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

Abstract

The first objective of this invention is to provide a transfer film in which, during film transport, the photosensitive composition layer does not easily adhere to the guide roller at the contact surface between the composition layer and the guide roller, and when heat-laminated onto a substrate with a stepped difference, such as a wiring substrate, it exhibits excellent step difference tracking performance over a wide range of lamination temperatures. Furthermore, the second objective of this invention is to provide a method for manufacturing a laminate using the above-described transfer film and a method for manufacturing circuit wiring. The transfer film of this invention comprises a temporary support and a composition layer disposed on the temporary support. The composition layer includes a photosensitive composition layer. When the dynamic viscoelasticity of the composition layer at 25–150°C is measured under 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): Formula (1A) tanδ T25 ≤1.5, Equation (2A)tanδ T120 ≥0.80, Equation (3A) 0.50≤tanδ T120 / tanδ T80 ≤10, and in addition, in the above equations (1A) to (3A), tanδ T25 tanδ represents the value of tanδ at 25℃. T120 tanδ represents the value at 120℃. T80 This represents tanδ at 80℃.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a transfer film, a laminate, and a method for manufacturing circuit wiring. Background Technology

[0002] Because the number of steps required to obtain a specified pattern is small, the following method is widely used: a photosensitive composition layer is disposed on any substrate using a transfer film, and the photosensitive composition layer is exposed through a mask and then developed.

[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) disposed on the support film.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2015-121929 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] Based on the results of the inventor's research on the transfer film described in Patent Document 1, it was found that when the roll of transfer film is rolled out and the uncured photosensitive composition layer in the transfer film is in contact with the guide roller, the photosensitive composition layer may adhere to the guide roller and peel off.

[0009] Furthermore, the inventors discovered that when a transfer film is thermally laminated onto a substrate with a stepped difference, such as a wiring board, by contacting the uncured photosensitive composition layer in the transfer film with the substrate, air bubbles sometimes become trapped between the photosensitive composition layer and the substrate due to insufficient step difference following ability of the transfer film. In other words, it is clear that there is room for further improvement in the step difference following ability of the transfer film.

[0010] However, generally, the higher the lamination temperature, the lower the melt viscosity of the photosensitive composition layer, and the better the step difference following performance tends to be (i.e., air bubbles mixed between the photosensitive composition layer and the substrate are suppressed). However, depending on the type of substrate, the following problem may occur: when the lamination temperature is increased, 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, the lamination temperature is preferably set low. To meet these requirements, a large temperature margin of the lamination temperature (i.e., low temperature dependence relative to the lamination temperature) is also required when improving the step difference following performance of the transfer film during hot lamination.

[0011] Therefore, the objective of this invention is to provide a transfer film in which, during film transport, the photosensitive composition layer does not easily adhere to the guide roller at the contact surface between the photosensitive composition layer and the guide roller, and when heat-laminated on a substrate with a stepped difference, such as a wiring board, it exhibits excellent step difference following performance over a wide range of lamination temperatures.

[0012] Furthermore, the present invention also aims to provide a method for manufacturing a laminate using the above-described transfer film and a method for manufacturing circuit wiring.

[0013] means for solving technical problems

[0014] As a result of in-depth research on the above-mentioned issues, the inventors discovered that the above-mentioned issues can be solved by the following configuration.

[0015] [1] A transfer film having:

[0016] Temporary support structure; and

[0017] The composition layer disposed on the aforementioned temporary support,

[0018] The above-mentioned composition layer includes a photosensitive composition layer.

[0019] When the dynamic viscoelasticity of the above-mentioned composition layer at 25 to 150°C is measured at a frequency of 1 Hz and a heating rate of 5°C / min, all the requirements of the following formulas (1A) to (3A) are met.

[0020] Equation (1A)tanδ T25 ≤1.5

[0021] Equation (2A)tanδ T120 ≥0.80

[0022] Equation (3A) 0.50≤tanδ T120 / tanδ T80 ≤10

[0023] In equations (1A) to (3A) above, tanδ T25 tanδ represents the value of tanδ at 25℃. T120 tanδ represents the value at 120℃. T80 This represents tanδ at 80℃.

[0024] [2] The transfer film according to [1] satisfies the requirements of the following formula (1A').

[0025] Equation (1A')tanδ T25 ≤1.2

[0026] [3] The transfer film according to [1] or [2] satisfies the requirements of the following formula (1A”).

[0027] Equation (1A”)tanδ T25 ≤1.0

[0028] [4] The transfer film according to any one of [1] to [3] satisfies the requirements of the following formula (3A').

[0029] Equation (3A')1.0≤tanδ T120 / tanδ T80 ≤8.0

[0030] [5] The transfer film according to any one of [1] to [4] satisfies the requirements of the following formula (2A').

[0031] Equation (2A')tanδ T120 ≥1.0

[0032] [6] The transfer film according to any one of [1] to [5], wherein,

[0033] The film thickness of the above-mentioned photosensitive composition layer is less than 20 μm.

[0034] [7] The transfer film according to any one of [1] to [6], wherein,

[0035] The aforementioned photosensitive composition layer comprises an adhesive polymer, a photopolymerizable compound, and a photopolymerization initiator.

[0036] [8] The transfer film according to any one of [1] to [7] is used to form a protective film for a touch panel.

[0037] [9] A method for manufacturing a laminate, comprising:

[0038] In the bonding process, the surface opposite to the temporary support of the transfer film described in any one of [1] to [8] is brought into contact with the substrate having a conductive layer and bonded together to obtain a substrate having the substrate, the conductive layer, the composition layer and the temporary support in sequence.

[0039] In the exposure process, the above-mentioned composite layer is patterned and exposed; and

[0040] The developing process develops the exposed composite layer to form a protective film pattern that protects the conductive layer.

[0041] The manufacturing method of the laminate also includes:

[0042] In the peeling process, between the bonding process and the exposure process or between the exposure process and the developing process, the temporary support is peeled off from the substrate with the composite layer.

[0043]

[10] The method for manufacturing the laminated body according to [9], wherein,

[0044] The substrate with the conductive layer described above is a substrate having at least one of an electrode for a touch panel and wiring for a touch panel.

[0045]

[11] A method for manufacturing circuit wiring, comprising:

[0046] In the bonding process, the surface of the transfer film opposite to the temporary support of any one of [1] to [8] is brought into contact with the substrate having a conductive layer, thereby obtaining a substrate having the substrate, the conductive layer, the composition layer and the temporary support in sequence.

[0047] In the exposure process, the above-mentioned composite layer is patterned and exposed; and

[0048] The developing process involves developing the exposed composite layer to form a resin pattern.

[0049] The etching process involves etching the conductive layer in areas where the resin pattern is not present.

[0050] The manufacturing methods for circuit wiring also include:

[0051] In the peeling process, between the bonding process and the exposure process or between the exposure process and the development process, a temporary support is peeled off from the substrate with the photosensitive composition layer.

[0052] Invention Effects

[0053] According to the present invention, a transfer film can be provided in which, when the film is carried, the photosensitive composition layer does not easily adhere to the guide roller at the contact surface between the composition layer and the guide roller, and when heat-laminated on a substrate with a stepped difference, such as a wiring board, it has excellent step difference following performance over a wide range of lamination temperatures.

[0054] Furthermore, according to the present invention, a method for manufacturing a laminate using the above-described transfer film and a method for manufacturing circuit wiring can be provided. Attached Figure Description

[0055] Figure 1 This is a schematic diagram illustrating an example of the structure of the transfer film according to the first embodiment.

[0056] Figure 2 This is a schematic diagram illustrating an example of the structure of the transfer film in the second embodiment.

[0057] Figure 3 This is a schematic diagram used to illustrate the step difference followability evaluation of the embodiments.

[0058] Figure 4 Viewed from the lamination direction Figure 3 A schematic diagram of the side (both sides) of the membrane substrate 43 with stepped differences is shown.

[0059] Figure 5 Viewed from a direction orthogonal to the lamination direction Figure 3 A schematic diagram of the side (both sides) of the membrane substrate 43 with stepped differences is shown. Detailed Implementation

[0060] The present invention will now be described in detail.

[0061] In this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0062] In this specification, within a range of numerical values ​​described in stages, the upper or lower limit value recorded within a certain range can be replaced by the upper or lower limit value of other ranges of numerical values ​​described in stages. Furthermore, within the range of numerical values ​​described in this specification, the upper or lower limit value recorded within a certain range can also be replaced with the value shown in the embodiments.

[0063] In this specification, the term "process" includes not only independent processes, but also processes that achieve the intended purpose of the process, even if they cannot be clearly distinguished from other processes.

[0064] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400-700nm is 80% or more, preferably 90% or more.

[0065] In this specification, the average transmittance of visible light is a value measured by a spectrophotometer, for example, a Hitachi, Ltd. spectrophotometer U-3310.

[0066] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​converted from the standard polystyrene measured using the following methods: TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard, measured by a gel permeation chromatography (GPC) analyzer.

[0067] Unless otherwise specified, the molecular weight of compounds with molecular weight distribution in this specification is the weight-average molecular weight (Mw).

[0068] Unless otherwise specified, the content of metal elements in this specification is the value determined using an inductively coupled plasma (ICP) spectrophotometer.

[0069] Unless otherwise specified, the refractive index in this specification is the value measured using an ellipsometer at a wavelength of 550 nm.

[0070] Unless otherwise specified, the hue in this instruction manual is the value measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0071] In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth)acryloyloxy" is a concept that includes both acryloyloxy and methacryloyloxy.

[0072] In addition, in this specification, "alkali solubility" means that the solubility is 0.1g or more in 100g of a 1% by mass aqueous solution of sodium carbonate at 22°C.

[0073] In this specification, "water-soluble" means having a solubility of 0.1g or more in 100g of water at pH 7.0 and a liquid temperature of 22°C. Therefore, for example, a water-soluble resin refers to a resin that meets the above solubility condition.

[0074] In this specification, "solid components" of a composition refer to components used to form the composition layer formed using the composition. When the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. Furthermore, liquid components are also considered solid components as long as they form the composition layer.

[0075] [Transfer film]

[0076] The transfer film of the present invention has a temporary support and a composition layer disposed on the temporary support, wherein the composition layer comprises a photosensitive composition layer. A characteristic feature of the transfer film of the present invention is that, when the dynamic viscoelasticity of the composition layer at 25°C to 150°C is measured at a frequency of 1 Hz and a heating rate of 5°C / min, it satisfies all the requirements of formulas (1A) to (3A) described later.

[0077] With the above-described configuration, the transfer film of the present invention is designed to prevent the photosensitive composition layer from adhering to the guide roller at the contact surface between the composition layer and the guide roller during film transport.

[0078] Furthermore, when thermally laminated onto substrates with stepped differences, such as wiring boards, it exhibits excellent step difference tracking across a wide range of lamination temperatures (e.g., 80°C, 120°C). In other words, the transfer film of the present invention can suppress the incorporation of air bubbles between the photosensitive composition layer and the substrate while being thermally laminated onto substrates with stepped differences, such as wiring boards, at a wide range of lamination temperatures (e.g., 80°C, 120°C).

[0079] Furthermore, as described below, the transfer film may contain at least one composition layer, or it may contain composition layers other than the photosensitive composition layer. Moreover, when the transfer film contains two or more composition layers, the composition layer located furthest from the temporary support may be a layer other than the photosensitive composition layer. In other words, in the transfer film of the present invention, the composition layer may be a composition layer other than the photosensitive composition layer. Generally, when the transfer film contains two or more composition layers, the thickness of the composition layer disposed on the side of the photosensitive composition layer opposite to the temporary support side is often thinner than the photosensitive composition layer. Therefore, even if other composition layers exist on the side of the photosensitive composition layer opposite to the temporary support side, the contact surface between the composition layer and the guide roller during film transport is dominated by the physical properties of the photosensitive composition layer, which is greater than the other composition layers directly contacting the guide roller. In fact, components originating from the photosensitive composition layer are also observed in the residue on the guide roller during transport.

[0080] Hereinafter, the situation where the photosensitive composition layer is less likely to adhere to the guide roller at the contact surface between the composition layer and the guide roller during film transport and / or the situation where there is better step difference following performance over a wide range of lamination temperatures during thermal lamination on substrates with step differences, such as wiring boards, is also referred to as "the effect of the present invention is better".

[0081] tanδ (loss tangent), expressed as the ratio of storage modulus G' to loss modulus G” (G” / G'), is an indicator of the ratio of elastic to viscous properties in polymer materials. A higher tanδ value indicates stronger viscous properties, while a lower tanδ value indicates weaker elastic properties. Recently, the inventors discovered a correlation between the aforementioned problems and the tanδ value of the composition layer of the transfer film. Specifically, they found that adjusting the tanδ value of the composition layer of the transfer film to specified conditions can solve the aforementioned problems.

[0082] The mechanism of action of the transfer film of the present invention is not yet clear, but it is speculated to be as follows.

[0083] A higher tanδ value results in better wettability (adhesion) of the composition layer to the guide roller at the contact surface between the composition layer and the guide roller during film transfer. Furthermore, the composition layer is more prone to deformation under small forces, thus increasing the likelihood of guide roller contamination (adhesion of the photosensitive composition layer within the composition layer to the guide roller). Contamination of the guide roller can be suppressed when the composition layer of the transfer film satisfies the requirements of formula (1A).

[0084] Furthermore, when the composition layer of the transfer film satisfies the requirements of formulas (2A) and (3A), and the transfer film is thermally laminated onto a substrate with a stepped difference, such as wiring, by means of contact between the composition layer and the substrate, the adhesion of the composition layer is appropriate and air bubbles are not easily mixed between the composition layer and the substrate. Moreover, the temperature margin of the lamination temperature for step difference following is highly correlated with the temperature dependence of tanδ, therefore tanδ can be used as an indicator 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 difference following performance over a wide range of lamination temperatures.

[0085] Furthermore, in the determination of the tanδ of the composite layer of the transfer film, the test sample shown below was used. The method for preparing the test sample will be described below.

[0086] When the transfer film has a protective film on the composition layer, the protective film is first peeled off from the transfer film. The film obtained by peeling off the protective film is folded and bonded to each other with the surfaces of the composition layers exposed by peeling off the protective film facing each other, thereby creating a temporary support / composition layer (2 layers) / temporary support laminate 1. Next, one side of the temporary support in the above-mentioned laminate 1 is peeled off. Moreover, the laminate 1 with the temporary support peeled off is folded and bonded to each other with the composition layers (2 layers) exposed by peeling off the temporary support, thereby creating a temporary support / composition layer (4 layers) / temporary support laminate 2. Moreover, one side of the temporary support in the above-mentioned laminate 2 is peeled off. Moreover, the laminate 2 with the temporary support peeled off is folded and bonded to each other with the composition layers (4 layers) exposed by peeling off the temporary support, thereby creating a temporary support / composition layer (8 layers) / temporary support laminate 3. By repeatedly bonding the composition layers in the same order, a laminate N consisting of a temporary support / composition layer of a specified thickness / temporary support is created. Furthermore, by removing the temporary support from the laminate N, a test sample consisting of a composition layer of a specified thickness is created. The thickness of the composition layer used as the test sample can be selected to suit the dynamic viscoelasticity measuring apparatus used (typically 0.1 to 1.0 mm). For example, when measuring tanδ using a DHR-2 rheometer (manufactured by TA Instruments Japan Inc.), a thickness of 0.5 mm (the gap of the peltier plate) can be set.

[0087] The transfer film of the present invention will be described below.

[0088] The transfer film of the present invention has a temporary support and a composition layer disposed on the temporary support, wherein the composition layer comprises a photosensitive composition layer.

[0089] There are no particular limitations as long as the above-mentioned composition layer contains a photosensitive composition layer.

[0090] The aforementioned photosensitive composition layer can be a negative photosensitive composition layer or a chemically amplified photosensitive composition layer, preferably a negative photosensitive composition layer.

[0091] Furthermore, the aforementioned composition layer can be a single-layer structure or a structure with two or more layers. When the aforementioned composition layer includes other composition layers besides the photosensitive composition layer, examples of other composition layers include thermoplastic resin layers, intermediate layers, and refractive index adjustment layers.

[0092] Furthermore, the transfer film can be a structure with a protective film on the composition layer.

[0093] Furthermore, in the transfer film of the present invention, when the dynamic viscoelasticity of the composition layer at 25°C to 150°C is measured under the conditions of a frequency of 1 Hz and a heating rate of 5°C / min, all the requirements of formulas (1A) to (3A) are satisfied.

[0094] Equation (1A)tanδ T25 ≤1.5

[0095] Equation (2A)tanδ T120 ≥0.80

[0096] Equation (3A) 0.50≤tanδ T120 / tanδ T80 ≤10

[0097] Furthermore, in the following equations (1A) to (3A), tanδ T25 This represents the tanδ at 25°C (tanδ of the composite layer at 25°C). T120 This represents tanδ at 120℃ (tanδ of the composite layer at 120℃). T80 This represents tanδ at 80℃ (tanδ of the composite layer at 80℃).

[0098] In view of the superior effects of the present invention, it is preferable to satisfy the requirement of the following formula (1A'), and more preferably to satisfy the requirement of the following formula (1A”).

[0099] Equation (1A')tanδ T25 ≤1.2

[0100] Equation (1A”)tanδ T25 ≤1.0

[0101] In addition, the above tanδ T25 There is no particular limitation on the lower limit, but considering the superior effect of the present invention, it is preferred to be 0.20 or higher.

[0102] Furthermore, from the viewpoint of achieving better results from the present invention, it is preferable to satisfy the requirements of the following formula (2A').

[0103] Equation (2A')tanδ T120 ≥1.0

[0104] In addition, the above tanδ T120 There is no particular upper limit to the value, but considering the superior effect of the present invention, it is preferable to use 12 or less.

[0105] Furthermore, from the viewpoint of achieving better results from the present invention, it is preferable to satisfy the requirements of the following formula (3A').

[0106] Equation (3A')1.0≤tanδ T120 / tanδ T80 ≤8.0

[0107] The following illustrates one example of the transfer film of the present invention, but it is not limited thereto.

[0108] (1) "Temporary support / photosensitive composition layer / refractive index adjustment layer / protective film"

[0109] (2) "Temporary support / photosensitive composition layer / protective film"

[0110] (3) "Temporary support / intermediate layer / photosensitive composition layer / protective film"

[0111] (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film"

[0112] Furthermore, in each of the above structures, the photosensitive composition layer is preferably a negative photosensitive composition layer. Moreover, the photosensitive composition layer is more preferably a coloring resin layer.

[0113] As described below, the transfer film of the present invention can be used as a transfer film for wiring protection film, or as a transfer film for resist.

[0114] When used as a transfer film for wiring protection, the structure of the transfer film is preferably, for example, the structure described in (1) or (2) above. Furthermore, when used as a transfer film for resist, the structure of the transfer film is preferably, for example, the structure described in (2) to (4) above.

[0115] In the case where the photosensitive composition layer has a structure in which other composition layers are further provided on the side opposite to the temporary support side of the photosensitive composition layer, the total thickness of the other layers disposed on the side opposite to the temporary support side of the photosensitive composition layer is preferably 0.1 to 30% relative to the thickness of the photosensitive composition layer, more preferably 0.1 to 20%.

[0116] Hereinafter, an example of a specific embodiment will be given to describe the transfer film of the present invention. Furthermore, the transfer film of the first embodiment described below is a structure suitable for use as a transfer film for wiring protection films, and the transfer film of the second embodiment described below is a structure suitable for use as a transfer film for photoresists.

[0117] [Transfer film of the first embodiment]

[0118] Hereinafter, an example of an embodiment of the transfer film of the first embodiment will be described.

[0119] Figure 1The transfer film 10 shown sequentially comprises 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. Furthermore, the composition layer 2 satisfies all the requirements of the above formulas (1A) to (3A).

[0120] in addition, Figure 1 The transfer film 10 shown is configured with a protective film 7, but it is also possible to omit the protective film 7.

[0121] and, Figure 1 The transfer film 10 shown is configured with a refractive index adjustment layer 5, but it is also possible to omit the refractive index adjustment layer 5.

[0122] The elements that make up the transfer film are explained below.

[0123] Temporary support

[0124] The transfer film has a temporary support.

[0125] The temporary support is a component that supports the composite layer and is eventually removed through a peeling process.

[0126] The temporary support can be a single-layer structure or a multi-layer structure.

[0127] The temporary support is preferably a membrane, more preferably a resin membrane. As a temporary support, a membrane that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat is preferred.

[0128] Examples of such membranes include polyethylene terephthalate membranes (e.g., biaxially stretched polyethylene terephthalate membranes), polymethyl methacrylate membranes, cellulose triacetate membranes, polystyrene membranes, polyimide membranes, and polycarbonate membranes.

[0129] Among them, polyethylene terephthalate film is preferred as a temporary support.

[0130] Furthermore, the membrane used as a temporary support is preferably free from deformations such as wrinkles and scratches.

[0131] From the perspective of enabling pattern exposure through a temporary support, the temporary support preferably has high transparency, and the transmittance at 365nm is preferably 60% or more, more preferably 70% or more.

[0132] From the perspective of pattern formation properties during pattern exposure through a temporary support and the transparency of the temporary support, the haze of the temporary support is preferably low. 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.

[0133] Considering the pattern formation properties and transparency of the temporary support during pattern exposure, the number of particles, foreign objects, and defects contained in the temporary support is preferably low. The number of particles, foreign objects, and defects with a diameter of 1 μm or larger in the temporary support is preferably 50 per 10 mm. 2 Below, 10 pieces / 10mm is preferred. 2 Below, 3 / 10mm is further preferred. 2 The following is particularly preferred: 0 / 10mm 2 .

[0134] There is no particular limitation on the thickness of the temporary support, preferably 5 to 200 μm, and more preferably 10 to 150 μm, and even more preferably 10 to 50 μm, considering ease of handling and versatility.

[0135] The thickness of the temporary support was calculated as the average of five arbitrary points measured by cross-sectional observations using SEM (Scanning Electron Microscope).

[0136] Examples of temporary supports include biaxially stretched polyethylene terephthalate films with a thickness of 16 μm, 12 μm, and 9 μm.

[0137] Preferred methods for temporary supports include, for example, paragraphs

[0017] to

[0018] of Japanese Patent Application Publication No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Application Publication No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370, the contents of which are incorporated herein by reference.

[0138] From a processability perspective, a layer containing microparticles (lubricant layer) can also be provided on the surface of the temporary support. The lubricant layer can 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.

[0139] Furthermore, the thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0140] Photosensitive Composite Layer

[0141] The transfer film has a photosensitive composition layer.

[0142] By transferring a photosensitive composition layer onto a substrate and then exposing and developing it, a pattern can be formed on the substrate.

[0143] Negative photosensitive composition layers are preferred. Furthermore, a negative photosensitive composition layer refers to a photosensitive composition layer in which the solubility of the exposed portion in the developer decreases due to exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the resulting pattern is equivalent to a cured layer.

[0144] The following is a detailed description of the components that may be contained in the photosensitive composition layer.

[0145] <Adhesive Polymers>

[0146] The photosensitive composition layer may contain an adhesive polymer.

[0147] Examples of adhesive polymers include (meth)acrylic resins, styrene resins, epoxy resins, polyamide resins, polyamide epoxy resins, alkyd resins, phenolic resins, polyester resins, polyurethane resins, epoxy acrylate resins obtained by reacting epoxy resins with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting epoxy acrylate resins with acid anhydrides.

[0148] As one of the preferred adhesive polymers, (meth)acrylic resins are an example, considering their excellent alkali developability and film-forming properties.

[0149] Furthermore, in this specification, (meth)acrylic resin refers to a resin having structural units derived from (meth)acrylic acid compounds. The content of structural units derived from (meth)acrylic acid compounds relative to all structural units of the (meth)acrylic acid resin is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0150] (Meth)acrylic resins can consist solely of structural units derived from (meth)acrylic acid compounds, or they can contain structural units derived from polymerizable monomers other than (meth)acrylic acid compounds. Specifically, the maximum content of structural units derived from (meth)acrylic acid compounds is less than 100% by mass relative to all structural units of the (meth)acrylic resin.

