Method for manufacturing a conductive pattern, touch sensor, electromagnetic wave shielding member, antenna, wiring board, conductive heating element, and structure

Abstract

The present invention provides a method for manufacturing a conductive pattern and its application, the method for manufacturing a conductive pattern comprising: a step of preparing a laminate, the laminate comprising: a transparent substrate, a light-shielding pattern on the transparent substrate, and a negative photosensitive resin layer, which is arranged on the transparent substrate and the light-shielding pattern and is in contact with the transparent substrate; a step of irradiating light onto the surface of the transparent substrate opposite to the surface facing the light-shielding pattern; a step of forming a resin pattern in an area defined by the transparent substrate and the light-shielding pattern by developing the negative photosensitive resin layer; and a step of forming a conductive pattern on the light-shielding pattern.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a conductive pattern, a touch sensor, an electromagnetic wave shielding member, an antenna, a wiring substrate, a conductive heating element, and a structure. Background Art

[0002] Conductive patterns resembling fine metal wires are used in a variety of applications. Examples of these applications include touch sensors in touch panels, antennas, fingerprint authentication units, foldable devices, and transparent FPCs (flexible printed circuits). For example, fine conductive patterns are formed on substrates during the manufacture of semiconductor packages, printed wiring boards, and the redistribution layers of interposers. Substrates include films, sheets, metal substrates, ceramic substrates, and glass.

[0003] As a general method for forming a conductive pattern, for example, a subtractive method and a semi-additive method are known (for example, Patent Document 1 and Patent Document 2). In the subtractive method, for example, after protecting the conductive layer on the substrate with a resist pattern, the conductive layer not protected by the resist pattern is removed by etching, thereby forming a conductive pattern. On the other hand, in the semi-additive method, for example, after an electroless copper plating layer called a seed layer is provided on the substrate, a resist pattern is also provided on the electroless copper plating layer. Then, after forming a conductive pattern by plating on the electroless copper plating layer where the resist pattern is not provided, the unnecessary resist pattern and the electroless copper plating layer (seed layer) are removed.

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-225650

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2015-065376 Summary of the Invention

[0008] Technical issues to be solved by the invention

[0009] For example, in order to reduce the resistance of the conductive pattern, a thick conductive pattern is sometimes formed. However, in the subtractive method, due to the phenomenon that etching is also isotropically performed in the in-plane direction of the substrate provided with the conductive layer (for example, called "side etching"), the conductive layer protected by the resist pattern may also be eroded by the liquid. Since the occurrence of side etching affects the manner (for example, shape and size) of the conductive pattern formed by etching, it is difficult to form, for example, a thick rectangular conductive pattern. In the semi-additive method, due to the close adhesion between the seed layer and the resist pattern, there is a problem that the formation of the conductive pattern becomes unstable. In addition, since a portion of the conductive pattern may be removed when removing the unnecessary seed layer, the semi-additive method also has the same problems as the subtractive method.

[0010] The present invention has been accomplished in view of the above circumstances.

[0011] One embodiment of the present invention aims to provide a method for manufacturing a conductive pattern, which is used to form a thick conductive pattern that reduces the occurrence of morphological abnormalities (for example, the generation of a tapered shape due to cracking, peeling, fragmentation, side etching, and dimensional instability due to etching changes. The same applies hereinafter).

[0012] Another aspect of the present invention aims to provide a touch sensor having a thick conductive pattern that reduces the occurrence of morphological abnormalities.

[0013] Another aspect of the present invention aims to provide an electromagnetic shielding material having a thick conductive pattern that reduces the occurrence of morphological abnormalities.

[0014] Another aspect of the present invention aims to provide an antenna having a thick conductive pattern that reduces the occurrence of morphological abnormalities.

[0015] Another aspect of the present invention aims to provide a wiring board having a thick conductive pattern with reduced occurrence of morphological abnormalities.

[0016] Another aspect of the present invention aims to provide a conductive heating element having a thick conductive pattern that reduces the occurrence of morphological abnormalities.

