlapping compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and phthalic acid-based compounds such as β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters. These are used alone or in combination of two or more.

[0115] Examples of the compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable.

[0116] Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., etc.), ethoxylated glycerol triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

[0117] As the polymerizable compound (particularly, an ethylenically unsaturated compound), those containing an ester bond are particularly preferable in terms of excellent developability of the photosensitive composition layer after transfer. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable in terms of excellent effects of the present invention, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable. From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure. Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0118] One preferred embodiment of the polymerizable compound includes a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). As the above-mentioned polymerizable compound, a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably, a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferable, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecane dimethanol di(meth)acrylate is even more preferable. As the above-mentioned aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects of the present invention, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure is preferable.

[0119] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and particularly preferably 300 to 2,200. Among the polymerizable compounds contained in the photosensitive composition layer, the proportion of the content of the polymerizable compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less with respect to the content of all the polymerizable compounds contained in the photosensitive composition layer.

[0120] As one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains an ethylenically unsaturated compound having two or more functional groups, more preferably contains an ethylenically unsaturated compound having three or more functional groups, and even more preferably contains an ethylenically unsaturated compound having three or four functional groups.

[0121] Also, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring.

[0122] Also, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M), a polymerizable compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0123] Also, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0124] Also, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a polymerizable compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a polymerizable compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0125] Also, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a polyfunctional ethylenically unsaturated compound having three or more functional groups (preferably a polyfunctional (meth)acrylate compound having three or more functional groups).

[0126] Also, as one of the preferred embodiments of the photosensitive composition layer, from the viewpoint of rust prevention, the photosensitive composition layer preferably contains a compound represented by formula (M) and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure. Further, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group from the viewpoints of substrate adhesion, development residue suppression, and rust prevention properties. More preferably, it contains a compound represented by formula (M), a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group. Even more preferably, it contains a compound represented by formula (M), a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having three or more functional groups, and an ethylenically unsaturated compound having an acid group. Further, in addition to these, it is also preferable that the photosensitive composition layer further contains a urethane (meth) acrylate compound. Further, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group from the viewpoints of substrate adhesion, development residue suppression, and rust prevention properties. More preferably, it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. Even more preferably, it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group. Further, in addition to these, it is also preferable that the photosensitive composition layer further contains a urethane (meth) acrylate compound.

[0127] The photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the ethylenically unsaturated compound having two or more functional groups in the above ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass based on the total content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0128] The polymerizable compound (especially, ethylenically unsaturated compound) may be used alone or in combination of two or more kinds. As the lower limit of the content of the polymerizable compound (especially, ethylenically unsaturated compound) in the photosensitive composition layer, 1% by mass or more is preferable, 5% by mass or more is more preferable, 10% by mass or more is still more preferable, and 15% by mass or more is particularly preferable with respect to the total mass of the photosensitive composition layer. As the upper limit, 70% by mass or less is preferable, 60% by mass or less is more preferable, and 50% by mass or less is still more preferable.

[0129] <Polymerization initiator> The photosensitive composition layer may contain a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferable. There is no particular limitation on the photopolymerization initiator, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, also referred to as "α-aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as "N-phenylglycine-based photopolymerization initiator").

[0130] The photopolymerization initiator preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator, and more preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

[0131] In addition, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A No. 2011-095716 and paragraphs

[0064] to

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

[0132] Commercially available photoinitiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, manufactured by IGM Resins B.V.], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad® 907, manufactured by IGM Resins B.V.], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad® 127, manufactured by IGM Resins B.V.], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad® 369, manufactured by IGM Resins B.V.], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad® 1173, manufactured by IGM Resins B.V.], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad® 184, manufactured by IGM Resins B.V.], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: Omnirad® 651, manufactured by IGM Resins B.Examples include oxime ester-based products such as those manufactured by Valve Corporation [product name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) [product name: TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.], 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acet yloxime) [product name: TR-PBG-326, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.], 3-cyclohexyl-1-(6-(2-(benzoyloximino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) [product name: TR-PBG-391, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.], APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.), and the like.

[0133] The photoinitiator may be used alone or in combination of two or more. When the photosensitive composition layer contains a photoinitiator, the content of the photoinitiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more based on the total mass of the photosensitive composition layer. Also, as the upper limit value, it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less based on the total mass of the photosensitive composition layer.

[0134] <Heterocyclic compound> The photosensitive composition layer may contain a heterocyclic compound. The heterocyclic ring of the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of the heteroatom of the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0135] Examples of the heterocyclic ring compound include, for example, a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound. Among them, as the heterocyclic ring compound, at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound, and a benzoxazole compound is preferable, and at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, and a benzoxazole compound is more preferable.

[0136] Preferable specific examples of the heterocyclic ring compound are shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

[0137]

Chemical formula

[0138]

Chemical formula

[0139] Examples of the tetrazole compound include the following compounds.

[0140]

Chemical formula

[0141]

Chemical formula

[0142] Examples of the thiadiazole compound include the following compounds.

[0143]

Chemical formula

[0144] Examples of the triazine compound include the following compounds.

[0145]

Chemical formula

[0146] Examples of the rhodanine compound include the following compounds.

[0147]

Chemical formula

[0148] Examples of the thiazole compound include the following compounds.

[0149]

Chemical formula

[0150] Examples of the benzothiazole compound include the following compounds.

[0151]

Chemical formula

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

[0153]

Chemical formula

[0154] [Chemical formula]

[0155] Examples of the benzoxazole compound include the following compounds.

[0156] [Chemical formula]

[0157] The heterocyclic compound may be used alone or in combination of two or more. When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, still more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass with respect to the total mass of the photosensitive composition layer.

[0158] <Aliphatic thiol compound> The photosensitive composition layer may contain an aliphatic thiol compound. When the photosensitive composition layer contains an aliphatic thiol compound, the en-thiol reaction between the aliphatic thiol compound and a radically polymerizable compound having an ethylenically unsaturated group suppresses the curing shrinkage of the formed film and relaxes the stress.

[0159] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, an aliphatic thiol compound having two or more functional groups) is preferable.

[0160] Among them, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is preferable from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure).

[0161] In this specification, the "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0162] As the polyfunctional aliphatic thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0163] As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, from the viewpoint of the adhesion of the formed pattern, 2 to 10 functional groups are preferable, 2 to 8 functional groups are more preferable, and 2 to 6 functional groups are even more preferable.

[0164] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.

[0165] Among them, as the polyfunctional aliphatic thiol compound, at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferable.

[0166] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0167] The photosensitive composition layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds.

[0168] When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, still more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass based on the total mass of the photosensitive composition layer.

[0169] <Thermosetting compound> From the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive composition layer preferably contains a thermosetting compound. In this specification, the thermosetting compound having an ethylenically unsaturated group described later is treated as a thermosetting compound and not as an ethylenically unsaturated compound. Examples of the thermosetting compound include an epoxy compound, an oxetane compound, a methylol compound, and a blocked isocyanate compound. Among them, a blocked isocyanate compound is preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Since the blocked isocyanate compound reacts with hydroxy groups and carboxy groups, for example, when at least one of a binder polymer and a radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to be enhanced. The blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".

[0170] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter". As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

[0171] Examples of the blocking agent having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and compounds having a structure represented by -C(=N-OH)- in the molecule such as cyclohexanone oxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160°C, for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.

[0172] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoints of improving the brittleness of the film and enhancing the adhesion to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferable because it is easier to set the dissociation temperature in a preferable range and to reduce development residues than a compound having no oxime structure.

[0173] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, and a radical polymerizable group is preferable. Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as glycidyl group. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0174] Commercially available products can be used as the blocked isocyanate compound. Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), and blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0175] The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0176] <Surfactant> The photosensitive composition layer may contain a surfactant. Examples of the surfactant include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0177] As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferred. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), Photogen 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 (all manufactured by NEOS Co., Ltd.), U-120E (manufactured by Unichem Co., Ltd.), and the like. In addition, as the fluorosurfactant, an acrylic compound having a molecular structure with a functional group containing a fluorine atom and, when heated, the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes can also be preferably used. As such a fluorosurfactant, the MegaFac DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, MegaFac DS-21 can be mentioned. In addition, as the fluorosurfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. In addition, as the fluorosurfactant, block polymers can also be used. In addition, as the fluorosurfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably an ethyleneoxy group, a propyleneoxy group) can also be preferably used. In addition, as the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Examples include MegaFac RS-101, RS-102, RS-718K, RS-72-K (all of the above are manufactured by DIC Corporation). As the fluorosurfactant, from the viewpoint of improving environmental suitability, it is preferably a surfactant derived from a substitute material for compounds having a linear perfluoroalkyl group with 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Corporation), Pyonin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0178] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified silicone polymers with organic groups introduced into the side chains or terminals.

[0179] Specific examples of the silicone-based surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Toray Dow Corning 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, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (manufactured by BYK Chemie), etc.

[0180] The surfactant may be used alone or in combination of two or more. When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 0.80% by mass based on the total mass of the photosensitive composition layer.

[0181] <Polymerization inhibitor> The photosensitive composition layer may contain a polymerization inhibitor. The polymerization inhibitor means a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0182] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; hindered phenol compounds such as bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis〔(laurylthio)methyl〕-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among them, in terms of more excellent effects of the present invention, as the polymerization inhibitor, at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or its salt, and a hindered phenol compound is preferable, and phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylene bis(oxyethylene)]2,4-bis〔(laurylthio)methyl〕-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), and N-nitrosophenylhydroxylamine aluminum salt are more preferable.

[0183] The polymerization inhibitor may be used alone or in combination of two or more. When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, and still more preferably 0.04 to 3.0% by mass based on the total mass of the photosensitive composition layer.

[0184] <Hydrogen donating compound> The photosensitive composition layer may contain a hydrogen donating compound. The hydrogen donating compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound by oxygen.

[0185] Examples of the hydrogen donating compound include amines and amino acid compounds.

[0186] Examples of amines include compounds described in "Journal of Polymer Society", Vol. 10, p. 3173 (1972) by M.R. Sander et al., Japanese Patent Publication No. 44-020189, Japanese Unexamined Patent Application Publication No. 51-082102, Japanese Unexamined Patent Application Publication No. 52-134692, Japanese Unexamined Patent Application Publication No. 59-138205, Japanese Unexamined Patent Application Publication No. 60-084305, Japanese Unexamined Patent Application Publication No. 62-018537, Japanese Unexamined Patent Application Publication No. 64-033104, and Research Disclosure No. 33825. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline can be mentioned. Among them, in terms of more excellent effects of the present invention, as amines, at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferable.

[0187] Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, in terms of more excellent effects of the present invention, as the amino acid compound, N-phenylglycine is preferable.

[0188] Examples of hydrogen-donating compounds also include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithiane) described in Japanese Unexamined Patent Application Publication No. 6-308727.

[0189] The hydrogen-donating compounds may be used alone or in combination of two or more. When the photosensitive composition layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and still more preferably 0.03 to 5.0% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer.

[0190] <Impurities, etc.> The photosensitive composition layer may contain a predetermined amount of impurities. Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so it is preferable to set the content as follows.

[0191] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and still more preferably 2 ppm or less, based on mass. The content of impurities in the photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more, based on mass.

[0192] Examples of the method for setting the impurities within the above range include selecting a raw material for the photosensitive composition layer with a low content of impurities, preventing the mixing of impurities during the formation of the photosensitive composition layer, and washing and removing them. By such methods, the amount of impurities can be made within the above range.

[0193] Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0194] In the photosensitive composition layer, the contents of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane are preferably low. As the content of these compounds in the photosensitive composition layer, based on mass, 100 ppm or less is preferable, 20 ppm or less is more preferable, and 4 ppm or less is even more preferable. The lower limit can be 10 ppb or more, and can be 100 ppb or more, based on mass. The contents of these compounds can be suppressed by the same method as the impurities of the above metals. Also, they can be quantified by known measurement methods.

[0195] From the viewpoint of improving reliability and laminatability, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass.

[0196] <Residual monomer> The photosensitive composition layer may contain residual monomers of each structural unit of the above-described alkali-soluble resin. From the viewpoints of patterning properties and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, based on the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but 1 ppm by mass or more is preferable, and 10 ppm by mass or more is more preferable. From the viewpoints of patterning properties and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, based on the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but 0.1 ppm by mass or more is preferable, and 1 ppm by mass or more is more preferable.

[0197] When synthesizing an alkali-soluble resin by a polymer reaction, it is also preferable that the amount of residual monomer of the monomer be within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the content of glycidyl acrylate be within the above range. The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0198] <Other components> The photosensitive composition layer may contain components other than the above-described components (hereinafter also referred to as "other components"). Examples of other components include colorants, antioxidants, and particles (for example, metal oxide particles). Further, as other components, other additives described in paragraphs

[0058] to

[0071] of JP-A-2000-310706 are also included.

[0199] -Particles- As the particles, metal oxide particles are preferable. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and calculating the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0200] When the photosensitive composition layer contains particles, it may contain only one kind of particles having different metal species, sizes, etc., or may contain two or more kinds. The photosensitive composition layer either contains no particles, or when the photosensitive composition layer contains particles, the content of the particles is preferably more than 0% by mass and 35% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably more than 0% by mass and 5% by mass or less, even more preferably more than 0% by mass and 1% by mass or less, and particularly preferably contains no particles, based on the total mass of the photosensitive composition layer.

[0201] -Colorant- The photosensitive composition layer may contain a small amount of a colorant (such as a pigment or a dye), but for example, from the viewpoint of transparency, it is preferably substantially free of a colorant. When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive composition layer.

