Laminate and method for manufacturing laminate

Abstract

The present invention provides a multilayer body which comprises a base material and a resin pattern, wherein if the intensity of at least one component that is selected from the group consisting of sodium ions and potassium ions detected in the surface of the resin pattern is taken as 100% on the basis of the depth direction analysis of the resin pattern as performed along the direction from the resin pattern toward the base material, the abundance depth of at least one component that is selected from the group consisting of sodium ions and potassium ions in the resin pattern is from 0.3 μm to 3.0 μm, the abundance depth being defined by the distance from the surface of the resin pattern to the point at which the intensity of at least one component that is selected from the group consisting of sodium ions and potassium ions reaches 90% for the first time. The present invention also provides a method for producing this multilayer body.

Description

[Technical Field]

[0001] The present disclosure relates to laminates and methods for making laminates. [Background technology]

[0002] Resin patterns formed using the photosensitive composition are used, for example, as protective films for electrodes such as electrodes for touch panels and as protective films against chemical reactions such as etching. In the former application, a cured product of the photosensitive composition is preferably used.

[0003] For example, Patent Document 1 discloses a method for forming a cured resin film pattern. Specifically, Patent Document 1 discloses a method for forming a cured resin film pattern, comprising: a first step of providing a photosensitive layer having a thickness of 10 μm or less on a substrate, the photosensitive layer comprising a photosensitive resin composition containing a binder polymer having a carboxyl group with an acid value of 75 mgKOH / g or more, a photopolymerizable compound, and a photopolymerization initiator; a second step of curing a predetermined portion of the photosensitive layer by irradiation with actinic rays; and a third step of removing the photosensitive layer except for the predetermined portion to form a cured film pattern in the predetermined portion of the photosensitive layer, wherein the photosensitive resin composition contains an oxime ester compound and / or a phosphine oxide compound as a photopolymerization initiator.

[0004] Patent Document 1: International Publication No. 2013 / 084886 Summary of the Invention [Problem to be solved by the invention]

[0005] For example, a resin pattern used as a protective film is preferably resistant to damage such as scratches. However, according to conventional techniques, it has been difficult to achieve both a resin pattern's resistance to physical actions that cause damage such as scratches and the edge quality of the resin pattern. The edge quality is determined by factors such as the shape, dimensions, and surface properties of the edge of the resin pattern. In particular, the edge quality requires suppression of the phenomenon in which the edge of the resin pattern lifts off the substrate (meaning that the edge of the resin pattern separates from the substrate; hereinafter, this phenomenon may be referred to as "edge lift").

[0006] An object of one embodiment of the present disclosure is to provide a laminate including a resin pattern having excellent scratch resistance and in which edge lifting is prevented or reduced.Another embodiment of the present disclosure is to provide a method for manufacturing a laminate including a resin pattern having excellent scratch resistance and in which edge lifting is prevented or reduced. [Means for solving the problem]

[0007] The present disclosure includes the following aspects. <1> A laminate comprising a substrate and a resin pattern, wherein, based on a depth direction analysis of the resin pattern performed along a direction from the resin pattern toward the substrate, when the intensity of at least one component selected from the group consisting of sodium ions and potassium ions detected on the surface of the resin pattern is defined as 100%, the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is defined as the distance from the surface of the resin pattern to a point where the intensity of the at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90%, and is 0.3 μm to 3.0 μm. <2> the ratio of the depth of the resin pattern to the thickness of the resin pattern is 0.1 to 0.9; <1> The laminate according to claim 1. <3> The resin pattern is a cured product of a photosensitive composition. <1> or <2> The laminate according to claim 1. <4> The photosensitive composition contains a polymerizable compound and a polymerization initiator. <3> The laminate according to claim 1. <5> The photosensitive composition comprises a polymer. <3> or <4> The laminate according to claim 1. <6> The polymer has a polymerizable group. <5> The laminate according to claim 1. <7> A transparent electrode is included between the substrate and the resin pattern. <1> ~ <6> 10. The laminate according to claim 9, wherein the first and second laminates are oriented in a direction perpendicular to the plane of the <8> It is a touch panel, <1> ~ <7> 10. The laminate according to claim 9, wherein the first and second laminates are oriented in a direction perpendicular to the plane of the <9> a depth profile analysis of the resin pattern, which is performed along a direction from the resin pattern after the substrate and the resin pattern have been left standing, to a depth of 0.3 μm to 3.0 μm, where the depth is defined as the distance from the surface of the resin pattern to a point where the intensity of the at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90%, where the depth is defined as the distance from the surface of the resin pattern to a point where the intensity of the at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90%. [Effects of the Invention]

[0008] According to one embodiment of the present disclosure, there is provided a laminate including a resin pattern having excellent scratch resistance and in which edge lifting is prevented or reduced. According to another embodiment of the present disclosure, there is provided a method for manufacturing a laminate including a resin pattern having excellent scratch resistance and in which edge lifting is prevented or reduced. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic cross-sectional view showing the structure of a laminate according to one embodiment. [Figure 2] FIG. 2 is a schematic cross-sectional view showing the structure of a laminate according to another embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments. The following embodiments may be modified as appropriate within the scope of the present disclosure.

[0011] In the present disclosure, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0012] In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.

[0013] In the present disclosure, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0014] In the present disclosure, "transparent" means that the average transmittance of visible light in the wavelength range of 400 nm to 700 nm is 80% or more. The average transmittance is measured using a spectrophotometer (for example, spectrophotometer U-3310 manufactured by Hitachi, Ltd.).

[0015] In the present disclosure, "(meth)acrylic" means acrylic, methacrylic, or both acrylic and methacrylic.

[0016] In this disclosure, "(meth)acrylate" means acrylate, methacrylate, or both acrylate and methacrylate.

[0017] In the present disclosure, "(meth)acryloyl" means acryloyl, methacryloyl, or both acryloyl and methacryloyl.

[0018] In the present disclosure, the notation of a group (atomic group) without the notation "substituted" or "unsubstituted" encompasses both a group having no substituent and a group having a substituent. For example, an "alkyl group" encompasses not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (a substituted alkyl group).

[0019] In this disclosure, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, light used for exposure generally includes the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays (active energy rays).

[0020] Chemical structural formulae in the present disclosure may be described as simplified structural formulae in which hydrogen atoms are omitted.

[0021] In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

[0022] In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0023] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this disclosure are molecular weights determined by gel permeation chromatography (GPC) using columns of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation), detection with a differential refractometer using THF (tetrahydrofuran) as a solvent, and conversion using polystyrene as a standard substance.

[0024] In the present disclosure, unless otherwise specified, the numerical values ​​attached to each structural unit of the polymer represent mole %.

[0025] In this disclosure, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

[0026] In this disclosure, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0027] In the present disclosure, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more.

[0028] In this disclosure, "solids" means all components except solvent.

[0029] <Laminate> A laminate according to one embodiment of the present disclosure includes a substrate and a resin pattern. Furthermore, based on a depth profile analysis of the resin pattern performed along a direction from the resin pattern toward the substrate, the intensity of at least one component selected from the group consisting of sodium ions and potassium ions detected at the surface of the resin pattern is defined as 100%, and the depth of the presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is defined as the distance from the surface of the resin pattern to the point where the intensity of at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90%. Hereinafter, the "at least one component selected from the group consisting of sodium ions and potassium ions" may be referred to as the "specific component." The depth of the presence of the specific component in the resin pattern is measured by depth profile analysis using time-of-flight secondary ion mass spectrometry (TOF-SIMS), as described below, and is expressed as the distance from the "surface of the resin pattern" to the "point where the intensity of at least one component selected from the group consisting of sodium ions and potassium ions reaches a reference value." Studies on improving the scratch resistance of resin patterns and reducing edge lifting have yielded results suggesting that the degree of penetration of developer components into resin patterns affects the scratch resistance and edge lifting of resin patterns, although the causal relationship is unclear. A developer is a chemical used for development. Sodium ions and potassium ions are known to be typical components of developers. Further studies have confirmed that when the depth of specific components in a resin pattern is 0.3 μm to 3.0 μm, the scratch resistance of the resin pattern is improved and edge lifting is reduced. Therefore, according to one embodiment of the present disclosure, a laminate including a resin pattern is provided that has excellent scratch resistance and prevents or reduces edge lifting.

[0030] (base material) A laminate according to an embodiment of the present disclosure includes a substrate. Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. The substrate is preferably a resin substrate. Examples of the resin substrate include a cycloolefin polymer film, a polypropylene film, a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film. The substrate preferably includes a polymer, more preferably includes at least one selected from the group consisting of a cycloolefin polymer and a polyimide, and even more preferably includes a cycloolefin polymer.

[0031] The thickness of the substrate is preferably 5 μm to 200 μm, and more preferably 10 μm to 100 μm. The thickness of the substrate is represented by the arithmetic mean of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0032] A preferred embodiment of the substrate is described in paragraph

[0140] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0033] (resin pattern) A laminate according to an embodiment of the present disclosure includes a resin pattern. The resin pattern may be disposed in contact with a substrate. Other components may be disposed between the substrate and the resin pattern.

[0034] The shape, width and spacing of the resin patterns are determined depending on, for example, the application. The width of the resin patterns is preferably within a range of 5 μm to 1,000 μm. The spacing between the resin patterns is preferably within a range of 5 μm to 1,000 μm.

[0035] From the viewpoint of strength, the thickness of the resin pattern is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 3 μm or more, and particularly preferably 5 μm or more. The upper limit of the thickness of the resin pattern may be 40 μm, 30 μm, 20 μm, or 10 μm. The thickness of the resin pattern is represented by the arithmetic average of thicknesses measured at five locations by cross-sectional observation using a scanning electron microscope (SEM).

[0036] The depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is 0.3 μm to 3.0 μm. In the present disclosure, the embodiment "the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is 0.3 μm to 3.0 μm" encompasses the following (1) to (3). However, in the present disclosure, the depth of presence of either the sodium ions or the potassium ions may be specified. That is, in the present disclosure, the depth of presence of sodium ions in the resin pattern may be 0.3 μm to 3.0 μm, or the depth of presence of potassium ions in the resin pattern may be 0.3 μm to 3.0 μm. (1) The depth at which sodium ions exist in the resin pattern is 0.3 μm or more and 3.0 μm or less, and the depth at which potassium ions exist in the resin pattern is 0.3 μm or more and 3.0 μm or less. (2) The depth at which sodium ions exist in the resin pattern is 0.3 μm or more and 3.0 μm or less, and the depth at which potassium ions exist in the resin pattern is less than 0.3 μm or more than 3.0 μm. (3) The depth at which sodium ions exist in the resin pattern is less than 0.3 μm or more than 3.0 μm, and the depth at which potassium ions exist in the resin pattern is 0.3 μm or more and 3.0 μm or less.

[0037] From the viewpoint of improving scratch resistance, the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is preferably 0.5 μm or more, more preferably 1.0 μm or more, and even more preferably 1.5 μm or more. From the viewpoint of reducing edge lifting, the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is preferably 2.8 μm or less, more preferably 2.5 μm or less, and even more preferably 2.2 μm or less.

[0038] The depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is measured by depth profile analysis using time-of-flight secondary ion mass spectrometry (TOF-SIMS). First, a known measuring device (e.g., SIMS5 and Ar manufactured by IONTOF) used for TOF-SIMS is used. + The distribution of the target component (i.e., sodium ions or potassium ions) in the depth direction of the resin pattern is measured using a cluster sputter gun. The depth direction analysis is carried out in the direction from the resin pattern to the substrate. Specifically, the measurement target is Ar +Sodium or potassium ions are detected by TOF-SIMS while sputtering with a cluster sputter gun. Next, assuming that the intensity of the target component detected on the surface of the resin pattern is 100%, the sputtering time when the intensity of the target component first reaches 90% is converted into a depth (i.e., the distance from the surface of the resin pattern to the point where the intensity of the target component first reaches 90%) based on the sputtering rate. The above-described "depth" is measured at three arbitrary points in the pattern where edge lifting does not occur, each at least 10 μm away from the edge lifting in the substrate plane direction and at least 100 μm away from each other. The arithmetic mean of the three measurements is defined as the "existence depth." If another layer (e.g., Optical Clear Adhesive (OCA)) is attached to the resin pattern, sodium or potassium ions are detected by TOF-SIMS while sputtering the other layer as well. In the TOF-SIMS measurement results, the interface between the resin pattern and the other layer is determined based on the thickness of each layer, the sputtering rate, and the components detected in each layer. For example, at the interface between a resin pattern and another layer that does not contain sodium ions or potassium ions, a peak of sodium ions or potassium ions rises, and therefore the location where the peak of sodium ions or potassium ions rises can be considered the surface of the resin pattern.