[0151] Examples of (meth)acrylic acid compounds include, for example, (meth)acrylic acid, (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile.

[0152] Examples of (meth)acrylates include, for example, alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred.

[0153] Examples of (meth)acrylamides include, for example, diacetone acrylamide and other acrylamides.

[0154] Examples of alkyl methacrylates include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, and dodecyl methacrylate, which are straight-chain or branched alkyl groups having 1 to 12 carbon atoms; and alkyl methacrylates with cyclic alkyl groups having 6 to 12 carbon atoms, such as hexyl methacrylate and heptyl methacrylate.

[0155] As a preferred type of (meth)acrylate, examples include alkyl (meth)acrylates having a straight-chain or branched alkyl group having 1 to 4 carbon atoms, wherein methyl (meth)acrylate or ethyl (meth)acrylate is preferred.

[0156] Furthermore, as another preferred type of (meth)acrylate, alkyl (meth)acrylates having cyclic alkyl groups having 6 to 12 carbon atoms are mentioned, among which hexyl (meth)acrylate and dicyclopentyl (meth)acrylate are preferred. The cyclic alkyl group can be monocyclic or polycyclic.

[0157] (Meth)acrylic resins can have structural units other than those derived from (meth)acrylic acid compounds.

[0158] As the polymerizable monomer that forms the above-mentioned structural unit, there are no particular restrictions as long as it is a compound other than (meth)acrylic acid compound that can copolymerize with (meth)acrylic acid compound. Examples include styrene compounds such as styrene, vinyltoluene and α-methylstyrene that can have substituents at the α-position or on the aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester and maleic acid monoisopropyl ester, fumaric acid, cinnamic acid, α-cyanocinonic acid, itaconic acid and crotonic acid.

[0159] These polymerizable monomers can be used in one or in combination of two or more.

[0160] Furthermore, as described below, (meth)acrylic resins can have reactive groups.

[0161] Furthermore, from the perspective of further improving alkaline developability, (meth)acrylic resin preferably contains structural units having acid groups. Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups.

[0162] The (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0163] From the perspective of excellent developability, the content of structural units having acid groups (preferably structural units derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin. Furthermore, there is no particular upper limit, but from the perspective of excellent alkali resistance, it is preferably 50% by mass or less, more preferably 40% by mass or less.

[0164] Furthermore, the (meth)acrylic resin is more preferably composed of structural units derived from the aforementioned alkyl (meth)acrylic esters.

[0165] The content of structural units derived from alkyl methacrylates in (meth)acrylic resins is preferably 50-90% by mass, more preferably 60-90% by mass, and even more preferably 65-90% by mass, relative to all structural units of (meth)acrylic resins.

[0166] Furthermore, the (meth)acrylic resin preferably has reactive groups, and more preferably contains structural units having reactive groups.

[0167] As a reactive group, a free radical polymerizable group is preferred, and an olefinically unsaturated group is more preferred. Furthermore, when the (meth)acrylic resin has an olefinically unsaturated group, the (meth)acrylic resin preferably contains structural units with olefinically unsaturated groups in the side chains.

[0168] In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to a group of atoms that branch off from the main chain.

[0169] As an olefinic unsaturated group, allyl or (meth)acryloyloxy is preferred.

[0170] Examples of structural units with reactive groups include those shown below, but are not limited to these.

[0171] [Chemical Formula 1]

[0172]

[0173] (Meth)acrylic resins may contain one structural unit with a reactive group, or they may contain two or more.

[0174] When (meth)acrylic resin contains structural units having reactive groups, from the viewpoint of further improving the effects of the present invention, the content of structural units having reactive groups relative to all structural units of (meth)acrylic resin is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

[0175] As a preferred embodiment of (meth)acrylic resin, a resin having both structural units derived from (meth)acrylic acid and structural units derived from alkyl methacrylates is preferred.

[0176] As another preferred embodiment of (meth)acrylic resin, examples include resins composed solely of structural units derived from (meth)acrylic acid and structural units derived from alkyl methacrylates.

[0177] Furthermore, as another preferred embodiment of (meth)acrylic resin, resins having structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid alkyl esters, and structural units having reactive groups can be cited.

[0178] Furthermore, as another preferred embodiment of (meth)acrylic resin, an acrylic resin having structural units derived from methacrylic acid, structural units derived from methyl methacrylate, and structural units derived from ethyl acrylate can be cited.

[0179] Furthermore, as another preferred embodiment of (meth)acrylic resin, resins having structural units derived from methacrylic acid, structural units derived from methyl methacrylate, structural units derived from cyclohexyl methacrylate, and structural units having reactive groups can be cited.

[0180] Furthermore, from the viewpoint of further enhancing the effects of the present invention, the (meth)acrylic resin preferably has at least one structural unit selected from methacrylic acid and structural units derived from alkyl methacrylates, and preferably has both structural units derived from methacrylic acid and structural units derived from alkyl methacrylates.

[0181] From the perspective of further enhancing the effects of the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, relative to all structural units of the (meth)acrylic resin. There is no particular upper limit, and it can be 100% by mass or less, preferably 80% by mass or less.

[0182] Furthermore, from the viewpoint of further enhancing the effects of the present invention, the (meth)acrylic resin preferably has at least one structural unit selected from methacrylic acid and structural units selected from alkyl methacrylates, and at least one structural unit selected from acrylic acid and structural units selected from alkyl acrylates.

[0183] From the perspective of further improving the effects of the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates is preferably 60 / 40 to 80 / 20 by mass relative to the total content of structural units derived from acrylic acid and structural units derived from alkyl acrylates.

[0184] From the perspective of excellent developability of the photosensitive composition layer after transfer, (meth)acrylic resin preferably has ester groups at the ends.

[0185] Furthermore, the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in its synthesis. (Meth)acrylic resins with ester groups at the terminals are synthesized using a polymerization initiator that generates free radicals containing ester groups.

[0186] Furthermore, alkali-soluble resins are another preferred type of adhesive polymer.

[0187] For example, from the perspective of developability, the adhesive polymer is preferably an adhesive polymer with an acid value of 60 mg KOH / g or higher.

[0188] Furthermore, for example, from the viewpoint of easily forming a strong film by heating and thermal crosslinking with the crosslinking components, the adhesive polymer is more preferably a carboxyl-containing resin with an acid value of 60 mg KOH / g or higher (so-called carboxyl-containing resin), and even more preferably a carboxyl-containing (meth)acrylic resin with an acid value of 60 mg KOH / g or higher (so-called carboxyl-containing (meth)acrylic resin).

[0189] When the adhesive polymer is a resin containing carboxyl groups, thermal crosslinking can be performed by adding thermally crosslinking compounds such as end-capped isocyanate compounds, thereby increasing the three-dimensional crosslinking density. Furthermore, if the carboxyl groups of the resin are dehydrated and hydrophobic, the resistance to damp heat can be improved.

[0190] As for carboxyl-containing (meth)acrylic resins with an acid value of 60 mg KOH / g or higher, there are no particular restrictions as long as the above acid value condition is met, and they can be appropriately selected from known (meth)acrylic resins.

[0191] For example, acrylic resins containing carboxyl groups in polymers with an acid value of 60 mg KOH / g or higher, as described in paragraph

[0025] of Japanese Patent Application Publication No. 2011-095716, and acrylic resins containing carboxyl groups in polymers with an acid value of 60 mg KOH / g or higher, as described in paragraphs

[0033] to

[0052] of Japanese Patent Application Publication No. 2010-237589, are preferred.

[0192] Other preferred types of adhesive polymers include styrene-acrylic acid copolymers.

[0193] In addition, in this specification, styrene-acrylic acid copolymer refers to a resin having structural units derived from styrene compounds and structural units derived from (meth)acrylic acid compounds, wherein the total content of the aforementioned structural units derived from styrene compounds and the aforementioned structural units derived from (meth)acrylic acid compounds is preferably 30% by mass or more, more preferably 50% by mass or more, relative to all structural units of the aforementioned copolymer.

[0194] Furthermore, the content of structural units derived from styrene compounds relative to all structural units of the aforementioned copolymer is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass.

[0195] Furthermore, the content of the structural units derived from the (meth)acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, relative to all structural units of the copolymer.

[0196] From the perspective of further improving the effects of the present invention, the adhesive polymer preferably has an aromatic ring structure, and more preferably contains structural units having an aromatic ring structure.

[0197] Examples of monomers that form structural units with aromatic ring structures include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, as well as benzyl methacrylate.

[0198] Among them, styrene compounds are preferred, and styrene is more preferred.

[0199] Furthermore, from the viewpoint of further enhancing the effects of the present invention, the adhesive polymer more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0200] [Chemical Formula 2]

[0201]

[0202] When the adhesive polymer contains structural units having aromatic ring structures, from the perspective of further enhancing the effects of the present invention, the content of structural units having aromatic ring structures relative to all structural units of the adhesive polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass.

[0203] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of the structural unit having an aromatic ring structure in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 60 mol%, relative to all structural units of the adhesive polymer.

[0204] Furthermore, considering the superior effects of the present invention, the content of the structural unit represented by the above formula (S) in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, further preferably 20 to 60 mol%, and especially preferably 20 to 50 mol%, relative to all structural units of the adhesive polymer.

[0205] Furthermore, in this specification, when the content of "structural unit" is specified using a molar ratio, the meaning of "structural unit" is the same as that of "monomer unit." Also, in this specification, the aforementioned "monomer unit" can be modified after polymerization, such as through polymer reactions. The same applies below.

[0206] From the perspective of further enhancing the effects of the present invention, the adhesive polymer preferably has an aliphatic hydrocarbon ring structure. That is, the adhesive polymer preferably contains structural units having an aliphatic hydrocarbon ring structure. More preferably, the adhesive polymer has a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings.

[0207] Examples of rings that constitute aliphatic hydrocarbon ring structures include tricyclic decane rings, cyclohexane rings, cyclopentane rings, norbornene rings, and isophorone rings.

[0208] In particular, considering the superior effects of the present invention, a ring formed by the fusion of two or more aliphatic hydrocarbon rings is preferred, and a tetrahydrodicyclopentadiene ring (tricyclic [5.2.1.0]) is more preferred. 2，6 [decane ring].

[0209] Examples of monomers that form structural units with aliphatic hydrocarbon ring structures include dicyclopentyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.

[0210] Furthermore, from the perspective of further superior effects of the present invention, the adhesive polymer more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0211] [Chemical Formula 3]

[0212]

[0213] In equation (Cy), R M R represents a hydrogen atom or a methyl group. Cy This indicates a monovalent group having an aliphatic hydrocarbon ring structure.

[0214] R in equation (Cy) M Methyl is preferred.

[0215] From the perspective of achieving better results in this invention, R in formula (Cy) Cy Preferably, it is a monovalent group with an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group with an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and even more preferably a monovalent group with an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

[0216] Furthermore, considering the superior effects of the present invention, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in the sample is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornene ring structure, or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.

[0217] Furthermore, considering the superior effects of the present invention, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in the sample is preferably a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings, and more preferably a ring structure formed by the fusion of two to four aliphatic hydrocarbon rings.

[0218] Furthermore, considering the superior effects of the present invention, R in formula (Cy) Cy Preferably, the oxygen atom of -C(=O)O- in formula (Cy) is a group that is directly bonded to the aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon cyclic group, more preferably cyclohexyl or dicyclopentyl, and even more preferably dicyclopentyl.

[0219] The adhesive polymer may have one structural unit with an aliphatic hydrocarbon ring structure, or it may have two or more structural units.

[0220] When the adhesive polymer contains structural units having an aliphatic hydrocarbon ring structure, from the perspective of further improving the effects of the present invention, the content of structural units having an aliphatic hydrocarbon ring structure relative to all structural units of the adhesive polymer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass.

[0221] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of structural units having aliphatic hydrocarbon ring structures in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to all structural units of the adhesive polymer.

[0222] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of the structural unit represented by the above formula (Cy) in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol% relative to all structural units of the adhesive polymer.

[0223] When the adhesive polymer contains structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures, from the perspective of further improving the effects of the present invention, the total content of structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures relative to all structural units of the adhesive polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass.

[0224] Furthermore, from the perspective of further superior effects of the present invention, the total content of structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures in the adhesive polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to all structural units of the adhesive polymer.

[0225] Furthermore, from the perspective of further superior effects of the present invention, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the adhesive polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol% relative to all structural units of the adhesive polymer.

[0226] Furthermore, from the perspective of further superior 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 adhesive polymer preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2).

[0227] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0228] 0.30≤nS / (nS+nCy)≤0.75 Formula (SCy-1)

[0229] 0.40≤nS / (nS+nCy)≤0.70 Formula (SCy-2)

[0230] From the perspective of further advantages of the present invention, the adhesive polymer preferably contains structural units having acid groups.

[0231] Examples of acid groups include carboxyl, sulfonyl, phosphonic acid, and phosphate groups, with carboxyl being the most preferred.

[0232] As the above-mentioned structural unit having an acid group, the structural unit derived from (meth)acrylic acid as shown below is preferred, and the structural unit derived from methacrylic acid is more preferred.

[0233] [Chemical Formula 4]

[0234]

[0235] The adhesive polymer may contain one structural unit with an acid group, or it may contain two or more structural units.

[0236] When the adhesive polymer contains structural units with acid groups, from the perspective of further improving the effects of the present invention, the content of structural units with acid groups relative to all structural units of the adhesive polymer is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass.

[0237] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of the structural units having acid groups in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, relative to all structural units of the adhesive polymer.

[0238] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of structural units derived from (meth)acrylic acid in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, relative to all structural units of the adhesive polymer.

[0239] From the perspective of further improving the effects of the present invention, the adhesive polymer preferably has reactive groups, and more preferably contains structural units having reactive groups.

[0240] As reactive groups, free radical polymerizable groups are preferred, and olefinically unsaturated groups are more preferred. Furthermore, when the adhesive polymer has olefinically unsaturated groups, the adhesive polymer preferably contains structural units with olefinically unsaturated groups in the side chains.

[0241] In this specification, "main chain" refers to the longest bonded chain in the polymer compound that constitutes the resin, and "side chain" refers to a group of atoms that branch off from the main chain.

[0242] As an olefinic unsaturated group, allyl or (meth)acryloyloxy is preferred.

[0243] Examples of structural units with reactive groups include those shown below, but are not limited to these.

[0244] [Chemical Formula 5]

[0245]

[0246] Adhesive polymers may contain one structural unit with a reactive group, or they may contain two or more.

[0247] When the adhesive polymer contains structural units having reactive groups, from the viewpoint of further enhancing the effects of the present invention, the content of structural units having reactive groups relative to all structural units of the adhesive polymer is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

[0248] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of structural units having reactive groups in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to all structural units of the adhesive polymer.

[0249] As a method for introducing reactive groups into adhesive polymers, examples include reacting compounds such as epoxy compounds, terminal isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, hydroxymethyl compounds, and carboxylic anhydrides with functional groups such as hydroxyl, carboxyl, primary amino, secondary amino, acetoacetyl, and sulfonyl groups.

[0250] As a preferred example of a method for introducing reactive groups into an adhesive polymer, a method can be described as follows: after synthesizing a polymer having carboxyl groups through a polymerization reaction, glycidyl (meth)acrylate reacts with a portion of the carboxyl groups of the obtained polymer through a polymer reaction, thereby introducing (meth)acryloyloxy groups into the polymer. By this method, an adhesive polymer having (meth)acryloyloxy groups in its side chains can be obtained.

[0251] The polymerization reaction described above is preferably carried out at a temperature of 70–100°C, more preferably at a temperature of 80–90°C. As the polymerization initiator used in the above polymerization reaction, an azo initiator is preferred; for example, more preferably, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. The above polymer reaction is preferably carried out at a temperature of 80–110°C. In the above polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0252] As the adhesive polymer, the polymers shown below are preferred for better performance of the present invention. Furthermore, the content ratios (a to d) and weight-average molecular weight Mw of each structural unit shown below can be appropriately changed according to the purpose.

[0253] [Chemical Formula 6]

[0254]

[0255] [Chemical Formula 7]

[0256]

[0257] Furthermore, the adhesive polymer may comprise a polymer (hereinafter also referred to as "polymer X") containing structural units having a carboxylic anhydride structure.

[0258] The carboxylic anhydride structure can be either a chain-like carboxylic anhydride structure or a cyclic carboxylic anhydride structure, preferably a cyclic carboxylic anhydride structure.

[0259] The ring in the cyclic carboxylic anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0260] The structural unit having a carboxylic anhydride structure is preferably a structural unit in which a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 is included in the main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is directly or via a divalent linker bonded to the main chain.

[0261] [Chemical Formula 8]

[0262]

[0263] In equation P-1, R A1a Indicates substituent, n 1a R A1a They can be the same or different, Z 1a This indicates a divalent group forming a ring containing -C(=O)-OC(=O)-, n 1aRepresents integers greater than or equal to 0.

[0264] As a result of R A1a The substituents are represented, for example, alkyl groups.

[0265] As Z 1a Preferably, the alkylene group has 2 to 4 carbon atoms, more preferably it has 2 or 3 carbon atoms, and even more preferably it has 2 carbon atoms.

[0266] n 1a Represents integers greater than or equal to 0. In Z... 1a When representing alkylene groups with 2 to 4 carbon atoms, n 1a Preferably, it is an integer from 0 to 4, more preferably an integer from 0 to 2, and even more preferably 0.

[0267] n 1a When representing integers greater than 2, there exist multiple R values. A1a They can be the same or different. Furthermore, there can be multiple R. A1a They can bond together to form a ring, but it is preferable that they do not bond together to form a ring.

[0268] As a structural unit having a carboxylic anhydride structure, a structural unit derived from an unsaturated carboxylic anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride is even more preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0269] The following are specific examples of structural units having a carboxylic anhydride structure, but structural units having a carboxylic anhydride structure are not limited to these specific examples. In the structural units described below, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0270] [Chemical Formula 9]

[0271]

[0272] [Chemical Formula 10]

[0273]

[0274] The structural units with carboxylic anhydride structures in polymer X can be a single type or two or more types.

[0275] The total content of structural units having a carboxylic anhydride structure relative to all structural units of polymer X is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 35 mol%.

[0276] The photosensitive composition layer may contain only one polymer X, or it may contain two or more polymers X.

[0277] When the photosensitive composition layer contains polymer X, from the viewpoint of further enhancing the effects of the present invention, the content of polymer X relative to the total mass of the photosensitive composition layer is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, even more preferably 0.5 to 20% by mass, and even more preferably 1.0 to 20% by mass.

[0278] From the viewpoint of further enhancing the effects of the present invention, the weight-average molecular weight (Mw) of the adhesive polymer is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 10,000 to 100,000, and particularly preferably 15,000 to 80,000.

[0279] The acid value of the adhesive polymer is preferably 10-200 mg KOH / g, more preferably 60-200 mg KOH / g, even more preferably 60-150 mg KOH / g, and especially preferably 60-110 mg KOH / g.

[0280] In addition, the acid value of the adhesive polymer was determined according to the method described in JIS K0070:1992.

[0281] The photosensitive composition layer may contain only one type of adhesive polymer, or it may contain two or more types.

[0282] From the perspective of further improving the effects of the present invention, the content of the adhesive polymer relative to the total mass of the photosensitive composition layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0283] <Polymerizing compounds>

[0284] The photosensitive composition layer may contain polymeric compounds.

[0285] Polymerizable compounds are compounds having polymerizable groups. Examples of polymerizable groups include free radical polymerizable groups and cationic polymerizable groups, with free radical polymerizable groups being preferred.

[0286] The polymerizable compound preferably comprises a free radical polymerizable compound having an olefin unsaturated group (hereinafter also simply referred to as "olefin unsaturated compound").

[0287] As an olefinic unsaturated group, (meth)acryloyloxy is preferred.

[0288] In addition, the olefinic unsaturated compounds in this specification are compounds other than the aforementioned adhesive polymers, and preferably have a molecular weight of less than 5,000.

[0289] As one of the preferred methods for polymerizable compounds, compounds represented by the following formula (M) (also simply referred to as "compound M") can be cited.

[0290] Q 2 -R 1 -Q 1 Formula (M)

[0291] In formula (M), Q 1 and Q 2 Each independently represents (meth)acryloyloxy, R 1 This represents a divalent linker with a chain-like structure.

[0292] Regarding Q in equation (M) 1 and Q 2 From the perspective of ease of synthesis, Q 1 and Q 2 Preferably, they are the same group.

[0293] Furthermore, considering reactivity, Q in equation (M) 1 and Q 2 Acryloyloxy is preferred.

[0294] As R in equation (M) 1 From the perspective of achieving better results in this invention, alkylene or alkoxyalkylene (-L) is preferred. 1 -OL 1 -) or polyalkoxyalkylene (-(L 1 -O) p -L 1 -), more preferably a hydrocarbon group or polyalkoxyalkylene group having 2 to 20 carbon atoms, even more preferably an alkylene group having 4 to 20 carbon atoms, and especially preferably a straight-chain alkylene group having 6 to 18 carbon atoms.

[0295] The hydrocarbon group mentioned above may have a chain structure in at least a portion. There are no particular restrictions on the portion other than the chain structure. For example, it may be any one of branched, cyclic, or straight-chain alkylene, aryl, ether bond, and combinations thereof with 1 to 5 carbon atoms. Preferably, it is an alkylene group or a group composed of two or more alkylene groups and one or more aryl groups. More preferably, it is an alkylene group. Even more preferably, it is a straight-chain alkylene group.

[0296] In addition, the above L 1 Each alkyl group is independently represented, preferably vinyl, propenyl, or butenyl, more preferably vinyl or 1,2-propenyl. p represents an integer of 2 or more, preferably an integer from 2 to 10.

[0297] Furthermore, considering the superior effects of the present invention, the compound M is connected to Q. 1 With Q2 The shortest connecting chain between atoms preferably has 3 to 50 atoms, more preferably 4 to 40 atoms, even more preferably 6 to 20 atoms, and especially preferably 8 to 12 atoms.

[0298] In this specification, "Connecting Q" 1 With Q 2 "Number of atoms in the shortest link chain between Q" refers to the number of atoms in the shortest link chain between Q and Q. 1 Connected R 1 The atoms in Q are connected to 2 Connected R 1 The shortest number of atoms up to the last atom in the sequence.

[0299] 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, tricyclodecanediethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. These ester monomers can also be used as mixtures.

[0300] Of the above-mentioned compounds, from the viewpoint of achieving better results in this invention, it is preferable to select at least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate, more preferably at least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate, and even more preferably at least one compound selected from 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

[0301] Furthermore, as one of the preferred types of polymerizable compounds, olefinic unsaturated compounds with more than two functions can be cited.

[0302] In this specification, "a 2 or more functional olefin unsaturated compound" refers to a compound having two or more olefin unsaturated groups in one molecule.

[0303] As an olefinic unsaturated group in an olefinic unsaturated compound, (meth)acryloyl group is preferred.

[0304] As an olefinic unsaturated compound, (meth)acrylate compounds are preferred.

[0305] As a difunctional olefinic unsaturated compound, there are no particular restrictions, and it is possible to appropriately select from known compounds.

[0306] Other difunctional olefinic unsaturated compounds besides compound M mentioned above include tricyclodecanediethanol di(meth)acrylate.

[0307] Examples of commercially available difunctional olefinic unsaturated compounds include tricyclodecanediethanol diacrylate (trade name: NK ESTETR A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), tricyclodecanediethanol dimethacrylate (trade name: NK ESTETR DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK ESTETR A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK ESTETR A-HD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

[0308] As an olefinic unsaturated compound with more than three functions, there are no particular restrictions, and it is possible to appropriately select from known compounds.

[0309] Examples of olefinic unsaturated compounds with three or more functions include dipentaerythritol (tris / tetras / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds with a glycerol tri(meth)acrylate skeleton.

[0310] Here, "(tri / tetra / penta / hexa)meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0311] Examples of polymerizable compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), epoxy-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., and EBECRYL 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxylated glycerol triacrylates (such as NK ESTER A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

[0312] Other examples of polymerizable compounds include urethane (meth)acrylate compounds.

[0313] Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.