[0202] -Antioxidant- Examples of the antioxidant include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among them, from the viewpoint that the effects of the present invention are more excellent, 3-pyrazolidones are preferably used as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferably used.

[0203] When the photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 1% by mass or less.

[0204] <Thickness of the photosensitive composition layer> The thickness of the photosensitive composition layer is not particularly limited, but is often 30 μm or less. In terms of more excellent effects of the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5.0 μm or less. As the lower limit, in terms of excellent strength of the film obtained by curing the photosensitive composition layer, it is preferably 0.60 μm or more, and more preferably 1.5 μm or more. The thickness of the photosensitive composition layer can be calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM), for example.

[0205] <Refractive index of the photosensitive composition layer> The refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, and more preferably 1.49 to 1.54.

[0206] <Color of the photosensitive composition layer> The photosensitive composition layer is preferably achromatic. Specifically, for total reflection (incident angle 8°, light source: D-65 (2° field of view)), in the CIE1976 (L*, a*, b*) color space, the L * value is preferably 10 to 90, the a * value is preferably -1.0 to 1.0, and the b * value is preferably -1.0 to 1.0.

[0207] Note that the pattern obtained by curing the photosensitive composition layer (the cured film of the photosensitive composition layer) is preferably achromatic. Specifically, for total reflection (incident angle 8°, light source: D-65 (2° field of view)), in the CIE1976 (L*, a*, b*) color space, the L * value of the pattern is preferably 10 to 90, and the a *The value is preferably -1.0 to 1.0, and for pattern b * The value is preferably -1.0 to 1.0.

[0208] In the transfer film of the first embodiment, the tanδ of the photosensitive composition layer can greatly affect the tanδ of the entire composition layer. The composition layer satisfying the requirements of formulas (1A) to (3A) can be easily formed by appropriately selecting the types of the constituent components of the above-described photosensitive composition layer and appropriately adjusting its manufacturing procedure.

[0209] <<Protective Film>> The transfer film may have a protective film. As the protective film, a resin film having heat resistance and solvent resistance can be used. Examples include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. Also, a resin film made of the same material as the above-described temporary support may be used as the protective film. Among them, as the protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is even more preferable.

[0210] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and preferably 100 μm or less in terms of relatively low cost.

[0211] Also, in the protective film, the number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5 pieces / m 2 or less. Note that "fish eyes" are formed when manufacturing a film by methods such as heat-melting a material, kneading, extruding, biaxially stretching, and casting, and foreign substances, undissolved substances, and oxidation degradation products of the material are incorporated into the film.

[0212] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 particles / mm 2 The following is preferable, and 10 particles / mm 2 The following is more preferable, and 5 particles / mm 2 The following is even more preferable. This can suppress defects caused by unevenness due to particles contained in the protective film being transferred to the photosensitive composition layer or the conductive layer.

[0213] From the viewpoint of imparting winding properties, the arithmetic mean roughness Ra of the surface on the side opposite to the surface in contact with the composition layer of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface in contact with the composition layer of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0214] <<Refractive Index Adjusting Layer>> The transfer film preferably has a refractive index adjusting layer. As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the materials contained in the refractive index adjusting layer include binder polymers, polymerizable compounds, metal salts, and particles. The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples include a method of using a resin with a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin.

[0215] Examples of the binder polymer and the polymerizable compound include the binder polymer and the polymerizable compound described in the above item "photosensitive composition layer".

[0216] Examples of the particles include metal oxide particles and metal particles. The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be mentioned. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0217] From the viewpoint of the transparency of the cured film, for example, the average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and calculating the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0218] Specific examples of the metal oxide particles include zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), silicon dioxide particles (SiO 2 particles), and at least one selected from the group consisting of these composite particles is preferred. Among these, as the metal oxide particles, for example, from the viewpoint of easy adjustment of the refractive index, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred.

[0219] Examples of commercially available metal oxide particles include fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nano Use OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nano Use OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0220] The particles may be used alone or in combination of two or more. The content of the particles in the refractive index adjusting layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 85% by mass, based on the total mass of the refractive index adjusting layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 85% by mass, based on the total mass of the refractive index adjusting layer.

[0221] The refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive composition layer. The refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, still more preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less, and particularly preferably 1.74 or less.

[0222] The thickness of the refractive index adjusting layer is preferably 50 to 500 nm, more preferably 55 to 110 nm, and still more preferably 60 to 100 nm. The thickness of the refractive index adjusting layer is calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0223] <<Method for manufacturing transfer film of first embodiment>> The method for manufacturing the transfer film of the first embodiment is not particularly limited, and known methods can be used. As the method for manufacturing the transfer film 10 described above, for example, a step of applying a photosensitive composition onto the surface of the temporary support 1 to form a coating film, and further drying this coating film to form a photosensitive composition layer 3; and a step of applying a composition for forming a refractive index adjustment layer onto the surface of the photosensitive composition layer 3 to form a coating film, and further drying this coating film to form a refractive index adjustment layer 5, are included.

[0224] The transfer film 10 is manufactured by pressing the protective film 7 onto the refractive index adjustment layer 5 of the laminate manufactured by the above manufacturing method. As the method for manufacturing the transfer film of the first embodiment, by including a step of providing the protective film 7 so as to contact the surface of the transfer film 10 on the side opposite to the side having the temporary support 1 of the refractive index adjustment layer 5, it is preferable to manufacture the transfer film 10 including the temporary support 1, the photosensitive composition layer 3, the refractive index adjustment layer 5, and the protective film 7. After manufacturing the transfer film 10 by the above manufacturing method, the transfer film 10 may be wound up to produce and store the transfer film in roll form. The transfer film in roll form can be provided in its original form in the bonding step with the substrate by the roll-to-roll method described later.

[0225] Also, as the method for manufacturing the transfer film 10 described above, a method may be used in which after forming the refractive index adjustment layer 5 on the protective film 7, a photosensitive resin layer 3 is formed on the surface of the refractive index adjustment layer 5. Also, as the method for manufacturing the transfer film 10 described above, a method may be used in which a photosensitive composition layer 3 is formed on the temporary support 1, separately, a refractive index adjustment layer 5 is formed on the protective film 7, and the refractive index adjustment layer 5 and the photosensitive composition layer 3 are bonded together to form.

[0226] <Formation method of photosensitive composition and photosensitive composition layer> In terms of excellent productivity and the ease of forming a composition layer that satisfies the requirements of the above-described formulas (1A) to (3A), the photosensitive composition layer in the transfer film is preferably formed by a coating method using a photosensitive composition containing components (for example, a binder polymer, a polymerizable compound, a polymerization initiator, etc.) constituting the above-described photosensitive composition layer and a solvent. Specifically, as a method for manufacturing the transfer film of the first embodiment, it is preferable to apply a photosensitive composition onto a temporary support to form a coating film, and subject this coating film to a drying treatment at a predetermined temperature to form a photosensitive composition layer. Note that the amount of residual solvent is adjusted by the drying treatment of the coating film, and as a result, it is presumed that the tan δ of the photosensitive composition layer is appropriately adjusted, and a composition layer that satisfies the requirements of the above-described formulas (1A) to (3A) is easily formed.

[0227] As the solvent that can be included in the photosensitive composition, an organic solvent is preferable. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0228] In addition, as the solvent, an organic solvent (high-boiling solvent) having a boiling point of 180 to 250°C can be used as necessary.

[0229] The solvent may be used alone or in combination of two or more. The total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and still more preferably 5 to 30% by mass with respect to the total mass of the photosensitive composition. That is, the content of the solvent in the photosensitive composition is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and still more preferably 70 to 95% by mass with respect to the total mass of the photosensitive composition.

[0230] The viscosity of the photosensitive composition at 25°C is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and still more preferably 3 to 30 mPa·s, for example, from the viewpoint of coatability. The viscosity is measured using a viscometer. As the viscometer, for example, a viscometer (trade name: VISCOMETER TV-22) manufactured by Toki Sangyo Co., Ltd. can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

[0231] The surface tension of the photosensitive composition at 25°C is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and still more preferably 15 to 40 mN / m, for example, from the viewpoint of coatability. The surface tension is measured using a surface tensiometer. As the surface tensiometer, for example, a surface tensiometer (trade name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. can be preferably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0232] Examples of the coating method of the photosensitive composition include printing method, spraying method, roll coating method, bar coating method, curtain coating method, spin coating method, and die coating method (i.e., slit coating method).

[0233] As the drying method of the coating film of the photosensitive composition, heat drying and vacuum drying are preferable. In this specification, "drying" means removing at least a part of the solvent contained in the composition. In terms of easily forming a composition layer in which the tanδ of the photosensitive composition layer is appropriately adjusted to satisfy the requirements of the above formulas (1A) to (3A), the drying temperature is preferably 90°C or higher, more preferably 100°C or higher, and still more preferably 110°C or higher. Also, although the upper limit value is not particularly limited, it is preferably 130°C or lower, more preferably 120°C or lower. In addition, in terms of the ease of forming a composition layer in which the tanδ of the photosensitive composition layer is appropriately adjusted to satisfy the requirements of the above-described formulas (1A) to (3A), the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. Further, although the upper limit value is not particularly limited, it is preferably 450 seconds or less, and more preferably 300 seconds or less.

[0234] <Composition for Forming Refractive Index Adjustment Layer and Method for Forming Refractive Index Adjustment Layer> The composition for forming a refractive index adjustment layer preferably contains various components for forming the above-described refractive index adjustment layer and a solvent. In the composition for forming a refractive index adjustment layer, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the above-described refractive index adjustment layer. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjustment layer, and at least one selected from the group consisting of water and water-miscible organic solvents is preferable, and a mixed solvent of water or a water-miscible organic solvent and water is more preferable. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and still more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.

[0235] The method for forming the refractive index adjustment layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. Examples thereof include known coating methods (such as slit coating, spin coating, curtain coating, and inkjet coating).

[0236] Further, the transfer film of the first embodiment can be manufactured by laminating a protective film on the refractive index adjustment layer. The method of bonding the protective film to the refractive index adjusting layer is not particularly limited, and known methods can be mentioned. Examples of the apparatus for bonding the protective film to the refractive index adjusting layer include known laminators such as a vacuum laminator and an auto cut laminator. The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0237] 〔Transfer Film of the Second Embodiment〕 Hereinafter, an example of the embodiment of the transfer film of the second embodiment will be described. The transfer film 20 shown in FIG. 2 has, in this order, a temporary support 11, a composition layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive composition layer 17, and a protective film 19. The composition layer 12 satisfies all of the requirements of the above-described formulas (1A) to (3A). Note that the transfer film 20 shown in FIG. 2 has the protective film 19 disposed thereon, but the protective film 19 may not be disposed. Also, the transfer film 20 shown in FIG. 2 has the thermoplastic resin layer 13 and the intermediate layer 15 disposed thereon, but the thermoplastic resin layer 13 and the intermediate layer 15 may not be disposed. Hereinafter, each element constituting the transfer film will be described. In the transfer film of the second embodiment, examples of the temporary support 11 and the protective film 17 are the same as those of the temporary support 1 and the protective film 9 of the first embodiment described above, and the preferred embodiments are also the same.

[0238] <<Photosensitive Composition Layer>> In a display device (such as an organic electroluminescence (EL) display device and a liquid crystal display device) equipped with a touch panel of a capacitive input device or the like, a conductive layer pattern such as an electrode pattern corresponding to a sensor in a visual recognition part, wiring in a peripheral wiring part and a lead-out wiring part, etc. is provided inside the touch panel. Generally, for forming a patterned layer, a method is widely adopted in which a negative photosensitive composition layer (photosensitive layer) is provided on a substrate using a transfer film or the like, exposed through a mask having a desired pattern to the photosensitive layer, and then developed. Therefore, as the photosensitive composition layer, a negative photosensitive composition layer is preferably used. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.

[0239] When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a resin, a polymerizable compound, and a polymerization initiator. Further, when the photosensitive composition layer is a negative photosensitive composition layer, as will be described later, it is also preferable to contain an alkali-soluble resin (such as polymer A which is an alkali-soluble resin) as part or all of the resin. That is, in one aspect, the photosensitive composition layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Such a photosensitive composition layer (negative photosensitive composition layer) preferably contains, based on the total mass of the photosensitive composition layer: resin: 10 to 90% by mass; polymerizable compound: 5 to 70% by mass; polymerization initiator: 0.01 to 20% by mass. Hereinafter, each component will be described in order.

[0240] <Polymer A (resin)> When the photosensitive composition layer is a negative photosensitive composition layer, the resin contained in the photosensitive composition layer is also particularly referred to as polymer A. Polymer A is preferably an alkali-soluble resin. The acid value of polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g from the viewpoint of more excellent resolution by suppressing the swelling of the negative photosensitive composition layer by the developer. The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, still more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more.

[0241] Incidentally, the acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of polymer A may be adjusted according to the types of constitutional units constituting polymer A and the content of constitutional units containing acid groups.

[0242] The weight average molecular weight of polymer A is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge fuse property and cut chip property when forming a negative photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property refers to the degree of ease of the negative photosensitive composition layer protruding from the end face of the roll when wound in a roll shape as a negative photosensitive resin laminate. The cut chip property refers to the degree of ease of the chips flying when the unexposed film is cut with a cutter. If these chips adhere to the upper surface or the like of the negative photosensitive resin laminate, they will be transferred to the mask in a subsequent exposure process or the like, causing defective products. The dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0243] From the perspective of suppressing line width thickening and resolution deterioration when the focus position during exposure is deviated, it is preferable that the polymer A contains a structural unit based on a monomer having an aromatic hydrocarbon group. Examples of such an aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A. Although there is no particular limitation on the upper limit, it is preferably 95% by mass or less, more preferably 85% by mass or less. When a plurality of types of polymer A are included, it is preferable that the average value of the content of the structural unit based on the monomer having an aromatic hydrocarbon group is within the above range.