[0039] The depth of the specific component (i.e., at least one component selected from the group consisting of sodium ions and potassium ions) in the resin pattern is adjusted, for example, by the manufacturing conditions of the resin pattern. For example, as described in the section "Method for Manufacturing a Laminate" below, when a developer containing a specific component is used in the manufacturing process of the resin pattern, the depth of the specific component in the resin pattern varies depending on the penetration level of the developer components into the resin pattern. For example, as the penetration level of the developer components into the resin pattern increases, the depth of the specific component in the resin pattern increases. On the other hand, as the penetration level of the developer components into the resin pattern decreases, the depth of the specific component in the resin pattern decreases. As described in the section "Method for Manufacturing a Laminate" below, the penetration level of the developer components into the resin pattern is adjusted, for example, by the development conditions (e.g., the temperature and processing time of the developer), the washing conditions (e.g., the temperature and processing time of water), and the standing time after washing. However, the method for adjusting the depth of the specific component in the resin pattern is not limited to the specific examples above.

[0040] From the viewpoints of scratch resistance, edge quality (particularly, reduction of edge lift), and strength, the ratio of the depth where the specific component is present in the resin pattern to the thickness of the resin pattern is preferably 0.1 to 0.9, more preferably 0.2 to 0.7, and even more preferably 0.3 to 0.5. From the viewpoints of scratch resistance, edge quality (particularly, reduction of edge lift), and strength, the absolute value of the difference between the thickness of the resin pattern and the depth where the specific component is present in the resin pattern is preferably 0.5 μm to 10 μm, more preferably 1 μm to 6 μm, and even more preferably 2 μm to 4 μm.

[0041] The moisture permeability of a resin pattern with a thickness of 40 μm is 500 g / (m 2 24hr) or less, and 300g / (m 2 24hr) or less is more preferable, and 100g / (m 2 24 hr) or less is more preferable. A specific preferable value is, for example, 80 g / (m2 24hr), 150g / (m 2 24hr) and 220g / (m 2 The moisture permeability is measured in accordance with JIS Z 0208 (1976) (cup method). It is preferable that the moisture permeability is as above under any of the test conditions of a temperature of 40°C and a humidity of 90%, a temperature of 65°C and a humidity of 90%, and a temperature of 80°C and a humidity of 95%.

[0042] Examples of components of the resin pattern include polymers. Examples of the polymer include the polymers described as components of the photosensitive layer in the section below titled "Method for producing a laminate." Examples of the polymer also include polymers of polymerizable compounds described as components of the photosensitive layer in the section below titled "Method for producing a laminate."

[0043] The resin pattern is preferably a cured product of a photosensitive composition. The photosensitive composition preferably contains a polymer. It is also preferable that the photosensitive composition contains a polymerizable compound and a polymerization initiator. It is also preferable that the photosensitive composition contains a polymer, a polymerizable compound, and a polymerization initiator. The polymer preferably has a polymerizable group, more preferably has a radically polymerizable group. The aspects of the photosensitive composition are described in the section "Method for producing a laminate" below. The method for curing the photosensitive composition is determined, for example, depending on the components of the photosensitive composition. A preferred method for curing the photosensitive composition is, for example, exposure as described in the section "Method for producing a laminate" below.

[0044] (Other components) The laminate according to an embodiment of the present disclosure may further include other components as needed. The types, arrangements, and numbers of the other components are determined, for example, depending on the purpose. Examples of the other components include transparent electrodes and routing wiring.

[0045] The laminate according to an embodiment of the present disclosure preferably includes a transparent electrode. Specifically, the laminate according to an embodiment of the present disclosure preferably includes a transparent electrode between the substrate and the resin pattern. That is, the laminate according to an embodiment of the present disclosure preferably includes a substrate, a transparent electrode, and a resin pattern, in this order. The laminate according to an embodiment of the present disclosure also preferably includes a resin pattern, a transparent electrode, a substrate, a transparent electrode, and a resin pattern, in this order. Examples of components of the transparent electrode include metal oxides. Examples of metal oxides include indium tin oxide (ITO) and indium zinc oxide (IZO). The transparent electrode may be composed of thin metal wires such as metal nanowires. Examples of thin metal wires include thin silver wires and thin copper wires. The transparent electrode may be composed of a metal mesh. A silver conductive material such as a silver mesh or silver nanowires is preferred. The transparent electrode may be a transparent electrode pattern.

[0046] The laminate according to an embodiment of the present disclosure preferably includes a lead wiring. The lead wiring is preferably disposed between the substrate and the resin pattern. When the laminate includes a transparent electrode and a lead wiring, the lead wiring is preferably electrically connected to the transparent electrode. Examples of components of the lead wiring include metals. Examples of metals include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese. The metal may be an alloy. The components of the lead wiring are preferably copper, molybdenum, aluminum, or titanium, and more preferably copper.

[0047] Other components include, for example, a refractive index adjusting layer, such as the refractive index adjusting layer described as a component of the transfer film in the section "Method for manufacturing a laminate" below.

[0048] (structure) The structure of the laminate will be described with reference to Figures 1 and 2. Figure 1 is a schematic cross-sectional view showing the structure of a laminate according to one embodiment. Figure 2 is a schematic cross-sectional view showing the structure of a laminate according to another embodiment. However, the structure of the laminate is not limited to the structures shown in each figure.

[0049] The laminate 90 shown in FIG. 1 has an image display area 74 and an image non-display area 75 (i.e., a frame portion). The laminate 90 has touch panel electrodes on both sides of the substrate 32. Specifically, the laminate 90 has a first conductive metal material 70 on one side of the substrate 32 and a second conductive metal material 72 on the other side of the substrate 32. In the laminate 90, a lead wiring 56 is connected to each of the first conductive metal material 70 and the second conductive metal material 72. Examples of the lead wiring 56 include copper wiring and silver wiring. The lead wiring 56 is surrounded by the resin pattern 18 and the first conductive metal material 70 or the second conductive metal material 72. In the laminate 90, a resin pattern 18 is formed on one side of the substrate 32 so as to cover the first transparent electrode pattern 70 and the routing wiring 56, and a resin pattern 18 is formed on the other side of the substrate 32 so as to cover the second metal conductive material 72 and the routing wiring 56.

[0050] The laminate 100 shown in FIG. 2 includes a substrate 10, a first wiring portion 20B, a second island-shaped electrode portion 30A, a second wiring portion 30B, a resin pattern 60, and a transparent layer 80. The first wiring portion 20B and the first island-shaped electrode portion (not shown) are alternately arranged from the front to the back of FIG. 2, and electrically connect two adjacent first island-shaped electrode portions (not shown). The second wiring portion 30B electrically connects two adjacent second island-shaped electrode portions 30A. The first island-shaped electrode portion 20B and the second island-shaped electrode portion 30A are covered with a resin pattern 60. Furthermore, the resin pattern 60 and the second wiring portion 30B are covered with a transparent layer 80. The transparent layer 80 can be, for example, OCA.

[0051] (Application) A laminate according to an embodiment of the present disclosure is applied to applications such as a touch panel. The laminate according to an embodiment of the present disclosure is preferably a touch panel, and more preferably a capacitive touch panel. In a laminate used as a touch panel, the resin pattern preferably functions as a protective film for the touch panel electrodes or touch panel wiring.

[0052] A laminate according to an embodiment of the present disclosure can be used in applications involving precision microfabrication using photolithography. In applications involving precision microfabrication using photolithography, the resin pattern preferably functions as an etching resist. When the resin pattern is used as an etching resist, the laminate according to an embodiment of the present disclosure preferably includes a conductive layer between the substrate and the resin pattern. Examples of the conductive layer include a metal layer, a metal oxide layer, and a layer containing fine metal wires. Examples of materials for the layer containing the metal layer, the metal oxide layer, and the fine metal wires include the substances described in the "Other Components" section above. When the resin pattern is used as an etching resist, the laminate is preferably formed through the steps of forming a photosensitive layer on a conductive layer disposed on a substrate, pattern-exposing the photosensitive layer, removing unnecessary portions from the exposed photosensitive layer, and removing the conductive layer in the portions where the photosensitive layer has been removed to obtain a conductive pattern.

[0053] A laminate according to an embodiment of the present disclosure can be applied to various wiring formation applications for semiconductor packages, printed circuit boards, and sensor substrates, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, and the formation of structures in the fields of micromachines and microelectronics.

[0054] However, the uses of the laminate according to an embodiment of the present disclosure are not limited to the above specific examples.

[0055] <Method of manufacturing laminate> Next, a method for producing a laminate according to an embodiment of the present disclosure will be described. The method for producing a laminate is not limited as long as the desired laminate can be obtained. The method for producing a laminate according to an embodiment of the present disclosure includes, in this order, disposing a photosensitive layer on a substrate (hereinafter referred to as a "disposing step"), pattern-exposing the photosensitive layer (hereinafter referred to as an "exposing step"), removing exposed or unexposed portions of the photosensitive layer using a developer containing at least one component selected from the group consisting of sodium ions and potassium ions to form a resin pattern (hereinafter referred to as a "developing step"), washing the resin pattern with water (hereinafter referred to as a "washing step"), and leaving the substrate and the resin pattern standing (hereinafter referred to as a "standing step"). Based on a depth profile analysis of the resin pattern performed along the direction from the resin pattern that has undergone the above-described process toward the substrate, the intensity of at least one component selected from the group consisting of sodium ions and potassium ions detected on the surface of the resin pattern is defined as 100%, and the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern, as defined by the distance from the surface of the resin pattern to the point where the intensity of at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90%, is preferably 0.3 μm to 3.0 μm. Prior art, such as the method for forming a cured resin film pattern disclosed in Patent Document 1, has not conducted detailed studies on processes aimed at adjusting the depth of presence of specific components in the resin pattern. On the other hand, the series of processes in the present disclosure, including the developing process, washing process, and standing process, affect the depth of presence of the specific component (i.e., at least one component selected from the group consisting of sodium ions and potassium ions) in the resin pattern. In particular, the standing process significantly contributes to the objective of adjusting the depth of presence of the specific component in the resin pattern within a specific range. For example, the degree of penetration of the developer components into the resin pattern varies depending on the conditions of the developing step, the washing step, and the standing step, and the depth of the specific component in the resin pattern is adjusted to 0.3 μm to 3.0 μm.Therefore, according to one embodiment of the present disclosure, there is provided a method for producing a laminate including a resin pattern that has excellent scratch resistance and in which edge lifting is prevented or reduced.

[0056] (Placement process) In the disposing step, a photosensitive layer is disposed on a substrate. In the disposing step, the photosensitive layer may be disposed in contact with the substrate. Other components may be disposed between the substrate and the photosensitive layer. For example, a method for manufacturing a laminate including a substrate, a transparent electrode, and a resin pattern in this order preferably includes preparing a substrate including a substrate and a transparent electrode in this order before the disposing step.

[0057] The embodiment of the substrate is described above in the section "Laminate." The preferred embodiment of the substrate is the same as the preferred embodiment of the substrate described above in the section "Laminate."

[0058] The photosensitive layer is preferably a negative photosensitive layer, which has the property that the solubility of exposed areas in a developer is lower than that of unexposed areas.

[0059] The thickness of the photosensitive layer is determined, for example, depending on the thickness of the desired resin pattern. The preferred embodiments of the thickness of the resin pattern described in the "Laminate" section above apply mutatis mutandis to the preferred embodiments of the thickness of the photosensitive layer. The thickness of the photosensitive layer may be 30 μm or less. From the viewpoint of improving developability, the thickness of the photosensitive layer is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less. From the viewpoint of improving the strength of the resin pattern, the thickness of the photosensitive layer is preferably 0.60 μm or more, more preferably 1.5 μm or more. The thickness of the photosensitive layer is represented by the arithmetic average of thicknesses measured at five locations by cross-sectional observation using a scanning electron microscope (SEM).

[0060] The refractive index of the photosensitive layer is preferably from 1.41 to 1.59, and more preferably from 1.47 to 1.56.

[0061] The photosensitive layer is preferably achromatic. * ,a * ,b * ) color space, L * The value is preferably 10 to 90, and a * The value is preferably -1.0 to 1.0, and b * The value is preferably between -1.0 and 1.0.

[0062] From the viewpoint of the rust prevention of the electrodes or wiring and the reliability of the laminate, the visible light transmittance per 1.0 μm of thickness of the photosensitive layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more. The visible light transmittance is preferably 80% or more for the average transmittance at wavelengths of 400 nm to 800 nm, the minimum transmittance at wavelengths of 400 nm to 800 nm, and the transmittance at a wavelength of 400 nm. Preferable transmittance values ​​include, for example, 87%, 92%, and 98%.