[0314] Furthermore, examples of urethane (meth)acrylates include those with 3 or more functional groups. As a lower limit for the number of functional groups, 6 or more functional groups are more preferred, and 8 or more functional groups are even more preferred. Additionally, as an upper limit for the number of functional groups, 20 or fewer functional groups are preferred. Examples of urethane (meth)acrylates with trifunctionality or higher 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., as well as UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0315] As one of the preferred methods for polymerizable compounds, olefinic unsaturated compounds having acid groups can be cited.

[0316] Examples of acid groups include phosphate, sulfonate, and carboxyl groups.

[0317] Among these, the carboxyl group is preferred as the acid group.

[0318] Examples of olefinic unsaturated compounds with acid groups include 3- to 4-functional olefinic unsaturated compounds with acid groups (formed by introducing carboxyl groups into the pentaerythritol tri- and tetraacrylate (PETA) backbone (acid value: 80-120 mg KOH / g)) and 5- to 6-functional olefinic unsaturated compounds with acid groups (formed by introducing carboxyl groups into the dipentaerythritol penta- and hexaacrylate (DPHA) backbone (acid value: 25-70 mg KOH / g)).

[0319] These trifunctional or higher olefinic unsaturated compounds with acid groups can also be used simultaneously with difunctional olefinic unsaturated compounds with acid groups, as needed.

[0320] As an olefinic unsaturated compound having an acid group, it is preferably selected from at least one of olefinic unsaturated compounds having a carboxyl group and a carboxylic anhydride thereof.

[0321] If the olefinic unsaturated compound with an acidic group is selected from at least one of olefinic unsaturated compounds with two or more functions having a carboxyl group and their carboxylic anhydrides, the reproducibility and film strength are further improved.

[0322] There are no particular restrictions on olefinic unsaturated compounds with more than two functions, including carboxyl groups, and appropriate selection can be made from known compounds.

[0323] Examples of olefinic unsaturated compounds with more than two functions, including a carboxyl 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.).

[0324] As an olefinic unsaturated compound having an acid group, the preferred polymeric compound having an acid group is the one described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942, the contents of which are incorporated herein by reference.

[0325] Furthermore, as an olefinic unsaturated compound with an acid group, an olefinic unsaturated compound with a phosphoric acid group, such as ethylene oxide-modified dimethacrylate phosphate (KAYAMER PM-21, manufactured by Nippon Kayaku Co., Ltd.), can also be used.

[0326] Examples of polymerizable compounds include, for instance, compounds obtained by reacting a polyol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a compound containing a glycidyl group with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having urethane bonds, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, and alkyl (meth)acrylates.

[0327] These can be used individually or in combination of two or more.

[0328] Examples of compounds obtained by reacting polyols with α,β-unsaturated carboxylic acids include, for example, bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate with 2 to 14 ethylene oxide alkyl groups; polyethylene glycol di(meth)acrylate with 2 to 14 propylene oxide alkyl groups; and polyethylene glycol di(meth)acrylate with 2 to 14 ethylene oxide alkyl groups and 2 to 14 propylene oxide alkyl groups. Acrylates, 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.

[0329] Preferably, the compounds are olefinic unsaturated compounds having a tetrahydroxymethylmethane structure or a trihydroxymethylpropane structure, and more preferably tetrahydroxymethylmethane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate or di(trihydroxymethylpropane)tetraacrylate.

[0330] Examples of polymerizable compounds include caprolactone-modified olefinic compounds (e.g., KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.), epoxide-modified olefinic compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., EBECRYL 135 manufactured by DAICEL-ALLNEX LTD., etc.), and ethoxylated glycerol triacrylates (A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.).

[0331] As a polymerizable compound (especially an olefinic unsaturated compound), it is also preferable to contain ester bonds, which is desirable for the purpose of excellent developability of the photosensitive composition layer after transfer.

[0332] As an olefinic unsaturated compound containing ester bonds, there are no particular limitations as long as the molecule contains ester bonds. From the perspective of the superior effect of the present invention, olefinic unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate are more preferred.

[0333] From the perspective of imparting reliability, as an olefinic unsaturated compound, it is preferable to include an olefinic unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an olefinic unsaturated compound having the above-mentioned tetrahydroxymethylmethane structure or trihydroxymethylpropane structure.

[0334] Examples of olefinic unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecanediethanol di(meth)acrylate.

[0335] As one of the preferred types of polymerizable compounds, polymerizable compounds having an aliphatic hydrocarbon ring structure (preferably difunctional olefinic unsaturated compounds) can be cited.

[0336] As the above-mentioned polymerizable compound, a polymerizable compound having a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings (preferably a structure selected from tricyclodecane and tricyclodecene structures) is preferred, a difunctional olefinic unsaturated compound having a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings is more preferred, and tricyclodecanediethanol di(meth)acrylate is even more preferred.

[0337] From the perspective of achieving better results in this invention, the preferred aliphatic hydrocarbon ring structures are cyclopentane, cyclohexane, tricyclodecane, tricyclodecene, norbornene, or isophorone.

[0338] 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 especially preferably 300 to 2,200.

[0339] Relative to the total content of all polymeric compounds contained in the photosensitive composition layer, the proportion of polymeric compounds with a molecular weight of 300 or less among the polymeric compounds contained in the photosensitive composition layer is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0340] As one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably contains olefinic unsaturated compounds with two or more functions, more preferably contains olefinic unsaturated compounds with three or more functions, and even more preferably contains olefinic unsaturated compounds with three or four functions.

[0341] Furthermore, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably comprises a difunctional olefinic unsaturated compound having an aliphatic hydrocarbon ring structure and an adhesive polymer containing structural units having an aliphatic hydrocarbon ring.

[0342] Furthermore, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably comprises a compound represented by formula (M), a polymeric compound having an aliphatic hydrocarbon ring structure, and an olefinic unsaturated compound having an acid group; more preferably, it comprises 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, and a polyfunctional olefinic unsaturated compound having a carboxylic acid group; and even more preferably, it comprises a succinic acid modified form of 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, and dipentaerythritol pentaacrylate.

[0343] Furthermore, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably comprises a compound represented by formula (M), an olefinic unsaturated compound having an acid group, and a thermally crosslinking compound described later, and more preferably comprises a compound represented by formula (M), an olefinic unsaturated compound having an acid group, and a capped isocyanate compound described later.

[0344] Furthermore, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably comprises a polymeric compound having an aliphatic hydrocarbon ring structure, an olefinic unsaturated compound having an acid group, and a thermally crosslinking compound described later; more preferably, it comprises a polymeric compound having an aliphatic hydrocarbon ring structure, an olefinic unsaturated compound having an acid group, and a terminal isocyanate compound described later.

[0345] Furthermore, as one of the preferred embodiments of the photosensitive composition layer, the photosensitive composition layer preferably comprises a difunctional olefin unsaturated compound (preferably a difunctional (meth)acrylate compound) and a trifunctional or higher olefin unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound).

[0346] Furthermore, as one of the preferred methods for the photosensitive composition layer, from the perspective of rust prevention, the photosensitive composition layer preferably contains a compound represented by formula (M) and a difunctional olefinic unsaturated compound having an aliphatic hydrocarbon ring structure.

[0347] Furthermore, as one of the preferred embodiments of the photosensitive composition layer, considering aspects such as substrate adhesion, developer residue suppression, and rust prevention, the photosensitive composition layer preferably comprises a compound represented by formula (M) and an olefin unsaturated compound having an acid group; more preferably, it comprises a compound represented by formula (M), a difunctional olefin unsaturated compound having an aliphatic hydrocarbon ring structure, and an olefin unsaturated compound having an acid group; even more preferably, it comprises a compound represented by formula (M), a difunctional olefin unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher olefin unsaturated compound, and an olefin unsaturated compound having an acid group. In addition, the aforementioned photosensitive composition layer preferably also comprises a urethane (meth)acrylate compound.

[0348] Furthermore, as one of the preferred embodiments of the photosensitive composition layer, considering aspects such as substrate adhesion, developer residue suppression, and rust prevention, the photosensitive composition layer preferably comprises 1,9-nonanediol diacrylate and a polyfunctional olefinic unsaturated compound having a carboxylic acid group. More preferably, it comprises 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, and a polyfunctional olefinic unsaturated compound having a carboxylic acid group. Even more preferably, it comprises 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and an olefinic unsaturated compound having a carboxylic acid group. In addition, the aforementioned photosensitive composition layer preferably also comprises a urethane (meth)acrylate compound.

[0349] The photosensitive composition layer may contain a monofunctional olefin unsaturated compound as an olefin unsaturated compound.

[0350] The content of the olefinic unsaturated compounds with more than two functions in the above-mentioned olefinic unsaturated compounds is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total content of all olefinic unsaturated compounds contained in the photosensitive composition layer.

[0351] Polymerizable compounds (especially olefinic unsaturated compounds) can be used alone or in combination with two or more compounds.

[0352] As a lower limit for the content of polymeric compounds (especially olefinically unsaturated compounds) in the photosensitive composition layer, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and especially preferably 15% by mass or more, relative to the total mass of the photosensitive composition layer. Furthermore, as an upper limit, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0353] <Polymerization initiator>

[0354] The photosensitive composition layer may contain a polymerization initiator.

[0355] Photopolymerization initiators are preferred as polymerization initiators.

[0356] There are no particular restrictions on the use of photopolymerization initiators; any known photopolymerization initiator can be used.

[0357] Examples of photopolymerization initiators include photopolymerization initiators with oxime ester structures (hereinafter also referred to as "oxime-based photopolymerization initiators"), photopolymerization initiators with α-aminoalkylphenyl ketone structures (hereinafter also referred to as "α-aminoalkylphenyl ketone-based photopolymerization initiators"), photopolymerization initiators with α-hydroxyalkylphenyl ketone structures (hereinafter also referred to as "α-hydroxyalkylphenyl ketone-based polymerization initiators"), photopolymerization initiators with acylphosphine oxide structures (hereinafter also referred to as "acylphosphine oxide-based photopolymerization initiators"), and photopolymerization initiators with N-phenylglycine structures (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiators").

[0358] The photopolymerization initiator preferably includes at least one selected from oxime-based photopolymerization initiators, α-aminoalkylphenyl ketone-based photopolymerization initiators, α-hydroxyalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably includes at least one selected from oxime-based photopolymerization initiators, α-aminoalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

[0359] Furthermore, as a photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of Japanese Patent Application Publication No. 2011-095716 and paragraphs

[0064] to

[0081] of Japanese Patent Application Publication No. 2015-014783 may also be used.

[0360] Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(O-acetyl oxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], IRGACURE (registered trademark) OXE03 (manufactured by BASF), IRGACURE (registered trademark) OXE04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad (registered trademark) 379EG, IGM Resins] [BV manufactured], 2-methyl-1-(4-methylthiophenyl)-2-morpholinylprop-1-one [trade name: Omnirad (registered trademark) 907, manufactured by IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylprop-1-one [trade name: Omnirad (registered trademark) 127, manufactured by IGM Resins B.V.], 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 [trade name: Omnirad (registered trademark) 369, manufactured by IGM Resins BV], 2-hydroxy-2-methyl-1-phenylprop-1-one [trade name: Omnirad (registered trademark) 1173, manufactured by IGM Resins BV], 1-hydroxycyclohexylphenyl ketone [trade name: Omnirad (registered trademark) 184, manufactured by IGM Resins [BV manufactured], 2,2-dimethoxy-1,2-diphenylethyl-1-one [trade name: Omnirad (registered trademark) 651, manufactured by TGM Resins BV], etc., oxime ester photopolymerization initiators [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan KK], 1-[4-(phenylthio)phenyl]-3-cyclopentylprop-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furan carbonyl)-9H-carbazole-3-yl]-,2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.).(Prepared by) 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-prop-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.), APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinylprop-1-one, manufactured by Shenzhen UV-ChemTech Ltd.), etc.

[0361] Photopolymerization initiators can be used alone or in combination with two or more.

[0362] When the photosensitive composition layer contains a photopolymerization initiator, the content of the photopolymerization initiator relative to the total mass of the photosensitive composition layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. Furthermore, as an upper limit, it is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, relative to the total mass of the photosensitive composition layer.

[0363] <Heterocyclic compounds>

[0364] The photosensitive composition layer may contain heterocyclic compounds.

[0365] Heterocyclic compounds can have any heterocyclic ring, whether it is a monocyclic or polycyclic heterocyclic ring.

[0366] Examples of heteroatoms found in heterocyclic compounds include nitrogen, oxygen, and sulfur atoms. Heterocyclic compounds preferably have at least one atom selected from nitrogen, oxygen, and sulfur atoms, and more preferably have a nitrogen atom.

[0367] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, razotanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

[0368] In the above, the heterocyclic compound is preferably selected from at least one compound selected from triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably selected from at least one compound selected from triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0369] Preferred examples of heterocyclic compounds are shown below. The following compounds can be exemplified as triazole and benzotriazole compounds.

[0370] [Chemical Formula 11]

[0371]

[0372] [Chemical Formula 12]

[0373]

[0374] The following compounds can be cited as examples of tetrazolium compounds.

[0375] [Chemical Formula 13]

[0376]

[0377] [Chemical Formula 14]

[0378]

[0379] The following compounds can be cited as examples of thiadiazole compounds.

[0380] [Chemical Formula 15]

[0381]

[0382] The following compounds can be cited as examples of triazine compounds.

[0383] [Chemical Formula 16]

[0384]

[0385] The following compounds can be cited as examples of cyclotannin compounds.

[0386] [Chemical Formula 17]

[0387]

[0388] The following compounds can be cited as examples of thiazole compounds.

[0389] [Chemical Formula 18]

[0390]

[0391] The following compounds can be cited as examples of benzothiazole compounds.

[0392] [Chemical Formula 19]

[0393]

[0394] The following compounds can be cited as examples of benzimidazole compounds.

[0395] [Chemical Formula 20]

[0396]

[0397] [Chemical Formula 21]

[0398]

[0399] The following compounds can be cited as examples of benzoxazole compounds.

[0400] [Chemical Formula 22]

[0401]

[0402] Heterocyclic compounds can be used alone or in combination with two or more compounds.

[0403] When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound relative to the total mass of the photosensitive composition layer is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, even more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass.

[0404] <Aliphatic thiols>

[0405] The photosensitive composition layer may contain aliphatic thiol compounds.

[0406] By including aliphatic thiol compounds in the photosensitive composition layer, the curing shrinkage of the film formed by the olefin-thiol reaction of the aliphatic thiol compounds with free radical polymerizable compounds having olefin unsaturated groups is suppressed, and the stress is relaxed.

[0407] As aliphatic thiols, monofunctional aliphatic thiols or polyfunctional aliphatic thiols (i.e., aliphatic thiols with two or more functions) are preferred.

[0408] Of the above, from the perspective of the adhesion of the formed pattern (especially the adhesion after exposure), a multifunctional aliphatic thiol compound is preferred as the aliphatic thiol compound.

[0409] In this specification, "polyfunctional aliphatic thiols" refers to aliphatic compounds having two or more thiol groups (also called "mercapto groups") within their molecules.

[0410] As a polyfunctional aliphatic thiol compound, a low molecular weight compound with a molecular weight of 100 or more is preferred. 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.

[0411] As for the number of functional groups in a multifunctional aliphatic thiol compound, for example, considering the tightness of the formed pattern, 2 to 10 functional groups are preferred, 2 to 8 functional groups are more preferred, and 2 to 6 functional groups are even more preferred.

[0412] Examples of polyfunctional aliphatic thiols include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetra(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, and trimethylolpropionyloxyethyl thiocyanate. Propane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethylenedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethylthiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.

[0413] In the above, the polyfunctional aliphatic thiol compound is preferably selected from at least one compound selected from 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.

[0414] Examples of monofunctional aliphatic thiols include 1-octylthiol, 1-dodecylthiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0415] The photosensitive composition layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds.

[0416] When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound relative to the total mass of the photosensitive composition layer is preferably 5% by mass or more, more preferably 5 to 50% by mass, even more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass.

[0417] <Thermocrosslinking compounds>

[0418] Considering the strength of the cured film and the adhesion of the uncured film, the photosensitive composition layer preferably contains a thermally crosslinking compound. Furthermore, in this specification, the thermally crosslinking compounds having olefinic unsaturated groups described later are considered thermally crosslinking compounds, not olefinic unsaturated compounds.

[0419] Examples of thermally crosslinking compounds include epoxy compounds, oxetane compounds, hydroxymethyl compounds, and end-capped isocyanate compounds. Among these, end-capped isocyanate compounds are preferred considering both the strength of the cured film and the adhesion of the uncured film.

[0420] Since the capped isocyanate compound reacts with hydroxyl and carboxyl groups, there is a tendency for the hydrophilicity of the formed film to decrease and its function as a protective film to be enhanced, for example, when at least one of the adhesive polymers and the free radical polymerizable compounds having olefinic unsaturated groups has at least one hydroxyl and carboxyl group.

[0421] In addition, capped isocyanate compounds are defined as "compounds having a structure in which isocyanate groups of isocyanate are protected (so-called masked) by capping agents".

[0422] There is no particular limitation on the dissociation temperature of the capped isocyanate compound, but it is preferred to be 100–160°C, and more preferably 130–150°C.

[0423] The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates when analyzed and determined by DSC (Differential Scanning Calorimetry) using a differential scanning calorimeter".

[0424] As a differential scanning calorimeter, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. is preferred, for example. However, the differential scanning calorimeter is not limited to this.

[0425] Examples of end-capping agents with dissociation temperatures of 100–160°C include active methylene compounds (malonate esters (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 cyclohexanone oxime, etc., which have an intramolecular structure represented by -C (=N-OH)-).

[0426] Among these, at least one of the oxime compounds is preferred as a capping agent with a dissociation temperature of 100 to 160°C, for example, from the perspective of storage stability.

[0427] For example, considering factors such as improving the brittleness of the film and enhancing the adhesion to the substrate, the end-capped isocyanate compound preferably has an isocyanurate structure.

[0428] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuration of hexamethylene diisocyanate.

[0429] Among the isocyanurate-capped isocyanate compounds, compounds with an oxime structure are preferred for use as capping agents because they make it easier to set the dissociation temperature within a preferred range and reduce development residue compared to compounds without an oxime structure.

[0430] End-capped isocyanate compounds can have polymerizable groups.

[0431] There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, with free radical polymerizable groups being preferred.

[0432] Examples of polymerizable groups include olefinic unsaturated groups such as (meth)acryloyloxy, (meth)acrylamido, and styryl, as well as groups with epoxy groups such as glycidyl.

[0433] Among them, as a polymerizable group, an olefinic unsaturated group is preferred, (meth)acryloyloxy is more preferred, and acryloyloxy is even more preferred.

[0434] As a capped isocyanate compound, it can be used in commercially available products.

[0435] Examples of commercially available isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and the end-capped Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Corporation).

[0436] A single thermally crosslinking compound can be used alone, or two or more compounds can be used simultaneously.

[0437] When the photosensitive composition layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound relative to the total mass of the photosensitive composition layer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.

[0438] <surfactants>

[0439] The photosensitive composition layer may contain a surfactant.

[0440] As surfactants, examples include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Unexamined Patent Publication No. 2009-237362.

[0441] Fluorinated surfactants or silicone surfactants are preferred as surfactants.

[0442] Commercially available fluorinated surfactants include, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, etc. MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-6 31. 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 (the above is DIC (Manufactured by 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.), Ftergent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 (all manufactured by Neos Corporation), U-120E (Uni-chem Co., Ltd), etc.

[0443] Furthermore, acrylic compounds that have a molecular structure containing a functional group (containing a fluorine atom) and which, upon heating, partially break down the functional group containing the fluorine atom, causing the fluorine atom to volatilize, are preferred as fluorine surfactants. Examples of such fluorine surfactants include the MEGAFACE DS series manufactured by DIC Corporation (The Chemical Daily Co., Ltd. (February 22, 2016), NIKKEI BUSINESS DAILY (February 23, 2016)), such as MEGAFACE DS-21.

[0444] Furthermore, as a fluorinated surfactant, a polymer of a fluorinated vinyl ether compound having a fluorinated alkyl or fluorinated alkylene ether group and a hydrophilic vinyl ether compound is preferred.

[0445] Furthermore, as a fluorinated surfactant, block polymers can also be used.

[0446] Furthermore, as a fluorinated surfactant, it is preferable to use a fluorinated polymer compound that contains structural units derived from (meth)acrylate compounds having fluorine atoms and structural units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propyleneoxy groups).

[0447] Furthermore, as a fluorinated surfactant, it can also be used on fluorinated polymers with olefinically unsaturated bond groups in the side chain. Examples include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0448] From the perspective of improving environmental adaptability, surfactants derived from alternative materials of straight-chain perfluoroalkyl compounds with 7 or more carbon atoms, such as perfluorooctane acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are preferred as fluorinated surfactants.

[0449] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., propoxyglycerol, ethoxyglycerol, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), SOLSPERSE 20000 (all manufactured by The Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical). PIONIN D-6112, D-6112-W, D-6315 (all manufactured by TAKEMOTO OIL&FAT Co., Ltd.), OLFINE E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), etc.

[0450] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends.

[0451] Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, TORAY SILICONE DC3PA, TORAY SILICONE SHTPA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, and TORAY SILICONE SH8400 (all manufactured by Dow Corning Toray). Co., Ltd. manufactures) 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-3 23. KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (the above are Shin-Etsu Silicone (manufactured by Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 and BYK323 (the above are manufactured by BYK-Chemie GmbH), etc.

[0452] Surfactants can be used alone or in combination with two or more.

[0453] When the photosensitive composition layer contains a surfactant, the surfactant content relative to the total mass of the photosensitive composition layer is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.80% by mass.

[0454] <Polymerization Inhibitor>

[0455] The photosensitive composition layer may contain polymerization inhibitors.

[0456] Polymerization inhibitors are compounds that have the function of delaying or inhibiting polymerization reactions. For example, known compounds that are used as polymerization inhibitors can be used as polymerization inhibitors.

[0457] Examples of polymerization inhibitors include phenothiazine compounds such as bis-(1-dimethylbenzyl)phenothiazine and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinylbis(oxyvinyl)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5- Hindered phenolic compounds such as triazine and pentaerythritol tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxyamine and N-nitrosophenylhydroxyamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; phenolic compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tert-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate.

[0458] In view of the superior effects of the present invention, as a polymerization inhibitor, it is preferably selected from at least one of phenothiazine compounds, nitroso compounds or their salts and hindered phenolic compounds, more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinylbis(oxyvinyl)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt.

[0459] Polymerization inhibitors can be used alone or in combination with two or more.

[0460] When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total mass of the photosensitive composition layer is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, and even more preferably 0.04 to 3.0% by mass.

[0461] <Hydrogen-donating compounds>

[0462] The photosensitive composition layer may contain a hydrogen-donating compound.

[0463] Hydrogen-donating compounds can further enhance the sensitivity of photopolymerization initiators to active light and inhibit the polymerization hindrance of polymerizable compounds by oxygen.

[0464] Examples of hydrogen-donating compounds include, for example, amines and amino acid compounds.

[0465] Examples of amines include compounds described in, for instance, the Journal of Polymer Society, Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Publication No. 51-082102, Japanese Patent Application Publication No. 52-134692, Japanese Patent Application Publication No. 59-138205, Japanese Patent Application Publication No. 60-084305, Japanese Patent Application Publication No. 62-018537, Japanese Patent Application Publication No. 64-033104, and Research Disclosure No. 33825. More specifically, examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0466] In view of the superior effects of the present invention, the amine is preferably selected from at least one of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0467] Examples of amino acid compounds include, for example, N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0468] In view of the superior effects of the present invention, N-phenylglycine is preferred as the amino acid compound.

[0469] Furthermore, examples of hydrogen-donating compounds include organometallic compounds (such as tributyltin acetate) disclosed in Japanese Patent Publication No. 48-042965, hydrogen donors disclosed in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithianes) disclosed in Japanese Patent Application Publication No. 6-308727.

[0470] One hydrogen-donating compound can be used alone, or two or more can be used simultaneously.