[0244] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferable. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content of the structural unit based on styrene is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, still more preferably 30 to 60% by mass, and particularly preferably 30 to 55% by mass, based on the total mass of the polymer A.

[0245] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding the benzyl group) and a substituted or unsubstituted benzyl group, etc., and a substituted or unsubstituted benzyl group is preferable.

[0246] Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate, etc.

[0247] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinyl benzyl alcohol. Among them, benzyl (meth)acrylate is preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in Polymer A is benzyl (meth)acrylate, the content of the structural unit based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass based on the total mass of Polymer A.

[0248] Polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one monomer having an aromatic hydrocarbon group and at least one of the first monomer described below and / or at least one of the second monomer described below.

[0249] Polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, and more preferably obtained by copolymerizing at least one of the first monomers described below and at least one of the second monomers described below.

[0250] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semi-ester. Among these, (meth)acrylic acid is preferred. The content of the structural unit based on the first monomer in Polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass based on the total mass of Polymer A. Setting the above content percentage to 5% by mass or more is preferable from the viewpoints of achieving good developability and controlling edge fusion properties. Setting the above content percentage to 50% by mass or less is preferable from the viewpoints of high resolution of the resist pattern and the SUS shape, and further from the viewpoint of the chemical resistance of the resist pattern.

[0251] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile and the like. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferable, and methyl (meth)acrylate is more preferable. The content of the structural unit based on the second monomer in polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and still more preferably 17 to 45% by mass with respect to the total mass of polymer A.

[0252] When polymer A contains a structural unit based on a monomer having an aralkyl group and / or a structural unit based on styrene as a monomer, it is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focus position during exposure is shifted. For example, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, a structural unit based on benzyl methacrylate, and a structural unit based on styrene are preferable. In one aspect, it is preferable that the polymer A is a polymer containing 25 to 55% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of a structural unit based on a first monomer, and 15 to 45% by mass of a structural unit based on a second monomer. Further, in another aspect, it is preferable that the polymer is a polymer containing 70 to 90% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit based on a first monomer.

[0253] The polymer A may have a branched structure and / or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. Specific examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate is preferable, and i-propyl methacrylate or t-butyl methacrylate is more preferable. Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are included. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2-methyl-2-adamantyl, (meth)acrylic acid 2-ethyl-2-adamantyl, (meth)acrylic acid 3-hydroxy-1-adamantyl, (meth)acrylic acid octahydro-4,7-menthanoninden-5-yl, (meth)acrylic acid octahydro-4,7-menthanoninden-1-ylmethyl, (meth)acrylic acid-1-menthyl, (meth)acrylic acid tricyclodecane, (meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl, (meth)acrylic acid (nor)bornyl, (meth)acrylic acid isobornyl, (meth)acrylic acid fenchyl, (meth)acrylic acid-2,2,5-trimethylcyclohexyl, and (meth)acrylic acid cyclohexyl, etc.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenthyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecanyl (meth)acrylate is preferable, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecanyl (meth)acrylate is more preferable.

[0254] Polymer A may be used alone or in combination of two or more. When using two or more, it is preferable to mix and use two types of Polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group, or to mix and use Polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group and Polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group. In the latter case, the usage ratio of Polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more based on the total mass of Polymer A.

[0255] The synthesis of Polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting the above-mentioned single or plural monomers with a solvent such as acetone, methyl ethyl ketone, and isopropanol, and heating and stirring. In some cases, synthesis may be carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, the solvent may be further added to adjust to a desired concentration. As the synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

[0256] The glass transition temperature Tg of the polymer A is preferably 30 to 135°C. By using the polymer A having a Tg of 135°C or lower, it is possible to suppress line width thickening and deterioration of resolution when the focus position during exposure is shifted. From this viewpoint, the Tg of the polymer A is more preferably 130°C or lower, still more preferably 120°C or lower, and particularly preferably 110°C or lower. Also, using the polymer A having a Tg of 30°C or higher is preferable from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0257] The negative photosensitive composition layer may contain other resins than those described above as the polymer A. Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0258] As the polymer A, an alkali-soluble resin described in the description of the thermoplastic resin layer to be described later may be used.

[0259] The content of the polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass with respect to the total mass of the negative photosensitive composition layer. Setting the content of the polymer A to 90% by mass or less is preferable from the viewpoint of controlling the development time. On the other hand, setting the content of the polymer A to 10% by mass or more is preferable from the viewpoint of improving edge fuse resistance.

[0260] <Polymerizable compound> When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a polymerizable compound having a polymerizable group. The "polymerizable compound" mentioned above means a compound that polymerizes under the action of a polymerization initiator described later and is different from the above-mentioned polymer A.

[0261] The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction. For example, groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group such as an epoxy group and an oxetane group can be mentioned. As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

[0262] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferable in terms of more excellent photosensitivity of the negative photosensitive composition layer, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferable. Also, in terms of more excellent resolution and peelability, the number of ethylenically unsaturated groups possessed by the ethylenically unsaturated compound in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0263] In terms of more excellent balance between the photosensitivity, resolution, and peelability of the negative photosensitive composition layer, it is preferable to contain a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and it is more preferable to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. The content of the bifunctional ethylenically unsaturated compound with respect to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more from the viewpoint of excellent peelability with respect to the total mass of the negative photosensitive composition layer. The upper limit is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. In addition, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.

[0264] (Polymerizable Compound B1) The negative photosensitive composition layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-described polymerizable compounds B.

[0265] In the negative photosensitive composition layer, from the viewpoint of better resolution, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit is not particularly limited, but from the viewpoint of peelability, for example, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0266] Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof. An aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable. The above aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring or two or more aromatic rings.

[0267] From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive composition layer by the developer, the polymerizable compound B1 preferably has a bisphenol structure. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). The bisphenol A structure is preferred.

[0268] Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferred, and an ethyleneoxy group is more preferred. The number of added alkyleneoxy groups to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the content described in this publication is incorporated herein.

[0269] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0270] As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferable.

[0271] [Chemical formula]

[0272] In the general formula B1, R 1 and R 2 each independently represent a hydrogen atom or a methyl group. A represents C 2 H 4 B represents C 3 H 6 n1 and n3 are each independently an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the structural units of -(A-O)- and -(B-O)- may be random or block. And in the case of a block, either -(A-O)- or -(B-O)- may be on the bisphenol group side. In one aspect, n1 + n2 + n3 + n4 is preferably from 2 to 20, more preferably from 2 to 16, still more preferably from 4 to 12. Also, n2 + n4 is preferably from 0 to 10, more preferably from 0 to 4, still more preferably from 0 to 2, and particularly preferably 0.

[0273] The polymerizable compound B1 may be used alone or in combination of two or more. From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive composition layer. The upper limit is not particularly limited, but from the viewpoints of transferability and edge fusion (the phenomenon in which the photosensitive resin oozes out from the edge of the transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0274] The negative photosensitive composition layer may contain a polymerizable compound other than the above-described polymerizable compound B1. The polymerizable compound other than the polymerizable compound B1 is not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a polyfunctional ethylenically unsaturated compound having three or more functional groups can be mentioned.

[0275] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0276] Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of the urethane di(meth)acrylate include propylene oxide-modified urethane di(meth)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of the commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0277] Examples of the ethylenically unsaturated compounds having three or more functional groups include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and their alkylene oxide-modified products. Here, “(tri / tetra / penta / hexa)(meth)acrylate” is a concept encompassing tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra)(meth)acrylate” is a concept encompassing tri(meth)acrylate and tetra(meth)acrylate. In one aspect, it is also preferable that the negative photosensitive composition layer contains the above-described polymerizable compound B1 and an ethylenically unsaturated compound having a functionality of 3 or more, and it is more preferable that the negative photosensitive composition layer contains the above-described polymerizable compound B1 and two or more ethylenically unsaturated compounds having a functionality of 3 or more. In this case, the mass ratio of the polymerizable compound B1 to the ethylenically unsaturated compound having a functionality of 3 or more is preferably (total mass of polymerizable compound B1):(total mass of ethylenically unsaturated compound having a functionality of 3 or more)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. Also, in one aspect, it is preferable that the negative photosensitive composition layer contains the above-described polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0278] Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having a functionality of 3 or more include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd., etc.), ethoxylated glycerol triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ALLONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ALLONIX M-520 (manufactured by Toagosei Co., Ltd.), and ALLONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0279] In addition, as the polymerizable compound, a polymerizable compound having an acid group (such as a carboxy group) may be used. The above acid group may form an acid anhydride group. Examples of the polymerizable compound having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). As the polymerizable compound having an acid group, for example, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.

[0280] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and still more preferably 20 to 70% by mass based on the total mass of the negative photosensitive composition layer.

[0281] The molecular weight (weight average molecular weight in the case of having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200.

[0282] <Polymerization initiator> When the photosensitive composition layer is a negative photosensitive composition layer, it is also preferable that the negative photosensitive composition layer contains a polymerization initiator. The polymerization initiator is selected according to the type of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0283] The negative photosensitive composition layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates the polymerization of the polymerizable compound upon receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include, for example, a photo radical polymerization initiator and a photo cationic polymerization initiator, and a photo radical polymerization initiator is preferred.

[0284] Examples of the photo radical polymerization initiator include, for example, a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0285] In addition, from the viewpoints of photosensitivity, visibility of the exposed portion and the unexposed portion, and resolution, the negative photosensitive composition layer preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof as the photo radical polymerization initiator. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of the derivative of the 2,4,5-triarylimidazole dimer include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0286] As the photo radical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783 may be used.

[0287] Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0288] Examples of commercially available photo radical polymerization initiators include 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxyoxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.oxime ester-based photoinitiators (trade name: Lunar 6, manufactured by DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-, 2-(O-acetoxime) (trade name: TR-PBG-326, manufactured by Changzhou Qiangli Electronic New Materials), and 3-cyclohexyl-1-(6-(2-(benzoyloximino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Qiangli Electronic New Materials) can be mentioned.

[0289] A photo cationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving actinic rays. As the photo cationic polymerization initiator, a compound that is sensitive to actinic rays having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm, and generates an acid is preferred, but its chemical structure is not limited. Also, for a photo cationic polymerization initiator that is not directly sensitive to actinic rays having a wavelength of 300 nm or more, if it is a compound that is sensitive to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer, it can be preferably used in combination with the sensitizer. As the photo cationic polymerization initiator, a photo cationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photo cationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photo cationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. The lower limit value of the pKa is not particularly defined, but for example, -10.0 or more is preferred.

[0290] Examples of the photo cationic polymerization initiator include an ionic photo cationic polymerization initiator and a non-ionic photo cationic polymerization initiator. Examples of the ionic photo cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As the ionic photo cationic polymerization initiator, the ionic photo cationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-085643 may be used.

[0291] Examples of the non-ionic photo cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds and imide sulfonate compounds, the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 may be used. As the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of WO2018 / 179640 may be used.

[0292] The negative photosensitive composition layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof.

[0293] The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator (preferably a photo polymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more based on the total mass of the negative photosensitive composition layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less based on the total mass of the negative photosensitive composition layer.

[0294] <Dye> From the viewpoints of the visibility of the exposed and unexposed portions, the pattern visibility after development, and the resolution, it is also preferable that the photosensitive composition layer contains a dye (also referred to as "dye N") having a maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development of 450 nm or more, and the maximum absorption wavelength of which changes due to an acid, a base, or a radical. When the dye N is contained, although the detailed mechanism is unknown, the adhesion to an adjacent layer (for example, a water-soluble resin layer) is improved and the resolution is more excellent.

[0295] In this specification, the phrase "the maximum absorption wavelength of a dye changes due to an acid, a base, or a radical" may mean any of the following modes: a mode in which a dye in a colored state is decolorized by an acid, a base, or a radical; a mode in which a dye in a decolorized state is colored by an acid, a base, or a radical; and a mode in which a dye in a colored state changes to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state by exposure, or a compound that changes from a colored state to a decolorized state by exposure. In this case, it may also be a dye in which an acid, a base, or a radical is generated and acts in the photosensitive composition layer by exposure, thereby changing the colored or decolorized state, or a dye in which the state (for example, pH) in the photosensitive composition layer is changed by an acid, a base, or a radical, thereby changing the colored or decolorized state. Further, it may also be a dye that directly receives an acid, a base, or a radical as a stimulus without exposure and changes the colored or decolorized state.

[0296] Among them, from the viewpoints of the visibility of the exposed and unexposed portions and the resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes due to a radical. When the photosensitive composition layer is a negative photosensitive composition layer, from the viewpoints of the visibility of the exposed and unexposed portions and the resolution, it is preferable that the negative photosensitive composition layer contains both a dye whose maximum absorption wavelength changes due to a radical as the dye N and a photo radical polymerization initiator. Further, from the viewpoint of the visibility of the exposed and unexposed portions, the dye N is preferably a dye that is colored by an acid, a base, or a radical.

[0297] As an example of the color development mechanism of Dye N, a photo radical polymerization initiator, a photo cationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition layer, and after exposure, radicals, acids, or bases generated from the photo radical polymerization initiator, the photo cationic polymerization initiator, or the photobase generator cause a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) to develop color.

[0298] From the viewpoint of the visibility of the exposed and unexposed portions, the maximum absorption wavelength of Dye N in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or more, more preferably 550 to 700 nm, and still more preferably 550 to 650 nm. Further, Dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development, or may have two or more maximum absorption wavelengths. When Dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development, it is sufficient that the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0299] The maximum absorption wavelength of Dye N is obtained by measuring the transmission spectrum of a solution (liquid temperature: 25°C) containing Dye N in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) under an air atmosphere and detecting the wavelength at which the light intensity becomes minimum (maximum absorption wavelength).