[0017] Another embodiment of the present invention aims to provide a structure useful as a material for forming a thick conductive pattern with reduced occurrence of morphological abnormalities.

[0018] Another aspect of the present invention aims to provide a structure having a thick conductive pattern with reduced occurrence of morphological abnormalities.

[0019] Means for solving technical problems

[0020] <1> A method for manufacturing a conductive pattern, comprising: a step of preparing a laminate having: a transparent substrate, a light-shielding pattern on the transparent substrate, and a negative photosensitive resin layer, which is arranged on the transparent substrate and the light-shielding pattern and is in contact with the transparent substrate; a step of irradiating light onto a surface of the transparent substrate opposite to the surface facing the light-shielding pattern; a step of forming a resin pattern in an area defined by the transparent substrate and the light-shielding pattern by developing the negative photosensitive resin layer; and a step of forming a conductive pattern on the light-shielding pattern.

[0021] <2> according to <1> In the method for manufacturing the conductive pattern, in the step of forming the conductive pattern, the conductive pattern is formed by plating.

[0022] <3> according to <2> In the method for manufacturing a conductive pattern, the plating is electroplating.

[0023] <4> according to <2> In the method for manufacturing the conductive pattern, the plating is copper electroplating.

[0024] <5> according to <1> to <4> The method for manufacturing a conductive pattern according to any one of the preceding claims, wherein the light-shielding pattern has conductivity.

[0025] <6> according to <1> to <5> The method for producing a conductive pattern according to any one of claims 1 to 5, wherein the light-shielding pattern has an average thickness of 2 μm or less.

[0026] <7> according to <1> to <6> The method for manufacturing a conductive pattern as described in any one of the above, wherein the step of preparing the stacked body includes: a step of preparing a stacked precursor, wherein the stacked precursor has the above-mentioned transparent substrate and the above-mentioned light-shielding pattern on the above-mentioned transparent substrate; and a step of forming the above-mentioned negative photosensitive resin layer on the above-mentioned transparent substrate and the above-mentioned light-shielding pattern.

[0027] <8> according to <1> to <6> The method for manufacturing a conductive pattern as described in any one of the above, wherein the step of preparing the stacked body includes: a step of preparing the above-mentioned transparent substrate; a step of forming a light-shielding pattern on the above-mentioned transparent substrate; and a step of forming the above-mentioned negative photosensitive resin layer on the above-mentioned transparent substrate and the above-mentioned light-shielding pattern.

[0028] <9> according to <8> The method for manufacturing a conductive pattern, wherein the step of forming the light-shielding pattern includes: a step of forming a light-shielding layer on the transparent substrate; a step of forming a photosensitive resin layer on the light-shielding layer; a step of forming an anti-etching pattern by exposing and developing the photosensitive resin layer; and a step of removing the light-shielding layer not covered by the anti-etching pattern.

[0029] <10> according to <7> to <9> The method for producing a conductive pattern according to any one of the preceding claims, wherein, in the step of forming the negative photosensitive resin layer, the negative photosensitive resin layer is formed using a photosensitive transfer material.

[0030] <11> according to <1> to <10> The method for manufacturing a conductive pattern as described in any one of the above includes the step of removing the resin pattern after the step of forming the conductive pattern.

[0031] <12> according to <1> to <11> The method for manufacturing a conductive pattern as described in any one of the above, wherein an average thickness of the resin pattern is greater than an average thickness of the light-shielding pattern.

[0032] <13> according to <1> to <12> The method for producing a conductive pattern according to any one of the above, wherein the average thickness of the resin pattern is 3 μm or greater.

[0033] <14> according to <1> to <13> The method for producing a conductive pattern according to any one of claims 1 to 5, wherein the average thickness of the resin pattern is 5 μm or greater.

[0034] <15> according to <1> to <14> The method for producing a conductive pattern according to any one of claims 1 to 5, wherein the average thickness of the resin pattern is 10 μm or greater.