[0471] When the photosensitive composition layer contains a hydrogen-donating compound, from the viewpoint of improving the curing speed by balancing the polymerization growth rate and chain transfer, the content of the hydrogen-donating compound relative to the total mass of the photosensitive composition layer is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and even more preferably 0.03 to 5.0% by mass.

[0472] <Impurities, etc.>

[0473] The photosensitive composition layer may contain a specified amount of impurities.

[0474] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, since halide ions, sodium ions, and potassium ions are easily introduced as impurities, the following concentrations are preferred.

[0475] Based on mass, the impurity content in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. Based on mass, the impurity content in the photosensitive composition layer can be set to 1 ppb or more or 0.1 ppm or more.

[0476] As a method for setting impurities within the aforementioned range, examples include a method of selecting raw materials with low impurity content as raw materials for the photosensitive composition layer; a method of preventing impurities from being introduced during the formation of the photosensitive composition layer; and a method of cleaning and removing impurities. By using these methods, the amount of impurities can be kept within the aforementioned range.

[0477] For example, impurities can be quantified using known methods such as CP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0478] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably low. The content of these compounds in the photosensitive composition layer, on a mass basis, is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less. The lower limit, on a mass basis, can be set to 10 ppb or more, or 100 ppb or more. The content of these compounds can be suppressed using the same method as for the aforementioned metal impurities. Furthermore, they can be quantified using known methods.

[0479] From the perspective of improving reliability and lamination, 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.

[0480] <Residual Monomer>

[0481] The photosensitive composition layer may sometimes contain residual monomers of the structural units of the aforementioned alkali-soluble resin.

[0482] From the perspective of pattern formation and reliability, the content of residual monomer relative to the total mass of alkali-soluble resin 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. There is no particular limitation on the lower limit, but preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more.

[0483] From the perspective of pattern formation and reliability, the residual monomer of each structural unit of the alkali-soluble resin relative to the total mass of the photosensitive composition layer 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. There is no particular limitation on the lower limit, but it is preferably 0.1 ppm by mass or more, more preferably 1 ppm by mass or more.

[0484] The residual monomer content of monomers during the synthesis of alkali-soluble resins via polymer reactions is preferably within the above-mentioned range. For example, when synthesizing alkali-soluble resins by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above-mentioned range.

[0485] The amount of residual monomers can be determined by known methods such as liquid chromatography and gas chromatography.

[0486] <Other Ingredients>

[0487] The photosensitive composition layer may contain components other than those described above (hereinafter also referred to as "other components"). Examples of other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Furthermore, other additives described in paragraphs

[0058] to

[0071] of Japanese Patent Application Publication No. 2000-310706 may also be included as other components.

[0488] -particle-

[0489] As particles, metal oxide particles are preferred.

[0490] Metals in metal oxide particles also include half-metals such as B, Si, Ge, As, Sb, and Te.

[0491] For example, considering the transparency of the cured film, the average primary particle size is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0492] The average first-order particle size was calculated by measuring the particle size of any 200 particles using an electron microscope and then arithmetically averaging the results. Additionally, when the particle shape is not spherical, the longest side was used as the particle size.

[0493] When the photosensitive composition layer contains particles, it may contain only one type of metal and different particles of different sizes, or it may contain two or more types.

[0494] The photosensitive composition layer does not contain particles, or when the photosensitive composition layer contains particles, preferably the particle content is more than 0% by mass and less than 35% by mass relative to the total mass of the photosensitive composition layer; more preferably it does not contain particles, or the particle content is more than 0% by mass and less than 10% by mass relative to the total mass of the photosensitive composition layer; even more preferably it does not contain particles, or the particle content is more than 0% by mass and less than 5% by mass relative to the total mass of the photosensitive composition layer; even more preferably it does not contain particles, or the particle content is more than 0% by mass and less than 1% by mass relative to the total mass of the photosensitive composition layer; and most preferably it does not contain particles.

[0495] -Coloring agents-

[0496] The photosensitive composition layer may contain trace amounts of colorants (pigments, dyes, etc.), but preferably does not contain colorants, for example, from the perspective of transparency.

[0497] When the photosensitive composition layer contains a colorant, the content of the colorant relative to the total mass of the photosensitive composition layer is preferably less than 1% by mass, more preferably less than 0.1% by mass.

[0498] -Antioxidants-

[0499] Examples of antioxidants include 3-pyrazolone derivatives such as 1-phenyl-3-pyrazolone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; and p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

[0500] In view of the superior effects of the present invention, 3-pyrazolones are preferred as antioxidants, and 1-phenyl-3-pyrazolones are more preferred.

[0501] When the photosensitive composition layer contains an antioxidant, the antioxidant content relative to the total mass of the photosensitive composition layer is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more. There is no particular upper limit, but it is preferably 1% by mass or less.

[0502] <Thickness of the photosensitive composition layer>

[0503] The thickness of the photosensitive composition layer is not particularly limited, and is often below 30 μm. However, for better performance of the present invention, a thickness of 20 μm or less is preferred, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less. As a lower limit, for excellent film strength obtained from curing the photosensitive composition layer, a thickness of 0.60 μm or more is preferred, and more preferably 1.5 μm or more.

[0504] For example, the thickness of the photosensitive composition layer can be calculated as the average of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0505] <Refractive index of the photosensitive composite layer>

[0506] The refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

[0507] <Color of the photosensitive composition layer>

[0508] The photosensitive composition layer is preferably achromatic. Specifically, total internal reflection (8° incident angle, light source: D-65 (2° field of view)) in the CIE1976 (L*, a*, b*) color space, L * The preferred value is 10 to 90, a * The preferred value is -1.0 to 1.0, b * The preferred value is -1.0 to 1.0.

[0509] Furthermore, the pattern obtained by curing the photosensitive composition layer (the cured film of the photosensitive composition layer) is preferably colorless.

[0510] Specifically, total internal reflection (8° incident angle, light source: D-65 (2° field of view)) in the CIE1976 (L*, a*, b*) color space, the L of the pattern * The preferred value is 10 to 90, and the a value of the pattern is... * The preferred value is -1.0 to 1.0, and the b value of the pattern is... * The preferred value is -1.0 to 1.0.

[0511] In the transfer film of the first embodiment, the tanδ of the photosensitive composition layer may have a significant impact on the overall tanδ of the composition layer.

[0512] The composition layer that satisfies the requirements of formulas (1A) to (3A) can be easily formed by appropriately selecting the types of constituent components of the above-mentioned photosensitive composition layer and appropriately adjusting their manufacturing sequence.

[0513] Protective Film

[0514] Transfer films can have a protective film.

[0515] As a protective film, resin films with heat resistance and solvent resistance can be used, such as polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

[0516] Furthermore, as a protective film, a resin film made of the same material as the temporary support described above can be used.

[0517] Among them, polyolefin film is preferred as the protective film, polypropylene film or polyethylene film is more preferred, and polyethylene film is even more preferred.

[0518] The thickness of the protective film is preferably 1-100 μm, more preferably 5-50 μm, even more preferably 5-40 μm, and especially preferably 15-30 μm.

[0519] From the perspective of excellent mechanical strength, the thickness of the protective film is preferably above 1μm, and from the perspective of relative cost, it is preferably below 100μm.

[0520] Furthermore, the protective film preferably contains 5 fisheyes with a diameter of 80 μm or larger per meter. 2 the following.

[0521] In addition, "fisheye" refers to defects that occur when foreign matter, undissolved matter, and oxidized deterioration products are introduced into the film during the process of hot melting of materials and film formation through methods such as mixing, extrusion, biaxial stretching, and casting.

[0522] The protective film preferably contains 30 particles with a diameter of 3μm or larger per mm. 2 Below, 10 pieces / mm is preferred. 2 The following is a further preferred option: 5 per mm 2 the following.

[0523] Therefore, it is possible to suppress defects caused by unevenness due to particles contained in the protective film being transferred onto the photosensitive composition layer or conductive layer.

[0524] From the perspective of imparting rollability, the arithmetic mean roughness Ra of the surface of the protective film on the side opposite to the contact composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably less than 0.40 μm, and even more preferably less than 0.30 μm.

[0525] From the perspective of defect suppression during transfer, the surface roughness Ra of the surface of the protective film in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably less than 0.40 μm, and even more preferably less than 0.30 μm.

[0526] Refractive index adjustment layer

[0527] The transfer film preferably has a refractive index adjustment layer.

[0528] As a refractive index adjusting layer, known refractive index adjusting layers can be used. Materials included in the refractive index adjusting layer include, for example, adhesive polymers, polymeric compounds, metal salts, and particles.

[0529] There are no particular limitations on the methods for controlling the refractive index of the refractive index adjustment layer. For example, methods such as using a resin with a specified refractive index alone, using a resin and particles, and using a composite of a metal salt and a resin can be cited.

[0530] As adhesive polymers and polymeric compounds, examples include the adhesive polymers and polymeric compounds described in the above-mentioned "photosensitive composition layer" section.

[0531] As particles, examples include metal oxide particles and metal particles.

[0532] There are no particular restrictions on the types of metal oxide particles; well-known metal oxide particles can be cited. Metals in metal oxide particles also include half-metals such as B, Si, Ge, As, Sb, and Te.

[0533] For example, considering the transparency of the cured film, the average primary particle size is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0534] The average first-order particle size was calculated by measuring the particle size of any 200 particles using an electron microscope and then arithmetically averaging the results. Additionally, when the particle shape is not spherical, the longest side was used as the particle size.

[0535] As a metal oxide particle, it is preferably selected from at least one of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof.

[0536] Among these, as metal oxide particles, for example, considering the ease of adjusting the refractive index, at least one selected from zirconium oxide particles and titanium oxide particles is more preferred.

[0537] Commercially available metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (NanoUse OZ-S30M, manufactured by Nissan Chemical Corporation), and zirconia particles (NanoUse OZ-S30K, manufactured by Nissan Chemical Corporation).

[0538] One type of particle can be used alone, or two or more types can be used simultaneously.

[0539] The particle content in the refractive index adjustment layer relative to the total mass of the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass.

[0540] When titanium oxide is used as a metal oxide particle, the content of titanium oxide particles relative to the total mass of the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass.

[0541] The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive composition layer.

[0542] The refractive index of the refractive index adjustment layer is preferably 1.50 or higher, more preferably 1.55 or higher, even more preferably 1.60 or higher, and especially preferably 1.65 or higher. The upper limit of the refractive index of the refractive index adjustment layer is preferably 2.10 or lower, more preferably 1.85 or lower, even more preferably 1.78 or lower, and especially preferably 1.74 or lower.

[0543] The thickness of the refractive index adjustment layer is preferably 50–500 nm, more preferably 55–110 nm, and even more preferably 60–100 nm.

[0544] The thickness of the refractive index adjustment layer was calculated as the average of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0545] Method for manufacturing transfer film according to the first embodiment

[0546] The method for manufacturing the transfer film in the first embodiment is not particularly limited, and known methods can be used.

[0547] As a method for manufacturing the transfer film 10, for example, a method including the following steps can be described: coating a photosensitive composition on the surface of a temporary support 1 to form a coating film, and further drying the coating film to form a photosensitive composition layer 3; and coating a refractive index adjustment layer forming composition on the surface of the photosensitive composition layer 3 to form a coating film, and further drying the coating film to form a refractive index adjustment layer 5.

[0548] A protective film 7 is pressed onto the refractive index adjustment layer 5 of the laminate manufactured by the above manufacturing method, thereby manufacturing a transfer film 10.

[0549] As a method for manufacturing the transfer film according to the first embodiment, it is preferable to manufacture a transfer film 10 having a temporary support 1, a photosensitive composition layer 3, a refractive index adjustment layer 5 and a protective film 7 by a process including setting a protective film 7 to contact the side of the refractive index adjustment layer 5 opposite to the side having the temporary support 1.

[0550] After the transfer film 10 is manufactured using the above manufacturing method, it is wound up, thereby enabling the production and storage of a roll-shaped transfer film. The roll-shaped transfer film is provided directly in roll form during the bonding process with the substrate, which is performed in a roll-to-roll manner as described later.

[0551] Furthermore, as a method for manufacturing the above-mentioned transfer film 10, it can be as follows: after forming a 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.

[0552] Furthermore, as a method for manufacturing the above-mentioned transfer film 10, it can be formed by: forming a photosensitive composition layer 3 on a temporary support 1, forming a refractive index adjustment layer 5 on a protective film 7, and bonding the photosensitive composition layer 3 and the refractive index adjustment layer 5 together.

[0553] <Photosensitive composition and method for forming photosensitive composition layer>

[0554] From the perspective of excellent productivity and ease of forming a composition layer that satisfies the requirements of formulas (1A) to (3A) above, the photosensitive composition layer in the transfer film is preferably formed by coating a photosensitive composition comprising the components constituting the photosensitive composition layer (e.g., adhesive polymers, polymeric compounds, and polymerization initiators) and a solvent. Specifically, the method for manufacturing the transfer film according to the first embodiment is preferably as follows: coating a photosensitive composition onto a temporary support to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer. Furthermore, it is presumed that by adjusting the residual solvent content through the drying treatment of the coating film, the tanδ of the photosensitive composition layer can be appropriately adjusted, thus facilitating the formation of a composition layer that satisfies the requirements of formulas (1A) to (3A) above.

[0555] Organic solvents are preferred as solvents that may be contained in the photosensitive composition. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0556] Furthermore, organic solvents with boiling points of 180–250°C (high-boiling-point solvents) can also be used as solvents as needed.

[0557] One solvent can be used alone, or two or more solvents can be used at the same time.

[0558] The total solid content of the photosensitive composition relative to the total mass of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass.

[0559] That is, the content of the solvent in the photosensitive composition, relative to the total mass of the photosensitive composition, is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass.

[0560] For example, considering coatability, the viscosity of the photosensitive composition at 25°C is preferably 1–50 mPa·s, more preferably 2–40 mPa·s, and even more preferably 3–30 mPa·s. Viscosity is measured using a viscometer. For example, a viscometer manufactured by TOKI SANGYO CO., LTD. (trade name: VISCOMETERTV-22) is preferably used. However, the viscometer is not limited to the aforementioned type.

[0561] For example, considering coatability, the surface tension of the photosensitive composition at 25°C is preferably 5–100 mN / m, more preferably 10–80 mN / m, and even more preferably 15–40 mN / m. The surface tension is measured using a surface tension meter. As a surface tension meter, a surface tension meter manufactured by Kyowa Interface Science Co., Ltd. (product name: Automatic Surface Tensiometer CBVP-Z) is preferred. However, the surface tension meter is not limited to the one described above.

[0562] Examples of coating methods for photosensitive compositions include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0563] As a drying method for the coating film of the photosensitive composition, heating drying and vacuum drying are preferred. Furthermore, in this specification, "drying" means removing at least a portion of the solvent contained in the composition.

[0564] From the perspective of facilitating the formation of a composition layer that satisfies the requirements of formulas (1A) to (3A) by appropriately adjusting the tanδ of the photosensitive composition layer, a drying temperature of 90°C or higher is preferred, more preferably 100°C or higher, and even more preferably 110°C or higher is preferred. Furthermore, there is no particular limitation on the upper limit, but 130°C or lower is preferred, and 120°C or lower is more preferably preferred.

[0565] Furthermore, considering the ease with which a composition layer can be formed that satisfies the requirements of formulas (1A) to (3A) by appropriately adjusting the tanδ of the photosensitive composition layer, a drying time of 20 seconds or more is preferred, more preferably 40 seconds or more, and even more preferably 60 seconds or more is preferred. There is no particular limitation on the upper limit, but 450 seconds or less is preferred, and 300 seconds or less is more preferably preferred.

[0566] <Composition for forming a refractive index adjusting layer and method for forming a refractive index adjusting layer>

[0567] The composition for forming the refractive index adjustment layer preferably includes various components and solvents used to form the refractive index adjustment layer. Furthermore, in the composition for forming the refractive index adjustment layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjustment layer.

[0568] As a solvent, there are no particular limitations as long as it can dissolve or disperse the components contained in the refractive index adjustment layer. It is preferred to select at least one of water and water-mixed organic solvents, and more preferably water or a mixture of water and water-mixed organic solvents.

[0569] Examples of water-mixable organic solvents include alcohols, acetone, ethylene glycol, and glycerol having 1 to 3 carbon atoms, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0570] One solvent can be used alone, or two or more solvents can be used.

[0571] The solvent content is preferably 50 to 2,500 parts by mass relative to 100 parts by mass of the total solids of the composition, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0572] There are no particular limitations on the method for forming the refractive index adjustment layer, as long as it is a method capable of forming a layer containing the above-mentioned components. For example, well-known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0573] Furthermore, by attaching the protective film to the refractive index adjustment layer, the transfer film of the first embodiment can be manufactured.

[0574] There are no particular limitations on the method of bonding a protective film onto the refractive index adjustment layer; well-known methods can be cited.

[0575] As a device for bonding a protective film onto a refractive index adjustment layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[0576] The laminator is preferably equipped with any heatable roller, such as a rubber roller, and is capable of applying pressure and heating.

[0577] [Transfer film of the second embodiment]

[0578] Hereinafter, an example of an embodiment of the transfer film of the second embodiment will be described.

[0579] Figure 2 The transfer film 20 shown sequentially comprises a temporary support 11, a composition layer 12 comprising a thermoplastic resin layer 13, an intermediate layer 15 and a photosensitive composition layer 17, and a protective film 19. Furthermore, the composition layer 12 satisfies all the requirements of the above formulas (1A) to (3A).

[0580] in addition, Figure 2 The transfer film 20 shown is configured with a protective film 19, but it is also possible to omit the protective film 19.

[0581] and, Figure 2 The transfer film 20 shown is configured with a thermoplastic resin layer 13 and an intermediate layer 15, but it is also possible to omit the thermoplastic resin layer 13 and the intermediate layer 15.

[0582] The elements that make up the transfer film are explained below.

[0583] In the transfer film of the second embodiment, the temporary support 11 and the protective film 17 can be the same as those of the temporary support 1 and the protective film 9 in the first embodiment, and the preferred embodiment is also the same.

[0584] Photosensitive Composite Layer

[0585] In display devices (such as organic electroluminescent (EL) display devices and liquid crystal display devices) with touch panels including capacitive input devices, conductive layer patterns, such as electrode patterns of sensors (equivalent to visual recognition units), peripheral wiring portions, and wiring portions for extraction wiring portions, are formed inside the touch panel. Typically, in the formation of the patterned layer, the following method is widely used: a negative photosensitive composition layer (photosensitive layer) is formed on a substrate using a transfer film or the like, and the photosensitive layer is exposed through a mask with the desired pattern, followed by development. Therefore, a negative photosensitive composition layer is preferred as the photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern is equivalent to a cured layer.

[0586] When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably comprises a resin, a polymerizable compound, and a polymerization initiator. Furthermore, when the photosensitive composition layer is a negative photosensitive composition layer, as described below, it is also preferable to include an alkali-soluble resin (such as polymer A as an alkali-soluble resin) as part or all of the resin. That is, in one embodiment, the photosensitive composition layer preferably comprises a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

[0587] Based on the total mass of the photosensitive composition layer, this type of photosensitive composition layer (negative photosensitive composition layer) preferably contains: 10-90% by mass of resin; 5-70% by mass of polymerizable compound; and 0.01-20% by mass of polymerization initiator.

[0588] The following is a description of each component.

[0589] <Polymer A (Resin)>

[0590] When the photosensitive composition layer is a negative photosensitive composition layer, the resin contained in the photosensitive composition layer is also specifically referred to as polymer A.

[0591] Polymer A is preferably an alkali-soluble resin.

[0592] From the viewpoint of achieving better resolution by suppressing the swelling of the negative photosensitive composition layer caused by the developer, the acid value of polymer A is preferably below 220 mg KOH / g, more preferably below 200 mg KOH / g, and even more preferably below 190 mg KOH / g.

[0593] There is no particular limitation on the lower limit of the acid value of polymer A. From the viewpoint of better developability, it is preferred to have an acid value of 60 mg KOH / g or higher, more preferably 120 mg KOH / g or higher, even more preferably 150 mg KOH / g or higher, and especially preferably 170 mg KOH / g or higher.

[0594] Additionally, acid value (mgKOH / g) refers to the mass [mg] of potassium hydroxide desired to neutralize 1g of the sample. Acid value can be calculated, for example, from the average content of acid groups in a compound.

[0595] The acid value of polymer A can be adjusted according to the types of structural units that make up polymer A and the content of structural units containing acid groups.

[0596] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferred from the viewpoint of improving resolution and developability. A weight-average molecular weight of 100,000 or less is more preferred, and 60,000 or less is even more preferred. On the other hand, a weight-average molecular weight of 5,000 or more is preferred from the viewpoint of controlling the properties of the developed aggregates, and the properties of the unexposed film, such as edge melting and shavings, when it is a negative photosensitive resin laminate. A weight-average molecular weight of 10,000 or more is more preferred, 20,000 or more is even more preferred, and 30,000 or more is particularly preferred. Edge melting refers to the ease with which the negative photosensitive composition layer bleeds from the roll end when the negative photosensitive resin laminate is wound in a roll. Shavings refer to the degree to which the chips scatter easily when the unexposed film is cut with a knife. If the chips adhere to the upper surface of the negative photosensitive resin laminate, they will be transferred to the mask in subsequent exposure processes, resulting in defective products. The dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0597] In the negative photosensitive composition layer, from the viewpoint of suppressing linewidth thickening or resolution reduction due to focus position deviation during exposure, polymer A preferably contains structural units based on monomers having aromatic hydrocarbon groups. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of structural units based on monomers having aromatic hydrocarbon groups in polymer A relative to the total mass of polymer A is preferably 20% by mass or more, more preferably 30% by mass or more. There is no particular upper limit, but preferably 95% by mass or less, more preferably 85% by mass or less. Furthermore, when multiple polymers A are included, the average content of structural units based on monomers having aromatic hydrocarbon groups is preferably within the above-mentioned range.

[0598] Examples of monomers having aromatic hydrocarbon groups include, for example, monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Among these, monomers having aralkyl groups or styrene are preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is styrene, the content of styrene structural units relative to the total mass of polymer A is preferably 20–70% by mass, more preferably 25–65% by mass, even more preferably 30–60% by mass, and particularly preferably 30–55% by mass.

[0599] Examples of aryl alkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0600] Examples of monomers containing phenyl alkyl groups include phenylethyl (meth)acrylate.

[0601] Examples of monomers containing a benzyl group include (meth)acrylates such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride; and vinyl monomers such as vinyl benzyl chloride and vinyl benzyl alcohol. Benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component containing an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the (meth)acrylate structural unit relative to the total mass of polymer A is preferably 50–95% by mass, more preferably 60–90% by mass, further preferably 70–90% by mass, and particularly preferably 75–90% by mass.

[0602] The polymer A comprising structural units based on monomers having aromatic hydrocarbon groups is preferably obtained by polymerizing monomers having aromatic hydrocarbon groups with at least one first monomer described later and / or at least one second monomer described later.

[0603] Polymer A, which does not contain structural units based on monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing at least one first monomer (described later), and more preferably by copolymerizing at least one first monomer and at least one second monomer (described later).

[0604] The first monomer is a monomer having a carboxyl group in its molecule. Examples of first monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half-ester. Among these, (meth)acrylic acid is preferred.

[0605] The content of the structural unit based on the first monomer in polymer A relative to the total mass of polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass.

[0606] From the viewpoints of good developability and control of edge melting, it is preferable to set the above content to 5% by mass or more. From the viewpoints of high resolution and tailing shape of the resist pattern, and the chemical resistance of the resist pattern, it is preferable to set the above content to 50% by mass or less.

[0607] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include, for instance, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate; esters of vinyl alcohols such as vinyl acetate; and methacrylonitrile. Among these, methyl methacrylate, 2-ethylhexyl methacrylate, or n-butyl methacrylate are preferred, and methyl methacrylate is more preferred.

[0608] The content of the structural unit based on the second monomer in polymer A relative to the total mass of polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 17 to 45% by mass.