[0300] Examples of the dye that develops color or fades by exposure include leuco compounds. Examples of the dye that fades by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. From the viewpoint of the visibility of the exposed and unexposed portions, leuco compounds are preferred as Dye N.

[0301] Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane-based dye), a leuco compound having a spiropyran skeleton (spiropyran-based dye), a leuco compound having a fluoran skeleton (fluoran-based dye), a leuco compound having a diarylmethane skeleton (diarylmethane-based dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a leuco compound having an indolyl phthalide skeleton (indolyl phthalide-based dye), and a leuco compound having a leuco auramine skeleton (leuco auramine-based dye). Among them, a triarylmethane-based dye or a fluoran-based dye is preferable, and a leuco compound having a triphenylmethane skeleton (triphenylmethane-based dye) or a fluoran-based dye is more preferable.

[0302] From the viewpoint of visibility of the exposed portion and the non-exposed portion, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. Thereby, the lactone ring, the sultine ring, or the sultone ring of the leuco compound can be reacted with a radical generated from a photo radical polymerization initiator or an acid generated from a photo cationic polymerization initiator to change the leuco compound into a closed-ring state to decolorize it, or change the leuco compound into an open-ring state to cause color development. As the leuco compound, a compound having a lactone ring, a sultine ring, or a sultone ring and in which the lactone ring, the sultine ring, or the sultone ring is opened by a radical or an acid to cause color development is preferable, and a compound having a lactone ring and in which the lactone ring is opened by a radical or an acid to cause color development is more preferable.

[0303] Examples of the dye N include the following dyes and leuco compounds. Specific examples of the dyes among the coloring matters N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsin, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Metanil Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Para Methyl Red, Congo Red, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Para Fuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-Diethylaminophenyliminonaphthoquinone, 2-Carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-Carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-Phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-Naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0304] Specific examples of the leuco compound among the pigments N include p,p’,p”-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chloro-fluorane, 3-(N,N-diethylamino)-6-methoxy-7-amino-fluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chloro-fluorane, 3-(N,N-diethylamino)-7-benzylamino-fluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-xaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3’,6’-bis(diphenylamino)spiroisobenzofuran-1(3H),9’-[9H]xanthen-3-one.

[0305] From the viewpoints of the visibility of the exposed and unexposed areas, the pattern visibility after development, and the resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue - naphthalene sulfonate is preferable.

[0306] The dye N may be used alone or in combination of two or more. From the viewpoints of the visibility of the exposed and unexposed areas, the pattern visibility after development, and the resolution, the content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 - 10% by mass, still more preferably 0.1 - 5% by mass, and particularly preferably 0.1 - 1% by mass based on the total mass of the photosensitive composition layer.

[0307] The content of the dye N means the content of the dye when all the dye N contained in the total mass of the photosensitive composition layer is in the developed state. Hereinafter, taking the dye that develops color due to radicals as an example, the method for quantifying the content of the dye N will be described. Prepare a solution by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone. To each of the obtained solutions, add the photo - radical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.), and irradiate with light of 365 nm to generate radicals and make all the dyes in the developed state. Then, in an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25°C and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are developed in the same manner as above except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye. Calculate the content of the dye contained in the photosensitive composition layer based on the calibration curve from the absorbance of the solution containing the photosensitive composition layer obtained. Note that 3 g of the photosensitive composition layer is the same as 3 g of the total solid content in the photosensitive resin composition.

[0308] <Thermosetting compound> When the photosensitive composition layer is a negative photosensitive composition layer, it is preferable to contain a thermosetting compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In this specification, the thermosetting compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound but is treated as a thermosetting compound. Examples of the thermosetting compound include methylol compounds and blocked isocyanate compounds. Among them, blocked isocyanate compounds are preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound etc. has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film decreases, and the function when using the film obtained by curing the negative photosensitive composition layer as a protective film tends to be enhanced. Note that the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected with a blocking agent (so-called masked)".

[0309] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 °C, more preferably 130 to 150 °C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter". As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

[0310] Examples of the blocking agent having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and compounds having a structure represented by -C(=N-OH)- in the molecule such as cyclohexanone oxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160°C, at least one selected from oxime compounds is preferable, for example, from the viewpoint of storage stability.

[0311] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoints of improving the brittleness of the film and enhancing the adhesion to the transfer body. The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among the blocked isocyanate compounds having an isocyanurate structure, the compound having an oxime structure using an oxime compound as a blocking agent is preferable from the viewpoints that it is easier to make the dissociation temperature in a preferable range than the compound having no oxime structure and that it is easier to reduce the development residue.

[0312] The blocked isocyanate compound may have a polymerizable group. There is no particular limitation on the polymerizable group, and known polymerizable groups can be used, with radical polymerizable groups being preferable. Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as glycidyl group. Among them, the ethylenically unsaturated group is preferable as the polymerizable group, the (meth)acryloxy group is more preferable, and the acryloxy group is even more preferable.

[0313] Commercially available products can be used as the blocked isocyanate compound. Examples of commercially available block isocyanate compounds include Karens (registered trademark) AOI-BM, Karens (registered trademark) MOI-BM, Karens (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), and the block type Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Also, as the block isocyanate compound, a compound having the following structure can also be used.

[0314] [Chemical formula]

[0315] The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0316] [Other additives] The photosensitive composition layer may contain known additives as necessary in addition to the above components. Examples of the additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazole), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants. Each additive may be used alone or in combination of two or more.

[0317] The photosensitive composition layer may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include, for example, the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitroso phenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition layer, it is preferable to use nitroso phenylhydroxyamine aluminum salt as a radical polymerization inhibitor.

[0318] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0319] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole. As the carboxybenzotriazoles, commercially available products such as CBT-1 (Shiroki Chemical Industry Co., Ltd., trade name) can be used.

[0320] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and the suppression of dye decoloration are more excellent.

[0321] The photosensitive composition layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0322] The sensitizer may be used alone or in combination of two or more. When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. From the viewpoints of improving the sensitivity to the light source and improving the curing rate by the balance between the polymerization rate and the chain transfer, 0.01 to 5% by mass is preferable, and 0.05 to 1% by mass is more preferable with respect to the total mass of the photosensitive composition layer.

[0323] The photosensitive composition layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound. Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0324] Further, the photosensitive composition layer may further contain known additives such as metal oxide particles, an antioxidant, a dispersant, an acid generator, a development accelerator, a conductive fiber, an ultraviolet absorber, a thickener, a crosslinking agent, and an organic or inorganic anti-precipitation agent. The additives contained in the photosensitive composition layer are described in paragraphs 0165 to 0184 of JP-A No. 2014-085643, and the contents of this publication are incorporated herein.

[0325] The water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminability.

[0326] The layer thickness (film thickness) of the photosensitive composition layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm. Thereby, the developability of the photosensitive composition layer is improved, and the resolution can be improved. Also, in one aspect, 0.5 to 5 μm is preferable, 0.5 to 4 μm is more preferable, and 0.5 to 3 μm is still more preferable.

[0327] Also, from the viewpoint of excellent adhesion, the transmittance of light with a wavelength of 365 nm in the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but preferably 99.9% or less.

[0328] <Impurities, etc.> The photosensitive composition layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so it is preferable to have the following content.

[0329] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and still more preferably 2 ppm or less on a mass basis. The content of impurities can be 1 ppb or more and may be 0.1 ppm or more on a mass basis.

[0330] Methods for controlling the amount of impurities within the above range include selecting raw materials for the composition that have a low content of impurities, preventing impurities from being mixed in during the preparation of the photosensitive composition layer, and removing the impurities by washing. By such methods, the amount of impurities can be controlled within the above range.

[0331] Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0332] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably small. The content of these compounds relative to the total mass of the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit, based on mass, can be 10 ppb or more, and can be 100 ppb or more, based on the total mass of the photosensitive composition layer. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Also, they can be quantified by known measurement methods.

[0333] The water content in the photosensitive composition layer is preferably from 0.01 to 1.0% by mass, and more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0334] <Pigments> The photosensitive composition layer may be a colored resin layer containing a pigment. In some cases, in order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc. is attached to the liquid crystal display window. A colored resin layer can be used to form such a light-shielding layer. The pigment may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and colored pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.

[0335] As the black pigment, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as long as the effects of the present invention are not impaired. Among them, from the viewpoint of optical density, examples of the black pigment include carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, etc., and carbon black is particularly preferable. From the viewpoint of surface resistance, carbon black having at least a part of its surface coated with a resin is preferable as the carbon black.

[0336] From the viewpoint of dispersion stability, the particle diameter of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, in terms of number average particle diameter. Here, the particle diameter refers to the diameter of a circle when considering a circle having the same area as the area of the pigment particle obtained from a photographic image of the pigment particle taken with an electron microscope, and the number average particle diameter is an average value obtained by obtaining the above particle diameter for any 100 particles and averaging the 100 obtained particle diameters.

[0337] As pigments other than black pigments, for white pigments, the white pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used. Specifically, among white pigments, as inorganic pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, titanium oxide or zinc oxide is more preferable, and titanium oxide is still more preferable. As the inorganic pigment, rutile-type or anatase-type titanium oxide is still more preferable, and rutile-type titanium oxide is particularly preferable. In addition, the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, and two or more treatments may be applied. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance, light fading resistance, etc. are improved. From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, as the surface treatment on the surface of titanium oxide, at least one of alumina treatment and zirconia treatment is preferable, and both alumina treatment and zirconia treatment are particularly preferable.

[0338] In addition, when the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive composition layer further contains a colored pigment other than a black pigment and a white pigment. When a colored pigment is included, the particle size of the colored pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, in terms of better dispersibility. Examples of the colored pigments include Victoria Pure Blue BO (Color Index (hereinafter referred to as C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hostaperm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fast Pink B Sprays (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1), carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, and C.I. Pigment Violet 23, etc. Among them, C.I. Pigment Red 177 is preferred.

[0339] When the photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, still more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less with respect to the total mass of the photosensitive composition layer.

[0340] When the photosensitive composition layer contains pigments other than black pigments (white pigments and colored pigments), the content of the pigments other than black pigments is preferably 30% by mass or less, more preferably 1 to 20% by mass, and still more preferably 3 to 15% by mass with respect to the black pigment.

[0341] In addition, when the photosensitive composition layer contains a black pigment and the photosensitive composition layer is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle refers to the part of the medium in which the pigment is dispersed when it is a pigment dispersion, is liquid, and includes a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0342] There is no particular limitation on the dispersing machine, and examples thereof include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Further, fine pulverization may be performed by utilizing frictional force by mechanical grinding. For the dispersing machine and fine pulverization, reference can be made to the description in "Dictionary of Pigments" (written by Kunizo Asakura, first edition, Asakura Shoten, 2000, pages 438 and 310).

[0343] <<Thermoplastic resin layer>> The thermoplastic resin layer is usually disposed between the temporary support and the photosensitive composition layer. By providing the transfer film with a thermoplastic resin layer, the followability to the substrate in the step of bonding the transfer film and the substrate is improved, and the incorporation of air bubbles between the substrate and the transfer film can be suppressed. As a result, the adhesion to the layer adjacent to the thermoplastic resin layer (for example, the temporary support) can be ensured.

[0344] The thermoplastic resin layer contains a resin. The above resin contains a thermoplastic resin as part or all thereof. That is, in one aspect, it is also preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.

[0345] <Alkali-soluble resin (thermoplastic resin)> The thermoplastic resin is preferably an alkali-soluble resin. Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0346] From the viewpoints of developability and adhesion to an adjacent layer, an acrylic resin is preferred as the alkali-soluble resin. Here, the acrylic resin means a resin having at least one structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylamides. As the acrylic resin, the total content of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylic acid esters, and the structural units derived from (meth)acrylamides is preferably 50% by mass or more based on the total mass of the acrylic resin. Among them, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid esters is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

[0347] Further, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferred. From the viewpoint of developability, an alkali-soluble resin having an acid value of 60 mgKOH / g or more is more preferred as the alkali-soluble resin, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is even more preferred. The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, still more preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0348] The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited and can be appropriately selected from known resins for use. For example, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-095716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162 can be mentioned. The copolymerization ratio of the structural unit having a carboxy group in the above carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 12 to 30% by mass with respect to the total mass of the acrylic resin. As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoints of developability and adhesion to an adjacent layer.

[0349] The alkali-soluble resin may have a reactive group. The reactive group may be an addition-polymerizable group, such as an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; a polyaddition-reactive group such as an epoxy group and a (block) isocyanate group.

[0350] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and still more preferably 20,000 to 50,000.

[0351] The alkali-soluble resin may be used alone or in combination of two or more. From the viewpoints of developability and adhesion to an adjacent layer, the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, still more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass with respect to the total mass of the thermoplastic resin layer.

[0352] <Dye> The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes due to an acid, a base, or a radical. Preferred embodiments of dye B are the same as the preferred embodiments of dye N described above, except for the points described below.

[0353] From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, dye B is preferably a dye whose maximum absorption wavelength changes due to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes due to an acid. From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes due to an acid as dye B and a compound that generates an acid by light, which will be described later.

[0354] Dye B may be used alone or in combination of two or more. From the viewpoint of visibility of the exposed portion and the non-exposed portion, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, still more preferably 0.2 to 5% by mass, and particularly preferably 0.25 to 3.0% by mass with respect to the total mass of the thermoplastic resin layer.