[0063] From the viewpoint of suppressing residues during development, the dissolution rate of the photosensitive layer in a 1.0 mass % aqueous sodium carbonate solution is preferably 0.01 μm / sec or more, more preferably 0.10 μm / sec or more, and even more preferably 0.20 μm / sec or more. From the viewpoint of pattern edge shape, the dissolution rate of the photosensitive layer in a 1.0 mass % aqueous sodium carbonate solution is preferably 5.0 μm / sec or less, more preferably 4.0 μm / sec or less, and even more preferably 3.0 μm / sec or less. Specific preferred values ​​include 1.8 μm / sec, 1.0 μm / sec, and 0.7 μm / sec. The dissolution rate of the photosensitive layer in a 1.0 mass % aqueous sodium carbonate solution is measured by the following method. A photosensitive layer (thickness: within the range of 1.0 μm to 10 μm), from which the solvent has been thoroughly removed, is subjected to shower development using a 1.0 mass % aqueous sodium carbonate solution at 25°C until the photosensitive layer is completely dissolved. However, the upper limit of shower development time is 2 minutes. The shower nozzle used for development is a 1 / 4MINJJX030PP manufactured by Ikeuchi Co., Ltd. The shower spray pressure is 0.08MPa. The shower flow rate per unit time is 1,800mL / min. The dissolution rate is calculated by dividing the thickness of the photosensitive layer by the time required for the photosensitive layer to completely dissolve. If the photosensitive layer does not completely dissolve within 2 minutes, the dissolution rate is calculated in the same way using the amount of film thickness change up to that point.

[0064] From the viewpoint of improving pattern formability, the swelling ratio of the photosensitive layer after exposure to a 1.0 mass % aqueous sodium carbonate solution is preferably 100% or less, more preferably 50% or less, and even more preferably 30% or less. Specific preferred values ​​include, for example, 4%, 13%, and 25%. The swelling ratio of the photosensitive layer after exposure to a 1.0 mass % aqueous sodium carbonate solution is measured by the following method: A photosensitive layer (thickness: in the range of 1.0 μm to 10 μm) from which the solvent has been thoroughly removed is irradiated with 500 mJ / cm using an ultra-high pressure mercury lamp. 2The photosensitive layer is exposed to light (i-line measurement). The photosensitive layer is immersed in a 1.0% by mass aqueous solution of sodium carbonate at 25°C, and the thickness of the photosensitive layer is measured after 30 seconds. The percentage increase in thickness of the photosensitive layer after immersion relative to the thickness of the photosensitive layer before immersion is calculated.

[0065] From the viewpoint of pattern formation, the number of foreign particles with a diameter of 1.0 μm or more in the photosensitive layer should be 10 / mm 2 It is preferable that the number of particles is less than 5 / mm 2 More preferably, the number is 0 pieces / mm or less. 2 , 1 piece / mm 2 , 4 pieces / mm 2 and 8 pieces / mm 2 The number of foreign particles is measured by the following method: Five randomly selected areas (1 mm × 1 mm) on the surface of the photosensitive layer are visually observed using an optical microscope from the normal direction to the surface of the photosensitive layer, and the number of foreign particles with a diameter of 1.0 μm or more in each area is counted, and the arithmetic average is calculated as the number of foreign particles.

[0066] From the viewpoint of preventing the generation of aggregates during development, 1.0 cm of the solution was added to 1.0 L of a 1.0% by weight sodium carbonate solution at 30°C. 3 The haze of the solution obtained by dissolving the photosensitive layer is preferably 60% or less, more preferably 30% or less, even more preferably 10% or less, and particularly preferably 1% or less. Specific preferred values ​​include, for example, 0.4%, 1%, 9%, and 24%. The haze is measured by the following method. First, a 1.0% by mass aqueous solution of sodium carbonate is prepared, and the liquid temperature is adjusted to 30°C. 1.0 cm3 of sodium carbonate solution is added to 1.0 L of the aqueous solution of sodium carbonate. 3 The photosensitive layer is added. Stir for 4 hours at 30°C, taking care not to introduce air bubbles. After stirring, the haze of the solution in which the photosensitive layer has dissolved is measured. Haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) with a liquid measurement unit and a dedicated liquid measurement cell with an optical path length of 20 mm.

[0067] Examples of components of the photosensitive layer include polymers, polymerizable compounds, polymerization initiators, heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, surfactants, polymerization inhibitors, and hydrogen donor compounds.

[0068] The photosensitive layer preferably contains a polymer, which will be described below.

[0069] Examples of the polymer include (meth)acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy acrylate resin obtained by reacting an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resin obtained by reacting an epoxy acrylate resin with an acid anhydride.

[0070] One preferred embodiment of the polymer is a (meth)acrylic resin, which has excellent alkali developability and film formability. In the present disclosure, the term "(meth)acrylic resin" refers to a resin having structural units derived from (meth)acrylic compounds. The content of structural units derived from (meth)acrylic compounds is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed solely of structural units derived from (meth)acrylic compounds, or may also contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. In other words, the upper limit of the content of structural units derived from (meth)acrylic compounds is 100% by mass, based on the total structural units of the (meth)acrylic resin.

[0071] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, and (meth)acrylonitrile.

[0072] Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl ester is preferred.

[0073] The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. The (meth)acrylic acid ester is preferably a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, more preferably a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and even more preferably methyl (meth)acrylate or ethyl (meth)acrylate.

[0074] Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0075] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth)acrylic compound that is copolymerizable with the (meth)acrylic compound. Examples include styrene compounds such as styrene, vinyltoluene, and α-methylstyrene, which may have a substituent at the α-position or aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0076] In addition, the (meth)acrylic resin preferably has a structural unit having an acid group in order to improve alkaline developability. Examples of the acid group include a carboxy group, a sulfo group, a phosphate group, and a phosphonate group. The (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0077] The content of structural units having an acid group in the (meth)acrylic resin (preferably structural units derived from (meth)acrylic acid) is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin in terms of excellent developability. While there is no particular upper limit, it is preferably 50% by mass or less, and more preferably 40% by mass or less, in terms of excellent alkali resistance.

[0078] Furthermore, the (meth)acrylic resin more preferably has structural units derived from the above-mentioned (meth)acrylic acid alkyl ester. The content of structural units derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50% by mass to 90% by mass, more preferably 60% by mass to 90% by mass, and even more preferably 65% ​​by mass to 90% by mass, based on the total structural units of the (meth)acrylic resin.

[0079] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferred, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is more preferred. Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

[0080] The (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and more preferably has both structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters. The total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total structural units of the (meth)acrylic resin. The upper limit is not particularly limited, and may be 100% by mass or less, and is preferably 80% by mass or less.

[0081] The (meth)acrylic resin preferably contains at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters. The total content of the structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters is preferably in a mass ratio of 60 / 40 to 80 / 20 relative to the total content of the structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters.

[0082] The (meth)acrylic resin preferably has an ester group at its terminal, since this provides excellent developability for the photosensitive layer. The terminal portion of the (meth)acrylic resin is composed of a moiety derived from the polymerization initiator used in the synthesis. The (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0083] Another preferred embodiment of the polymer is an alkali-soluble resin. From the viewpoint of developability, the polymer is preferably a polymer with an acid value of 60 mgKOH / g or more. Furthermore, the polymer is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (a so-called carboxy group-containing resin), and even more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (a so-called carboxy group-containing (meth)acrylic resin), because it is easily thermally crosslinked with a crosslinking component by heating to form a strong film. When the polymer is a resin having a carboxy group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound for thermal crosslinking. Furthermore, when the carboxy group of a resin having a carboxy group is anhydrous and hydrophobicized, the wet heat resistance can be improved.

[0084] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above-mentioned acid value requirement, and can be appropriately selected from known (meth)acrylic resins. For example, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph

[0025] of JP-A No. 2011-095716, and carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs

[0033] to

[0052] of JP-A No. 2010-237589 can be preferably used.

[0085] Another preferred embodiment of the polymer is a styrene-acrylic copolymer. A styrene-acrylic copolymer refers to a resin having structural units derived from a styrene compound and structural units derived from a (meth)acrylic compound. The total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, and more preferably 50% by mass or more, based on the total structural units of the copolymer. The content of the structural units derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5% to 80% by mass, based on the total structural units of the copolymer. The content of the structural units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% to 95% by mass, based on the total structural units of the copolymer.

[0086] In one embodiment, the polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure. Examples of monomers that form structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, monomers having an aralkyl group or styrene are preferred. Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0087] Examples of the monomer having a phenyl alkyl group include phenylethyl (meth)acrylate.

[0088] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of these, benzyl (meth)acrylate is preferred.

[0089] In one embodiment, the polymer more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0090] [ka]

[0091] When the polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and even more preferably 20% by mass to 60% by mass, based on the total structural units of the polymer.

[0092] The content of the structural units having an aromatic ring structure in the polymer is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 60 mol %, based on all structural units of the polymer.

[0093] The content of the structural unit represented by the above formula (S) in the polymer is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, even more preferably 20 mol % to 60 mol %, and particularly preferably 20 mol % to 50 mol %, based on all structural units of the polymer.

[0094] In the present disclosure, when the content of a "structural unit" is defined as a molar ratio, the "structural unit" is synonymous with a "monomer unit." In addition, in the present disclosure, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0095] In one embodiment, the polymer preferably has an aliphatic hydrocarbon ring structure. That is, the polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. In particular, the polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

[0096] Examples of the ring that constitutes the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring. A ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0]) is particularly preferred. 2,6 ]decane ring) is more preferred.

[0097] Examples of monomers that form a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0098] In one embodiment, the polymer more preferably has a constitutional unit represented by the following formula (Cy), and more preferably has a constitutional unit represented by the above formula (S) and a constitutional unit represented by the following formula (Cy).

[0099] [ka]

[0100] In the formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0101] R in formula (Cy) M is preferably a methyl group.

[0102] R in formula (Cy) Cy is preferably a monovalent group having an aliphatic hydrocarbon ring structure of 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure of 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure of 8 to 14 carbon atoms.

[0103] R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.

[0104] R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring in which two to four aliphatic hydrocarbon rings are condensed.

[0105] R in formula (Cy) Cyis preferably a group in which the oxygen atom of —C(═O)O— in formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and even more preferably a dicyclopentanyl group.

[0106] The polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or two or more types.

[0107] When the polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and even more preferably 20% by mass to 70% by mass, relative to all structural units of the polymer.

[0108] The content of structural units having an aliphatic hydrocarbon ring structure in the polymer is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, based on all structural units of the polymer.

[0109] The content of the structural unit represented by the above formula (Cy) in the polymer is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, based on all structural units of the polymer.

[0110] When the polymer has structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 40% by mass to 75% by mass, based on all structural units of the polymer.

[0111] The total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure in the polymer is preferably 10 mol % to 80 mol %, more preferably 20 mol % to 70 mol %, and even more preferably 40 mol % to 60 mol %, based on all structural units of the polymer.

[0112] The total content of the structural units represented by the formula (S) and the structural units represented by the formula (Cy) in the polymer is preferably 10 mol % to 80 mol %, more preferably 20 mol % to 70 mol %, and even more preferably 40 mol % to 60 mol %, based on the total structural units of the polymer.

[0113] In the polymer, 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) 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). 0.2≦nS / (nS+nCy)≦0.8: Formula (SCy) 0.30≦nS / (nS+nCy)≦0.75: Formula (SCy-1) 0.40≦nS / (nS+nCy)≦0.70: Formula (SCy-2)

[0114] The polymer preferably has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and the carboxy group is preferred. As the structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0115] [ka]

[0116] The polymer may have one type of structural unit having an acid group, or two or more types of structural units.

[0117] When the polymer has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 30% by mass, relative to all structural units of the polymer.

[0118] The content of structural units having an acid group in the polymer is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 50 mol %, and even more preferably 20 mol % to 40 mol %, based on all structural units of the polymer.

[0119] The content of the (meth)acrylic acid-derived structural units in the polymer is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 50 mol %, and even more preferably 20 mol % to 40 mol %, based on all structural units of the polymer.

[0120] The polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group. As the reactive group, a polymerizable group is preferred, a radically polymerizable group is more preferred, and an ethylenically unsaturated group is even more preferred. Furthermore, when the polymer has an ethylenically unsaturated group, the polymer preferably has a structural unit having an ethylenically unsaturated group in a side chain. In this disclosure, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the term "side chain" refers to an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferred. Examples of structural units having a reactive group include, but are not limited to, those shown below.

[0121] [ka]

[0122] The polymer may have one type of structural unit having a reactive group, or two or more types of structural units.

[0123] When the polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass, based on the total structural units of the polymer.

[0124] Furthermore, the content of the structural units having a reactive group in the polymer is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, based on all structural units of the polymer.