[0609] When polymer A comprises structural units based on monomers having aralkyl groups and / or structural units based on styrene monomers, it is preferable from the viewpoint of suppressing linewidth thickening or resolution reduction due to focal position deviation during exposure. For example, copolymers comprising structural units based on methacrylic acid, structural units based on benzyl methacrylate, and structural units based on styrene are preferred, as are copolymers comprising structural units based on methacrylic acid, structural units based on methyl methacrylate, structural units based on benzyl methacrylate, and structural units based on styrene.

[0610] In one embodiment, polymer A is preferably a polymer comprising 25-55% by mass of structural units based on monomers having aromatic hydrocarbon groups, 20-35% by mass of structural units based on a first monomer, and 15-45% by mass of structural units based on a second monomer. Furthermore, in another embodiment, it is preferably a polymer comprising 70-90% by mass of structural units based on monomers having aromatic hydrocarbon groups and 10-25% by mass of structural units based on the first monomer.

[0611] Polymer A may have a branched structure and / or an alicyclic structure in its side chain. The branched or alicyclic structure can be introduced into the side chain of polymer A by using monomers containing groups with branched structures in their side chains or monomers containing groups with alicyclic structures in their side chains.

[0612] Specific examples of monomers containing groups having branched structures in their side chains include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl (meth)acrylate are preferred, and isopropyl (meth)acrylate or tert-butyl (meth)acrylate are more preferred.

[0613] Specific examples of monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Furthermore, (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are also examples. More specific examples include (bicyclo[2.2.1]heptyl-2)-(meth)acrylate, 1-adamantyl-(meth)acrylate, 2-adamantyl-(meth)acrylate, 3-methyl-1-adamantyl-(meth)acrylate, 3,5-dimethyl-1-adamantyl-(meth)acrylate, 3-ethyladamantyl-(meth)acrylate, 3-methyl-5-ethyl-1-adamantyl-(meth)acrylate, 3,5,8-triethyl-1-adamantyl-(meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl-(meth)acrylate, 2-methyl-2-adamantyl-(meth)acrylate, 2-ethyl-2-adamantyl-(meth)acrylate, 3-hydroxy-1- Adamantyl-(meth)acrylate, octahydro-4,7-mentanoinden-5-yl-(meth)acrylate, octahydro-4,7-mentanoinden-1-ylmethyl-(meth)acrylate, 1-menthyl-(meth)acrylate, tricyclodecyl (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl-(meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl-(meth)acrylate, (nor)bornyl (meth)acrylate, (meth)acrylate isobornyl (meth)acrylate, (meth)acrylate fenestrate, (meth)acrylate-2,2,5-trimethylcyclohexyl (meth)acrylate, and (meth)acrylate cyclohexyl, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl-(meth)acrylate, 2-adamantyl-(meth)acrylate, fentanyl (meth)acrylate, 1-menthyl-(meth)acrylate or tricyclodecyl (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl-(meth)acrylate or tricyclodecyl (meth)acrylate are more preferred.

[0614] Polymer A can be used alone or in combination with two or more polymers.

[0615] When using two or more types, it is preferable to use a mixture of two polymers A containing structural units based on monomers having aromatic hydrocarbon groups, or to use a mixture of polymer A containing structural units based on monomers having aromatic hydrocarbon groups and polymer A not containing structural units based on monomers having aromatic hydrocarbon groups. In the latter case, the proportion of polymer A containing structural units based on monomers having aromatic hydrocarbon groups relative to the total mass of polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

[0616] The synthesis of polymer A is preferably carried out by the following method: Adding an appropriate amount of free radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution prepared by diluting one or more of the above monomers with solvents such as acetone, methyl ethyl ketone, and isopropanol, and heating and stirring. Sometimes, a portion of the mixture is added dropwise to the reaction solution while the synthesis is being carried out. Sometimes, after the reaction is complete, further solvent is added to adjust to the desired concentration. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used as synthesis methods.

[0617] The glass transition temperature (Tg) of polymer A is preferably 30–135°C. By using polymer A with a Tg below 135°C, it is possible to suppress linewidth thickening or resolution reduction when the focus position deviates during exposure. From this viewpoint, a Tg of polymer A is more preferably below 130°C, further preferably below 120°C, and especially preferably below 110°C. Furthermore, from the viewpoint of improving edge melt resistance, it is preferable to use polymer A with a Tg of 30°C or higher. From this viewpoint, a Tg of polymer A is more preferably above 40°C, further preferably above 50°C, especially preferably above 60°C, and most preferably above 70°C.

[0618] The negative photosensitive composition layer may contain other resins besides those mentioned above as polymer A.

[0619] 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.

[0620] As polymer A, an alkali-soluble resin described in the following description of the thermoplastic resin layer can be used.

[0621] The content of polymer A relative to the total mass of the negative photosensitive composition layer is preferably 10-90% by mass, more preferably 20-80% by mass, even more preferably 30-70% by mass, and particularly preferably 40-60% by mass. From the viewpoint of controlling the development time, it is preferable to set the content of polymer A to 90% by mass or less. On the other hand, from the viewpoint of improving resistance to edge melting, it is preferable to set the content of polymer A to 10% by mass or more.

[0622] <Polymerizing compounds>

[0623] When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a polymeric compound having polymeric groups.

[0624] In addition, the aforementioned "polymerizable compound" refers to a compound that is polymerized by the polymerization initiator described later and is different from polymer A.

[0625] As a polymerizable compound, the polymerizable group is not particularly limited as long as it participates in the polymerization reaction. For example, groups with olefinic unsaturated groups such as vinyl, acryloyl, methacryloyl, styrene, and maleimide can be cited; as well as groups with cationic polymerizable groups such as epoxy and oxetane.

[0626] As a polymerizable group, it is preferred to have a group having an olefinic unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

[0627] As a polymerizable compound, from the viewpoint of having better photosensitivity of the negative photosensitive composition layer, a compound having one or more olefin unsaturated groups (olefin unsaturated compound) is preferred, and a compound having two or more olefin unsaturated groups in one molecule (polyfunctional olefin unsaturated compound) is more preferred.

[0628] Furthermore, considering superior resolution and peelability, the number of olefinic unsaturated groups in one molecule of the olefinic unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0629] From the perspective of achieving a better balance between photosensitivity, resolution, and peelability of the negative photosensitive composition layer, it is preferable to include a difunctional or trifunctional olefin unsaturated compound having two or three olefin unsaturated groups in one molecule, and more preferably a difunctional olefin unsaturated compound having two olefin unsaturated groups in one molecule.

[0630] From the viewpoint of excellent peelability, the content of the difunctional olefin unsaturated compound relative to the total mass of the polymerizable compound and the total mass of the negative photosensitive composition layer is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more. There is no particular upper limit, and it can be 100% by mass. That is, the polymerizable compound can be entirely composed of difunctional olefin unsaturated compounds.

[0631] Furthermore, as an olefinic unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0632] (Polymer compound B1)

[0633] The negative photosensitive composition layer preferably comprises a polymeric compound B1 having an aromatic ring and two olefinic unsaturated groups. In the above-mentioned polymeric compound B, polymeric compound B1 is a difunctional olefinic unsaturated compound having one or more aromatic rings in one molecule.

[0634] From the viewpoint of superior resolution, the mass ratio of polymeric compound B1 in the negative photosensitive composition layer relative to the total mass of the polymeric compound is preferably 40% or more, more preferably 50% or more, further preferably 55% or more, and especially preferably 60% or more. There is no particular upper limit, but from the viewpoint of peelability, it is, for example, 100% or less, preferably 99% or less, more preferably 95% or less, further preferably 90% or less, and especially preferably 85% or less.

[0635] The aromatic rings present in the polymerizable compound B1 may include, for example, aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings, as well as their fused rings, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. Furthermore, the aforementioned aromatic rings may have substituents.

[0636] Polymerizable compound B1 may have only one aromatic ring or more than two aromatic rings.

[0637] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive composition layer caused by the developer, polymeric compound B1 preferably has a bisphenol structure.

[0638] Examples of bisphenol structures include, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0639] As a polymeric compound B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymeric groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0640] The two ends of the bisphenol structure can be directly bonded to two polymerizable groups, or they can be bonded through one or more alkene oxygen groups. As the alkene oxygen groups added to the two ends of the bisphenol structure, ethyleneoxy or propenoxy are preferred, and ethyleneoxy is more preferred. There is no particular limitation on the number of alkene oxygen groups added to the bisphenol structure, but 4 to 16 are preferred per molecule, and 6 to 14 are more preferred.

[0641] Regarding polymeric compound B1 having a bisphenol structure, it is described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated herein by reference.

[0642] As the polymerizable compound B1, a difunctional olefinic unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0643] Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include, for instance, 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, manufactured by SHIN-NAKAMURACHEMICAL Co., Ltd.), 2,2-bis(4-(methacryloyloxypentaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by SHIN-NAKAMURA CHEMICAL). 2,2-bis(4-(methacryloyloxydiethoxy)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.).

[0644] As a polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0645] [Chemical Formula 23]

[0646]

[0647] In general formula B1, R1 and R2 independently represent a hydrogen atom or a methyl group, respectively. A represents C2H4. B represents C3H6. n1 and n3 are each independently integers from 1 to 39, and n1+n3 is an integer from 2 to 40. n2 and n4 are each independently integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The arrangement of the structural units -(AO)- and -(BO)- can be random or block. Moreover, in the case of block, either -(AO)- or -(B-O)- can be on the diphenyl side.

[0648] In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0649] Polymer compound B1 can be used alone or in combination with two or more compounds.

[0650] From the viewpoint of superior resolution, the content of polymeric compound B1 relative to the total mass of the negative photosensitive composition layer is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but from the viewpoint of transferability and edge melting (the phenomenon of photosensitive resin seeping out from the end of the transfer part), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0651] The negative photosensitive composition layer may contain polymeric compounds other than the polymeric compound B1 mentioned above.

[0652] There are no particular restrictions on polymerizable compounds other than B1, and appropriate selections can be made from known compounds. For example, compounds having one olefinic unsaturated group in the molecule (monofunctional olefinic unsaturated compounds), difunctional olefinic unsaturated compounds without an aromatic ring, and olefinic unsaturated compounds with three or more functions can be cited.

[0653] Examples of monofunctional alkenyl unsaturated compounds include, for example, ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0654] Examples of difunctional olefinic unsaturated compounds that do not have an aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.

[0655] Examples of alkylene glycol di(meth)acrylates include tricyclodecanediethanol diacrylate (A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), tricyclodecanediethanol 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.

[0656] Examples of polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di(meth)acrylate.

[0657] Examples of urethane dimethacrylates include, for example, propylene oxide-modified urethane dimethacrylates and ethylene oxide and propylene oxide-modified urethane dimethacrylates. Commercially available examples include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by SHTN-NAKAMURACHEMICAL Co., Ltd.), and UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

[0658] Examples of olefinic unsaturated compounds with three or more functions include, for example, dipentaerythritol (tris / tetras / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and epoxide-modified versions of these.

[0659] Here, "(tri / tetra / penta / hexa)meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0660] In one embodiment, the negative photosensitive composition layer preferably comprises the aforementioned polymeric compound B1 and a trifunctional or higher olefinic unsaturated compound, more preferably comprising the aforementioned polymeric compound B1 and two or more trifunctional or higher olefinic unsaturated compounds. In this case, the mass ratio of polymeric compound B1 to the trifunctional or higher olefinic unsaturated compounds is preferably (total mass of polymeric compound B1) : (total mass of trifunctional or higher olefinic unsaturated compounds) = 1 : 1 to 5 : 1, more preferably 1.2 : 1 to 4 : 1, and even more preferably 1.5 : 1 to 3 : 1.

[0661] Furthermore, in one embodiment, the negative photosensitive composition layer preferably comprises the aforementioned polymeric compound B1 and two or more trifunctional olefinic unsaturated compounds.

[0662] Examples of epoxide-modified compounds that are trifunctional or higher-functionalized olefinic unsaturated compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), epoxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., and EBECRYL 135 manufactured by DAICEL-ALLNEX LTD.), ethoxylated glycerol triacrylates (such as A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and ARONIX TO-2349 (TOAGOSEI). (Manufactured by TOAGOSEI CO., LTD.), ARONIXM-520 (Manufactured by TOAGOSEI CO., LTD.) and ARONIXM-510 (Manufactured by TOAGOSEI CO., LTD.).

[0663] Furthermore, polymerizable compounds containing acid groups (such as carboxyl groups) can be used. These acid groups can form anhydride groups. Examples of polymerizable compounds containing acid groups 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.).

[0664] As a polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 can be used.

[0665] Polymers can be used alone or in combination with two or more compounds.

[0666] The content of the polymeric compound relative to the total mass of the negative photosensitive composition layer is preferably 10-70% by mass, more preferably 15-70% by mass, and even more preferably 20-70% by mass.

[0667] The molecular weight (weight-average molecular weight in the case of a molecular weight distribution) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0668] <Polymerization initiator>

[0669] When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably also contains a polymerization initiator.

[0670] The polymerization initiator is selected according to the form of polymerization reaction; for example, thermal polymerization initiators and photopolymerization initiators can be cited.

[0671] Polymerization initiators can be either free radical polymerization initiators or cationic polymerization initiators.

[0672] The negative photosensitive composition layer preferably contains a photopolymerization initiator.

[0673] Photopolymerization initiators are compounds that initiate the polymerization of polymerizable compounds by accepting active light such as ultraviolet light, visible light, and X-rays. There are no particular limitations on photopolymerization initiators, and well-known photopolymerization initiators can be used.

[0674] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0675] Examples of photoradical polymerization initiators include, for example, photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0676] Furthermore, from the viewpoints of photosensitivity, visual distinguishability of the exposed and unexposed areas, and resolution, the negative photosensitive composition layer preferably includes at least one selected from 2,4,5-triarylimidazolium dimers and their derivatives as a photoradical polymerization initiator. Additionally, the two 2,4,5-triarylimidazolium structures in the 2,4,5-triarylimidazolium dimer and its derivatives may be identical or different.

[0677] Examples of derivatives of 2,4,5-triarylimidazolium dimers include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0678] As a photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-14783 can be used.

[0679] Examples of photoradical polymerization initiators include, for example, ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisole (p,p'-dimethoxybenzyl, TAZ-110 (trade name: Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0680] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGMresins). Omnirad 907 (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropanoyl-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), 2-methyl-1-(4-morpholinylphenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV). Omnirad 651 (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethyl-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by TGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), and oxime ester photopolymerization initiators (trade name: Lunar 6, manufactured by DKSH Japan). 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (trade name: B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.).), 1-[4-(phenylthio)phenyl]-3-cyclopentylprop-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furan carbonyl)-9H-carbazole-3-yl]-,2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-prop-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.). (Manufactured by Co., LTD.)

[0681] Photocationic polymerization initiators (photoacid generators) are compounds that generate acids by accepting active light. As photocationic polymerization initiators, compounds that sense and generate acids from active light with wavelengths of 300 nm or higher (preferably 300–450 nm) are preferred, but their chemical structure is not limited. Furthermore, even photocationic polymerization initiators that do not directly sense active light with wavelengths of 300 nm or higher are preferred if they are compounds that sense and generate acids from active light with wavelengths of 300 nm or higher by being used in combination with a sensitizer.

[0682] As photocationic polymerization initiators, photocationic polymerization initiators that produce acids with a pKa of 4 or less are preferred, photocationic polymerization initiators that produce acids with a pKa of 3 or less are more preferred, and photocationic polymerization initiators that produce acids with a pKa of 2 or less are particularly preferred. The lower limit of pKa is not particularly limited, for example, -10.0 or more is preferred.

[0683] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0684] Examples of ionic photocationic polymerization initiators include, for example, onium salts such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts.

[0685] As an ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-085643 may be used.

[0686] Examples of nonionic photocationic polymerization initiators include trichloromethyltriazine derivatives, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among the trichloromethyltriazine derivatives, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494 can be used. Furthermore, among the oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Patent Publication No. 2018 / 179640 can be used.

[0687] The negative photosensitive composition layer preferably contains a photoradical polymerization initiator, more preferably it contains at least one selected from 2,4,5-triarylimidazolium dimers and their derivatives.

[0688] Polymerization initiators can be used alone or in combination with two or more.

[0689] The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the negative photosensitive composition layer. There is no particular upper limit, but is preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the negative photosensitive composition layer.

[0690] Pigment

[0691] From the viewpoints of visual recognition of the exposed and unexposed areas, visual recognition of the developed pattern, and resolution, the photosensitive composition layer preferably includes a pigment (also referred to as "pigment N") with a maximum absorption wavelength of 450 nm or more in the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength is altered by acids, bases, or free radicals. Although the detailed mechanism is not yet clear, the inclusion of pigment N improves adhesion to adjacent layers (e.g., water-soluble resin layers) and results in superior resolution.

[0692] In this specification, the phrase "the pigment absorbs wavelengths by a large amount of acid, alkali or free radicals" can refer to any of the following: the pigment in the color developing state is decolorized by acid, alkali or free radicals; the pigment in the decolorized state is color developed by acid, alkali or free radicals; and the pigment in the color developing state is transformed into a color developing state of other hues.

[0693] Specifically, pigment N can be a compound that changes color from a decolorized state through exposure, or a compound that changes color from a color-developed state through exposure. In this case, it can be a pigment that changes its color-developed or decolorized state by generating acids, bases, or free radicals within the photosensitive composition layer through exposure, or a pigment that changes its color-developed or decolorized state by altering the state (e.g., pH) within the photosensitive composition layer using acids, bases, or free radicals. Furthermore, it can also be a pigment that changes its color-developed or decolorized state directly by accepting acids, bases, or free radicals as stimuli without exposure.

[0694] From the perspective of visual recognition and resolution of the exposed and unexposed parts, pigment N is preferably a pigment whose maximum absorption wavelength is changed by acid or free radicals, and more preferably a pigment whose maximum absorption wavelength is changed by free radicals.

[0695] From the viewpoint of visual recognition and resolution of the exposed and unexposed areas, when the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a pigment whose maximum absorption wavelength is changed by free radicals and a photoradical polymerization initiator as pigment N.

[0696] Furthermore, from the viewpoint of visual recognition of the exposed and unexposed parts, pigment N is preferably a pigment that develops color through acid, alkali or free radicals.

[0697] Examples of the color development mechanism of pigment N include adding a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator to a photosensitive composition layer, and developing color after exposure by free radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator, resulting in a radical-reactive pigment, an acid-reactive pigment, or a base-reactive pigment (e.g., a colorless pigment).

[0698] From the viewpoint of visual recognition of the exposed and unexposed parts, the maximum absorption wavelength of pigment N in the wavelength range of 400-780nm during color development is preferably 550nm or more, more preferably 550-700nm, and even more preferably 550-650nm.

[0699] Furthermore, pigment N may have only one maximum absorption wavelength in the wavelength range of 400–780 nm during color development, or it may have two or more. When pigment N has two or more maximum absorption wavelengths in the wavelength range of 400–780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths must be 450 nm or higher.

[0700] The maximum absorption wavelength of pigment N can be obtained by the following method: Under atmospheric conditions, using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION), the transmission spectrum of a solution containing pigment N (liquid temperature 25℃) is measured in the range of 400–780 nm, and the wavelength at which the light intensity becomes minimal (maximum absorption wavelength) is detected.

[0701] As pigments that are developed or decolorized by exposure, colorless compounds can be cited as an example.

[0702] Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane pigments, oxazine pigments, xanthones, iminonaphthoquinone pigments, azomethyl alkaloid pigments, and anthraquinone pigments.

[0703] From the viewpoint of visual recognition of the exposed and unexposed areas, colorless compounds are preferred as pigment N.

[0704] Examples of colorless compounds include, for example, colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropyran skeleton (spiropyran pigments), colorless compounds having a fluorane skeleton (fluorane pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam pigments), colorless compounds having an indolephthalide skeleton (indolephthalide pigments), and colorless compounds having a colorless auramine skeleton (colorless auramine pigments).

[0705] Among them, triarylmethane pigments or fluorane pigments are preferred, and colorless compounds (triphenylmethane pigments) or fluorane pigments having a triphenylmethane skeleton are more preferred.

[0706] From the viewpoint of visual recognition of both the exposed and unexposed areas, it is preferable for the colorless compound to have a lactone ring, a sultine ring, or a sulfonyl ring. This allows the lactone ring, sultine ring, or sulfonyl ring of the colorless compound to react with free radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator, thereby changing the colorless compound into a closed-ring state and decolorizing it, or changing the colorless compound into an open-ring state and making it colored. Preferably, a colorless compound is a compound having a lactone ring, sultine ring, or sulfonyl ring that develops color through ring-opening by a free radical or acid; more preferably, a compound having a lactone ring that develops color through ring-opening by a free radical or acid.

[0707] As pigment N, examples include the following dyes and colorless compounds.

[0708] Specific examples of dyes in pigment N include, for instance, Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsin, Methyl Violet 2B, Quinaldinine Red, Rose Red, m-aniline Yellow, Thymol Blue, Xylenol Blue, Methyl Orange, p-Methyl Red, Congo Red, Benzo[a]rubidium violet 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Coupled Fuchsin, Victoria Blue-Naphthalene Sulfonate, Victoria 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), OILGREEN#5O2 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD), Spilon BEH special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonyl rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazoline and 1-β-naphthyl-4-p-binaphthyldiethylaminophenylimino-5-pyrazoline.

[0709] Specific examples of colorless compounds in pigment N include p,p',p”-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy AG), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-tolyl)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilino fluorane, 3-(N,N-diethylamino)-6-methyl-7-aniline fluorane, 3-(N,N-diethylamino)-6-methyl-7-dimethylaminofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroaniline)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-di-di-... 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-aniline fluorane, 3-(N,N-dibutylamino)-6-methyl-7-dimethylaminofluorane, 3-piperidin-6-methyl-7-aniline fluorane, 3-pyrrolidine-6-methyl-7-aniline fluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n- Butyl-2-methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthon-3-one.

[0710] From the viewpoint of visual recognition of the exposed and unexposed areas, visual recognition of the pattern after development, and resolution, pigment N is preferably a pigment whose maximum absorption wavelength is changed by free radicals, and more preferably a pigment that develops color by free radicals.

[0711] As pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate are preferred.

[0712] Pigment N can be used alone or in combination with two or more pigments.

[0713] From the viewpoint of visual recognition of the exposed and unexposed areas, visual recognition of the developed pattern, and resolution, the content of pigment N relative to the total mass of the photosensitive composition layer is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass.

[0714] The content of pigment N refers to the amount of pigment required to bring all pigment N contained in the total mass of the photosensitive composition layer to a colored state. The following explanation uses pigments that develop color via free radicals as an example to illustrate the quantitative method for determining the content of pigment N.

[0715] Solutions containing 0.001 g and 0.01 g of pigment were prepared in 100 mL of methyl ethyl ketone. Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.) was added to each of the obtained solutions, and the solutions were irradiated with 365 nm light, thereby generating free radicals and causing all the pigments to become colored. Subsequently, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION), and calibration curves were constructed.

[0716] Next, instead of the pigments, 3g of the photosensitive composition layer was dissolved in methyl ethyl ketone. Otherwise, the absorbance of the solution that developed all the pigments was measured using the same method as above. Based on the calibration curve, the pigment content in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer.

[0717] In addition, the 3g of the photosensitive composition layer is the same as the 3g of the total solids in the photosensitive resin composition.

[0718] <Thermocrosslinking compounds>

[0719] When the photosensitive composition layer is a negative photosensitive composition layer, from the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film, it is preferable to include a thermally crosslinking compound. Furthermore, in this specification, the thermally crosslinking compounds having olefinic unsaturated groups described later are considered thermally crosslinking compounds, not polymeric compounds.

[0720] Examples of thermally crosslinking compounds include hydroxymethyl compounds and end-capped isocyanate compounds. Among these, end-capped isocyanate compounds are preferred from the viewpoint of the strength of the cured film and the adhesion of the uncured film.

[0721] Since the capped isocyanate compound reacts with hydroxyl and carboxyl groups, when, for example, the resin and / or polymeric compound has at least one of hydroxyl and carboxyl groups, there is a tendency for the hydrophilicity of the formed film to decrease and the function of the film obtained by curing the negative photosensitive composition layer to be enhanced when used as a protective film.