[0355] Here, the content of dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content of dye B will be described by taking a dye that develops color due to a radical as an example. Prepare a solution by dissolving 0.001 g and 0.01 g of a dye in 100 mL of methyl ethyl ketone. To each of the resulting solutions, add the photo radical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.), and irradiate with light at 365 nm to generate radicals and bring all the dyes into a colored state. Then, in an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25°C and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are colored in the same manner as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. Calculate the amount of the dye contained in the thermoplastic resin layer based on the calibration curve from the absorbance of the resulting solution containing the thermoplastic resin layer. Note that 3 g of the thermoplastic resin layer is the same as 3 g of the solid content of the composition.

[0356] <Compound that generates an acid, a base, or a radical by light> The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (also simply referred to as "Compound C"). As Compound C, a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible light is preferable. As Compound C, known photoacid generators, photobase generators, and photo radical polymerization initiators (photo radical generators) can be used.

[0357] (Photoacid generator) From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator. Examples of the photoacid generator include the photo cationic polymerization initiators that may be contained in the negative photosensitive composition layer described above, and the preferred embodiments are the same except as described below.

[0358] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably contains an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. Also, as the photoacid generator, a photoacid generator having the following structure is also preferable.

[0359] [Chemical formula]

[0360] (Photo radical polymerization initiator) The thermoplastic resin layer may contain a photo radical polymerization initiator. Examples of the photo radical polymerization initiator include those that may be contained in the negative photosensitive composition layer described above, and the preferred embodiments are the same.

[0361] (Photo base generator) The thermoplastic resin composition may contain a photo base generator. The photo base generator is not particularly limited as long as it is a known photo base generator. For example, 2-nitrobenzyl cyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethyl borate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine may be mentioned.

[0362] Compound C may be used alone or in combination of two or more. From the viewpoints of visibility and resolution of the exposed and unexposed portions, the content of Compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer.

[0363] <Plasticizer> From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the thermoplastic resin layer preferably contains a plasticizer. The plasticizer preferably has a smaller molecular weight (weight average molecular weight in the case of an oligomer or polymer having a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and a polyalkylene glycol compound is more preferable. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0364] Further, from the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to an adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described as the polymerizable compounds contained in the negative photosensitive composition layer described above. In the transfer film, when the thermoplastic resin layer and the negative photosensitive composition layer are directly contacted and laminated, it is preferable that both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound. This is because the diffusion of components between the layers is suppressed and the storage stability is improved by the thermoplastic resin layer and the negative photosensitive composition layer each containing the same (meth)acrylate compound.

[0365] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of the adhesion between the thermoplastic resin layer and the adjacent layer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed portion after exposure. Further, as the (meth)acrylate compound used as the plasticizer, from the viewpoints of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferable. Furthermore, as the (meth)acrylate compound used as the plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferable.

[0366] The plasticizer may be used alone or in combination of two or more. From the viewpoints of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability, the content of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass with respect to the total mass of the thermoplastic resin layer.

[0367] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include sensitizers that the above-described negative photosensitive composition layer may contain.

[0368] The sensitizer may be used alone or in combination of two or more. The content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoints of improving the sensitivity to the light source and the visibility of the exposed portion and the non-exposed portion, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass with respect to the total mass of the thermoplastic resin layer.

[0369] <Additives, etc.> In addition to the above components, the thermoplastic resin layer may contain known additives as necessary. In addition, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-085643, and the content described in this publication is incorporated herein.

[0370] The layer thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion to an adjacent layer, 1 μm or more is preferable, and 2 μm or more is more preferable. The upper limit is not particularly limited, but from the viewpoints of developability and resolution, 20 μm or less is preferable, 10 μm or less is more preferable, and 8 μm or less is still more preferable.

[0371] <<Intermediate layer>> In the transfer film 20, the intermediate layer 15 is present between the thermoplastic resin layer 13 and the photosensitive composition layer 17, so that mixing of components that may occur during the coating formation of the thermoplastic resin layer 13 and the photosensitive composition layer 17 and during storage after the coating formation can be suppressed. As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used. In addition, as the intermediate layer, an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in JP-A-5-072724, can also be used. When the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and the productivity is improved, which is preferable. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications and the like. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous solution of sodium carbonate at 22°C) is preferable.

[0372] Hereinafter, each component that the water-soluble resin layer (intermediate layer) may contain will be described.

[0373] The water-soluble resin layer (intermediate layer) contains a resin. The above resin contains a water-soluble resin as part or all thereof. Examples of resins that can be used as water-soluble resins include resins such as polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. In addition, as the water-soluble resin, a copolymer of (meth)acrylic acid / vinyl compound or the like can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / allyl (meth)acrylate is preferable, and a copolymer of methacrylic acid / allyl methacrylate is more preferable. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol%) is preferably, for example, 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0374] The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and still more preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and still more preferably 50,000 or less. The dispersity (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0375] In addition, in terms of further improving the ability to suppress interlayer mixing in the water-soluble resin layer (intermediate layer), the resin in the water-soluble resin layer (intermediate layer) is preferably a resin different from the resin contained in the layer disposed on one surface side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other surface side. For example, when polymer A is contained in the photosensitive composition layer 17 and a thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer 13, the resin of the water-soluble resin layer (intermediate layer) 15 is preferably a resin different from polymer A and the thermoplastic resin (alkali-soluble resin).

[0376] The water-soluble resin preferably contains polyvinyl alcohol in terms of further improving oxygen barrier properties and the ability to suppress interlayer mixing, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0377] The water-soluble resin may be used alone or in combination of two or more. The content of the water-soluble resin is not particularly limited, but in terms of further improving oxygen barrier properties and the ability to suppress interlayer mixing, 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more is preferable with respect to the total mass of the water-soluble resin layer (intermediate layer). The upper limit is not particularly limited, but for example, 99.9% by mass or less is preferable, and 99.8% by mass or less is still more preferable.

[0378] The layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but 0.1 to 5 μm is preferable, and 0.5 to 3 μm is more preferable. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier properties are not deteriorated, and the ability to suppress interlayer mixing is excellent. Further, an increase in the removal time of the water-soluble resin layer (intermediate layer) during development can also be suppressed.

[0379] <<Manufacturing Method of Transfer Film of Second Embodiment>> The manufacturing method of the transfer film of the second embodiment is not particularly limited, and a known method can be used. As the manufacturing method of the above transfer film 20, for example, a step of applying a thermoplastic resin composition on the surface of the temporary support 11 to form a coating film, and further drying this coating film to form a thermoplastic resin layer 13; a step of applying a water-soluble resin composition on the surface of the thermoplastic resin layer 13 to form a coating film, and further drying this coating film to form an intermediate layer 15; and a step of applying a photosensitive composition on the surface of the intermediate layer 15 to form a coating film, and further drying this coating film to form a photosensitive composition layer 17 are included.

[0380] The transfer film 20 is manufactured by pressing a protective film 19 onto the photosensitive composition layer 17 of the laminate manufactured by the above manufacturing method. As a method for manufacturing the transfer film of the second embodiment, it preferably includes a step of providing a protective film 19 so as to be in contact with the surface of the temporary support 11 of the photosensitive resin layer 17 on the side opposite to the side having the temporary support 11, thereby manufacturing a transfer film 20 including the temporary support 11, the thermoplastic resin layer 13, the intermediate layer 15, the photosensitive composition layer 17, and the protective film 19. After manufacturing the transfer film 20 by the above manufacturing method, the transfer film 20 may be wound up to produce and store a roll-shaped transfer film. The roll-shaped transfer film can be provided in its original form in the bonding step with the substrate by the roll-to-roll method described later.

[0381] Further, as the method for manufacturing the transfer film 20, a method may be used in which after forming the photosensitive resin layer 17 and the intermediate layer 15 on the cover film 19, the thermoplastic resin layer 3 is formed on the surface of the intermediate layer 15.

[0382] <Composition for forming thermoplastic resin layer and method for forming thermoplastic resin layer> The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and known methods can be used. For example, it can be formed by applying a composition for forming a thermoplastic resin layer on the temporary support and drying it if necessary. The composition for forming the thermoplastic resin layer preferably contains various components for forming the thermoplastic resin layer described above and a solvent. In the composition for forming the thermoplastic resin layer, the preferred range of the content of each component with respect to 100 parts by mass of the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the thermoplastic resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Examples of the solvent include the same solvents as those contained in the photosensitive composition described later, and the preferred embodiments are also the same. The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, with respect to 100 parts by mass of the total solid content of the composition.

[0383] The method for forming the thermoplastic resin layer is not particularly limited as long as it can form a layer containing the above components. For example, known coating methods (such as slit coating, spin coating, curtain coating, and inkjet coating) can be mentioned.

[0384] <Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)> The water-soluble resin composition preferably contains various components for forming the above-mentioned intermediate layer (water-soluble resin layer) and a solvent. In the water-soluble resin composition, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the above-mentioned water-soluble resin layer. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin. At least one selected from the group consisting of water and water-miscible organic solvents is preferred, and a mixed solvent of water or water and a water-miscible organic solvent is more preferred. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and still more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.

[0385] The method for forming the water-soluble resin layer is not particularly limited as long as it can form a layer containing the above components. For example, known coating methods (such as slit coating, spin coating, curtain coating, and inkjet coating) can be mentioned.

[0386] <Photosensitive composition and method for forming photosensitive composition layer> In terms of excellent productivity and easy formation of the composition layer satisfying the requirements of the above-described formulas (1A) to (3A), it is desirable to use a photosensitive composition containing components (for example, a binder polymer, a polymerizable compound, a polymerization initiator, etc.) constituting the above-described photosensitive composition layer and a solvent, and to form it by a coating method. As a method for manufacturing the transfer film of the second embodiment, specifically, it is preferable to apply a photosensitive composition on an intermediate layer to form a coating film, and to perform a drying treatment on this coating film at a predetermined temperature to form a photosensitive composition layer. Note that the amount of residual solvent is adjusted by the drying treatment of the coating film, and as a result, it is presumed that the tan δ of the photosensitive composition layer is appropriately adjusted and a composition layer satisfying the requirements of the above-described formulas (1A) to (3A) is easily formed.

[0387] The photosensitive composition preferably contains various components for forming the above-described photosensitive composition layer and a solvent. In the photosensitive composition, the suitable range of the content of each component with respect to the total solid content of the composition is the same as the suitable range of the content of each component with respect to the total mass of the above-described photosensitive composition layer. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Specifically, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents (such as n-propyl acetate), amide solvents, lactone solvents, and mixed solvents containing two or more of these can be mentioned.

[0388] As the solvent, it is preferable to contain at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable, and a mixed solvent containing at least three types of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferable.

[0389] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of Japanese Patent Application Laid-Open No. 2018-177889 may be used, and the contents thereof are incorporated herein. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.

[0390] Examples of the method for applying the photosensitive composition include printing methods, spraying methods, roll coating methods, bar coating methods, curtain coating methods, spin coating methods, and die coating methods (i.e., slit coating methods).

[0391] As the method for drying the coating film of the photosensitive composition, heat drying and reduced-pressure drying are preferable. In terms of the ease of forming a composition layer in which the tanδ of the photosensitive composition layer is appropriately adjusted to satisfy the requirements of the above-described formulas (1A) to (3A), the drying temperature is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher. Further, although the upper limit value is not particularly limited, it is preferably 130°C or lower, and more preferably 120°C or lower. In terms of the ease of forming a composition layer in which the tanδ of the photosensitive composition layer is appropriately adjusted to satisfy the requirements of the above-described formulas (1A) to (3A), the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. Further, although the upper limit value is not particularly limited, it is preferably 450 seconds or shorter, and more preferably 300 seconds or shorter.

[0392] Furthermore, the transfer film of the second embodiment can be manufactured by laminating a protective film on the photosensitive composition layer. The method for laminating the protective film on the photosensitive composition layer is not particularly limited, and known methods can be mentioned. Examples of the apparatus for laminating the protective film on the photosensitive composition layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator preferably includes an arbitrary heatable roller such as a rubber roller and can apply pressure and heat.

[0393] [Method for manufacturing a laminate] By using the above-described transfer film, the composition layer can be transferred onto the object to be transferred. Among them, the transfer film of the present invention is preferably used in the manufacture of a touch panel. Among them, the method for manufacturing the laminate of the present invention includes a bonding step of bringing the surface of the transfer film opposite to the temporary support into contact with a substrate having a conductive portion and bonding them to obtain a substrate with a composition layer having the substrate, the conductive layer, the composition layer, and the temporary support in this order, an exposure step of pattern-exposing the composition layer, and a development step of developing the exposed composition layer to form a protective film pattern for protecting the conductive layer, and has Furthermore, it is preferable that the method for manufacturing the laminate has a peeling step of peeling the temporary support from the substrate with the composition layer between the bonding step and the exposure step, or between the exposure step and the development step. Hereinafter, the procedures of the above steps will be described in detail.

[0394] 〔Bonding Step〕 The bonding step is a step of bringing the surface of the transfer film opposite to the temporary support into contact with a substrate having a conductive portion and bonding them to obtain a substrate with a composition layer having the substrate, the conductive layer, the photosensitive composition layer, and the temporary support in this order. When the transfer film has a protective film, the bonding step is performed after peeling the protective film.

[0395] In the above bonding, pressure bonding is performed so that the conductive layer and the surface of the composition layer are in contact. The method of the above pressure bonding is not particularly limited, and known transfer methods and laminating methods can be used. Among them, it is preferable that the surface of the composition layer is overlapped with a substrate having a conductive portion, and pressure and heat are applied by a roll or the like. For bonding, known laminators such as a vacuum laminator and an auto cut laminator can be used. The laminating temperature is not particularly limited, but for example, it is preferably 70 to 130°C.

[0396] The substrate having the conductive layer has the conductive layer on the substrate, and any layer may be formed as necessary. That is, the substrate having the conductive layer is a conductive substrate having at least the substrate and the conductive layer disposed on the substrate.

[0397] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the substrate are described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, the content of which is incorporated herein.