[0125] Examples of methods for introducing reactive groups into polymers include reacting functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups with compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides. A preferred example of a method for introducing reactive groups into a polymer is to synthesize a polymer having carboxyl groups by polymerization, and then react some of the carboxyl groups of the resulting polymer with glycidyl (meth)acrylate by a polymer reaction to introduce (meth)acryloxy groups into the polymer. This method can produce a polymer having (meth)acryloxy groups in its side chains. The polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably at a temperature of 80°C to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo-based initiator, and more preferably, for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The polymerization reaction is preferably carried out at a temperature of 80°C to 110°C. In the polymerization reaction, it is preferable to use a catalyst such as an ammonium salt.

[0126] The polymer is preferably one shown below: The content ratios (a to d) of the structural units shown below and the weight average molecular weight Mw can be changed appropriately depending on the purpose.

[0127] [ka]

[0128] The preferred ranges for the content ratios (a to d) of the respective structural units are shown below. a: 20% by mass ~ 60% by mass b: 10% by mass ~ 50% by mass c: 5.0% by mass ~ 25% by mass d: 10% by mass to 50% by mass

[0129] [ka]

[0130] The preferred ranges for the content ratios (a to d) of the respective structural units are shown below. a: 20% by mass ~ 60% by mass b: 10% by mass ~ 50% by mass c: 5.0% by mass ~ 25% by mass d: 10% by mass to 50% by mass

[0131] [ka]

[0132] The preferred ranges for the content ratios (a to d) of the respective structural units are shown below. a: 30% by mass ~ 65% by mass b: 1.0% by mass ~ 20% by mass c: 5.0% by mass ~ 25% by mass d: 10% by mass to 50% by mass

[0133] [ka]

[0134] The preferred ranges for the content ratios (a to d) of the respective structural units are shown below. a: 1.0% by mass ~ 20% by mass b: 20% by mass ~ 60% by mass c: 5.0% by mass ~ 25% by mass d: 10% by mass to 50% by mass

[0135] The polymer may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X"). The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure. The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0136] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing, in its main chain, a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0137] [ka]

[0138] In formula P-1, R A1a represents a substituent, n 1a R A1a may be the same or different, and Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, and n 1a represents an integer greater than or equal to 0.

[0139] R A1a Examples of the substituent represented by the formula include an alkyl group.

[0140] Z 1a As the alkylene group, an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is even more preferable.

[0141] n 1a represents an integer greater than or equal to 0. Z1a When represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

[0142] n 1a If represents an integer of 2 or more, there are multiple R A1a may be the same or different. A1a may be bonded to each other to form a ring, but preferably do not bond to each other to form a ring.

[0143] As a structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid 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.

[0144] Specific examples of structural units having a carboxylic acid anhydride structure are listed below, but the structural units having a carboxylic acid anhydride structure are not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0145] [ka]

[0146] [ka]

[0147] The polymer X may contain one type of structural unit having a carboxylic acid anhydride structure, or two or more types of structural units.

[0148] The total content of structural units having a carboxylic acid anhydride structure relative to all structural units of polymer X is preferably 0 mol % to 60 mol %, more preferably 5 mol % to 40 mol %, and even more preferably 10 mol % to 35 mol %.

[0149] The photosensitive layer may contain only one type of polymer X, or may contain two or more types.

[0150] When the photosensitive layer contains polymer X, the content of polymer X is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, even more preferably 0.5% by mass to 20% by mass, and particularly preferably 1% by mass to 20% by mass, relative to the total mass of the photosensitive layer.

[0151] The weight average molecular weight (Mw) of the polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0152] The acid value of the polymer is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, even more preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 125 mgKOH / g. The acid value of the polymer is a value measured according to the method described in "JIS K 0070:1992".

[0153] From the viewpoint of developability, the dispersity of the polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, even more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0154] The photosensitive layer may contain only one type of polymer, or may contain two or more types of polymers.

[0155] The content of the polymer is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 30% by mass to 70% by mass, based on the total mass of the photosensitive layer.

[0156] The photosensitive layer preferably contains a polymerizable compound, which will be described below.

[0157] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationic polymerizable group, and the radically polymerizable group is preferred.

[0158] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound"). The ethylenically unsaturated group is preferably a (meth)acryloxy group. The ethylenically unsaturated compound in this specification is a compound other than the above-mentioned polymer, and preferably has a molecular weight of less than 5,000.

[0159] One preferred embodiment of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M"). Q 2 -R 1 -Q 1 :Formula(M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group, R 1 represents a divalent linking group having a chain structure.

[0160] Q in formula (M) 1 and Q 2 In terms of ease of synthesis, Q 1 and Q 2 It is preferable that Q in formula (M) are the same group. 1 and Q 2 is preferably an acryloyloxy group from the viewpoint of reactivity.

[0161] R in formula (M)1 Examples of the alkylene group include an alkyleneoxyalkylene group (-L 1 -OL 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 L is preferably -, more preferably a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group, even more preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a straight-chain alkylene group having 6 to 18 carbon atoms. The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited, and may be, for example, a branched, cyclic, or straight-chain alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. An alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a straight-chain alkylene group is even more preferred. 1 each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

[0162] Q in compound M 1 and Q 2 The number of atoms in the shortest linking chain connecting Q and Q is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, and particularly preferably 8 to 12. 1 and Q 2 The number of atoms in the shortest chain connecting the 1 Connect to R 1 Q from atoms in 2 Connect to R 1 is the shortest number of atoms that connects to the atom in

[0163] 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, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is even more preferred.

[0164] One preferred embodiment of the polymerizable compound is a difunctional or higher ethylenically unsaturated compound. In the present disclosure, the term "difunctional or higher ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group in the ethylenically unsaturated compound is preferably a (meth)acryloyl group. The ethylenically unsaturated compound is preferably a (meth)acrylate compound.

[0165] The bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0166] Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0167] The tri- or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0168] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0169] The polymerizable compound also includes a urethane (meth)acrylate compound. Examples of the urethane (meth)acrylate include urethane di(meth)acrylate, such as propylene oxide-modified urethane di(meth)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of the urethane (meth)acrylate also include trifunctional or higher urethane (meth)acrylate. The lower limit of the number of functional groups is more preferably 6 or more, and even more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of tri- or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., as well as UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0170] One preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group. Examples of the acid group include a phosphate group, a sulfo group, and a carboxy group. Among these, a carboxy group is preferred as the acid group. Examples of the ethylenically unsaturated compound having an acid group include a tri- or tetrafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a pentaerythritol tri- or tetraacrylate (PETA) skeleton (acid value: 80 to 120 mg KOH / g)], a penta- or hexafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a dipentaerythritol penta- or hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mg KOH / g)], and the like. These tri- or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group, if necessary.

[0171] The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of difunctional or higher ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of difunctional or higher ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, developability and film strength are further improved. The difunctional or higher ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of difunctional or higher ethylenically unsaturated compounds having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0172] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 is preferred, and the contents of this publication are incorporated herein by reference.

[0173] Examples of polymerizable compounds include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters. These may be used alone or in combination of two or more.

[0174] Examples of compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; Examples of the acrylate include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among these, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0175] As the polymerizable compound (particularly, an ethylenically unsaturated compound), one containing an ester bond is particularly preferred, as it provides excellent developability of the photosensitive layer after transfer. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0176] From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure. Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0177] One preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). The polymerizable compound is preferably a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused, and even more preferably tricyclodecane dimethanol di(meth)acrylate. The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure.

[0178] The molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, even more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200.

[0179] Of the polymerizable compounds contained in the photosensitive layer, the content ratio of polymerizable compounds having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the content of all polymerizable compounds contained in the photosensitive layer.

[0180] As one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a difunctional or higher ethylenically unsaturated compound, more preferably a trifunctional or higher ethylenically unsaturated compound, and even more preferably a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0181] In one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a polymer having a structural unit having an aliphatic hydrocarbon ring.

[0182] Furthermore, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by Formula (M) and an ethylenically unsaturated compound having an acid group, more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0183] Furthermore, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by Formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by Formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0184] In addition, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound) from the viewpoints of suppressing development residues and rust prevention.

[0185] The mass ratio of the content of the difunctional ethylenically unsaturated compound to the content of the tri- or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, and more preferably 30:70 to 70:30.

[0186] The content of the difunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass.

[0187] The content of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably from 10% to 60% by mass, and more preferably from 15% to 40% by mass.

[0188] In one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, from the viewpoint of rust prevention.

[0189] In one preferred embodiment of the photosensitive layer, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive layer preferably contains compound M and an ethylenically unsaturated compound having an acid group, more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, still more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound.

[0190] In one preferred embodiment of the photosensitive layer, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0191] The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the difunctional or higher ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive layer.

[0192] The polymerizable compound preferably has a bisphenol structure, from the viewpoint of suppressing swelling of the photosensitive layer due to a developer and thereby improving resolution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0193] Examples of polymerizable compounds having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be bonded directly to both ends of the bisphenol structure or via one or more alkyleneoxy groups. The alkyleneoxy groups attached to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, and more preferably ethyleneoxy groups. The number of alkyleneoxy groups attached to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. Polymerizable compounds having a bisphenol structure are described in paragraphs

[0072] to

[0080] of JP 2016-224162 A, the contents of which are incorporated herein by reference.

[0194] As the polymerizable compound having a bisphenol structure, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Showa Denko Materials Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane, and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.). Examples of suitable ethoxylated bisphenol A diacrylates include 2,2-bis(4-(methacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Showa Denko Materials Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0195] The polymerizable compound is also preferably a compound represented by the following general formula (B1).

[0196] [ka]

[0197] In general formula B1, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the -(AO)- and -(BO)- structural units may be random or in a block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably 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.

[0198] The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more kinds.

[0199] The content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, even more preferably 5% by mass to 60% by mass, and particularly preferably 5% by mass to 50% by mass, relative to the total mass of the photosensitive layer.

[0200] The photosensitive layer preferably contains a polymerization initiator, which will be described below.

[0201] The polymerization initiator is preferably a photopolymerization initiator. There are no particular limitations on the photopolymerization initiator, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include photopolymerization initiators having an oxime ester structure (hereinafter also referred to as "oxime-based photopolymerization initiators"), photopolymerization initiators having an α-aminoalkylphenone structure (hereinafter also referred to as "α-aminoalkylphenone-based photopolymerization initiators"), photopolymerization initiators having an α-hydroxyalkylphenone structure (hereinafter also referred to as "α-hydroxyalkylphenone-based polymerization initiators"), photopolymerization initiators having an acylphosphine oxide structure (hereinafter also referred to as "acylphosphine oxide-based photopolymerization initiators"), and photopolymerization initiators having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiators").

[0202] The photopolymerization initiator preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, a biimidazole-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator, and more preferably contains at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

[0203] Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP 2011-95716 A and paragraphs

[0064] to

[0081] of JP 2015-014783 A may be used.

[0204] Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, manufactured by IGM Resins], and the like. BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad® 907, IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad® 127, IGM Resins BV], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad® 369, IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad® 1173, IGM Resins BV], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad® 184, IGM Resins BV] BV)], 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad (registered trademark) 651, IGM Resins B.oxime esters [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), G-326 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0205] The photoradical polymerization initiator, which is one type of photopolymerization initiator, preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0206] The polymerization initiator may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to use an oxime-based photopolymerization initiator and at least one selected from an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator.

[0207] When the photosensitive layer contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the photosensitive layer, and the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

[0208] The photosensitive layer may contain a heterocyclic compound, which will be described below.

[0209] The heterocyclic ring contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

[0210] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. Among these, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0211] Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

[0212] [ka]

[0213] [ka]

[0214] Examples of the tetrazole compound include the following compounds.

[0215] [ka]

[0216] [ka]

[0217] Examples of the thiadiazole compound include the following compounds:

[0218] [ka]

[0219] Examples of the triazine compound include the following compounds:

[0220] [ka]

[0221] Examples of rhodanine compounds include the following compounds:

[0222] [ka]

[0223] Examples of the thiazole compound include the following compounds:

[0224] [ka]

[0225] Examples of the benzothiazole compound include the following compounds:

[0226] [ka]

[0227] Examples of the benzimidazole compound include the following compounds:

[0228] [ka]

[0229] [ka]

[0230] Examples of the benzoxazole compound include the following compounds:

[0231] [ka]

[0232] The heterocyclic compounds may be used alone or in combination of two or more.

[0233] When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, more preferably 0.10% by mass to 10.0% by mass, even more preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass, relative to the total mass of the photosensitive layer.

[0234] The photosensitive layer may contain an aromatic thiol compound other than an aliphatic thiol compound or a heterocyclic compound. The aliphatic thiol compound will be described below.

[0235] When the photosensitive layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with the radical polymerizable compound having an ethylenically unsaturated group, thereby suppressing the cure shrinkage of the film formed and alleviating stress.