[0722] In addition, capped isocyanate compounds are defined as "compounds having a structure in which isocyanate groups of isocyanate are protected (so-called masked) by capping agents".

[0723] There is no particular limitation on the dissociation temperature of the capped isocyanate compound, but it is preferred to be 100–160°C, and more preferably 130–150°C.

[0724] The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates when analyzed and determined by DSC (Differential Scanning Calorimetry) using a differential scanning calorimeter".

[0725] As a differential scanning calorimeter, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. is preferred, for example. However, the differential scanning calorimeter is not limited to this.

[0726] Examples of end-capping agents with dissociation temperatures of 100–160°C include active methylene compounds (malonate esters (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 cyclohexanone oxime, etc., which have an intramolecular structure represented by -C (=N-OH)-).

[0727] Among these, at least one of the oxime compounds is preferred as a capping agent with a dissociation temperature of 100 to 160°C, for example, from the viewpoint of storage stability.

[0728] For example, from the viewpoint of improving the brittleness of the film and enhancing the adhesion to the substrate, the end-capped isocyanate compound preferably has an isocyanurate structure.

[0729] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuration of hexamethylene diisocyanate.

[0730] Among isocyanate compounds with an isocyanurate structure, compounds with an oxime structure are preferred from the viewpoint that it is easier to set the dissociation temperature to a preferred range and easier to reduce development residue compared to compounds without an oxime structure.

[0731] End-capped isocyanate compounds can have polymerizable groups.

[0732] There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, with free radical polymerizable groups being preferred.

[0733] Examples of polymerizable groups include olefinic unsaturated groups such as (meth)acryloyloxy, (meth)acrylamido, and styryl, as well as groups with epoxy groups such as glycidyl.

[0734] Among them, as a polymerizable group, an olefinic unsaturated group is preferred, (meth)acryloyloxy is more preferred, and acryloyloxy is even more preferred.

[0735] As a capped isocyanate compound, it can be used in commercially available products.

[0736] Examples of commercially available isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and the end-capped Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Corporation).

[0737] Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0738] [Chemical Formula 24]

[0739]

[0740] A single thermal crosslinking compound can be used alone, or two or more compounds can be used.

[0741] When the photosensitive composition layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound relative to the total mass of the photosensitive composition layer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.

[0742] <Other Additives>

[0743] In addition to the above-mentioned components, the photosensitive composition layer may also contain known additives as needed.

[0744] Examples of additives include free radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (triazoles, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), purine bases (adenine, etc.), and surfactants.

[0745] Each additive can be used alone or in combination with two or more.

[0746] The photosensitive composition layer may contain free radical polymerization inhibitors.

[0747] Examples of free radical polymerization inhibitors include, for instance, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenotoxazine, or 4-methoxyphenol are preferred. Other free radical polymerization inhibitors include naphthylamine, cuprous chloride, aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive composition layer, aluminum nitrosophenylhydroxylamine is preferably used as the free radical polymerization inhibitor.

[0748] Examples of benzotriazoles include, for example, 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-methylbenzotriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0749] Examples of carboxybenzotriazoles include, for example, 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)aminovinyl carboxybenzotriazole. Commercially available products such as CBT-1 (JOHOKU CHEMICAL CO., LTD, trade name) can also be used as carboxybenzotriazoles.

[0750] The total content of free radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles relative to the total mass of the photosensitive composition layer is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is better. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and inhibition of dye decolorization are better.

[0751] The photosensitive composition layer may contain a sensitizer.

[0752] There are no particular limitations on the sensitizer; known sensitizers, dyes, and pigments can be used. Examples of sensitizers include, for instance, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthonesone compounds, thioxanthonesone compounds, acridinone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthimine compounds, triarylamine compounds, and aminoacridine compounds.

[0753] One type of sensitizer can be used alone, or two or more types can be used.

[0754] When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. From the viewpoint of improving the curing speed by increasing the sensitivity to the light source and balancing the polymerization rate and chain transfer, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer.

[0755] The photosensitive composition layer may contain at least one selected from plasticizers and heterocyclic compounds.

[0756] As plasticizers and heterocyclic compounds, examples include the compounds described in paragraphs 0097–0103 and 0111–0118 of International Publication No. 2018 / 179640.

[0757] Furthermore, the photosensitive composition layer may also contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferation agents, development promoters, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic antisettling agents.

[0758] Regarding the additives contained in the photosensitive composition layer, they are described in paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-085643, the contents of which are incorporated herein by reference.

[0759] From the viewpoint of improving reliability and lamination, 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.

[0760] The thickness (film thickness) of the photosensitive composition layer is typically 0.1–300 μm, preferably 0.2–100 μm, more preferably 0.5–50 μm, even more preferably 0.5–15 μm, particularly preferably 0.5–10 μm, and most preferably 0.5–8 μm. This improves the developability of the photosensitive composition layer and enhances resolution.

[0761] Furthermore, in one embodiment, 0.5–5 μm is preferred, 0.5–4 μm is more preferred, and 0.5–3 μm is even more preferred.

[0762] Furthermore, from the viewpoint of superior adhesion, the transmittance of the photosensitive composition layer to light with a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular upper limit, but 99.9% or less is preferred.

[0763] <Impurities, etc.>

[0764] The photosensitive composition layer may contain a specified amount of impurities.

[0765] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, since halide ions, sodium ions, and potassium ions are easily introduced as impurities, the following concentrations are preferred.

[0766] Based on mass, the impurity content in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content can be set to 1 ppb or more, or 0.1 ppm or more, based on mass.

[0767] Examples of methods for keeping impurities within the aforementioned range include selecting raw materials with low impurity content as raw materials for the composition; preventing impurities from being introduced during the fabrication of the photosensitive composition layer; and cleaning and removal methods. These methods enable the impurity content to be kept within the aforementioned range.

[0768] For example, impurities can be quantified using known methods such as CP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0769] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably low. The content of these compounds relative to the total mass of the photosensitive composition layer, on a mass basis, is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less.

[0770] Based on mass standards, the lower limit relative to the total mass of the photosensitive composition layer can be set to 10 ppb or more, and can also be set to 100 ppb or more. The content of these compounds can be suppressed using the same method as for the aforementioned metal impurities. Furthermore, they can be quantified using known methods.

[0771] From the viewpoint of improving reliability and lamination, 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.

[0772] Pigments

[0773] The photosensitive composition layer can be a coloring resin layer containing pigments.

[0774] Recent electronic devices sometimes have a cover glass on their liquid crystal display windows, which has a black frame-like light-shielding layer formed on the back periphery of a transparent glass substrate or the like to protect the liquid crystal display window. A colored resin layer can be used to form this type of light-shielding layer.

[0775] As a pigment, it can be selected appropriately according to the desired hue, and can be selected from black pigment, white pigment, and colored pigments other than black and white. Among them, when forming a black pattern, black pigment is preferred.

[0776] As the black pigment, any known black pigment (organic or inorganic pigment, etc.) can be appropriately selected, provided it does not impair the effects of the present invention. From the viewpoint of optical density, examples of preferred black pigments include carbon black, titanium dioxide, titanium carbide, iron oxide, titanium dioxide, and graphite, with carbon black being particularly preferred. From the viewpoint of surface resistivity, carbon black in which at least a portion of its surface is coated with resin is preferred.

[0777] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, based on the number-average particle size.

[0778] Here, particle size refers to the diameter of a circle that is the same area as the pigment particle when the area of ​​the pigment particle is calculated from an image of the pigment particle taken with an electron microscope. The number-average particle size is the average value obtained by averaging the above particle size for any 100 particles.

[0779] Regarding white pigments other than black pigments, the white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Publication No. 2005-007765 can be used. Specifically, among white pigments, titanium dioxide, zinc oxide, zinc barium white, light calcium carbonate, silica, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, titanium dioxide or zinc oxide are more preferred, and titanium dioxide is even more preferred. As inorganic pigments, rutile or anatase titanium dioxide is even more preferred, and rutile titanium dioxide is particularly preferred.

[0780] Furthermore, the surface of titanium oxide can be treated with silica, alumina, titanium dioxide, zirconium oxide, or organic substances, or two or more treatments can be applied. This inhibits the catalytic activity of titanium oxide and improves its heat resistance and fading properties.

[0781] From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, at least one of alumina treatment and zirconium oxide treatment is preferred as a surface treatment for the titanium oxide surface, and both alumina treatment and zirconium oxide treatment are particularly preferred.

[0782] Furthermore, when the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, the photosensitive composition layer preferably further includes colored pigments other than black and white pigments. When colored pigments are included, the particle size of the colored pigments is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility.

[0783] Examples of colored pigments include, for instance, Victoria Blue BO (Color Index: CI 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CT Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hotaberm Red ESB (CI Pigment Violet 19), Permanent Ruby Red FBH (CI Pigment Red 11), Fastel Pink B SUPRA (CI Pigment Red 81), and Phthalocyanine Blue (CI Pigment Blue 15). FAST Black B (CI Pigment Black 1) and other pigments including carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Among these, CI Pigment Red 177 is preferred.

[0784] When the photosensitive composition layer contains pigments, the pigment content, relative to the total mass of the photosensitive composition layer, is preferably more than 3% by mass and less than 40% by mass, more preferably more than 3% by mass and less than 35% by mass, even more preferably more than 5% by mass and less than 35% by mass, and particularly preferably more than 10% by mass and less than 35% by mass.

[0785] When the photosensitive composition layer contains pigments other than black pigments (white pigments and colored pigments), the content of pigments other than black pigments relative to black pigments is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass.

[0786] In addition, when the photosensitive composition layer contains a black pigment and the photosensitive composition layer is formed from a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion.

[0787] The dispersion can be prepared by adding a pre-mixed mixture of black pigment and pigment dispersant to an organic solvent (or carrier) and dispersing it using a disperser. The pigment dispersant can be selected based on the pigment and solvent; for example, a commercially available dispersant can be used. The carrier refers to the medium through which the pigment is dispersed in the pigment dispersion. This carrier is liquid and contains 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.

[0788] There are no particular limitations on what constitutes a dispersing machine; for example, well-known dispersing machines such as kneaders, roller mills, grinders, supermills, dissolvers, homogenizers, and sand mills can be cited. Furthermore, mechanical grinding can also be used to achieve micronization through friction. For more information on dispersing machines and micronization, please refer to the "Encyclopedia of Pigments" (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0789] Thermoplastic resin layer

[0790] Typically, a thermoplastic resin layer is disposed between the temporary support and the photosensitive composition layer. Because the transfer film has a thermoplastic resin layer, its conformability to the substrate is improved during the bonding process between the transfer film and the substrate, and air bubbles can be suppressed from entering between the substrate and the transfer film. As a result, good adhesion between the transfer film and adjacent layers (e.g., the temporary support) can be ensured.

[0791] The thermoplastic resin layer comprises resin. The resin may comprise thermoplastic resin as a part or all thereof. That is, in one embodiment, the resin of the thermoplastic resin layer is preferably a thermoplastic resin.

[0792] Alkali-soluble resins (thermoplastic resins)

[0793] Thermoplastic resin is preferably an alkali-soluble resin.

[0794] Examples of alkali-soluble resins include, for example, acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl alcohol formaldehyde, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0795] From the viewpoint of developability and adhesion to adjacent layers, acrylic resin is preferred as an alkali-soluble resin.

[0796] Here, acrylic resin refers to a resin having at least one structural unit selected from structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide.

[0797] As an acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide is preferably 50% by mass or more relative to the total mass of the acrylic resin.

[0798] The total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate relative to the total mass of acrylic resin is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

[0799] Furthermore, the alkali-soluble resin is preferably a polymer with acid groups.

[0800] Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl being the preferred group.

[0801] From the viewpoint of developability, alkali-soluble resins with an acid value of 60 mg KOH / g or higher are preferred, and acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher are even more preferred.

[0802] There is no particular limit to the upper limit of the acid value of alkali-soluble resins, but it is preferred to be below 300 mg KOH / g, more preferably below 250 mg KOH / g, even more preferably below 200 mg KOH / g, and especially preferably below 150 mg KOH / g.

[0803] There are no particular restrictions on the selection of acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher; appropriate selection can be made from known resins.

[0804] For example, examples include the alkali-soluble acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher described in paragraph 0025 of Japanese Patent Application Publication No. 2011-095716; the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589; and the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0805] The copolymerization ratio of carboxyl-containing structural units in the above-mentioned carboxyl-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, relative to the total mass of the acrylic resin.

[0806] From the viewpoint of developability and adhesion to adjacent layers, acrylic resins having structural units derived from (meth)acrylic acid are particularly preferred as alkali-soluble resins.

[0807] Alkali-soluble resins can possess reactive groups. Any group capable of addition polymerization can be considered a reactive group; examples include olefinic unsaturated groups; condensation groups such as hydroxyl and carboxyl groups; and addition polymerization reactive groups such as epoxy groups and (terminated) isocyanate groups.

[0808] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0809] Alkali-soluble resins can be used alone or in combination with two or more types.

[0810] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin relative to the total mass of the thermoplastic resin layer is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass.

[0811] Pigment

[0812] The thermoplastic resin layer preferably contains a pigment (also referred to as "pigment B") with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength is altered by acid, alkali, or free radicals.

[0813] Except as described below, the preferred method for pigment B is the same as that for pigment N described above.

[0814] From the viewpoint of visual recognition and resolution of the exposed and unexposed areas, pigment B is preferably a pigment whose maximum absorption wavelength is changed by acid or free radicals, and more preferably a pigment whose maximum absorption wavelength is changed by acid.

[0815] From the viewpoint of visual recognition and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a pigment whose maximum absorption wavelength as pigment B is altered by acid and a compound that generates acid by light, as described later.

[0816] Pigment B can be used alone or in combination with two or more pigments.

[0817] From the viewpoint of visual distinguishability of the exposed and unexposed areas, the content of pigment B relative to the total mass of the thermoplastic resin layer is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, even more preferably 0.2 to 5% by mass, and particularly preferably 0.25 to 3.0% by mass.

[0818] Here, the content of pigment B refers to the amount of pigment required for all pigments B contained in the thermoplastic resin layer to reach their colored state. The following explanation uses pigments that develop color via free radicals as an example to illustrate the quantitative method for determining the content of pigment B.

[0819] Solutions containing 0.001 g and 0.01 g of pigment were prepared in 100 mL of methyl ethyl ketone. Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.) was added to each of the obtained solutions, and the solutions were irradiated with 365 nm light, thereby generating free radicals and causing all the pigments to become colored. Subsequently, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION), and calibration curves were constructed.

[0820] Next, instead of pigments, 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone. Otherwise, the absorbance of the solution that caused all pigments to develop color was measured using the same method as described above. Based on the calibration curve, the amount of pigment contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer.

[0821] In addition, the 3g thermoplastic resin layer is the same as the 3g solid component of the composition.

[0822] <Compounds that generate acids, bases, or free radicals through light>

[0823] The thermoplastic resin layer may contain compounds that generate acids, bases, or free radicals through light (also referred to simply as "Compound C").

[0824] As compound C, it is preferred to be a compound that can generate acids, bases or free radicals by accepting active light such as ultraviolet and visible light.

[0825] As compound C, known photoacid generators, photoalkali generators, and photoradical polymerization initiators (photoradical generators) can be used.

[0826] (Photo-acid generator)

[0827] From a resolution perspective, the thermoplastic resin layer can contain a photoacid-generating agent.

[0828] As photoacid generators, examples include photocationic polymerization initiators that can be included in the aforementioned negative photosensitive composition layer, and the preferred methods are the same, except as described later.

[0829] As a photoacid generator, from the viewpoint of sensitivity and resolution, it is preferable to include at least one compound selected from onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, it is more preferable to include oxime sulfonate compounds.

[0830] Furthermore, as a photoacid generator, a photoacid generator having the following structure is preferred.

[0831] [Chemical Formula 25]

[0832]

[0833] (Photoradical polymerization initiator)

[0834] The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0835] As photoradical polymerization initiators, examples of photoradical polymerization initiators that can be included in the aforementioned negative photosensitive composition layer are given, and the preferred method is also the same.

[0836] (Photo-induced alkali production agent)

[0837] Thermoplastic resin compositions may contain photoalkali-generating agents.

[0838] As a photo-alkali-generating agent, there are no particular limitations as long as it is a well-known photo-alkali-generating agent. Examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinylethane, (4-morpholinylbenzoyl) )-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, tris(triphenylmethylboronic acid)hexaamminecobalt(III), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-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.

[0839] Compound C can be used alone or in more than two forms.

[0840] From the viewpoint of visual recognition and resolution of the exposed and unexposed areas, the content of compound C relative to the total mass of the thermoplastic resin layer is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

[0841] <Plasticizer>

[0842] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0843] The molecular weight (weight-average molecular weight when it is an oligomer or polymer with a molecular weight distribution) of the plasticizer is preferably less than that of the alkali-soluble resin. The molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000.

[0844] There are no particular limitations on plasticizers as long as they are compounds that exhibit plasticizing properties when miscible with alkali-soluble resins. From the viewpoint of imparting plasticizing properties, plasticizers preferably contain alkene groups in their molecules, and more preferably polyalkylene glycol compounds. The alkene groups contained in the plasticizer are more preferably polyvinyloxy or polyacryloxy structures.

[0845] Furthermore, from the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0846] Examples of (meth)acrylate compounds used as plasticizers include polymeric compounds contained in the aforementioned negative photosensitive composition layer.

[0847] In transfer films, when a thermoplastic resin layer and a negative photosensitive composition layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the negative photosensitive composition layer contain (meth)acrylate compounds. This is because by having the same (meth)acrylate compound in both the thermoplastic resin layer and the negative photosensitive composition layer, interlayer diffusion is suppressed, and storage stability is improved.

[0848] 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 in the exposed portion after exposure.

[0849] Furthermore, from the viewpoints of resolution of the thermoplastic resin layer, adhesion between adjacent layers, and developability, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in one molecule are preferred as (meth)acrylate compounds that can be used as plasticizers.

[0850] Furthermore, (meth)acrylate compounds that can be used as plasticizers are preferably (meth)acrylate compounds having acid groups or urethane (meth)acrylate compounds.

[0851] Plasticizers can be used alone or in combination with two or more.

[0852] From the viewpoints of resolution, adhesion to adjacent layers, and developability of the thermoplastic resin layer, the content of plasticizer relative to the total mass of the thermoplastic resin layer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass.

[0853] <Sensers>

[0854] The thermoplastic resin layer may contain sensitizers.

[0855] There are no particular limitations on the sensitizers used, and examples of sensitizers that may be included in the aforementioned negative photosensitive composition layer can be cited.

[0856] One type of sensitizer can be used alone, or two or more types can be used.

[0857] The content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and the visual distinguishability of the exposed and unexposed parts, it is preferable to be 0.01 to 5% by mass relative to the total mass of the thermoplastic resin layer, more preferably 0.05 to 1% by mass.

[0858] <Additives, etc.>

[0859] In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives as needed.

[0860] Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-085643, the contents of which are incorporated herein by reference.

[0861] There is no particular limitation on the thickness of the thermoplastic resin layer, but from the viewpoint of adhesion to adjacent layers, 1 μm or more is preferred, and 2 μm or more is more preferred. There is no particular upper limit, but from the viewpoint of developability and resolution, 20 μm or less is preferred, 10 μm or less is more preferred, and 8 μm or less is even more preferred.

[0862] The Intermediate Layer

[0863] In the transfer film 20, the intermediate layer 15 exists between the thermoplastic resin layer 13 and the photosensitive composition layer 17, which can suppress the 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 coating formation.

[0864] As an intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used.

[0865] Furthermore, as the intermediate layer, an oxygen barrier layer with oxygen barrier function, as described in Japanese Patent Application Publication No. 5-072724 (JP5-072724), can also be used. When the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and the productivity is increased, which is therefore preferred.

[0866] The oxygen barrier layer that can be used as the intermediate layer may be appropriately selected from those known layers described in the aforementioned publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0867] The following describes the components that may be included in the water-soluble resin layer (intermediate layer).

[0868] The water-soluble resin layer (intermediate layer) contains resin.

[0869] The aforementioned resins include water-soluble resins as part or all of them.

[0870] Examples of resins that can be used as water-soluble resins include, for example, polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

[0871] Furthermore, copolymers of (meth)acrylic acid / vinyl compounds can also be used as water-soluble resins. Among the copolymers of (meth)acrylic acid / vinyl compounds, copolymers of (meth)acrylic acid / allyl (meth)acrylate are preferred, and copolymers of methacrylic acid / allyl methacrylate are more preferred.

[0872] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the component ratio (mol%) is preferably 90 / 10 to 20 / 80, more preferably 80 / 20 to 30 / 70.

[0873] As a lower limit for the weight-average molecular weight of the water-soluble resin, it is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Furthermore, as an upper limit, it is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0874] The dispersion (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

[0875] Furthermore, from the perspective of further improving the interlayer mixing inhibition ability of the water-soluble resin layer (intermediate layer), the resin in the water-soluble resin layer (intermediate layer) is preferably a different resin from the resin contained in the layer disposed on one side and the resin contained in the layer disposed on the other side. For example, when the photosensitive composition layer 17 contains polymer A and the thermoplastic resin layer 13 contains thermoplastic resin (alkali-soluble resin), the resin in the water-soluble resin layer (intermediate layer) 15 is preferably a different resin from polymer A and thermoplastic resin (alkali-soluble resin).

[0876] To further improve oxygen barrier properties and interlayer mixing inhibition capabilities, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0877] Water-soluble resins can be used alone or in combination with two or more.

[0878] There is no particular limitation on the content of water-soluble resin. However, considering the need to further improve oxygen barrier properties and interlayer mixing inhibition, it is preferable to be 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the water-soluble resin layer (intermediate layer). Furthermore, there is no particular limitation on its upper limit; for example, it is preferable to be 99.9% by mass or less, and even more preferably 99.8% by mass or less.

[0879] The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1–5 μm, more preferably 0.5–3 μm. If the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the interlayer mixing inhibition ability is excellent without reducing oxygen barrier properties. Furthermore, it can further suppress the increase in removal time of the water-soluble resin layer (intermediate layer) during development.

[0880] Method for manufacturing transfer film according to the second embodiment

[0881] The method for manufacturing the transfer film in the second embodiment is not particularly limited, and known methods can be used.

[0882] As a method for manufacturing the transfer film 20, for example, a method including the following steps can be described: coating a thermoplastic resin composition onto the surface of a temporary support 11 to form a coating film and further drying the coating film to form a thermoplastic resin layer 13; coating a water-soluble resin composition onto the surface of the thermoplastic resin layer 13 to form a coating film and further drying the coating film to form an intermediate layer 15; and coating a photosensitive composition onto the surface of the intermediate layer 15 to form a coating film and further drying the coating film to form a photosensitive composition layer 17.

[0883] A protective film 19 is pressed onto the photosensitive composition layer 17 of the laminate manufactured by the above manufacturing method, thereby producing a transfer film 20.

[0884] As a method for manufacturing the transfer film according to the second embodiment, it is preferable to manufacture a transfer film 20 having a temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive composition layer 17, and a protective film 19 by a process including setting a protective film 19 to contact the side of the photosensitive resin layer 17 opposite to the side having the temporary support 11.

[0885] After the transfer film 20 is manufactured using the above manufacturing method, it is wound up, thereby enabling the production and storage of a roll-shaped transfer film. The roll-shaped transfer film is provided directly in roll form during the bonding process with the substrate, which is performed in a roll-to-roll manner as described later.

[0886] Furthermore, as a method for manufacturing the aforementioned transfer film 20, it can be a method of forming a thermoplastic resin layer 3 on the surface of the intermediate layer 15 after forming a photosensitive resin layer 17 and an intermediate layer 15 on the cover film 19.

[0887] <Composition for forming thermoplastic resin layers and method for forming thermoplastic resin layers>

[0888] There are no particular limitations on the method for forming a thermoplastic resin layer on a temporary support, and known methods can be used. For example, it can be formed by coating a thermoplastic resin layer forming composition onto the temporary support and then drying it as needed.

[0889] The composition for forming a thermoplastic resin layer preferably includes the various components and solvents described above for forming the thermoplastic resin layer. Furthermore, in the composition for forming a thermoplastic resin layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the thermoplastic resin layer.