[0398] As the conductive layer, from the viewpoints of conductivity and fine wire formability, it is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Also, only one conductive layer may be disposed on the substrate, or two or more conductive layers may be disposed. When two or more conductive layers are disposed, it is preferable to have conductive layers of different materials. Preferred embodiments of the conductive layer are described, for example, in paragraph

[0141] of International Publication No. 2018 / 155193, the content of which is incorporated herein.

[0399] As the substrate having a conductive layer, a substrate having at least one of a transparent electrode and a routing wiring is preferable. The substrate as described above can be suitably used as a substrate for a touch panel. The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal fine wire such as a metal mesh and silver nanowire. Examples of the metal fine wire include fine wires of silver, copper, etc. Among them, silver conductive materials such as a silver mesh and silver nanowire are preferable.

[0400] As the material of the routing wiring, a metal is preferable. Examples of the metal as the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements. As the material of the routing wiring, copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.

[0401] The electrode protection film for a touch panel formed using the photosensitive composition layer in the transfer film of the present invention is preferably provided so as to cover the electrode etc. (that is, at least one of the touch panel electrode and the touch panel wiring) directly or via another layer for the purpose of protecting the electrode etc.

[0402] 〔Exposure process〕 The exposure process is a process of pattern-exposing the composition layer. Here, "pattern exposure" refers to an exposure in a form of exposing in a pattern, that is, an exposure in a form where an exposed portion and a non-exposed portion exist. The positional relationship between the exposed region and the unexposed region in the pattern exposure is not particularly limited and is appropriately adjusted.

[0403] As the light source for the pattern exposure, any light source that can irradiate light in a wavelength range capable of curing at least the photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used. Among them, the main wavelength of the exposure light for the pattern exposure is preferably 365 nm. The main wavelength is the wavelength with the highest intensity.

[0404] Examples of the light source include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 to 200 mJ / cm 2 and more preferably 10 to 200 mJ / cm 2 is even more preferable.

[0405] Preferable embodiments of the light source, exposure amount, and exposure method used for the exposure are described, for example, in paragraphs

[0146] to

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

[0406] By performing the exposure process and the development process described later, a protective film pattern that protects at least a part of the conductive layer is formed on the conductive layer on the substrate.

[0407] 〔Peeling process〕 The peeling step is a step of peeling the temporary support from the substrate with the composition layer, between the laminating step and the exposure step, or between the exposure step and the developing step described later. The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A-2010-072589 can be used.

[0408] 〔Developing step〕 The developing step is a step of developing the exposed composition layer to form a pattern. The developing of the composition layer can be performed using a developer. As the developer, an alkaline aqueous solution is preferable. Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0409] Examples of the developing method include methods such as paddle development, shower development, spin development, and dip development.

[0410] Examples of the developer preferably used in the present specification include the developer described in paragraph

[0194] of WO 2015 / 093271, and examples of the developing method preferably used include the developing method described in paragraph

[0195] of WO 2015 / 093271.

[0411] 〔Post-exposure step and post-baking step〕 The method for producing the laminate may include a step of exposing the pattern obtained by the developing step (post-exposure step) and / or a step of heating (post-baking step). When both the post-exposure step and the post-baking step are included, it is preferable to perform post-baking after post-exposure.

[0412] 〔Use of the laminate〕 The laminate produced by the method for producing a laminate of the present invention can be applied to various devices. Examples of the device provided with the laminate include, for example, a display device, a printed wiring board, a semiconductor package, and an input device, etc., preferably a touch panel, and more preferably a capacitive touch panel. Further, the input device can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device. When the laminate is applied to a touch panel, the pattern formed from the composition layer is preferably used as a protective film for the touch panel electrode or the wiring for the touch panel. That is, the composition layer contained in the transfer film is preferably used for forming a protective film for the touch panel electrode or the wiring for the touch panel. Examples of the use of the pattern (cured film) formed from the composition layer include various electrode protective films, planarization films, overcoat films, hard coat films, passivation films, partitions, spacers, microlenses, optical filters, and antireflection films.

[0413] [Method for manufacturing circuit wiring] By using the above-described transfer film, circuit wiring can also be manufactured. The method for manufacturing circuit wiring is not particularly limited as long as it is a method for manufacturing circuit wiring using the above transfer film. Among them, the method for manufacturing circuit wiring of the present invention includes a laminating step of bringing the surface of the transfer film opposite to the temporary support into contact with a substrate having a conductive layer to obtain a substrate with a composition layer having the substrate, the conductive layer, the composition layer, and the temporary support in this order an exposure step of pattern-exposing the composition layer, a developing step of developing the exposed composition layer to form a resin pattern, an etching step of etching the conductive layer in a region where the resin pattern is not disposed, and further preferably includes a peeling step of peeling the temporary support from the substrate with the composition layer between the laminating step and the exposure step, or between the exposure step and the developing step.

[0414] Hereinafter, specific procedures of the method for manufacturing a circuit wiring will be described. Regarding the lamination step, exposure step, development step, and peeling step in the method for manufacturing a circuit wiring, they are the same as those in the method for manufacturing a laminate described above, and the preferred embodiments are also the same.

[0415] 〔Etching Step〕 The method for manufacturing a circuit wiring includes an etching step (etching step) of etching a conductive layer in a region where a resin pattern is not disposed in a laminate in which a substrate, a conductive layer (conductive layer of the substrate), and a resin pattern (more preferably, a resin pattern manufactured by a manufacturing method including the above lamination step, the above exposure step, and the above development step) are laminated in this order. In the above etching step, a resin pattern obtained from a photosensitive composition layer by the above development step is used as an etching resist, and the conductive layer is etched. As a method of etching, a known method can be applied. For example, the methods described in paragraphs

[0209] to

[0210] of Japanese Patent Application Laid-Open No. 2017-120435, paragraphs

[0048] to

[0054] of Japanese Patent Application Laid-Open No. 2010-152155, etc., a wet etching method of immersing in an etching solution, and a method by dry etching such as plasma etching can be mentioned.

[0416] As the etching solution used for wet etching, an acidic or alkaline etching solution may be appropriately selected according to the object to be etched. Examples of the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components. Examples of the alkaline etching solution include an aqueous solution of an alkali component alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), and a mixed aqueous solution of an alkali component and a salt (such as potassium permanganate). The alkali component may be a combination of multiple alkali components.

[0417] 〔Removal step〕 In the method for manufacturing a circuit wiring, it is preferable to perform a step of removing the remaining resin pattern (removal step). The removal step is not particularly limited and can be performed as necessary, but it is preferably performed after the etching step. The method for removing the remaining resin pattern is not particularly limited, but examples include a method of removing it by chemical treatment, and a method of removing it using a removal solution is preferable. Examples of the method for removing the photosensitive resin layer include a method of immersing a substrate having the remaining resin pattern in a stirring removal solution having a liquid temperature preferably of 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0418] Examples of the removal solution include a removal solution in which an inorganic alkali component or an organic alkali component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, it may be removed using a removal solution by a known method such as a spray method, a shower method, or a paddle method.

[0419] 〔Other steps〕 The method for manufacturing a circuit wiring may include any step (other steps) other than the steps described above. For example, there may be a step of reducing the visible light reflectance described in paragraph

[0172] of WO 2019 / 022089, a step of forming a new conductive layer on the insulating film described in paragraph

[0172] of WO 2019 / 022089, etc., but it is not limited to these steps.

[0420] <Step of reducing visible light reflectance> The method for manufacturing a circuit wiring may include a step of performing a process for reducing the visible light reflectance of some or all of a plurality of conductive layers included in a base material. Examples of the process for reducing the visible light reflectance include an oxidation process. When the base material has a conductive layer containing copper, the copper can be oxidized to form copper oxide, and by blackening the conductive layer, the visible light reflectance of the conductive layer can be reduced. Regarding the process for reducing the visible light reflectance, it is described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315, and the contents described in these publications are incorporated herein.

[0421] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for manufacturing a circuit wiring preferably also includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and examples include known methods for forming a permanent film. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0422] The method for manufacturing circuit wiring preferably uses a substrate having a plurality of conductive layers on both surfaces of a base material, and circuit formation is performed sequentially or simultaneously on the conductive layers formed on both surfaces of the base material. With such a configuration, circuit wiring for a touch panel can be formed in which a first conductive pattern is formed on one surface of the base material and a second conductive pattern is formed on the other surface. Further, it is also preferable to form circuit wiring for a touch panel having such a configuration by a roll-to-roll method from both sides of the base material.

[0423] 〔Use of Circuit Wiring〕 The circuit wiring manufactured by the method for manufacturing circuit wiring can be applied to various devices. Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include a display device, a printed wiring board, a semiconductor package, and an input device. A touch panel is preferable, and a capacitive touch panel is more preferable. Further, the above input device can be applied to display devices such as an organic EL display device and a liquid crystal display device.

Examples

[0424] The present invention will be described in more detail based on the following examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are based on mass. Further, in the following examples, the weight average molecular weight of the resin is the weight average molecular weight determined by polystyrene conversion by gel permeation chromatography (GPC). Also, the acid value used was the theoretical acid value.

[0425] 〔Synthesis Example〕 <Synthesis of Polymers P-1 to P-5> (Synthesis of Polymer P-1) Propylene glycol monomethyl ether (82.4 g, FUJIFILM Wako Pure Chemical Corporation) was charged into a flask and heated to 90 °C under a nitrogen stream. To this solution, a solution prepared by dissolving styrene (38.4 g, FUJIFILM Wako Pure Chemical Corporation), dicyclopentanyl methacrylate (30.1 g, Funacryl FA-513M, Hitachi Chemical Co., Ltd.), and methacrylic acid (34.0 g, FUJIFILM Wako Pure Chemical Corporation) in propylene glycol monomethyl ether (20 g), and a solution prepared by dissolving polymerization initiator V-601 (5.4 g, FUJIFILM Wako Pure Chemical Corporation) in propylene glycol monomethyl ether acetate (43.6 g, FUJIFILM Wako Pure Chemical Corporation) were simultaneously added dropwise over 3 hours. After completion of the addition, V-601 (0.75 g) was added 3 times at 1-hour intervals. Thereafter, the solution was further reacted for 3 hours. Thereafter, the obtained solution was diluted with propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). Under an air stream, the temperature of the solution was raised to 100 °C, and tetraethylammonium bromide (0.53 g, FUJIFILM Wako Pure Chemical Corporation) and p-methoxyphenol (0.26 g, FUJIFILM Wako Pure Chemical Corporation) were added. To the obtained solution, glycidyl methacrylate (25.5 g, NOF Corporation, Blemmer GH) was added dropwise over 20 minutes. The obtained solution was reacted at 100 °C for 7 hours to obtain a solution of polymer P-1. The solid content concentration of the obtained solution was 36.3 mass%. The weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersity (Mw / Mn) was 2.4, and the acid value of the polymer was 94.5 mgKOH / g. The amount of residual monomer measured by gas chromatography was less than 0.1 mass% with respect to the polymer solid content for any monomer.

[0426] (Synthesis of Polymers P-2 to P-3) Polymers P-2 to P-3 were synthesized in the same manner as Polymer P-1, except that the types of each structural unit contained in the polymer and the content of each structural unit were changed as shown in Table 1. Note that Polymer P-2 was also obtained in the form of a solution of Polymer P-2 with a solid content concentration of 36.3% by mass. Also, Polymer P-3 was obtained in the form of a solution of Polymer P-3 with a solid content concentration of 36.3% by mass.

[0427] (Synthesis of Polymer P-4) Propylene glycol monomethyl ether (55.8 g, FUJIFILM Wako Pure Chemical Corporation) and toluene (55.8 g, FUJIFILM Wako Pure Chemical Corporation) were mixed to prepare a first liquid. Also, methacrylic acid (12.0 g, FUJIFILM Wako Pure Chemical Corporation), methyl methacrylate (58.0 g, FUJIFILM Wako Pure Chemical Corporation), ethyl acrylate (30.0 g, FUJIFILM Wako Pure Chemical Corporation), polymerization initiator 2,2'-azobis(isobutyronitrile) (1.0 g, FUJIFILM Wako Pure Chemical Corporation), propylene glycol monomethyl ether (32.0 g), and toluene (32.0 g) were mixed and stirred at room temperature for 1 hour to dissolve the solid 2,2'-azobis(isobutyronitrile), thereby preparing a second liquid. The first liquid was placed in a flask and heated to 80°C under a nitrogen atmosphere. While maintaining the liquid temperature under stirring, the second liquid was added to the first liquid in the flask over 4 hours using a dropping pump. After the addition was completed, the liquid temperature of the mixed liquid was maintained at 80°C under stirring and allowed to react for an additional 6 hours to obtain a solution of Polymer P-4. The solid content concentration of the obtained solution was 36.3% by mass. The weight average molecular weight in terms of standard polystyrene in GPC was 65,000, and the acid value of the polymer was 78 mgKOH / g.

[0428] (Synthesis of Polymer P-5) A solution of Polymer P-5 was obtained by synthesizing in the same manner as Polymer P-4, except that the types and amounts of the monomers were changed. The solid content concentration of the obtained solution was 36.3% by mass. The weight average molecular weight in terms of standard polystyrene in GPC was 65,000.

[0429] The polymers P-1 to P-5 are shown in Table 1 below. In Table 1, for the structural units other than the structural units having a (meth)acryloyl group, they are indicated by the abbreviations of the monomers for forming each structural unit. For the structural units having a (meth)acryloyl group, they are indicated in the form of the addition structure of monomer to monomer. For example, MAA-GMA means a structural unit in which glycidyl methacrylate is added to the structural unit derived from methacrylic acid. The polymers P-1 to P-5 correspond to alkali-soluble resins.