[0236] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., a bifunctional or higher aliphatic thiol compound) is preferred. Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is preferred from the viewpoint of the adhesion of the formed pattern (particularly the adhesion after exposure). In the present disclosure, a "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also called "mercapto groups") in the molecule.

[0237] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of at least 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0238] The number of functional groups in the polyfunctional aliphatic thiol compound is, for example, preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of the adhesion of the pattern to be formed.

[0239] Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionyloxy)ethyl ester), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

[0240] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0241] Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0242] By including an aromatic thiol compound other than an aliphatic thiol compound or a heterocyclic compound in the photosensitive layer, when a layer containing silver is adjacent to the photosensitive layer (i.e., when a layer containing silver is adjacent to a resin pattern), deterioration and migration of silver can be suppressed.

[0243] The photosensitive layer may contain a single aliphatic thiol compound or an aromatic thiol compound other than a heterocyclic compound, or may contain two or more aliphatic thiol compounds.

[0244] When the photosensitive layer contains an aliphatic thiol compound or an aromatic thiol compound, the content of the aliphatic thiol compound is preferably 0.1% by mass or more, more preferably 0.1% by mass to 30% by mass, even more preferably 0.2% by mass to 20% by mass, and particularly preferably 0.5% by mass to 10% by mass, relative to the total mass of the photosensitive layer.

[0245] The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. The thermally crosslinkable compound will be described below.

[0246] In the present disclosure, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered an ethylenically unsaturated compound but is considered a thermally crosslinkable compound.

[0247] Examples of the thermally crosslinkable compound include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred in terms of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.

[0248] Since blocked isocyanate compounds react with hydroxy groups and carboxy groups, for example, when at least one of the polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to be enhanced. A blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

[0249] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, and more preferably 130°C to 150°C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (Model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited thereto.

[0250] Examples of blocking agents having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, the blocking agent having a dissociation temperature of 100°C to 160°C is preferably at least one selected from oxime compounds, for example, from the viewpoint of storage stability.

[0251] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer target. A blocked isocyanurate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate through isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred because it is easier to adjust the dissociation temperature to a preferred range and to reduce development residues than a compound not having an oxime structure.

[0252] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as groups having an epoxy group such as a glycidyl group. Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0253] Commercially available blocked isocyanate compounds can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0254] As the blocked isocyanate compound, a compound having the following structure can also be used.

[0255] [ka]

[0256] The thermally crosslinkable compound may be used alone or in combination of two or more kinds.

[0257] When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass, relative to the total mass of the photosensitive layer.

[0258] The photosensitive layer may contain a surfactant, which will be described below.

[0259] Examples of the surfactant include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of JP-A-2009-237362. Preferred surfactants are nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants.

[0260] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solsperse 20000 (all manufactured by Lubrizol Japan Corporation), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries Corporation), Paionin 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.), and the like.

[0261] Commercially available fluorine-based surfactants include, for example, Megafac (registered trademark) 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-566, F-567, F-568, F-569, F-570, F-571, F-572, F-573, F-574, F-575, F-576, F-577, F-579, F-582, F-583, F-584, F-585, F-586, F-587, F-588, F-589, F-589, F-580, F-581 ...90, F-591, F-592, F-593, F-594, F-595, F-596, F-597, F-598, F-599, F-599, F- -563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon (registered trademark) 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), Ftergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS Corporation).

[0262] Also suitable for use as fluorosurfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes. Examples of such fluorosurfactants include the Megafac (registered trademark) DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac (registered trademark) DS-21.

[0263] As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

[0264] Furthermore, a block polymer can also be used as the fluorine-based surfactant.

[0265] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used.

[0266] As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac (registered trademark) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0267] From the viewpoint of improving environmental friendliness, it is preferable that the fluorine-based surfactant be a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0268] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0269] Specific examples of silicone surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, 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.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, and KF-9 45, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie), and the like.

[0270] The surfactants may be used alone or in combination of two or more.

[0271] When the photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, more preferably 0.01% by mass to 1.0% by mass, and even more preferably 0.05% by mass to 0.80% by mass, relative to the total mass of the photosensitive layer.

[0272] The photosensitive layer may contain a polymerization inhibitor, which will be described below.

[0273] The polymerization inhibitor means a compound having the function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0274] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-te nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among these, the polymerization inhibitor is preferably at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds, and more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salt.

[0275] The polymerization inhibitor may be used alone or in combination of two or more kinds.

[0276] When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.02% by mass to 2.0% by mass, relative to the total mass of the photosensitive layer. The content of the polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.01% by mass to 1.0% by mass, relative to the total mass of the polymerizable compounds.

[0277] The photosensitive layer may contain a hydrogen donor compound, which will be described below.

[0278] The hydrogen donor compound has the effect of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing the inhibition of polymerization of the polymerizable compound by oxygen, etc. Examples of the hydrogen donor compound include amines and amino acid compounds.

[0279] Examples of amines include compounds described in MRSander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), JP-B-44-020189, JP-A-51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure No. 33825. More specific examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among these, the amines are preferably at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0280] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine, with N-phenylglycine being preferred among them.

[0281] Further, examples of the hydrogen donor compound include organometallic compounds (such as tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (such as trithiane) described in JP-A-6-308727.

[0282] The hydrogen donor compounds may be used alone or in combination of two or more.

[0283] When the photosensitive layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and even more preferably 0.03% by mass to 5.0% by mass, relative to the total mass of the photosensitive layer, from the viewpoint of improving the curing rate through a balance between the polymerization growth rate and chain transfer.

[0284] The photosensitive layer may contain a predetermined amount of impurities, which will be described below.

[0285] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following values.

[0286] The content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass, and may be 1 ppb or more or 0.1 ppm or more by mass.

[0287] Methods for keeping the impurity content within the above range include selecting raw materials for the photosensitive layer that contain a small amount of impurities, preventing impurities from being mixed in during the formation of the photosensitive layer, and removing them by washing. By using these methods, the amount of impurities can be kept within the above range.

[0288] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0289] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. The content of these compounds in the photosensitive layer is preferably 100 ppm or less by mass, more preferably 20 ppm or less, and even more preferably 4 ppm or less. The lower limit can be 10 ppb or more by mass, and can be 100 ppb or more. The content of these compounds can be reduced in the same manner as for the metal impurities described above. Furthermore, they can be quantified by known measurement methods.

[0290] The water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0291] The photosensitive layer may contain residual monomers of the respective structural units of the alkali-soluble resin. The residual monomers will be described below.

[0292] From the viewpoints of patterning ability and reliability, the content of residual monomers 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, relative to the total mass of the alkali-soluble resin. There is no particular lower limit, but it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning ability and reliability, the content of residual monomers of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer. There is no particular lower limit, but it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0293] The amount of residual monomers in the monomers used in synthesizing an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0294] The photosensitive layer may contain components other than those already described (hereinafter also referred to as "other components"). The other components will be described below.

[0295] Examples of the other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Other examples of the other components also include other additives described in paragraphs

[0058] to

[0071] of JP-A No. 2000-310706.

[0296] The photosensitive layer may contain a small amount of colorant (pigment, dye, etc.), but preferably does not substantially contain a colorant, for example, from the viewpoint of transparency. When the photosensitive layer contains a colorant, the content of the colorant is preferably less than 1% by mass, and more preferably less than 0.1% by mass, based on the total mass of the photosensitive layer.

[0297] Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; para-methylaminophenol, para-aminophenol, para-hydroxyphenylglycine, and para-phenylenediamine. Among these, 3-pyrazolidones are preferred, with 1-phenyl-3-pyrazolidone being more preferred. When the photosensitive layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, based on the total mass of the photosensitive layer. While there is no particular upper limit, it is preferably 1% by mass or less.

[0298] The particles are preferably metal oxide particles. Metals in metal oxide particles include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle diameter of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 random particles using an electron microscope and arithmetically averaging the measurement results. When the particles are not spherical, the particle diameter is determined as the longest side. When the photosensitive layer contains particles, the photosensitive layer may contain only one type of particles or two or more types of particles differing in metal type, size, etc. The photosensitive layer preferably does not contain particles, or if it does contain particles, the particle content is preferably more than 0% by mass and not more than 35% by mass, relative to the total mass of the photosensitive layer; more preferably does not contain particles, or the particle content is more than 0% by mass and not more than 10% by mass, relative to the total mass of the photosensitive layer; even more preferably does not contain particles, or the particle content is more than 0% by mass and not more than 5% by mass, relative to the total mass of the photosensitive layer; particularly preferably does not contain particles, or the particle content is more than 0% by mass and not more than 1% by mass, relative to the total mass of the photosensitive layer; and extremely preferably does not contain particles.

[0299] Next, a method for disposing a photosensitive layer on a substrate will be described. In the disposing step, the method for disposing the photosensitive layer on the substrate is not limited. In the disposing step, a photosensitive layer may be formed on the substrate, or a photosensitive layer prepared in advance may be disposed on the substrate. In the former method, for example, a photosensitive composition is applied to the substrate and, if necessary, the photosensitive composition is dried, thereby disposing the photosensitive layer on the substrate. In the latter method, for example, a transfer film including a temporary support and a photosensitive layer is laminated to the substrate, thereby disposing the photosensitive layer and temporary support in this order on the substrate. In the disposing step, it is preferable to dispose the photosensitive layer on the substrate using a transfer film.

[0300] The components of the photosensitive composition are selected from the components of the photosensitive layer described above depending on the composition of the target photosensitive layer. The matters regarding the components of the photosensitive layer described above are applied to the embodiment of the photosensitive composition by replacing "photosensitive layer" with "photosensitive composition" and "total mass of the photosensitive layer" with "photosensitive composition." The preferred components of the photosensitive composition are the same as the preferred components of the photosensitive layer described above.

[0301] The photosensitive composition may contain a solvent, if necessary. The solvent is preferably an organic solvent. Examples of the organic solvent 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. Furthermore, as the solvent, an organic solvent having a boiling point of 180 to 250°C (high boiling point solvent) can also be used, if necessary. The solvent may be used alone or in combination of two or more.

[0302] The total solid content of the photosensitive composition is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 5% by mass to 30% by mass, relative to the total mass of the photosensitive composition. In other words, the content of the solvent in the photosensitive composition is preferably 20% by mass to 95% by mass, more preferably 60% by mass to 95% by mass, and even more preferably 70% by mass to 95% by mass, relative to the total mass of the photosensitive composition.

[0303] The viscosity of the photosensitive composition at 25°C is, for example, preferably 1 mPa·s to 50 mPa·s, more preferably 2 mPa·s to 40 mPa·s, and even more preferably 3 mPa·s to 30 mPa·s, from the viewpoint of coatability. The viscosity is measured using a viscometer. For example, a viscometer manufactured by Toki Sangyo Co., Ltd. (product name: VISCOMETER TV-22) can be suitably used. However, the viscometer is not limited to the above-mentioned viscometers.

[0304] The surface tension of the photosensitive composition at 25°C is, for example, preferably 5 mN / m to 100 mN / m, more preferably 10 mN / m to 80 mN / m, and even more preferably 15 mN / m to 40 mN / m, from the viewpoint of coatability. The surface tension is measured using a surface tensiometer. For example, a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (product name: Automatic Surface Tensiometer CBVP-Z) can be suitably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0305] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0306] Preferred methods for drying the photosensitive composition are heat drying and vacuum drying. "Drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. The above methods can be applied alone or in combination. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The upper limit is not particularly limited, but is preferably 600 seconds or shorter, more preferably 300 seconds or shorter.

[0307] The transfer film used in the placement step preferably includes a temporary support and a photosensitive layer in this order. The transfer film will be described below. However, in the following description, the aspect of the photosensitive layer in the transfer film is omitted because it is the same as the aspect of the photosensitive layer already described.

[0308] The transfer film preferably includes a temporary support. The temporary support is a member that supports the photosensitive layer and is ultimately removed by a peeling treatment. The temporary support may have a single-layer structure or a multi-layer structure.

[0309] The temporary support is preferably a film, more preferably a resin film. The temporary support is preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heat. Examples of the film include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. Of these, polyethylene terephthalate film is preferred as the temporary support. Furthermore, the film used as the temporary support is preferably free of deformations such as wrinkles, scratches, etc.

[0310] The temporary support preferably has high transparency in order to enable pattern exposure through the temporary support, and the transmittance at 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. Preferred transmittance values ​​include, for example, 87%, 92%, and 98%.

[0311] From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.

[0312] From the viewpoint of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support is 50 / 10 mm. 2Preferably, it is 10 pieces / 10 mm or less. 2 It is more preferable that the number of pieces is 3 pieces / 10 mm or less. 2 More preferably, it is 0 pieces / 10 mm or less. 2 is particularly preferred.