[0890] There are no particular limitations on the solvent, as long as it can dissolve or disperse the components other than the solvent itself; any known solvent can be used. Examples of solvents that are the same as those contained in the photosensitive compositions described later are preferred.

[0891] The solvent content is preferably 50 to 1,900 parts by weight, more preferably 100 to 900 parts by weight, relative to 100 parts by weight of the total solids of the composition.

[0892] There are no particular limitations on the method of forming the thermoplastic resin layer, as long as it is a method that can form a layer containing the above-mentioned components. For example, well-known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0893] <Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)>

[0894] As a water-soluble resin composition, it is preferable to include various components and solvents that form the aforementioned intermediate layer (water-soluble resin layer). Furthermore, in the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the aforementioned water-soluble resin layer.

[0895] As a solvent, there are no particular limitations as long as it can dissolve or disperse water-soluble resins. It is preferred to select at least one of water and water-miscible organic solvents, and more preferably water or a mixture of water and water-miscible organic solvents.

[0896] Examples of water-mixable organic solvents include alcohols, acetone, ethylene glycol, and glycerol having 1 to 3 carbon atoms, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0897] One solvent can be used alone, or two or more solvents can be used.

[0898] The solvent content is preferably 50 to 2,500 parts by mass relative to 100 parts by mass of the total solids of the composition, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0899] There are no particular limitations on the method of forming the water-soluble resin layer, as long as it is a method that can form a layer containing the above-mentioned components. For example, well-known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0900] <Photosensitive composition and method for forming photosensitive composition layer>

[0901] From the perspective of excellent productivity and ease of forming of the composition layer that satisfies the requirements of the above formulas (1A) to (3A), it is preferable to use a photosensitive composition containing the components constituting the above photosensitive composition layer (e.g., adhesive polymer, polymeric compound and polymerization initiator, etc.) and solvent, and form it by coating method.

[0902] Specifically, the preferred method for manufacturing the transfer film according to the second embodiment is as follows: coating a photosensitive composition onto an intermediate layer to form a coating film, and drying the coating film at a specified temperature to form a photosensitive composition layer. Furthermore, it is presumed that by adjusting the residual solvent content through the drying process of the coating film, the tanδ of the photosensitive composition layer can be appropriately adjusted, and a composition layer satisfying the requirements of formulas (1A) to (3A) can be easily formed.

[0903] The photosensitive composition preferably includes the various components and solvents used to form the photosensitive composition layer. Furthermore, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive composition layer.

[0904] As a solvent, there are no particular restrictions as long as it can dissolve or disperse the components other than the solvent, and known solvents can be used. Specifically, examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents (such as n-propyl acetate), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0905] As a solvent, it is preferred to include at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, it includes a mixed solvent selected from at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from ketone solvents and cyclic ether solvents. More preferably, it includes a mixed solvent containing at least one solvent selected from at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0906] Examples of alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0907] Examples of solvents for alkylene glycol ether acetates include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0908] As solvents, solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated in this specification.

[0909] One solvent can be used alone, or two or more solvents can be used.

[0910] The solvent content is preferably 50 to 1,900 parts by mass relative to 100 parts by mass of the total solids of the composition, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass.

[0911] Examples of coating methods for photosensitive compositions include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0912] As a drying method for the coating film of the photosensitive composition, heating drying and vacuum drying are preferred.

[0913] From the perspective of facilitating the formation of a composition layer that satisfies the requirements of formulas (1A) to (3A) by appropriately adjusting the tanδ of the photosensitive composition layer, a drying temperature of 90°C or higher is preferred, more preferably 100°C or higher, and even more preferably 110°C or higher is preferred. Furthermore, there is no particular limitation on the upper limit, but 130°C or lower is preferred, and 120°C or lower is more preferably preferred.

[0914] Furthermore, considering the ease with which a composition layer can be formed that satisfies the requirements of formulas (1A) to (3A) by appropriately adjusting the tanδ of the photosensitive composition layer, a drying time of 20 seconds or more is preferred, more preferably 40 seconds or more, and even more preferably 60 seconds or more is preferred. There is no particular limitation on the upper limit, but 450 seconds or less is preferred, and 300 seconds or less is more preferably preferred.

[0915] Furthermore, by attaching the protective film to the photosensitive composition layer, the transfer film of the second embodiment can be manufactured.

[0916] There are no particular limitations on the method of attaching a protective film to the photosensitive composition layer, and well-known methods can be cited.

[0917] As a device for laminating a protective film onto a photosensitive composition layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[0918] The laminator is preferably equipped with any heatable roller, such as a rubber roller, and is capable of applying pressure and heating.

[0919] [Manufacturing method of laminated bodies]

[0920] By using the above-described transfer film, the composition layer can be transferred to the substrate.

[0921] The transfer film of the present invention is preferably used in the manufacture of touch panels.

[0922] Preferably, the manufacturing method of the laminate of the present invention includes: a bonding process, wherein the surface of the transfer film opposite to the temporary support is brought into contact with the substrate having a conductive portion to obtain a substrate having a substrate, a conductive layer, a composition layer and a temporary support in sequence.

[0923] The exposure process involves patterning the composite layer; and

[0924] The developing process forms a protective film pattern for the conductive layer by developing the exposed composite layer.

[0925] The method for manufacturing the laminate also includes a peeling process, in which a temporary support is peeled off from a substrate with a composite layer between a bonding process and an exposure process or between an exposure process and a development process.

[0926] The following is a detailed explanation of the sequence of the above-mentioned procedures.

[0927] [Lamination process]

[0928] The lamination process involves bonding the surface of the transfer film opposite to the temporary support to a substrate having a conductive portion, thereby obtaining a substrate with a composition layer that sequentially comprises a substrate, a conductive layer, a photosensitive composition layer, and a temporary support. Alternatively, if the transfer film has a protective film structure, the lamination process is performed after peeling off the protective film.

[0929] In the above bonding process, it is preferable to press-fit the conductive layer in such a way that the surfaces of the conductive layer and the composition layer come into contact.

[0930] There are no particular limitations on the above-described pressing method; known transfer and lamination methods can be used. Preferably, the surface of the composite layer is overlapped onto a substrate having conductive portions, and pressure and heating are applied using rollers or similar methods.

[0931] It can be laminated using well-known laminators such as vacuum laminators and automatic cutting laminators.

[0932] There are no particular limitations on the lamination temperature; for example, 70–130°C is preferred.

[0933] A substrate with a conductive layer has a conductive layer on the substrate, and any layer can be formed as needed. That is, a substrate with a conductive layer is a conductive substrate that has at least a substrate and a conductive layer disposed on the substrate.

[0934] Examples of substrates include resin substrates, glass substrates, and semiconductor substrates.

[0935] As a preferred substrate, for example, it is described in paragraph

[0140] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0936] From the perspective of conductivity and fine line formation, the conductive layer is preferably selected from at least one layer selected from metal layers, conductive metal oxide layers, graphene layers, carbon nanotube layers and conductive polymer layers.

[0937] Furthermore, a single conductive layer or two or more conductive layers can be disposed on the substrate. When two or more conductive layers are disposed, conductive layers of different materials are preferred.

[0938] As a preferred embodiment of the conductive layer, for example, it is described in paragraph

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

[0939] As a substrate having a conductive layer, a substrate having at least one of a transparent electrode and a circuitous wiring is preferred. The substrate described above can be preferably used as a substrate for a touch panel.

[0940] Transparent electrodes are preferably used as electrodes for touch panels. The transparent electrodes are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as fine metal wires such as metal mesh and silver nanowires.

[0941] Examples of fine metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0942] Metal is the preferred material for circuitous wiring.

[0943] Metals can be used as materials for circuit routing, including gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metallic elements. Copper, molybdenum, aluminum, or titanium are preferred materials for circuit routing, with copper being particularly preferred.

[0944] The electrode protective film for touch panels formed using the photosensitive composition layer in the transfer film of the present invention is preferably configured to directly cover or cover the electrodes or the like with other layers in order to protect the electrodes (i.e., at least one of the electrodes for touch panels and the wiring for touch panels).

[0945] [Exposure process]

[0946] The exposure process is the process of exposing the composite layer to a pattern.

[0947] In addition, "pattern exposure" here refers to exposure in a patterned manner, that is, exposure with exposed and unexposed areas.

[0948] There are no particular restrictions on the positional relationship between the exposed and unexposed areas in pattern exposure, and it can be adjusted appropriately.

[0949] As the light source for pattern exposure, any light source capable of illuminating at least a wavelength range of the curable photosensitive composition layer (e.g., 365 nm or 405 nm) can be appropriately selected. The dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. Furthermore, the dominant wavelength refers to the wavelength with the highest intensity.

[0950] As light sources, examples include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0951] The optimal exposure level is 5–200 mJ / cm. 2 More preferably 10–200 mJ / cm 2 .

[0952] Preferred methods for the light source, exposure amount, and exposure method used in the exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and are incorporated herein by reference.

[0953] By performing an exposure process and a subsequent development process, a protective film pattern is formed on the conductive layer of the substrate to protect at least a portion of the conductive layer.

[0954] [Stripping process]

[0955] The peeling process is the process of peeling a temporary support from a substrate with a composite layer between the bonding process and the exposure process, or between the exposure process and the development process described later.

[0956] There are no particular restrictions on the peeling method, and the same mechanism as the covering film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Publication No. 2010-072589 can be used.

[0957] [Developing process]

[0958] The developing process is the process of developing an exposed composite layer to form a pattern.

[0959] The above-mentioned composite layer can be developed using a developing solution.

[0960] As a developer, an alkaline aqueous solution is preferred. Examples of alkaline compounds that may be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0961] Examples of development methods include rotary immersion development, spray development, rotational development, and immersion development.

[0962] As a preferred developer used in this specification, for example, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271 can be cited as an example. As a preferred developing method, for example, the developing method described in paragraph

[0195] of International Publication No. 2015 / 093271 can be cited as an example.

[0963] [Post-exposure process and post-baking process]

[0964] The manufacturing method of the above-mentioned laminate may include a process of exposing the pattern obtained by the above-mentioned developing process (post-exposure process) and / or a process of heating (post-baking process).

[0965] When both post-exposure and post-baking processes are involved, post-baking is preferably performed after post-exposure.

[0966] [Applications of laminates]

[0967] The laminate manufactured by the method of the present invention can be applied to various devices. Examples of devices incorporating the above-described laminate include display devices, printed circuit boards, semiconductor packages, and input devices; a touch panel is preferred, and a capacitive touch panel is more preferred. Furthermore, the above-described input device can be applied to display devices such as organic light-emitting display devices and liquid crystal display devices.

[0968] When the laminate is applied to a touch panel, the pattern formed by the composition layer is preferably used as a protective film for electrodes or wiring of the touch panel. That is, the composition layer included in the transfer film is preferably used to form a protective film for electrodes or wiring of the touch panel.

[0969] As applications of patterns (cured films) formed by the composition layers, examples include various electrode protective films, planarization films, top coating films, hard coating films, passivation films, partitions, spacers, microlenses, optical filters, and anti-reflective films.

[0970] [Methods for manufacturing circuit wiring]

[0971] By using the above-mentioned transfer film, circuit wiring can also be manufactured.

[0972] There are no particular restrictions on the manufacturing method of circuit wiring as long as the above-mentioned transfer film is used.

[0973] The preferred method for manufacturing the circuit wiring of the present invention includes:

[0974] In the bonding process, a substrate with a composition layer is obtained by contacting the surface of the transfer film opposite to the temporary support with a substrate having a conductive layer, thereby obtaining a substrate having a substrate, a conductive layer, a composition layer and a temporary support in sequence.

[0975] The exposure process involves patterning the composite layer.

[0976] The developing process forms a resin pattern by developing the exposed composite layer; and

[0977] The etching process involves etching the conductive layer in areas where no resin pattern is configured.

[0978] The manufacturing methods for circuit wiring also include:

[0979] The peeling process involves peeling a temporary support from a substrate with a photosensitive composition layer between the bonding process and the exposure process, or between the exposure process and the development process.

[0980] The following describes the specific sequence of the circuit wiring manufacturing process.

[0981] The bonding, exposure, development, and stripping processes in the manufacturing method of the circuit wiring are the same as those in the manufacturing method of the laminate, and the preferred methods are also the same.

[0982] [Etching process]

[0983] The method for manufacturing circuit wiring includes an etching process (etching process) of etching the conductive layer located in the area where the resin pattern is not disposed on a laminate in which a substrate, a conductive layer (the conductive layer having the substrate) and a resin pattern (more preferably a resin pattern manufactured by a manufacturing method including the above-mentioned bonding process, the above-mentioned exposure process and the above-mentioned development process) are sequentially stacked.

[0984] In the above etching process, the resin pattern obtained from the photosensitive composition layer through the above developing process is used as a resist to perform etching treatment on the conductive layer.

[0985] As an etching process, known methods can be applied, such as the methods described in paragraphs

[0209] to

[0210] of Japanese Patent Application Publication No. 2017-120435, the methods described in paragraphs

[0048] to

[0054] of Japanese Patent Application Publication No. 2010-152155, and dry etching methods such as wet etching based on immersion in etching solution and plasma etching.

[0986] The etching solution used in wet etching can be selected appropriately, either acidic or alkaline, depending on the object being etched.

[0987] Examples of acidic etching solutions include, for instance, aqueous solutions of a single acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as aqueous solutions of the acidic component mixed with a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component can be a combination of multiple acidic components.

[0988] Examples of alkaline etching solutions include aqueous solutions of the alkaline component alone, selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), as well as aqueous solutions of the alkaline component mixed with salts (such as potassium permanganate). The alkaline component can be a combination of multiple alkaline components.

[0989] [Removal process]

[0990] In the manufacturing method of circuit wiring, it is preferable to perform a process to remove residual resin patterns (removal process).

[0991] There are no particular restrictions on the removal process; it can be carried out as needed, but it is preferred to be done after the etching process.

[0992] There are no particular limitations on the method for removing residual resin patterns. For example, methods such as removal by chemical treatment can be cited, but methods using a removal solution are preferred.

[0993] As a method for removing the photosensitive resin layer, an example is to immerse a substrate with residual resin patterns in a removal solution stirred at a liquid temperature of 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0994] Examples of removal solutions include those that dissolve an inorganic or organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic base components include sodium hydroxide and potassium hydroxide. Examples of organic base components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0995] Furthermore, it can be removed using a removal liquid and by known methods such as spraying, scrubbing, or immersion.

[0996] [Other processes]

[0997] The manufacturing method of circuit wiring may include any process other than those described above (other processes).

[0998] For example, the process of reducing visible light reflectivity described in paragraph

[0172] of International Publication No. 2019 / 022089, and the process of forming a new conductive layer on an insulating film described in paragraph

[0172] of International Publication No. 2019 / 022089, can be cited, but it is not limited to these processes.

[0999] <Process for reducing visible light reflectivity>

[1000] The manufacturing method of circuit wiring may include the following steps: performing a process to reduce the visible light reflectivity of some or all of the multiple conductive layers of the substrate.

[1001] Oxidation is an example of a process to reduce visible light reflectivity. When the substrate contains a copper-containing conductive layer, the copper is oxidized to produce copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectivity of the conductive layer.

[1002] The treatment for reducing visible light reflectance is described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, the contents of which are incorporated herein by reference.

[1003] <The process of forming an insulating film, and the process of forming a new conductive layer on the surface of the insulating film>

[1004] The manufacturing method of the circuit wiring also preferably 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.

[1005] Through the above process, a first electrode pattern and an insulating second electrode pattern can be formed.

[1006] There are no particular limitations on the process of forming the insulating film, and known methods for forming permanent films can be cited. Furthermore, an insulating film with a desired pattern can be formed by photolithography using a photosensitive material with insulating properties.

[1007] There are no particular limitations on the process of forming a new conductive layer on an insulating film. For example, a conductive photosensitive material can be used to form a new conductive layer with the desired pattern by photolithography.

[1008] The method for manufacturing circuit wiring preferably uses a substrate having multiple conductive layers on each of its two surfaces, and forms circuits sequentially or simultaneously on the conductive layers formed on the two surfaces of the substrate. With this structure, circuit wiring for touch panels can be formed such that a first conductive pattern is formed on one surface of the substrate, and a second conductive pattern is formed on the other surface. Furthermore, it is also preferable to form this type of circuit wiring for touch panels from both sides of the substrate by roll-to-roll.

[1009] [Applications of circuit wiring]

[1010] The circuit wiring manufactured using the circuit wiring manufacturing method can be applied to various devices. Examples of devices equipped with circuit wiring manufactured using the above-described method include display devices, printed circuit boards, semiconductor packages, and input devices; touch panels are preferred, and capacitive touch panels are more preferred. Furthermore, the aforementioned input devices can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[1011] Example

[1012] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing methods, and processing order shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be limited by the embodiments shown below.

[1013] In addition, unless otherwise specified, “parts” and “%” are quality standards.

[1014] Furthermore, in the following embodiments, the weight-average molecular weight of the resin was calculated using polystyrene based on gel permeation chromatography (GPC). Also, the theoretical acid value was used.

[1015] [Synthesis example]

[1016] <Synthesis of Polymers P-1 to P-5>

[1017] (Synthesis of polymer P-1)

[1018] Propylene glycol monomethyl ether (82.4 g, FUJIFILM Wako Pure Chemical Corporation) was added to a flask and heated to 90°C under a nitrogen atmosphere. Over 3 hours, a solution containing styrene (38.4 g, FUJIFILM Wako Pure Chemical Corporation), dicyclopentyl methacrylate (30.1 g, FANCRYL FA-513M, Hitachi Chemical Co., Ltd.), and methacrylic acid (34.0 g, FUJIFILM Wako Pure Chemical Corporation) dissolved in propylene glycol monomethyl ether (20 g), and a polymerization initiator V-601 (5.4 g, FUJIFILM Wako Pure Chemical Corporation) dissolved in propylene glycol monomethyl ether acetate (43.6 g, FUJIFILM Wako Pure Chemical Corporation) were added dropwise. After the addition was complete, V-601 (0.75 g) was added three times, every hour. The solution was then allowed to react for another 3 hours. The obtained solution was then diluted with propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). Under an air stream, the solution was heated 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. Glycidyl methacrylate (25.5 g, NOF CORPORATION, BLEMMER GH) was added dropwise to the obtained solution over 20 minutes. The solution was then reacted at 100°C for 7 hours to obtain a solution of polymer P-1. The solids content of the obtained solution was 36.3% by mass. The weight-average molecular weight converted from standard polystyrene in GPC was 17,000, the dispersity (Mw / Mn) was 2.4, and the polymer's acid value was 94.5 mg KOH / g. Of all monomers, the amount of residual monomers determined by gas chromatography was less than 0.1% of the polymer solids content.

[1019] (Synthesis of polymers P-2 to P-3)

[1020] The types and contents of each structural unit in the polymer were changed as shown in Table 1. Otherwise, polymers P-2 to P-3 were synthesized using the same method as polymer P-1. Furthermore, polymer P-2 was also obtained as a solution with a solid content concentration of 36.3% by mass. Similarly, polymer P-3 was also obtained as a solution with a solid content concentration of 36.3% by mass.

[1021] (Synthesis of polymer P-4)

[1022] A first solution was prepared by mixing propylene glycol monomethyl ether (55.8 g, FUJIFILM Wako Pure Chemical Corporation) and toluene (55.8 g, FUJIFILM Wako Pure Chemical Corporation). A second solution was prepared by mixing 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) and stirring at room temperature for 1 hour to dissolve the solid 2,2'-azobis(isobutyronitrile).

[1023] The first solution was added to a flask, and the mixture was heated to 80°C under nitrogen atmosphere. While maintaining the temperature with stirring, the second solution was added to the first solution in the flask using a drop pump over 4 hours. After the addition was complete, the temperature of the mixture was maintained at 80°C with stirring to allow the reaction to continue for another 6 hours, thereby obtaining a solution of polymer P-4. The solids concentration of the obtained solution was 36.3% by mass. The weight-average molecular weight of the standard polystyrene in GPC was 65,000, and the acid value of the polymer was 78 mg KOH / g.

[1024] (Synthesis of polymer P-5)

[1025] Except for changing the type and amount of monomers, a solution of polymer P-5 was obtained by synthesizing using the same method as polymer P-4. The solids concentration of the obtained solution was 36.3% by mass. The weight-average molecular weight of the standard polystyrene in GPC was 65,000.

[1026] The following are polymers P-1 to P-5 shown in Table 1.

[1027] In Table 1, structural units other than those with (meth)acryloyl groups are represented by abbreviations of the monomers used to form each structural unit.

[1028] Structural units having a (meth)acryloyl group are represented as monomer-monomer addition structures. For example, MAA-GMA refers to a structural unit formed by the addition of glycidyl methacrylate to a structural unit derived from methacrylic acid.

[1029] Polymers P-1 to P-5 are equivalent to alkali-soluble resins.

[1030] [Table 1]

[1031] (Table 1)

[1032]

[1033] The abbreviations in Table 1 are as follows.

[1034] St: Styrene (FUJIFILM Wako Pure Chemical Corporation)

[1035] BzMA: Benzyl Methacrylate (FUJIFILM Wako Pure Chemical Corporation)

[1036] CHMA: Cyclohexyl methacrylate (FUJIFILM Wako Pure Chemical Corporation)

[1037] MAA-GMA: A structural unit formed by adding glycidyl methacrylate to a structural unit derived from methacrylic acid.

[1038] MAA: Methacrylic Acid (FUJIFILM Wako Pure Chemical Corporation)

[1039] DCPMA: Dicyclopentyl methacrylate (FANCRYL FA-513M, Hitachi Chemical Co., Ltd.)

[1040] MMA: Methyl methacrylate (FUJIFILM Wako Pure Chemical Corporation)

[1041] EA: Ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1042] <Synthesis of Polymer P'-1>

[1043] Propylene glycol monomethyl ether (270.0 g) was introduced into a three-necked flask and heated to 70°C under a nitrogen atmosphere while stirring. Meanwhile, a dropping solution was prepared by dissolving allyl methacrylate (45.6 g, FUJIFILM Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) in propylene glycol monomethyl ether (270.0 g), and further dissolving V-65 (3.94 g, FUJIFILM Wako Pure Chemical Corporation). This solution was added dropwise to the flask over 2.5 hours. The resulting solution was stirred and allowed to react for 2 hours. Afterward, the solution was allowed to return to room temperature and added dropwise to 2.7 L of deionized water while stirring, resulting in redeposition and a suspension. The suspension was filtered through a suction filter lined with filter paper, and the filtrate was further washed with deionized water to obtain a wetted powder. Next, the product was dried by air at 45°C to ensure constant yield, and polymer P'-1 (structural formula below) was obtained as a powder with a yield of 70%.

[1044] Furthermore, in the structural formula of polymer P'-1 below, the ratio of each structural unit contained in the polymer is by mass.

[1045] [Chemical Formula 26]

[1046]

[1047] Synthesis of the capped isocyanate compound Q-1

[1048] Butanone oxime (453 g, manufactured by Idemitsu Kosan Co., Ltd.) was dissolved in methyl ethyl ketone (700 g) under a nitrogen atmosphere. 1,3-bis(methyl isocyanate)cyclohexane (500 g, a mixture of cis and trans isomers, manufactured by Mitsui Chemicals, Inc., Takenate 600) was added dropwise over 1 hour while the solution was cooled, and the reaction was allowed to continue for another hour. The resulting solution was then heated to 40°C and allowed to react for another hour. 1 H-NMR and HPLC confirmed the completion of the reaction, yielding a methyl ethyl ketone solution of the capped isocyanate compound Q-1 (structural formula below). The solids concentration of the obtained solution was 57.7% by mass.

[1049] [Chemical Formula 27]

[1050]

[1051] [Preparation of photosensitive composition]

[1052] Photosensitive compositions A-1 to A-18 and A'-1 to A'-3 with the components and proportions shown in Table 2 below were prepared.

[1053] In addition, the values ​​recorded in the component column of Table 2 represent the content (parts by mass) of each component. Among them, the amounts of polymers P-1 to P-5 in the alkali solubility column represent the amount of polymer solution.