[0430] [Table 1]

[0431] The abbreviations in Table 1 are as follows. St: Styrene (Fuji Film Wako Pure Chemical Corporation) BzMA: Benzyl methacrylate (Fuji Film Wako Pure Chemical Corporation) CHMA: Cyclohexyl methacrylate (Fuji Film Wako Pure Chemical Corporation) MAA-GMA: A structural unit in which glycidyl methacrylate is added to the structural unit derived from methacrylic acid MAA: Methacrylic acid (Fuji Film Wako Pure Chemical Corporation) DCPMA: Dicyclopentanyl methacrylate (Funacryl FA-513M, Hitachi Chemical Co., Ltd.) MMA: Methyl methacrylate (Fuji Film Wako Pure Chemical Corporation) EA: Ethyl acrylate (manufactured by Fuji Film Wako Pure Chemical Corporation)

[0432] <Synthesis of Polymer P'-1> Propylene glycol monomethyl ether (270.0 g) was introduced into a three-necked flask and heated to 70 °C under a nitrogen stream with stirring. On the other hand, allyl methacrylate (45.6 g, manufactured by Fujifilm Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) were dissolved in propylene glycol monomethyl ether (270.0 g), and further V-65 (3.94 g, manufactured by Fujifilm Wako Pure Chemical Corporation) was dissolved to prepare a dropping solution, which was then dropped into the flask over 2.5 hours. The resulting solution was reacted for 2 hours while maintaining the stirring state. Thereafter, the temperature of the obtained solution was returned to room temperature and dropped into ion-exchanged water (2.7 L) under stirring to perform reprecipitation, obtaining a suspension. Filtration was performed by introducing the suspension into a Buchner funnel with filter paper, and the filtrate was further washed with ion-exchanged water to obtain a wet powder. Next, it was subjected to air drying at 45 °C, and when it was confirmed to have reached a constant weight, polymer P'-1 (the following structural formula) was obtained as a powder with a yield of 70%. In the structural formula of the following polymer P'-1, the ratio of each structural unit contained in the polymer is in mass%.

[0433]

Chemical formula

[0434] <Synthesis of block isocyanate compound Q-1> Under a nitrogen stream, butanone oxime (453 g, manufactured by Idemitsu Kosan Co., Ltd.) was dissolved in methyl ethyl ketone (700 g). To this, 1,3-bis(isocyanatomethyl)cyclohexane (500 g, a cis / trans isomer mixture, manufactured by Mitsui Chemicals, Inc., Takenate 600) was dropped over 1 hour under ice cooling, and after the dropping, the solution was further reacted for 1 hour. Thereafter, the obtained solution was heated to 40 °C and reacted for 1 hour. 1 It was confirmed by 1H-NMR and HPLC that the reaction was completed, and a methyl ethyl ketone solution of block isocyanate compound Q-1 (the following structural formula) was obtained. The solid content concentration of the obtained solution was 57.7 mass%.

[0435]

Chemical formula

[0436] [Preparation of photosensitive composition] Photosensitive compositions A-1 to A-18 and A'-1 to A'-3 having the components and formulations shown in Table 2 below were prepared. In Table 2, the numerical values described in each component column represent the content (parts by mass) of each component. However, each amount of the polymers P-1 to P-5 in the alkali-soluble column means the amount of the polymer solution. Also, "SMA EF-40" in Table 2 is a copolymer of styrene / maleic anhydride = 4:1 (molar ratio) (acid anhydride value 1.94 mmol / g, Mw 10500, manufactured by Cray Valley).

[0437] [Table 2]

[0438] [Table 3]

[0439] [Preparation of composition for forming refractive index adjustment layer] Next, a composition B-1 for forming a refractive index adjustment layer was prepared with the components and formulations described in Table 3 below. In Table 3, the polymer P'-1 was the one synthesized in the synthesis example in the upper part. In Table 3, the numerical values described in each component column represent the content (parts by mass) of each component.

[0440] [Table 4]

[0441] [Preparation of transfer films of Examples 1 to 25 and Comparative Examples 1 to 4] [Preparation of transfer films of Examples 1 to 12, 18 to 25, and Comparative Examples 1 to 3] Any one of the prepared photosensitive compositions A-1 to A-18 and A'-1 to A'-3 was applied onto a temporary support of a 16-μm thick polyethylene terephthalate film (Lumirror 16KS40 (Lumirror 16QS62), manufactured by Toray Industries, Inc.) using a slit nozzle so that the film thickness of the photosensitive composition layer after drying would be the specified film thickness (the film thickness described in Table 4), and dried in a drying zone at 120°C for 3 minutes to form a photosensitive composition layer. Thereafter, a 25-μm thick polypropylene film (Trephan 25A-KW37, manufactured by Toray Industries, Inc.) was pressure-bonded as a protective film onto the photosensitive composition layer to produce transfer films of Examples 1 to 12, 18 to 25, and Comparative Examples 1 to 3.

[0442] <Production of Transfer Films of Examples 13 to 17> Any one of the prepared photosensitive compositions A-8 to A-12 was applied onto a temporary support of a 16-μm thick polyethylene terephthalate film (Lumirror 16KS40 (Lumirror 16QS62, manufactured by Toray Industries, Inc.) using a slit nozzle so that the film thickness of the photosensitive composition layer after drying would be the specified film thickness (the film thickness described in Table 4), and dried in a drying zone at 120°C for 3 minutes to form a photosensitive composition layer. Furthermore, the composition B-1 for forming a refractive index adjustment layer described in Table 3 was adjusted to an application amount such that the film thickness of the refractive index adjustment layer after drying would be 73 nm using a slit nozzle and applied onto the photosensitive composition layer. Next, the coating film was dried at a drying temperature of 80°C to form a refractive index adjustment layer. Thereafter, a 25-μm thick polypropylene film (Trephan 25A-KW37, manufactured by Toray Industries, Inc.) was pressure-bonded as a protective film onto the refractive index adjustment layer to produce transfer films of Examples 13 to 17.

[0443] <Production of Transfer Film of Comparative Example 4> A transfer film of Comparative Example 4 was produced in the same manner as in Example 19, except that the drying conditions (drying in a drying zone at 120°C for 3 minutes) after applying the photosensitive composition onto the temporary support were changed to drying in a drying zone at 100°C for 3 minutes.

[0444] [Measurement and Evaluation of Transfer Films] <Measurement of tanδ> For the transfer films of Examples 1 to 12, 18 to 25 and Comparative Examples 1 to 4 without a refractive index adjustment layer, the following was done. The prepared transfer films of Examples 1 to 12, 18 to 25 and Comparative Examples 1 to 4 were cut into a size of 240 mm × 240 mm, and the protective film was peeled off. Next, the obtained films were folded so that the surfaces of the photosensitive composition layers exposed by peeling off the protective film faced each other, and the surfaces of the photosensitive composition layers were bonded together to produce a laminate 1 of a temporary support / photosensitive composition layer (two-layer laminate) / temporary support. Furthermore, one of the temporary supports in the laminate 1 was peeled off. Next, the laminate 1 from which the temporary support was peeled off was folded so that the photosensitive composition layers (two-layer laminate) exposed by peeling off the temporary support faced each other, and the photosensitive composition layers (two-layer laminate) were bonded together to produce a laminate 2 of a temporary support / photosensitive composition layer (four-layer laminate) / temporary support. Furthermore, one of the temporary supports in the laminate 2 was peeled off. Next, the laminate 2 from which the temporary support was peeled off was folded so that the photosensitive composition layers (four-layer laminate) exposed by peeling off the temporary support faced each other, and the photosensitive composition layers (four-layer laminate) were bonded together to produce a laminate 3 of a temporary support / photosensitive composition layer (eight-layer laminate) / temporary support. By repeating the bonding of the photosensitive composition layers in the same procedure, a laminate N of a temporary support / photosensitive composition layer with a thickness of 0.5 mm / temporary support was produced.

[0445] Also, for the transfer films of Examples 13 to 17 having a refractive index adjustment layer, the following was done. The prepared transfer films of Examples 13 to 17 were cut into a size of 240 mm × 240 mm, and the protective film was peeled off. Next, the obtained films were folded so that the surfaces of the refractive index adjustment layers exposed by peeling off the protective film faced each other, and the surfaces of the photosensitive composition layers were bonded together to produce a laminate 1 of a temporary support / photosensitive composition layer / refractive index adjustment layer / refractive index adjustment layer / photosensitive composition layer / temporary support. Furthermore, one of the temporary supports in the laminate 1 was peeled off. Next, the laminate 1 with the temporary support peeled off was folded and bonded so that the photosensitive composition layers exposed by peeling off the temporary support faced each other, thereby producing a laminate 2 of temporary support / photosensitive composition layer / refractive index adjustment layer / refractive index adjustment layer / photosensitive composition layer / photosensitive composition layer / refractive index adjustment layer / refractive index adjustment layer / photosensitive composition layer / temporary support. By repeating the bonding of the photosensitive composition layer and the refractive index adjustment layer in the same procedure, a laminate N of temporary support / photosensitive composition layer + refractive index adjustment layer with a total thickness of 0.5 mm / temporary support was produced.

[0446] Thereafter, the temporary supports on both sides of the laminate N were peeled off and cut into a circle with a diameter of 20 mm to obtain a measurement sample for tanδ. The produced sample was subjected to the test after being conditioned at 23°C and RH50% for 24 hours. The tanδ of the sample produced by the above procedure was measured using a dynamic viscoelasticity measuring device, Rheometer DHR-2 (manufactured by TA Instruments Japan). The measurement was performed in a constant Gap (0.5 mm) mode using a parallel plate with a diameter of 20 mm and a Peltier plate (Gap: 0.5 mm). Specifically, dynamic viscoelasticity measurement was performed under the following conditions, and the values of tanδ at 25°C (tanδ T25 ), tanδ at 80°C (tanδ T80 ), and tanδ at 120°C (tanδ T120 ) were obtained. Also, from the obtained values, the value of tanδ T120 / tanδ T80 was calculated. The obtained results are shown in Table 4.

[0447] (Measurement conditions) Sample size: diameter 20 mm, thickness 0.5 mm Measurement temperature condition: 25 to 150°C Heating rate: 5°C / min Frequency: 1 Hz Strain: 1 deg (0.0174 rad)

[0448] <Evaluation of dirt (adhesion) of the photosensitive composition layer to the guide roll> (Transfer films of Examples 1 to 12, 18 to 25, and Comparative Examples 1 to 4) The transfer films of Examples 1 to 12, 18 to 25, and Comparative Examples 1 to 4 prepared above were placed on a 3.5-inch cylindrical branch pipe and linearly applied with a pressure of 200 kg / m to the branch pipe by a pressure roll with a rubber surface material arranged parallel to the winding axis width direction, and wound up at a tension of 15 kg / m for 200 m to obtain a photosensitive film roll with a width of 500 mm. Next, while peeling off the protective film of the photosensitive film roll, it was fed out, and the photosensitive film composed of a temporary support and a photosensitive composition layer from which the protective film was peeled off was conveyed at a conveyance speed of 20 m / min. Specifically, in a state where the surface of the photosensitive composition layer was in contact with a guide roll (diameter 100 mm, made of stainless steel) and the wrap angle between the guide roll and the photosensitive film was 90°, the tension of the photosensitive film was set to 60 N / m, and a 100-m long photosensitive film was conveyed with the surface of the photosensitive composition layer in contact with the guide roll. After conveying 100 m of the photosensitive film, the dirt on the guide roll was visually observed. Based on the observation results, the dirt (adhesion) to the guide roll was evaluated according to the following evaluation criteria. In the following evaluation criteria, if the evaluation is "C" or higher, it is suitable for practical use, and "A" is particularly preferable. The evaluation results are shown in Table 4.

[0449] - Evaluation criteria for dirt (adhesion) to the guide roll - A: No adhesion of the photosensitive composition layer to the guide roll is observed. B: The area where the photosensitive composition layer adheres to the guide roll is less than 5% of the observed area. C: The area where the photosensitive composition layer adheres to the guide roll is 5% or more and less than 10% of the observed area. D: The area where the photosensitive composition layer adheres to the guide roll is 10% or more and less than 20% of the observed area. E: The area where the photosensitive composition layer adheres to the guide roll is 20% or more of the observed area.

[0450] (Transfer films of Examples 13 to 17) The transfer films of Examples 13 to 17 prepared above were placed on a 3.5-inch cylindrical branch pipe and linearly applied with a pressure of 200 kg / m to the branch pipe by a pressure roll made of rubber with a surface material parallel to the winding axis width direction, and wound up at a tension of 15 kg / m for 200 m to obtain a photosensitive film roll with a width of 500 mm. Next, while peeling off the protective film of the photosensitive film roll, it was fed out, and the photosensitive film composed of a temporary support, a photosensitive composition layer, and a refractive index adjustment layer from which the protective film was peeled off was conveyed at a conveyance speed of 20 m / min. Specifically, in a state where the surface of the refractive index adjustment layer is in contact with a guide roll (diameter 100 mm, made of stainless steel) and the wrap angle between the guide roll and the photosensitive film is 90°, the tension of the photosensitive film was set to 60 N / m, and a photosensitive film with a total length of 100 m was conveyed with the surface of the refractive index adjustment layer in contact with the guide roll. After conveying 100 m of the photosensitive film, the dirt on the guide roll was visually observed. Based on the observation results, the dirt (adhesion) to the guide roll was evaluated according to the above-described evaluation criteria. In the above evaluation criteria, if the evaluation is "C" or higher, it is suitable for practical use, and "A" is particularly preferable. The evaluation results are shown in Table 4.

[0451] <Laminating property evaluation> (Preparation of laminate for laminating property evaluation) Next, as a laminate for laminating property evaluation, a base material 43 having steps shown in FIGS. 3 to 5 was prepared. Hereinafter, with reference to FIGS. 3 to 5, the configuration of the base material 43 having steps will be described.