[0313] The thickness of the temporary support is preferably 5 μm to 200 μm. From the viewpoints of ease of handling and versatility, the thickness of the temporary support is more preferably 5 μm to 150 μm, even more preferably 5 μm to 50 μm, and particularly preferably 5 μm to 25 μm. The thickness of the temporary support is represented by the arithmetic average of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0314] In order to improve the adhesion between the temporary support and the photosensitive layer, the surface of the temporary support facing the photosensitive layer may be surface-modified by ultraviolet irradiation, corona discharge, plasma, etc. When the surface is modified by ultraviolet irradiation, the exposure dose is 10 mJ / cm. 2 ~2000mJ / cm 2 and preferably 50 mJ / cm 2 ~1000mJ / cm 2 Examples of light sources for ultraviolet irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs), all of which emit light in the wavelength range of 150 nm to 450 nm. There are no limitations on the lamp output and illuminance as long as the light irradiation amount is within the above-mentioned ranges.

[0315] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. The temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning used films, etc., turning them into chips, and then forming films from these chips. Specific examples of recycled products include the Ecouse series from Toray Industries, Inc.

[0316] Preferred forms of the temporary support are described, for example, in paragraphs

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

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

[0029] to

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

[0317] To improve handling properties, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0318] Commercially available temporary supports include Lumirror (registered trademark) 16KS40, Lumirror (registered trademark) 16FB40, Lumirror (registered trademark) #38-U48, Lumirror (registered trademark) #75-U34, Lumirror (registered trademark) #25-T60 (all manufactured by Toray Industries, Inc.), COSMOSHINE (registered trademark) A4100, COSMOSHINE (registered trademark) A4300, COSMOSHINE (registered trademark) A8300, COSMOSHINE (registered trademark) A4160, and COSMOSHINE (registered trademark) A4360 (all manufactured by Toyobo Co., Ltd.).

[0319] The transfer film preferably further includes a refractive index adjusting layer. Specifically, the transfer film preferably includes a temporary support, a photosensitive layer, and a refractive index adjusting layer in this order. As the refractive index adjusting layer, a known refractive index adjusting layer can be used.

[0320] Materials contained in the refractive index adjusting layer include, for example, polymers, polymerizable compounds, metal salts, and particles. The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples include a method using a resin with a predetermined refractive index alone, a method using a polymer and particles, and a method using a composite of a polymer and a resin. Examples of polymers include the polymers already described as components of the photosensitive layer. Examples of polymerizable compounds include the polymerizable compounds already described as components of the photosensitive layer. Examples of particles include metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and examples include known metal oxide particles. Metals in metal oxide particles include semimetals such as B, Si, Ge, As, Sb, and Te.

[0321] Specifically, the metal oxide particles are preferably at least one selected from the group consisting of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof. Among these, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred as the metal oxide particles, for example, because the refractive index can be easily adjusted.

[0322] Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nanouse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0323] The average primary particle diameter of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 random particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the particle diameter is determined as the longest side.

[0324] The particles may be used alone or in combination of two or more types.

[0325] The content of particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and even more preferably 40% by mass to 85% by mass, relative to the total mass of the refractive index adjusting layer. When titanium oxide is used as the metal oxide particles, the content of titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and even more preferably 40% by mass to 85% by mass, relative to the total mass of the refractive index adjusting layer.

[0326] The refractive index of the refractive index-adjusting layer is preferably higher than that of the photosensitive layer. The refractive index of the refractive index-adjusting layer is preferably 1.50 or higher, more preferably 1.55 or higher, even more preferably 1.60 or higher, and particularly preferably 1.65 or higher. The refractive index of the refractive index-adjusting layer is preferably 2.10 or lower, more preferably 1.85 or lower, and even more preferably 1.78 or lower.

[0327] The thickness of the refractive index-matching layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm. The thickness of the refractive index-matching layer is represented by the arithmetic average of thicknesses measured at five locations by cross-sectional observation using a scanning electron microscope (SEM).

[0328] The refractive index adjusting layer is manufactured using, for example, a composition for forming a refractive index adjusting layer. The composition for forming a refractive index adjusting layer preferably contains the various components for forming the refractive index adjusting layer described above and a solvent. In the composition for forming a refractive index adjusting layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjusting layer described above.

[0329] The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer. It is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol are more preferred. One solvent may be used alone, or two or more solvents may be used. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0330] The refractive index adjusting layer may be produced by coating a composition for forming a refractive index adjusting layer, for example, by slit coating, spin coating, curtain coating, or inkjet coating.

[0331] The transfer film preferably further includes a protective film. Specifically, the transfer film preferably includes a temporary support, a photosensitive layer, and a protective film in this order. It is also preferable that the transfer film includes a temporary support, a photosensitive layer, a refractive index adjusting layer, and a protective film in this order.

[0332] The protective film may be a resin film having heat resistance and solvent resistance, such as a polyolefin film such as a polypropylene film or a polyethylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, or a polystyrene film. Alternatively, a resin film made of the same material as the temporary support may be used as the protective film. Among these, a polyolefin film is preferred as the protective film, a polypropylene film or a polyethylene film is more preferred, and a polyethylene film is even more preferred.

[0333] The thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, even more preferably 5 μm to 40 μm, and particularly preferably 15 μm to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of relatively low cost. The thickness of the protective film is represented by the arithmetic average of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0334] The number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 It is preferable that the number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm. "Fisheyes" are foreign matter, unmelted material, and oxidized / degraded material of the material that are trapped in the film when the film is produced by methods such as heat-melting the material, kneading, extrusion, biaxial stretching, and casting. 2 It is preferable that the number of particles is less than 10 / mm 2 It is more preferable that the number of particles is 5 or less per mm. 2 The following is more preferable: Reducing the number of fisheyes can suppress defects caused by irregularities due to particles contained in the protective film being transferred to a layer in contact with the protective film, such as a photosensitive layer.

[0335] In order to provide good winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. The roughness Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0336] In order to prevent defects during transfer, the surface roughness Ra of the protective film on the surface in contact with the photosensitive layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. The roughness Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0337] The protective film is incorporated into the transfer film by, for example, laminating the protective film with the photosensitive layer or the refractive index adjusting layer. The lamination of the protective film with the photosensitive layer or the refractive index adjusting layer is carried out, for example, using a known laminator. Examples of laminators include a vacuum laminator and an auto-cut laminator. The laminator preferably includes a heatable roller. The laminator preferably has the functions of applying pressure and heat during lamination.

[0338] The method for laminating the transfer film and the substrate is not limited. The lamination of the transfer film and the substrate is carried out, for example, using a known laminator. Examples of laminators include a vacuum laminator and an auto-cut laminator. The lamination of the transfer film and the substrate is preferably carried out under pressure and heat conditions. The temperature is preferably 70°C to 130°C. When the transfer film includes a protective film, the protective film is peeled off before laminating the transfer film and the substrate.

[0339] (Exposure process) In the exposure step, the photosensitive layer is exposed to a pattern. According to the exposure step, exposed and non-exposed portions are formed in the photosensitive layer. The positional relationship between the exposed and non-exposed portions is not limited. The positional relationship between the exposed and non-exposed portions is determined, for example, according to the shape of the desired resin pattern. In the exposure step, the light for pattern-exposing the photosensitive layer may be irradiated along the direction from the photosensitive layer to the substrate or the direction from the substrate to the photosensitive layer.

[0340] The light source used in the exposure step is selected from light sources that emit light having a wavelength (e.g., 365 nm or 405 nm) capable of inducing a chemical change in the photosensitive layer. The dominant wavelength of the light is preferably 365 nm. "Dominant wavelength" refers to the wavelength with the highest intensity. Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.

[0341] The exposure dose in the exposure process was 5 mJ / cm 2 ~200mJ / cm 2 and preferably 10 mJ / cm 2 ~200mJ / cm 2 It is more preferable that:

[0342] Preferred embodiments of the light source, exposure dose, and exposure method in the exposure step are described, for example, in paragraphs

[0146] to

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

[0343] (Development process) In the development step, exposed or unexposed areas of the photosensitive layer are removed using a developer containing at least one component selected from the group consisting of sodium ions and potassium ions to form a resin pattern. When the photosensitive layer is a negative type, the unexposed areas of the photosensitive layer are usually removed by the developer, and the exposed areas of the photosensitive layer form a resin pattern. When the photosensitive layer is a positive type, the exposed areas of the photosensitive layer are usually removed by the developer, and the unexposed areas of the photosensitive layer form a resin pattern.

[0344] The presence of at least one component selected from the group consisting of sodium ions and potassium ions in the developer can be confirmed by ion chromatography. A developer containing at least one component selected from the group consisting of sodium ions and potassium ions can be produced, for example, by mixing a solvent with at least one component selected from the group consisting of sodium compounds and potassium compounds. Examples of solvents include water. Examples of sodium compounds include compounds that generate sodium ions in the solvent (e.g., sodium salts). Examples of sodium salts include sodium hydroxide, sodium carbonate, and sodium bicarbonate. Examples of potassium compounds include compounds that generate potassium ions in the solvent (e.g., potassium salts). Examples of potassium salts include potassium hydroxide, potassium carbonate, and potassium bicarbonate.

[0345] The temperature of the developer is preferably 22° C. to 33° C., more preferably 24° C. to 30° C., and even more preferably 26° C. When the temperature of the developer is 22° C. or higher, development defects are reduced. When the temperature of the developer is 33° C. or lower, the depth of the specific component in the resin pattern is easily adjusted to 3.0 μm or less.

[0346] The processing time in the development step is preferably 22 to 50 seconds, more preferably 22 to 40 seconds, even more preferably 22 to 30 seconds, and particularly preferably 25 seconds. When the processing time is 22 seconds or more, development defects are reduced. When the processing time is 50 seconds or less, the depth of the specific component in the resin pattern is easily adjusted to 3.0 μm or less.

[0347] Examples of the development method include puddle development, shower development, spin development, and dip development. Preferred development methods include the development method described in paragraph

[0195] of WO 2015 / 093271.

[0348] (Cleaning process) In the washing step, the resin pattern is washed with water. This washing step not only removes residues after development and the developer adhering to the substrate and the resin pattern, but also allows the depth of a specific component in the resin pattern to be adjusted depending on, for example, the water temperature and treatment time.

[0349] In the cleaning step, the resin pattern may be cleaned by immersion in water. In the cleaning step, the resin pattern may be cleaned by jetting water. In the cleaning step, components other than the resin pattern may also be cleaned together with the resin pattern.

[0350] The temperature of the water in the washing step is preferably 21°C to 35°C, more preferably 21°C to 30°C, even more preferably 21°C to 25°C, and most preferably 21°C. When the water temperature is 21°C or higher, the depth of the specific component in the resin pattern is easily adjusted to 0.3 μm or more. When the water temperature is 35°C or lower, the depth of the specific component in the resin pattern is easily adjusted to 3.0 μm or less.

[0351] The treatment time in the cleaning step is preferably 21 to 50 seconds, more preferably 22 to 40 seconds, even more preferably 23 to 30 seconds, and particularly preferably 25 seconds. When the treatment time is 21 seconds or longer, the depth of the specific component in the resin pattern is likely to be adjusted to 0.3 μm or more. When the treatment time is 50 seconds or shorter, the depth of the specific component in the resin pattern is likely to be adjusted to 3.0 μm or less.

[0352] Examples of water used in the cleaning step include pure water and ultrapure water. In the cleaning step, a mixed solvent of water and a solvent other than water may be used as needed. When a mixed solvent is used in the cleaning step, the "temperature of water" described above is replaced with the "temperature of the mixed solvent."

[0353] (Standing process) In the standing process, the substrate and resin pattern are left standing. The standing process can significantly contribute to adjusting the depth of presence of a specific component in the resin pattern. The standing process can adjust the depth of presence of a specific component in the resin pattern, for example, depending on the standing time. Standing means allowing time to pass without performing a post-process. Therefore, if no post-process is performed on the substrate and resin pattern, the standing process is included even if they are transported or the ambient temperature and humidity change due to transportation. Post-processes include post-exposure and post-bake, which will be described later, and OCA bonding processing for device fabrication.

[0354] The standing time in the standing step is preferably 1 hour to 72 hours, more preferably 15 hours to 48 hours, and even more preferably 24 hours to 48 hours. When the standing time is 1 hour or more, the depth of the specific component in the resin pattern is likely to be adjusted to 0.3 μm or more. When the standing time is 72 hours or less, the depth of the specific component in the resin pattern is likely to be adjusted to 3.0 μm or less.

[0355] The temperature (for example, the ambient temperature) in the standing step is preferably 15°C to 35°C, and more preferably 20°C to 30°C.

[0356] The relative humidity in the leaving step is preferably 40% RH to 70% RH, and more preferably 50% RH to 60% RH.