[1054] Furthermore, “SMA EF-40” in Table 2 is a copolymer of styrene and anhydrous maleic anhydride in a ratio of 4:1 (molar ratio) (anhydride value 1.94 mmol / g, Mw10500, manufactured by Cray Valley).

[1055] [Table 2]

[1056]

[1057] [Table 3]

[1058]

[1059] <Preparation of Composition for Forming Refractive Index Adjustment Layer>

[1060] Next, composition B-1 for forming a refractive index adjustment layer was prepared with the components and proportions described in Table 3 below.

[1061] In addition, polymer P'-1 in Table 3 uses the polymer synthesized in the synthesis example in the upper section.

[1062] In Table 3, the values ​​recorded in each component column represent the content (parts by mass) of each component.

[1063] [Table 4]

[1064] (Table 3)

[1065]

[1066] [Preparation of transfer films for Examples 1-25 and Comparative Examples 1-4]

[1067] <Preparation of transfer films in Examples 1-12, 18-25, and Comparative Examples 1-3>

[1068] Using a slit nozzle, any one of the prepared photosensitive compositions A-1 to A-18 and A'-1 to A'-3 is coated onto a temporary support of a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (Lumirror 16QS62), manufactured by TORAY INDUSTRIES, INC.) until the film thickness of the dried photosensitive composition layer reaches the specified film thickness (film thicknesses listed in Table 4). The film is then dried in a drying zone at 120°C for 3 minutes, thereby forming the photosensitive composition layer.

[1069] Subsequently, a 25 μm thick polypropylene film (TORAYFAN25A-KW37, manufactured by TORAY INDUSTRIES, INC.) was laminated onto the photosensitive composition layer to produce transfer films of Examples 1-12, 18-25, and Comparative Examples 1-3.

[1070] <Preparation of transfer films in Examples 13-17>

[1071] Using a slit nozzle, any one of the prepared photosensitive compositions A-8 to A-12 is coated onto a temporary support of a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (Lumirror 16QS62), manufactured by TORAY INDUSTRIES, INC.) until the film thickness of the dried photosensitive composition layer reaches the specified film thickness (the film thickness listed in Table 4). The film is then dried in a drying zone at 120°C for 3 minutes, thereby forming the photosensitive composition layer.

[1072] Furthermore, using a slit nozzle, the refractive index adjustment layer forming composition B-1 described in Table 3 was adjusted to a coating thickness of 73 nm after drying and applied to the photosensitive composition layer. The coating was then dried at a drying temperature of 80°C to form the refractive index adjustment layer.

[1073] Subsequently, a 25 μm thick polypropylene film (TORAYFAN 25A-KW37, manufactured by TORAY INDUSTRIES, INC.) was laminated onto the refractive index adjustment layer as a protective film to produce the transfer films of Examples 13-17.

[1074] <Preparation of the transfer film in Comparative Example 4>

[1075] The drying conditions after coating the photosensitive composition on the temporary support (drying in a drying zone at 120°C for 3 minutes) were changed to drying in a drying zone at 100°C for 3 minutes. Otherwise, the transfer film of Comparative Example 4 was prepared in the same manner as in Example 19.

[1076] [Determination and Evaluation of Transfer Film]

[1077] <Measurement of tanδ>

[1078] Regarding 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 treatments were performed.

[1079] The transfer films of Examples 1 to 12, 18 to 25 and Comparative Examples 1 to 4 produced were cut into a size of 240 mm × 240 mm and the protective films were peeled off. Then, the obtained films were folded so that the surfaces of the photosensitive composition layers exposed by peeling off the protective films faced each other, and the surfaces of the photosensitive composition layers were adhered to each other, whereby a laminate 1 of a temporary support / photosensitive composition layer (laminated 2 layers) / temporary support was produced.

[1080] Moreover, one side temporary support in the laminate 1 was peeled off. Then, the laminate 1 with the temporary support peeled off was folded so that the photosensitive composition layers (laminated 2 layers) exposed by peeling off the temporary support faced each other, and the photosensitive composition layers (laminated 2 layers) were adhered to each other, whereby a laminate 2 of a temporary support / photosensitive composition layer (laminated 4 layers) / temporary support was produced.

[1081] Moreover, one side temporary support in the laminate 2 was peeled off. Then, the laminate 2 with the temporary support peeled off was folded so that the photosensitive composition layers (laminated 4 layers) exposed by peeling off the temporary support faced each other, and the photosensitive composition layers (laminated 4 layers) were adhered to each other, whereby a laminate 3 of a temporary support / photosensitive composition layer (laminated 8 layers) / temporary support was produced. The adhesion of the photosensitive composition layers was repeated in the same order, whereby a laminate N of a temporary support / photosensitive composition layer with a thickness of 0.5 mm / temporary support was produced.

[1082] And regarding the transfer films of Examples 13 to 17 having a refractive index adjustment layer, the following treatments were performed.

[1083] The transfer films of Examples 13 to 17 produced were cut into a size of 240 mm × 240 mm and the protective films were peeled off. Then, the obtained films were folded so that the surfaces of the refractive index adjustment layers exposed by peeling off the protective films faced each other, and the surfaces of the photosensitive composition layers were adhered to each other, whereby a laminate 1 of a temporary support / photosensitive composition layer / refractive index adjustment layer / refractive index adjustment layer / photosensitive composition layer / temporary support was produced.

[1084] Furthermore, one side of the temporary support in the aforementioned laminate 1 was peeled off. Next, the laminate 1 with the temporary support peeled off was folded and bonded together such that the photosensitive composition layers exposed by peeling off the temporary support were facing each other, thereby creating a laminate 2 consisting of a 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.

[1085] The photosensitive composition layer and the refractive index adjustment layer were bonded together in the same order to create a laminate N consisting of a temporary support / photosensitive composition layer + refractive index adjustment layer / temporary support with a total thickness of 0.5 mm.

[1086] Subsequently, the temporary supports on both sides of the laminate N were peeled off and cut into circles with a diameter of 20 mm, which served as the samples for tanδ determination. The prepared samples were conditioned at 23°C and 50% RH for 24 hours before being used for testing.

[1087] The tanδ of the samples prepared in the above order was measured using a DHR-2 rheometer (manufactured by TA Instruments Japan Inc.) for dynamic viscoelasticity measurement. Measurements were performed using a parallel plate with a diameter of 20 mm and a Peltier plate (Gap: 0.5 mm) in a fixed Gap (0.5 mm) mode. Specifically, dynamic viscoelasticity measurements were performed under the following conditions, and the tanδ at 25°C was determined. T25 ), tanδ at 80℃ T80 ) and tanδ(tanδ) at 120℃ T120 The values ​​of ) were obtained. Furthermore, based on these values, tanδ was calculated. T120 / tanδ T80 The values ​​are recorded in Table 4.

[1088] (Measurement conditions)

[1089] Sample dimensions: 20mm diameter, 0.5mm thickness

[1090] Measurement temperature conditions: 25~150℃

[1091] Heating rate: 5℃ / minute

[1092] Frequency: 1Hz

[1093] Strain: 1 deg (0.0174 rad)

[1094] <Evaluation of Contamination (Adhesion) of Photosensitive Composite Layer on Guide Roller>

[1095] (Transfer films of Examples 1-12, 18-25, and Comparative Examples 1-4)

[1096] The transfer films of Examples 1-12, 18-25 and Comparative Examples 1-4 prepared above were applied to a 3.5-inch cylindrical branch tube. A pressure roller with a surface material made of rubber was arranged parallel to the width direction of the roll to apply a linear pressure of 200 kg / m to the branch tube and to wind 200 m with a tension of 15 kg / m, thereby obtaining a photosensitive film roll with a width of 500 mm.

[1097] Next, the protective film of the photosensitive film roll is peeled off and simultaneously conveyed at a conveying speed of 20 m / min. The photosensitive film, consisting of a temporary support and a photosensitive composition layer, is then conveyed. Specifically, with the surface of the photosensitive composition layer in contact with the guide roller (100 mm in diameter, made of stainless steel) and the wrap angle between the guide roller and the photosensitive film is 90°, the tension of the photosensitive film is set to 60 N / m, and a total length of 100 m of photosensitive film is conveyed with the surface of the photosensitive composition layer in contact with the guide roller.

[1098] After transporting 100m of photosensitive film, the contamination of the guide roller was visually observed. Based on the observation results, the contamination (adhesion) on the guide roller was evaluated according to the following evaluation criteria.

[1099] In the following evaluation criteria, any rating of "C" or above is suitable for practical application, with "A" being the preferred rating. The evaluation results are shown in Table 4.

[1100] -Evaluation criteria for contamination (adhesion) on guide rollers-

[1101] A: No photosensitive composition layer was observed adhering to the guide roller.

[1102] B: The area on the guide roller with the photosensitive composition layer attached is less than 5% of the observation area.

[1103] C: The area on the guide roller with the photosensitive composition layer attached is more than 5% and less than 10% of the observation area.

[1104] D: The area on the guide roller with the photosensitive composition layer attached is more than 10% and less than 20% of the observation area.

[1105] E: The area on the guide roller with the photosensitive composition layer attached is more than 20% of the observation area.

[1106] (Transfer films of Examples 13-17)

[1107] The transfer films of Examples 13-17 prepared above were applied to a 3.5-inch cylindrical branch tube. A pressure roller with a rubber surface material was arranged parallel to the width direction of the roll. A pressure of 200 kg / m was applied linearly to the branch tube, and 200 m was wound up with a tension of 15 kg / m, thereby obtaining a photosensitive film roll with a width of 500 mm.

[1108] Next, the protective film of the photosensitive film roll is peeled off and simultaneously conveyed at a conveying speed of 20 m / min. The photosensitive film, consisting of a temporary support, a photosensitive composition layer, and a refractive index adjustment layer, is then conveyed. Specifically, with the surface of the refractive index adjustment layer in contact with the guide roller (100 mm in diameter, made of stainless steel) and the wrap angle between the guide roller and the photosensitive film is 90°, the tension of the photosensitive film is set to 60 N / m, and a total length of 100 m of photosensitive film is conveyed with the surface of the refractive index adjustment layer in contact with the guide roller.

[1109] After transporting 100m of photosensitive film, the contamination of the guide roller was visually observed. Based on the observation results, the contamination (adhesion) on the guide roller was evaluated according to the above evaluation criteria.

[1110] In the above evaluation criteria, any rating of "C" or above is suitable for practical application, with "A" being the preferred rating. The evaluation results are shown in Table 4.

[1111] <Laminability Assessment>

[1112] (Preparation of laminates for lamination evaluation)

[1113] Next, as a laminate for evaluating lamination properties, a [material / structure] was fabricated. Figures 3-5 The substrate 43 shown has a stepped difference. Hereinafter, reference is made to... Figures 3-5 The structure of the substrate 43 with stepped differences will be described.

[1114] like Figure 3 As shown, the substrate 43 with a stepped difference has a membrane substrate 1A and a stepped difference 41 with a thickness of 100 nm disposed on the membrane substrate 1A.

[1115] Regarding the step difference 41, when viewing the side of the film substrate 1A with the step difference 41 from above, if the lamination direction 42 is taken as the longitudinal direction, its shape is a rectangle with a longitudinal length of 2cm and a transverse length of 5cm, and its material is copper.

[1116] Furthermore, in Figure 4 The diagram shows a view of the side surfaces (both sides) of a substrate 43 with a stepped difference, viewed from a direction parallel to the lamination direction 42. Figure 5 The diagram shows a schematic view of the side surfaces (both sides) of the substrate 43 with a stepped difference when viewed from a direction orthogonal to the lamination direction 42. Figure 4 and Figure 5 As shown, when the substrate 43 with the stepped difference is viewed from the side, the length La of the upper portion 41a on the side opposite to the bottom 41c of the stepped difference 41 is shorter than the length Lc of the bottom 41c that contacts the film substrate 1A, forming a so-called conical shape. The angle θ between the side portion 41b of the stepped difference 41 and the film substrate 1A is approximately 78°. Furthermore, the gap length between the length La of the upper portion 41a and the length Lc of the bottom 41c in each side portion 41b of the stepped difference 41 is 20 nm.

[1117] (Evaluation of the number of air bubbles in a laminate (laminarity))

[1118] From Figure 3 The lamination direction 42 shown covers the entire step difference 41. Transfer films of Examples 1-12, 18-21, and Comparative Examples 1-4, with their protective films removed, are laminated onto a substrate 43 having a step difference, such that the photosensitive composition layer faces the substrate 43 having a step difference. Similarly, transfer films of Examples 13-17, with their protective films removed, are laminated onto the substrate 43 having a step difference, such that the refractive index adjustment layer faces the substrate 43 having a step difference.

[1119] The lamination conditions were evaluated under the following two conditions.

[1120] [1] Rubber roller temperature 80℃, linear pressure 100N / cm, conveying speed 2.0m / min

[1121] [2] Rubber roller temperature 120℃, linear pressure 100N / cm, conveying speed 2.0m / min

[1122] Furthermore, this lamination method includes a step-gradient rising process, in which the transfer film is sequentially laminated from the bottom 41c to the top 41a in the step difference 41, and a step-gradient descending process, in which the transfer film is sequentially laminated from the top 41a to the bottom 41c in the step difference 41. That is, in the process from... Figure 3 In the sequence of lamination direction 42 covering step difference 41, the step difference ascending process refers to the lamination process in region X1, and the step difference descending process refers to the lamination process in region X2.

[1123] Next, without removing the temporary support, the number of "infiltrating bubbles" in the area along the step difference was observed using an optical microscope and evaluated according to the following criteria.

[1124] The area along the step difference refers to the area in Figure 3 Within regions X1 and X2, the lower end of the side portion 41b extending from the upper part 41a to the bottom part 41c of the step difference 41, and in Figure 3The lower end of the side portion 41b of the step difference 41, which extends from the upper part 41a of the step difference 41 to the bottom part 41c.

[1125] The evaluation was conducted under two conditions: lamination temperature (rubber roller temperature) of 80℃ and 120℃.

[1126] In the following evaluation criteria, any rating of "C" or above is suitable for practical application, with "A" being the preferred rating. The evaluation results are shown in Table 4.

[1127] -Evaluation Criteria for Lamination-

[1128] A: There are fewer than 5 bubbles in the area along the step difference.

[1129] B: The number of bubbles in the area along the step difference is more than 5 but less than 30.

[1130] C: The number of bubbles in the area along the step difference is more than 30 but less than 100.

[1131] D: The number of bubbles in the area along the step difference is more than 100.

[1132] [Table 5]

[1133]

[1134] According to the results in Table 4, when the transfer film according to the embodiment is transported, the photosensitive composition layer is less likely to adhere to the guide roller at the contact surface between the composition layer and the guide roller, and it has excellent step difference following performance over a wide range of lamination temperatures when heat-lamination onto substrates with step differences, such as wiring boards.

[1135] Furthermore, according to the results in Table 4, it can be seen that at 25℃, tanδ(tanδ) T25 When the tanδ is 1.2 or less (in other words, when the composition layer of the transfer film satisfies the requirements of formula (1A'), the adhesion of the photosensitive composition layer to the guide roller is further suppressed. In particular, at 25°C, tanδ (tanδ... T25 When the value is 1.0 or less (in other words, when the composition layer of the transfer film satisfies the requirements of formula (1A”), the adhesion of the photosensitive composition layer to the guide roller is further suppressed.

[1136] Furthermore, according to the results in Table 4, it can be seen that at 120℃, tanδ(tanδ) T120 When the value is 1.0 or higher (in other words, when the composition layer of the transfer film satisfies the requirements of formula (2A'), the lamination performance is better.

[1137] Furthermore, according to the results in Table 4, the value obtained by dividing tanδ at 120℃ by tanδ at 80℃ (tanδ) T120 / tanδ T80 When the lamination strength is between 1.0 and 8.0 (in other words, when the composition layer of the transfer film satisfies the requirements of formula (3A'), the lamination performance is even better.

[1138] It can be seen that the desired effect could not be obtained in the transfer film of the comparative example.

[1139] [Example 101 (Fabrication of substrate for touch panel)]

[1140] Surface modification was performed on a cyclic olefin resin film with a thickness of 38 μm and a refractive index of 1.53 by subjecting it to a 3-second corona discharge treatment using a high-frequency oscillator with an output voltage of 100%, a power of 250 W, a 1.2 mm diameter linear electrode, an electrode length of 240 mm, and a working electrode spacing of 1.5 mm. The resulting film was used as a transparent film substrate.

[1141] Next, using a slit nozzle, the material C shown in Table 5 below (the values ​​of each component in the table are contents (parts by mass)) is coated onto the transparent film substrate, followed by ultraviolet irradiation (cumulative light intensity 300 mJ / cm²). 2 The film is dried at approximately 110°C to form a refractive index adjustment layer with a refractive index of 1.60 and a film thickness of 80 nm.

[1142] [Table 6]

[1143] (Table 5)

[1144]

[1145] [Chemical Formula 28]

[1146]

[1147] An ITO (Indium Tin Oxide) film with a thickness of 40 nm and a refractive index of 1.82 was formed on the refractive index adjustment layer of a transparent film substrate with a refractive index adjustment layer by DC multi-cavity magnetron sputtering. The formed ITO film was then patterned using photolithography, thereby forming an ITO transparent electrode pattern on the refractive index adjustment layer. The formation and patterning of the ITO film (i.e., the formation of the ITO transparent electrode pattern) were performed using the method described in paragraphs

[0119] to

[0122] of Japanese Patent Application Publication No. 2014-10814.

[1148] The above describes a substrate for a touch panel with a stacked structure of ITO transparent electrode pattern / refractive index adjustment layer / transparent film substrate.

[1149] (Transfer (lamination) of a photosensitive composition layer using a transfer film)

[1150] The protective film is peeled off from the transfer film of Example 1 above, and the transfer film with the protective film peeled off is laminated onto the substrate for the touch panel, thereby transferring the photosensitive composition layer of the transfer film to the side of the touch panel substrate on which the ITO transparent electrode pattern is formed. The lamination conditions are set as follows: temperature of the touch panel substrate 40°C, rubber roller temperature (i.e., lamination temperature) 110°C, linear pressure 3 N / cm, and conveyor speed 2 m / min.

[1151] Thus, a laminate with a stacked structure of temporary support / photosensitive composition layer / ITO transparent electrode pattern / refractive index adjustment layer / transparent film substrate was obtained.

[1152] (Creating a transparent layered structure)

[1153] The photosensitive composition layer of the above-mentioned laminate was patterned and exposed through a temporary support. A proximity exposure machine (manufactured by Hitachi High-Tech Corporation) equipped with an ultra-high pressure mercury lamp and an exposure mask were used, with an exposure dose of 100 mJ / cm² through the temporary support. 2 Pattern exposure was performed using i-rays. After pattern exposure, a temporary support was peeled off from the laminate, and the photosensitive composition layer of the laminate with the temporary support peeled off was developed for 45 seconds using a 1% by mass aqueous solution of sodium carbonate (liquid temperature 33°C). After development, moisture was removed by blowing air, and further exposure was performed at 375 mJ / cm². 2 After exposure with (i-rays), a heating (post-baking) process is performed at 145°C for 30 minutes, thereby obtaining a cured film for a touch panel protective film having an opening (i.e., the non-exposed portion) that exposes a portion of the ITO transparent electrode pattern.

[1154] The above describes a transparent laminate with a stacked structure of a protective film for touch panels, a cured film, an ITO transparent electrode pattern, a refractive index adjustment layer, and a transparent film substrate.

[1155] (The fabrication of an image display device (touch panel))

[1156] By bonding a pre-manufactured film comprising a transparent laminate of each embodiment to a liquid crystal display element manufactured by the method described in Japanese Patent Application Publication No. 2009-047936

[0097] to

[0119] , and further bonding it to a front glass plate, an image display device comprising a touch panel protective film and having an electrostatic capacitive input device as a component is manufactured by a known method. Upon confirming the operation of the manufactured image display device, the touch panel is found to function normally.

[1157] [Examples 102-124]

[1158] The transfer film was changed from the transfer film of Example 1 to the transfer film of Examples 2 to 24. Otherwise, the image display device (touch panel) (Examples 102 to 121) was manufactured in the same way as in Example 101. The touch panels all functioned normally.

[1159] Symbol Explanation

[1160] 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 step difference; 41a - Upper part of step difference 41; 41b - Side part of step difference 41; 41c - Bottom of step difference 4...

Claims

1. A transfer film, comprising: Temporary support structure; and The composition layer disposed on the temporary support, The composition layer comprises a photosensitive composition layer. When the photosensitive composition layer has additional layers on the side opposite to the temporary support side, the total thickness of the additional layers is 0.1% to 20% of the thickness of the photosensitive composition layer. The other layers are refractive index adjustment layers. The photosensitive composition layer contains an adhesive polymer, which contains (meth)acrylic resin. The (meth)acrylic resin is a resin having structural units derived from (meth)acrylic acid compounds, and the content of structural units derived from (meth)acrylic acid compounds is 50% by mass or more relative to all structural units of the (meth)acrylic resin. The content of structural units derived from (meth)acrylic acid in the adhesive polymer is 10 mol% to 50 mol% relative to all structural units of the adhesive polymer. When the dynamic viscoelasticity of the composition layer at 25°C to 150°C is measured at a frequency of 1 Hz and a heating rate of 5°C / min, all the requirements of the following formulas (1A) to (3A) are met. Equation (1A) tanδ T25 ≤1.5 Formula (2A) tanδ T120 ≥0.80 Equation (3A): 0.50 ≤ tanδ T120 / tanδ T80 ≤ 10 in, In equations (1A) to (3A) above, tanδ T25 tanδ represents the value of tanδ at 25℃. T120 tanδ represents the value at 120℃. T80 This represents tanδ at 80℃.

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

2.

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

0.

4. The transfer film according to claim 1 or 2, 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 claim 1 or 2, which satisfies the requirement of the following formula (2A'), Formula (2A’) tanδ T120 ≥1.0 6. The transfer film according to any one of claims 1-5, wherein, The weight-average molecular weight of the adhesive polymer is 10,000-80,000.

7. The transfer film according to any one of claims 1-6, wherein, The content of the adhesive polymer is 20% to 80% by mass relative to the total mass of the photosensitive composition layer.

8. The transfer film according to any one of claims 1-7, wherein, The content of polymeric compounds in the photosensitive composition layer is between 5% and 60% by mass relative to the total mass of the photosensitive composition layer.

9. The transfer film according to claim 1 or 2, wherein, The thickness of the photosensitive composition layer is less than 20 μm.

10. The transfer film according to claim 1 or 2, wherein, The photosensitive composition layer comprises a photopolymerizable compound and a photopolymerization initiator.

11. The transfer film according to claim 1 or 2, used to form a protective film for a touch panel.

12. A method for manufacturing a laminate, comprising: In the bonding process, the surface opposite to the temporary support of the transfer film as described in any one of claims 1 to 11 is brought into contact with a substrate having a conductive layer and bonded together to obtain a substrate having the substrate, the conductive layer, the composition layer and the temporary support in sequence. The exposure process involves patterning the composite layer. and The developing process involves developing the exposed composition layer to form a protective film pattern that protects the conductive layer. The method for manufacturing the laminated body further includes: In the peeling process, between the bonding process and the exposure process or between the exposure process and the developing process, the temporary support is peeled off from the substrate with the composite layer.

13. The method for manufacturing a laminate according to claim 12, wherein, The substrate having a conductive layer is a substrate having at least one of electrodes for a touch panel and wiring for a touch panel.

14. A method for manufacturing circuit wiring, comprising: In the bonding process, the surface opposite to the temporary support of the transfer film according to any one of claims 1 to 11 is brought into contact with a substrate having a conductive layer, thereby obtaining a substrate having the substrate, the conductive layer, the composition layer and the temporary support in sequence; The exposure process involves patterning the composite layer. The developing process involves developing the exposed composition layer to form a resin pattern; and The etching process involves etching the conductive layer in areas where the resin pattern is not present. The method for manufacturing the circuit wiring also includes: The peeling process involves peeling a temporary support from the substrate with the composite layer between the bonding process and the exposure process, or between the exposure process and the development process.

Images