[0452] As shown in FIG. 3, the base material 43 having steps has a film base material 1A and a step 41 with a thickness of 100 nm on the film base material 1A. When the surface of the film base material 1A having the step 41 is viewed from above, when the laminating direction 42 is the vertical direction, the shape of the step 41 is a rectangle with a length of 2 cm and a width of 5 cm, and the material thereof is copper. Further, FIG. 4 shows a schematic view of the side surfaces (both side surfaces) of the substrate 43 having a step in a direction parallel to the lamination direction 42, and FIG. 5 shows a schematic view of the side surfaces (both side surfaces) of the substrate 43 having a step in a direction perpendicular to the lamination direction 42. As shown in FIGS. 4 and 5, when the substrate 43 having a step is viewed from the side, the length La of the upper portion 41a on the side opposite to the bottom portion 41c is shorter than the length Lc of the bottom portion 41c in contact with the film substrate 1A for the step 41, and it has a so-called tapered shape. The angle θ formed between the side surface portion 41b of the step 41 and the film substrate 1A is approximately 78°. Also, in each side surface portion 41b of the step 41, the clearance length between the length La of the upper portion 41a and the length Lc of the bottom portion 41c is 20 nm.

[0453] (Evaluation of the number of bubbles in the laminate (laminability)) The transfer films of Examples 1 to 12, 18 to 21 and Comparative Examples 1 to 4 with the protective film peeled off were laminated on the substrate 43 having a step so that the photosensitive composition layer faced the substrate 43 having a step, covering all the steps 41 from the lamination direction 42 shown in FIG. 3. Also, in the same manner, the transfer films of Examples 13 to 17 with the protective film peeled off were laminated on the substrate 43 having a step so that the refractive index adjustment layer faced the substrate 43 having a step.

[0454] The lamination conditions were evaluated under the following two conditions. [1] Rubber roller temperature 80°C, linear pressure 100 N / cm, conveyance speed 2.0 m / min [2] Rubber roller temperature 120°C, linear pressure 100 N / cm, conveyance speed 2.0 m / min Note that this lamination method includes one step-up process of laminating the transfer film in this order from the bottom portion 41c to the upper portion 41a at the step 41 and one step-down process of laminating the transfer film in this order from the upper portion 41a to the bottom portion 41c at the step 41. That is, in the procedure of covering the step 41 from the lamination direction 42 shown in FIG. 3, the step-up process is the lamination process in the region X1, and the step-down process is intended to be the lamination process in the region X2.

[0455] Next, the "number of entrapped bubbles" in the region along the step was observed using an optical microscope without peeling the temporary support, and evaluation was performed according to the following criteria. The region along the step refers to the lower end portions of the side surface portions 41b that are continuous from the upper portion 41a to the bottom portion 41c in the step 41 in the regions X1 and X2 in FIG. 3, and the lower end portions of the side surface portions 41b that are continuous from the upper portion 41a to the bottom portion 41c in the step 41 in the regions Y1 and Y2 in FIG. 3. Evaluations were performed for two conditions of the lamination temperature (rubber roller temperature) of 80°C and 120°C, respectively. In the following evaluation criteria, if the evaluation is "C" or higher, it is suitable for practical use, and "A" is particularly preferable. The evaluation results are shown in Table 4.

[0456] - Evaluation Criteria for Laminability - A: The number of bubbles in the region along the step is less than 5. B: The number of bubbles in the region along the step is 5 or more and less than 30. C: The number of bubbles in the region along the step is 30 or more and less than 100. D: The number of bubbles in the region along the step is 100 or more.

[0457]

Table 5

[0458] From the results in Table 4, according to the transfer film of the example, during film conveyance, adhesion of the photosensitive composition layer to the guide roller hardly occurs at the contact surface between the composition layer and the guide roller. Furthermore, when thermally laminated to a substrate having a step such as a wiring board, it was confirmed that excellent step followability is exhibited for a wide variety of lamination temperatures. Also, from the results in Table 4, when tanδ (tanδ T25 ) at 25°C is 1.2 or less (in other words, when the composition layer of the transfer film satisfies the requirements of formula (1A')), it was found that adhesion of the photosensitive composition layer to the guide roller is further suppressed. In particular, tanδ (tanδ T25When () is 1.0 or less (in other words, when the composition layer of the transfer film satisfies the requirements of formula (1A'')), it was found that the adhesion of the photosensitive composition layer to the guide roll was more suppressed. Also, from the results in Table 4, when tanδ at 120 °C (tanδ T120 ) is 1.0 or more (in other words, when the composition layer of the transfer film satisfies the requirements of formula (2A')), it was found that the laminating property is more excellent. Also, from the results in Table 4, the value obtained by dividing tanδ at 120 °C by tanδ at 80 °C (tanδ T120 / tanδ T80 ) is 1.0 to 8.0 (in other words, when the composition layer of the transfer film satisfies the requirements of formula (3A')), it was found that the laminating property is more excellent.

[0459] It is clear that the desired effect cannot be obtained with the transfer film of the comparative example.

[0460] 〔Example 101 (Production of Substrate for Touch Panel)〕 A cycloolefin resin film with a film thickness of 38 μm and a refractive index of 1.53 was subjected to corona discharge treatment for 3 seconds under the conditions of an output voltage of 100%, an output of 250 W, a wire electrode with a diameter of 1.2 mm, an electrode length of 240 mm, and a distance between the work electrodes of 1.5 mm using a high-frequency oscillator to perform surface modification. The obtained film was used as a transparent film substrate. Next, Material-C shown in Table 5 below (the numerical values of each component in the table are the contents (parts by mass)) was coated on the transparent film substrate using a slit nozzle, and then irradiated with ultraviolet light (integrated light amount: 300 mJ / cm 2 ) and dried at about 110 °C to form a refractive index adjustment layer with a refractive index of 1.60 and a film thickness of 80 nm.

[0461]

Table 6

[0462]

Chemical formula

[0463] On the refractive index adjustment layer of a transparent film substrate with a refractive index adjustment layer, an ITO (Indium Tin Oxide) film having a thickness of 40 nm and a refractive index of 1.82 was formed by DC magnetron sputtering, and the formed ITO film was patterned by photolithography, thereby forming an ITO transparent electrode pattern on the refractive index adjustment layer. The formation of the ITO film and the patterning of the ITO film (i.e., the formation of the ITO transparent electrode pattern) were performed by the method described in paragraphs

[0119] to

[0122] of Japanese Patent Application Laid-Open No. 2014-10814. Thus, a substrate for a touch panel having a laminated structure of ITO transparent electrode pattern / refractive index adjustment layer / transparent film substrate was obtained.

[0464] (Transfer of the photosensitive composition layer using a transfer film (lamination)) The protective film was peeled off from the transfer film of Example 1 described above, and the transfer film from which the protective film was peeled off was laminated on the above-described substrate for a touch panel, whereby the photosensitive composition layer of the transfer film was transferred onto the surface of the substrate for a touch panel on the side where the ITO transparent electrode pattern was formed. The lamination conditions were a temperature of 40°C for the substrate for a touch panel, a temperature of the rubber roller (i.e., the lamination temperature) of 110°C, a line pressure of 3 N / cm, and a conveyance speed of 2 m / min. Thereby, a laminate having a laminated structure of temporary support / photosensitive composition layer / ITO transparent electrode pattern / refractive index adjustment layer / transparent film substrate was obtained.

[0465] (Production of a transparent laminate) The photosensitive composition layer of the above laminate was pattern-exposed through the temporary support. The pattern exposure was performed using a proximity type exposure machine having an ultra-high pressure mercury lamp (manufactured by Hitachi High-Technologies Corporation) and an exposure mask, and the exposure amount was 100 mJ / cm through the temporary support. 2It was exposed with (i-line). After pattern exposure, the temporary support was peeled off from the laminate, and the photosensitive composition layer of the laminate from which the temporary support was peeled off was developed for 45 seconds using a 1 mass% aqueous sodium carbonate solution (solution temperature: 33 °C) as the developer. After development, air was blown to remove moisture, and further, the exposure amount was 375 mJ / cm 2 After exposure with (i-line), a cured film of a protective film for a touch panel having an opening (i.e., unexposed portion) exposing a part of the ITO transparent electrode pattern was obtained by performing a heating (post-bake) treatment at 145 °C for 30 minutes. As described above, a transparent laminate having a laminated structure of a cured film of a protective film for a touch panel / ITO transparent electrode pattern / refractive index adjustment layer / transparent film substrate was obtained.

[0466] (Fabrication of an image display device (touch panel)) A film including the transparent laminate of each of the previously fabricated examples was bonded to a liquid crystal display element manufactured by the method described in

[0097] to

[0119] of JP-A-2009-047936, and further, a front glass plate was bonded thereto, whereby an image display device including a touch panel protective film, which includes a capacitive input device as a component, was fabricated by a known method. When the operation of the fabricated image display device was confirmed, the touch panel operated normally.

[0467] [Examples 102 to 124] An image display device (touch panel) was fabricated in the same manner as in Example 101, except that the transfer film was changed from the transfer film of Example 1 to the transfer films of Examples 2 to 24 (Examples 102 to 121). In all cases, the touch panel operated normally. [Explanation of reference numerals]

[0468] 1, 11 Temporary support 2, 12 Composition layer 3, 17 Photosensitive composition layer 5 Refractive index adjustment layer 13 Thermoplastic resin layer 15 Intermediate layer 10, 20 Transfer film 1A Film substrate 41 Step difference 42 Lamination direction 43 Substrate with a step difference 41a Upper part of the step 41 41b Side surface part of the step 41 41c Bottom part of the step 41 in contact with the film substrate 1A La Length of the upper part 41a Lc Length of the bottom part 41c θ Angle formed between the side surface part 41b and the film substrate 1A X1, X2, Y1, Y2 Regions

Claims

1. A transfer film having a temporary support and a composition layer disposed on the temporary support, wherein the temporary support is a polyethylene terephthalate film, the composition layer consists only of a photosensitive composition layer, the thickness of the photosensitive composition layer is 0.60 μm or more and 20 μm or less, the photosensitive composition layer contains a binder polymer and a solvent, the content of the binder polymer is 30 to 70% by mass based on the total mass of the photosensitive composition layer, the binder polymer contains any polymer that satisfies the following condition (a) or condition (b), Condition (a): A polymer having a structural unit derived from a (meth)acrylic compound, wherein the content of the structural unit derived from the (meth)acrylic compound is 50% by mass or more based on all the structural units of the polymer, Condition (b): A polymer having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth)acrylic compound is 50% by mass or more based on all the structural units of the polymer, the solvent contains at least one selected from the group consisting of an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, and a ketone solvent, a transfer film that satisfies all the requirements of the following formulas (1A) to (3A) when measuring the dynamic viscoelasticity of the composition layer at 25 to 150 °C under the conditions of a frequency of 1 Hz and a heating rate of 5 °C / min. Equation (1A) tanδ Ｔ２５ ≦ 1.5 Formula (2A) tanδ Ｔ１２０ ≥0.80 Formula (3A): 0.50 ≤ tanδ Ｔ１２０ / tanδ Ｔ８０ ≤ 10 In the above formulas (1A) to (3A), tanδ Ｔ２５ represents tanδ at 25°C, and tanδ Ｔ１２０ represents tanδ at 120°C, and tanδ Ｔ８０ represents tanδ at 80°C.

2. The transfer film according to claim 1, which satisfies the requirement of the following formula (1A'). Formula (1A') tanδ Ｔ２５ ≤1.2

3. The transfer film according to claim 1 or 2, which satisfies the requirement of the following formula (1A''). Formula (1A'') tanδ Ｔ２５ ≤ 1.0

4. The transfer film according to any one of claims 1 to 3, which satisfies the requirement of the following formula (3A'). Equation (3A') 1.0 ≦ tanδ Ｔ１２０ / tanδ Ｔ８０ ≦ 8.0

5. The transfer film according to any one of claims 1 to 4, which satisfies the requirement of the following formula (2A'). Expression (2A') tanδ Ｔ１２０ ≥ 1.0

6. The transfer film according to any one of claims 1 to 5, wherein the photosensitive composition layer contains a binder polymer, a photopolymerizable compound, and a photoinitiator.

7. The transfer film according to any one of claims 1 to 6, which is used for forming a protective film for a touch panel.

8. The surface of the transfer film according to any one of claims 1 to 7, which is opposite to the temporary support, is brought into contact with a substrate having a conductive layer and bonded thereto to obtain a substrate with a composition layer having the substrate, the conductive layer, the composition layer, and the temporary support in this order. A bonding step; An exposure step of pattern-exposing the composition layer; A developing step of developing the exposed composition layer to form a protective film pattern for protecting the conductive layer; Furthermore, a peeling step of peeling the temporary support from the substrate with the composition layer is provided between the bonding step and the exposure step, or between the exposure step and the developing step. A method for manufacturing a laminate.

9. The method for manufacturing a laminate according to claim 8, wherein the substrate having the conductive layer is a substrate having at least one of an electrode for a touch panel and a wiring for a touch panel.

10. The surface of the transfer film according to any one of claims 1 to 7, which is opposite to the temporary support, is brought into contact with a substrate having a conductive layer, and a substrate with a composition layer having the substrate, the conductive layer, the composition layer, and the temporary support in this order is obtained. A bonding step; An exposure step of pattern-exposing the composition layer; A developing step of developing the exposed composition layer to form a resin pattern; An etching step of etching the conductive layer in a region where the resin pattern is not disposed; Furthermore, a peeling step of peeling the temporary support from the substrate with the composition layer is included between the bonding step and the exposure step, or between the exposure step and the developing step. A method for manufacturing a circuit wiring.

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