[0357] (Other processes) The method for producing a laminate according to an embodiment of the present disclosure may include other steps as necessary. Examples of the other steps include a peeling step, a post-exposure step, and a post-bake step. However, the other steps are not limited to the above specific examples. The other steps may be selected from known steps depending on the application of the laminate.

[0358] In the peeling step, the temporary support is peeled off. The peeling step is preferably carried out between the positioning step and the exposure step or between the exposure step and the development step. In the peeling step, for example, a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP 2010-072589 A is used.

[0359] In the post-exposure step, the resin pattern is exposed to light. The post-exposure step is preferably carried out after the standing step. The exposure dose in the post-exposure step is 100 J / cm. 2 ~5,000mJ / cm 2 Preferably, it is 200 J / cm 2 ~3,000mJ / cm 2 It is more preferable that:

[0360] In the post-baking step, the resin pattern is heated. When the method for producing a laminate according to an embodiment of the present disclosure includes a post-exposure step and a post-baking step, the post-baking step is preferably carried out after the post-exposure step. The temperature in the post-baking step is preferably 80°C to 250°C, and more preferably 90°C to 160°C. The treatment time in the post-baking step is preferably 1 minute to 180 minutes, and more preferably 10 minutes to 60 minutes. [Example]

[0361] The present disclosure will be described in detail below with reference to examples. However, the present disclosure is not limited to the following examples. The materials, amounts used, ratios, processing details, and processing procedures in the following examples may be changed as appropriate without departing from the spirit of the present disclosure. "Parts" and "%" are by mass unless otherwise specified. The weight average molecular weight is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene. The acid value is the theoretical acid value.

[0362] Example 1 (Synthesis of Polymer P-1) 113.5 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen stream. A solution of 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid dissolved in 30 g of propylene glycol monomethyl ether and a solution of 27.6 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in 57.7 g of propylene glycol monomethyl ether were simultaneously added dropwise to the flask over a period of 3 hours. After the dropwise addition was completed, 2.5 g of V-601 was added three times every hour. The reaction was then continued for another 3 hours. The reaction solution was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. The reaction mixture was heated to 100°C under an air stream, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. Then, 71.9 g of glycidyl methacrylate (Blenmer G, manufactured by NOF Corporation) was added dropwise over 20 minutes. The resulting mixture was reacted at 100°C for 7 hours to obtain a solution containing polymer P-1 (hereinafter sometimes referred to as "P-1 solution") represented by the following chemical formula. The solids concentration of the resulting solution was 36.2% by mass. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass of the polymer solids for all monomers.

[0363] [ka]

[0364] The properties of polymer P-1 are as follows: The weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights measured by gel permeation chromatography (GPC) in terms of standard polystyrene. ·Weight average molecular weight (Mw): 18,000 ·Number average molecular weight (Mn): 7,800 ·Degree of dispersion: 2.3 ·Acid value: 124mgKOH / g

[0365] (Synthesis of blocked isocyanate compound Q-1) Under a nitrogen stream, 453 g of butanone oxime (Idemitsu Kosan Co., Ltd.) was dissolved in 700 g of methyl ethyl ketone. 500 g of 1,3-bis(isocyanatomethyl)cyclohexane (a mixture of cis-trans isomers, Mitsui Chemicals, Takenate 600) was added dropwise to the resulting mixture over 1 hour under ice cooling, and the mixture was allowed to react for another 1 hour. The temperature was then raised to 40°C, and the mixture was allowed to react for another 1 hour. 1 Completion of the reaction was confirmed by H-NMR (nuclear magnetic resonance) and HPLC (high performance liquid chromatography), yielding a methyl ethyl ketone solution of blocked isocyanate compound Q-1, which is represented by the following chemical formula:

[0366] [ka]

[0367] (Preparation of blocked isocyanate compound Q-2) As the blocked isocyanate compound Q-2, "Duranate TPA-B80E" (manufactured by Asahi Kasei Corporation) was prepared.

[0368] (Preparation of Photosensitive Composition A-1) Photosensitive composition A-1 was prepared by mixing the following components (1) to (5), methyl ethyl ketone, and 1-methoxy-2-propyl acetate. The contents of the following components (1) to (5) are expressed in parts by mass calculated as solid content. The amounts of methyl ethyl ketone and 1-methoxy-2-propyl acetate added were adjusted so that the solid content concentration of photosensitive composition A-1 was 25% by mass. The amount of methyl ethyl ketone added was adjusted so that the proportion of methyl ethyl ketone in the solvent in photosensitive composition A-1 was 60% by mass.

[0369] (1) Polymer ·P-1 solution: 49.04 parts by mass

[0370] (2) Polymerizable compound Tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.13 parts by mass Monomer having a carboxy group (Aronix TO2349, manufactured by Toagosei Co., Ltd.): 3.04 parts by mass Acrylic monomer (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.): 2.79 parts by mass Acrylic monomer (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.): 17.28 parts by mass

[0371] (3) Polymerization initiator 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (OXE-02, manufactured by BASF): 0.37 parts by mass ·1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (APi-307, manufactured by Shenzhen UV-ChemTech): 0.74 parts by mass

[0372] (4) Blocked isocyanate Blocked isocyanate compound Q-1: 12.50 parts by mass Blocked isocyanate compound Q-2: 2.97 parts by mass

[0373] (5) Additives N-phenylglycine (Tokyo Chemical Industry Co., Ltd.): 0.10 parts by mass Benzimidazole (Tokyo Chemical Industry Co., Ltd.): 0.52 parts by mass Isonicotinamide (Tokyo Chemical Industry Co., Ltd.): 0.13 parts by mass XIRAN EF-40 (Kawahara Oil Chemical Co., Ltd.): 1.20 parts by mass Megafac (registered trademark) F551A (manufactured by DIC Corporation): 0.19 parts by weight

[0374] (Creating transfer film) A 16 μm-thick polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was prepared as a temporary support. Photosensitive composition A-1 was applied onto the temporary support using a slit nozzle, and the solvent was evaporated in a drying zone at 100°C to form a photosensitive layer with a thickness of 5.5 μm. A protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded to the photosensitive layer to produce a transfer film.

[0375] (Preparation of substrate) A substrate including a base material (cycloolefin polymer film), a transparent film, and a transparent electrode pattern (ITO) in this order was obtained by the following procedure.

[0376] A cycloolefin polymer film (thickness: 38 μm, refractive index: 1.53) was prepared as a substrate. Using a high-frequency oscillator, the substrate was subjected to a corona discharge treatment under the following conditions. Output voltage: 100% Output: 250W Electrode: 1.2mm diameter wire electrode Electrode length: 240mm Distance between work electrodes: 1.5 mm Processing time: 3 seconds

[0377] Next, a composition containing the components shown in Table 1 (the numerical value of each component in Table 1 is the content (parts by mass)) was applied onto the substrate using a slit nozzle, and then irradiated with ultraviolet light (integrated light dose: 300 mJ / cm 2 ) and dried at about 110°C to form a transparent film (refractive index: 1.60, thickness: 80 nm).

[0378] [Table 1]

[0379] [ka]

[0380] An ITO (Indium Tin Oxide) film having a thickness of 40 nm and a refractive index of 1.82 was formed on the transparent film by DC magnetron sputtering, and the formed ITO film was patterned by photoetching to form a transparent electrode pattern on the transparent film. The formation of the ITO film and the patterning of the ITO film were performed by the method described in paragraphs

[0119] to

[0122] of JP 2014-10814 A.

[0381] (Preparation of laminate) After peeling off the protective film from the transfer film, the transfer film was laminated onto the substrate so that the photosensitive layer covered the transparent film and the transparent electrode pattern. The lamination was performed using a vacuum laminator manufactured by MCK Corporation under the following conditions: the temperature of the base material (i.e., cycloolefin polymer film) was 40°C, the temperature of the rubber roller was 100°C, the linear pressure was 3 N / cm, and the transport speed was 4 m / min. Next, an exposure mask (a quartz exposure mask having a pattern for forming an overcoat) was brought into close contact with the temporary support using a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, and 150 mJ / cm was applied via the temporary support. 2 The photosensitive layer was pattern-exposed with an exposure dose of 100 mJ / cm (measured with i-line). The exposed sample was left standing for 24 hours in an environment of 23°C and 55% RH (relative humidity), after which the temporary support was peeled off and developed for 25 seconds using a 1.0 mass % aqueous sodium carbonate solution (liquid temperature: 25°C). The developed sample was washed with pure water at 21°C by spraying it from an ultra-high pressure washing nozzle for 25 seconds. After removing moisture adhering to the sample by blowing air, the sample was left standing for 24 hours in an environment of 23°C and 55% RH (relative humidity). A post exposure machine (manufactured by Ushio Inc.) equipped with a high-pressure mercury lamp was used to expose the sample to 400 mJ / cm. 2 The resin pattern was exposed to light at an exposure dose of 1000 kJ / cm² (measured with i-line) (post-exposure). Finally, post-baking was performed at 145°C for 30 minutes to obtain a laminate including the substrate, the transparent film, the transparent electrode pattern, and the resin pattern in this order. The resin pattern was a cured product of the photosensitive composition A-1.

[0382] <Example 2> A laminate was obtained in the same manner as in Example 1, except that the temperature of the pure water used in the water washing treatment was changed to 25°C.

[0383] Example 3 A laminate was obtained in the same manner as in Example 1, except that the temperature of the pure water in the water washing treatment was changed to 25° C. and the time of the water washing treatment was changed to 45 seconds.

[0384] Example 4 A laminate was obtained in the same manner as in Example 1, except that the standing time after the water washing treatment was changed to 3 hours.

[0385] <Example 5> A laminate was obtained using the same procedure as in Example 1, except that the temperature of the pure water used in the water washing treatment was changed to 25°C, the time for the water washing treatment was changed to 45 seconds, and the time for leaving the laminate after the water washing treatment was changed to 72 hours.

[0386] Example 6 A laminate was obtained in the same manner as in Example 1, except that the standing time after the water washing treatment was changed to 48 hours.

[0387] Example 7 A laminate was obtained in the same manner as in Example 6, except that polymer P-1 was changed to polymer P-2 represented by the following chemical formula: In the following chemical formula, the numerical values ​​attached to each structural unit represent mol %.

[0388] [ka]

[0389] The properties of polymer P-2 are as follows: The weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights measured by gel permeation chromatography (GPC) in terms of standard polystyrene. ·Acid value: 95mgKOH / g ·Weight average molecular weight (Mw): 27,000 Number average molecular weight (Mn) is 15,000

[0390] Example 8 A laminate was obtained in the same manner as in Example 6, except that the components of the photosensitive composition were changed according to the description in Table 2.

[0391] Example 9 A laminate was obtained using the same procedure as in Example 6, except that polymer P-1 was replaced with polymer P-3. Polymer P-3 is a random copolymer of benzyl methacrylate and methacrylic acid. The molar ratio of benzyl methacrylate / methacrylic acid in polymer P-3 is 72 / 28. The weight-average molecular weight (Mw) of polymer P-3 is 37,000.

[0392] Example 10 A laminate was obtained in the same manner as in Example 6, except that the polymerizable compound in the photosensitive composition A-1 was changed to the following polymerizable compound. NK Ester BPE-500 (polymerizable compound, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.): 22.5 parts by mass NK Ester BPE-200 (polymerizable compound, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.): 10.0 parts by mass NK Ester A-TMPT (polymerizable compound, trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.): 10.0 parts by mass

[0393] Example 11 A laminate was obtained in the same manner as in Example 6, except that the components of the photosensitive composition were changed according to the description in Table 2.

[0394] Example 12 A laminate was obtained in the same manner as in Example 6, except that the components of the photosensitive composition were changed according to the description in Table 2.

[0395] Example 13 A laminate was obtained in the same manner as in Example 6, except that the thickness of the photosensitive layer was changed to 3.3 μm.

[0396] Example 14 A laminate was obtained in the same manner as in Example 6, except that the thickness of the photosensitive layer was changed to 10.9 μm.

[0397] Example 15 A laminate was obtained in the same manner as in Example 1, except that the developer in the development treatment was changed to a 1% by mass aqueous solution of potassium carbonate.

[0398] Example 16 A laminate was obtained in the same manner as in Example 4, except that the developer in the development treatment was changed to a 1% by mass aqueous solution of potassium carbonate.

[0399] Example 17 A laminate was obtained in the same manner as in Example 5, except that the developer in the development treatment was changed to a 1% by mass aqueous solution of potassium carbonate.

[0400] <Examples 18 to 20> A laminate was obtained by the same procedure as in Example 6, except that a photosensitive layer was formed using a photosensitive composition containing the components listed in Table 3. In preparing the photosensitive composition, methyl ethyl ketone and 1-methoxy-2-propyl acetate were added as solvents in appropriate amounts, and the amount of solvent was adjusted so that the proportion of methyl ethyl ketone in all solvents in the photosensitive composition was 50 mass % and the solids concentration of the photosensitive composition was 20 mass %.

[0401] <Examples 21 and 22> A laminate was obtained in the same manner as in Example 6, except that a photosensitive composition containing the components listed in Table 4 was used to form a photosensitive layer.

[0402] <Examples 23 to 25> A laminate was obtained in the same manner as in Example 6, except that a photosensitive composition containing the components listed in Table 5 was used to form a photosensitive layer.

[0403] <Comparative Example 1> A laminate was obtained in the same manner as in Example 6, except that the conditions for the development treatment and the washing treatment were changed to the following conditions. Developer temperature: 20℃ Development time: 20 seconds -Pure water temperature during washing: 20℃ Washing time: 20 seconds Time left after washing: 0 hours

[0404] <Comparative Example 2> A laminate was obtained in the same manner as in Example 6, except that the conditions for the development treatment and the washing treatment were changed to the following conditions. Developer temperature: 35℃ Development time: 60 seconds -Pure water temperature during washing: 40℃ Washing time: 60 seconds -Standing time after washing: 80 hours

[0405] <Depth of sodium ions or potassium ions> IONTOF SIMS5 and Ar + The distribution of sodium ions or potassium ions in the depth direction of the resin pattern was measured using a cluster sputtering gun. Specifically, sodium ions were detected in the resin pattern formed by development treatment using a 1% by mass aqueous solution of sodium carbonate, and potassium ions were detected in the resin pattern formed by development treatment using a 1% by mass aqueous solution of potassium carbonate. The depth direction analysis was carried out in the direction from the resin pattern to the substrate. Specifically, the measurement object was a 1% by mass aqueous solution of potassium carbonate. +Sodium or potassium ions were detected by TOF-SIMS while sputtering with a cluster sputter gun. The intensity of the target component (i.e., sodium or potassium ion) detected on the surface of the resin pattern was assumed to be 100%, and the sputtering time when the target component's intensity first reached 90% was converted into a depth (i.e., the distance from the surface of the resin pattern to the point where the target component's intensity first reached 90%) based on the sputtering rate. The "depth" measurement was performed at three random points in the pattern where no edge lifting occurred, each at least 10 μm away from the edge lifting in the substrate plane direction and at least 100 μm away from each other. The arithmetic mean of the three measurements was taken as the "existence depth." The measurement results are shown in Tables 2 to 5.

[0406] <Evaluation> The laminates obtained in the examples and comparative examples were evaluated for the following items. The evaluation results are shown in Tables 2 to 5.

[0407] (scratch resistance) The resin pattern was scratched with a spherical diamond scratching needle with a tip diameter of 75 μm at a load of 10 g and a length of 5 cm. The degree of scratches on the resin pattern was confirmed, and the scratch resistance was evaluated according to the following criteria A to D. A or B is a level that is acceptable for practical use, with A being preferred. A: No scratches are observed visually or under an optical microscope. B: Slight scratches are observed under an optical microscope. C: Scratches are observed under an optical microscope, but no scratches are observed with the naked eye. D: Significant scratches are observed by visual inspection.

[0408] (Edge lift) A cross section near the edge of the resin pattern in the laminate was observed using a scanning electron microscope. The width of the edge lift of the resin pattern (specifically, the length of the part where the edge of the resin pattern is lifted) was measured, and the edge lift was evaluated according to the following criteria A to D. A or B is a level that is not problematic in practical use, and A is preferred. A: No edge lifting is observed. B: The width of the edge lift is 0.1 μm or more and less than 5.0 μm. C: The width of the edge lift is 5.0 μm or more and less than 10.0 μm. D: The width of the edge lift is 10.0 μm or more.

[0409] [Table 2]

[0410] In Table 2, the unit of the content of components listed in the "Photosensitive composition" column is parts by mass converted to solid content. In Examples 1 to 14 and Comparative Examples 1 and 2, "depth of presence of sodium ions or potassium ions" specifically means the depth of presence of sodium ions. In Examples 15 to 17, "depth of presence of sodium ions or potassium ions" specifically means the depth of presence of potassium ions.

[0411] [Table 3]

[0412] In Table 3, the content of the components listed in the "Photosensitive composition" column is expressed in parts by mass converted into solid content.

[0413] [Table 4]

[0414] In Table 4, the units of the contents of components excluding the solvent listed in the "Photosensitive Composition" column are parts by mass converted to solid content. "P-1 Solution" in Table 4 means a solution containing polymer P-1. "P-2 Solution" in Table 4 means a solution containing polymer P-2.

[0415] [Table 5]

[0416] In Table 5, the units of the contents of components excluding the solvent listed in the "Photosensitive Composition" column are parts by mass converted to solid content. "P-2 Solution" in Table 5 means a solution containing polymer P-2. "P-3 Solution" in Table 5 means a solution containing polymer P-3.

[0417] Tables 2 to 5 show that, compared with Comparative Examples 1 and 2, Examples 1 to 25 have excellent scratch resistance and have reduced edge lifting.

[0418] <Examples 1A to 25A> Each transfer film was produced and evaluated in the same manner as in Examples 1 to 25, except that the temporary support and protective film used in producing the transfer film were changed to the following materials. The results were the same as in Examples 1 to 25. Temporary support: Product name "Cosmoshine (registered trademark) A4160", manufactured by Toyobo Co., Ltd., thickness 50 μm, PET film Protective film: Product name: Alphan (registered trademark) E-210F, manufactured by Oji F-Tex Co., Ltd., 50 μm thick, polypropylene film <Examples 1B to 25B> Each transfer film was produced and evaluated in the same manner as in Examples 1 to 25, except that the temporary support and protective film used in producing the transfer film were changed to the following materials. The results were the same as in Examples 1 to 25. Temporary support: Product name "Cosmoshine (registered trademark) A4360", manufactured by Toyobo Co., Ltd., thickness 38 μm, PET film Protective film: Product name: Alphan (registered trademark) FG-201, manufactured by Oji F-Tex Co., Ltd., 30 μm thick, polypropylene film <Examples 1C to 25C> Each transfer film was produced and evaluated in the same manner as in Examples 1 to 25, except that the temporary support and protective film used in producing the transfer film were changed to the following materials. The results were the same as in Examples 1 to 25. Temporary support: Product name "Lumirror (registered trademark) #38-U48", manufactured by Toray Industries, Inc., thickness 38 μm, PET film Protective film: Product name: Alphan (registered trademark) E-210F, manufactured by Oji F-Tex Co., Ltd., 50 μm thick, polypropylene film <Examples 1D to 25D> Each transfer film was produced and evaluated in the same manner as in Examples 1 to 25, except that the temporary support and protective film used in producing the transfer film were changed to the following materials. The results were the same as in Examples 1 to 25. Temporary support: Product name "Lumirror (registered trademark) #25-T60", manufactured by Toray Industries, Inc., thickness 25 μm, PET film Protective film: Product name: Alphan (registered trademark) FG-201, manufactured by Oji F-Tex Co., Ltd., 30 μm thick, polypropylene film <Examples 1E to 25E> Each transfer film was produced and evaluated in the same manner as in Examples 1 to 25, except that the temporary support and protective film used in producing the transfer film were changed to the following materials. The results were the same as in Examples 1 to 25. Temporary support: Product name "Lumirror (registered trademark) 16FB40", manufactured by Toray Industries, Inc., thickness 16 μm, PET film Protective film: Product name: Alphan (registered trademark) E-210F, manufactured by Oji F-Tex Co., Ltd., 50 μm thick, polypropylene film

[0419] <Examples 101 to 125> (Preparation of Transparent Resin Layer-Forming Composition Y-1) A transparent resin layer-forming composition Y-1 having the composition shown in Table 6 was prepared.

[0420] [Table 6]

[0421] (Creating transfer film) A photosensitive layer was formed on a temporary support according to the method described in "Preparation of a transfer film" in Example 1. A transparent resin layer was formed by applying composition Y-1 for forming a transparent resin layer onto the photosensitive layer and drying it. The amount of application was adjusted so that the thickness after curing would be 73 nm. A protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded to the transparent resin layer to prepare a transfer film.

[0422] (Preparation of laminate) The laminates of Examples 101 to 125 were obtained by the same procedure as in Examples 1 to 25, except that the laminates were produced using a transfer film containing the transparent resin layer described above. That is, except for the transparent resin layer, the manufacturing conditions for the laminates of Examples 101 to 125 corresponded to the manufacturing conditions for the laminates of Examples 1 to 25, respectively. The obtained laminates were evaluated for the "scratch resistance" and "edge lifting" described above. The evaluation results of Examples 101 to 125 were the same as those of Examples 1 to 25, respectively.

[0423] <Example 201> Using each of the transfer films of Examples 1 to 17 and 101 to 117, a liquid crystal display device equipped with a touch panel was manufactured by the following method.

[0424] A substrate was prepared in which an ITO transparent electrode pattern and copper wiring were formed on a cycloolefin polymer film. Using a transfer film from which the protective film had been peeled off, the transfer film was laminated onto the substrate in a position where it covered the ITO transparent electrode pattern and the copper wiring. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a cycloolefin polymer film temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. Next, an exposure mask (a quartz exposure mask having an overcoat formation pattern) was brought into close contact with a temporary support using a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp. After leaving the mask in an environment of 23°C and 55% RH (relative humidity) for 24 hours, 150 mJ / cm was applied through the temporary support. 2 The photosensitive layer was pattern-exposed with an exposure dose of 1200 mJ / cm (i-line). After peeling off the temporary support, the sample was developed for 30 seconds using a 1.0% by mass aqueous solution of sodium carbonate at 23°C. After development, the sample was rinsed with pure water at 22°C by spraying it from an ultra-high pressure cleaning nozzle for 30 seconds. Subsequently, air was blown onto the sample to remove moisture, and the sample was left to stand for 24 hours in an environment of 23°C and 55% RH (relative humidity). A post-exposure machine equipped with a high-pressure mercury lamp (manufactured by Ushio Inc.) was used to expose the sample to 1200 mJ / cm (i-line). 2 The resin pattern was exposed to light at an exposure dose of 1000 nm (measured with i-line) (post-exposure). A post-baking treatment was performed at 145°C for 30 minutes to obtain a laminate comprising an ITO transparent electrode pattern, copper wiring, and a resin pattern, in this order, on a cycloolefin polymer film. Next, a touch panel was manufactured using the prepared laminate by a known method. The manufactured touch panel was bonded to a liquid crystal display element manufactured by the method described in paragraphs

[0097] to

[0119] of JP 2009-47936 A, thereby manufacturing a liquid crystal display device equipped with a touch panel. It was confirmed that the liquid crystal display device equipped with a touch panel had excellent display characteristics and operated without any problems.

[0425] The disclosure of Japanese Patent Application No. 2021-058108, filed on March 30, 2021, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A substrate and a resin pattern, Based on a depth direction analysis of the resin pattern carried out along a direction from the resin pattern toward the substrate, when the intensity of at least one component selected from the group consisting of sodium ions and potassium ions detected on the surface of the resin pattern is defined as 100%, the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is defined as the distance from the surface of the resin pattern to a point where the intensity of the at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90% is 0.3 μm to 3.0 μm. Laminate.

2. 2. The laminate according to claim 1, wherein the ratio of the depth of the resin pattern to the thickness of the resin pattern is 0.1 to 0.

9.

3. The laminate according to claim 1 or 2, wherein the resin pattern is a cured product of a photosensitive composition.

4. The laminate according to claim 3 , wherein the photosensitive composition comprises a polymerizable compound and a polymerization initiator.

5. The laminate according to claim 3 or claim 4, wherein the photosensitive composition comprises a polymer.

6. The laminate according to claim 5 , wherein the polymer has a polymerizable group.

7. 7. The laminate according to claim 1, further comprising a transparent electrode between the substrate and the resin pattern.

8. The laminate according to any one of claims 1 to 7, which is a touch panel.

9. disposing a photosensitive layer on a substrate; patternwise exposing the photosensitive layer; removing the exposed or unexposed portion of the photosensitive layer using a developer containing at least one component selected from the group consisting of sodium ions and potassium ions to form a resin pattern; washing the resin pattern with water; allowing the substrate and the resin pattern to stand; Post-exposure and and post-baking, in that order; Based on a depth direction analysis of the resin pattern performed along a direction from the resin pattern toward the substrate after leaving the substrate and the resin pattern at rest, when the intensity of at least one component selected from the group consisting of sodium ions and potassium ions detected on the surface of the resin pattern is defined as 100%, the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is defined as the distance from the surface of the resin pattern to a point where the intensity of the at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90%, and is 0.3 μm to 3.0 μm. A method for manufacturing a laminate.

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