[0035] <16> according to <1> to <15> The method for producing a conductive pattern according to any one of claims 1 to 5, wherein the average width of the light-shielding pattern is 5 μm or less.

[0036] <17> according to <1> to <16> The method for producing a conductive pattern according to any one of claims 1 to 5, wherein the average width of the resin pattern is 5 μm or less.

[0037] <18> according to <1> to <17> The method for manufacturing a conductive pattern described in any one of claims 1 to 5, wherein the light has a wavelength of 365 nm.

[0038] <19> according to <1> to <18> The method for producing a conductive pattern according to any one of the above, wherein the negative photosensitive resin layer contains an alkali-soluble polymer, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator.

[0039] <20> A touch sensor having <1> to <19> A conductive pattern obtained by any one of the methods for producing a conductive pattern.

[0040] <21> An electromagnetic wave shielding member having <1> to <19> A conductive pattern obtained by any one of the methods for producing a conductive pattern.

[0041] <22> An antenna having <1> to <19> A conductive pattern obtained by any one of the methods for producing a conductive pattern.

[0042] <23> A wiring substrate having <1> to <19> A conductive pattern obtained by any one of the methods for producing a conductive pattern.

[0043] <24> A conductive heating element having <1> to <19> A conductive pattern obtained by any one of the methods for producing a conductive pattern.

[0044] <25> A structure comprising: a transparent substrate; a light-shielding pattern on the transparent substrate; and a resin pattern, which is arranged adjacent to the light-shielding pattern on the transparent substrate and in contact with the transparent substrate, wherein the average thickness of the light-shielding pattern is less than 2 μm, and the average thickness of the resin pattern exceeds 2 μm.

[0045] <26> according to <25> In the structure, the average width of the light-shielding pattern is 5 μm or less, and the average width of the resin pattern is 5 μm or less.

[0046] <27> A structure comprising: a transparent substrate; a conductive pattern on the transparent substrate; and a resin pattern, which is arranged adjacent to the conductive pattern on the transparent substrate and in contact with the transparent substrate, wherein the average thickness of the conductive pattern is greater than or equal to 2 μm and less than the average thickness of the resin pattern, and the average thickness of the resin pattern is greater than or equal to 2 μm.

[0047] <28> according to <27> In the structure, the average width of the conductive pattern is 5 μm or less, and the average width of the resin pattern is 5 μm or less.

[0048] Effects of the Invention

[0049] According to one aspect of the present invention, there is provided a method for manufacturing a conductive pattern for forming a thick conductive pattern in which occurrence of morphological abnormalities is reduced.

[0050] According to another aspect of the present invention, a touch sensor having a thick conductive pattern that reduces the occurrence of morphological abnormalities is provided.

[0051] According to another aspect of the present invention, there is provided an electromagnetic shielding material having a thick conductive pattern that reduces the occurrence of morphological abnormalities.

[0052] According to another aspect of the present invention, there is provided an antenna having a thick conductive pattern that reduces the occurrence of morphological abnormalities.

[0053] According to another aspect of the present invention, there is provided a wiring board having a thick conductive pattern in which occurrence of morphological abnormalities is reduced.

[0054] According to another aspect of the present invention, there is provided a conductive heating element having a thick conductive pattern that reduces the occurrence of morphological abnormalities.

[0055] According to another aspect of the present invention, there is provided a structure useful as a material for forming a thick conductive pattern in which occurrence of morphological abnormalities is reduced.

[0056] According to another aspect of the present invention, there is provided a structure having a thick conductive pattern with reduced occurrence of morphological abnormalities. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a schematic cross-sectional view showing an example of a method for producing a conductive pattern of the present invention.

[0058] Figure 2 This is a schematic cross-sectional view showing an example of the structure of the present invention.

[0059] Figure 3 This is a schematic cross-sectional view showing an example of the structure of the present invention. DETAILED DESCRIPTION

[0060] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the present invention.

[0061] When describing the embodiments of the present invention with reference to the drawings, overlapping components and reference numerals may be omitted. Components denoted by the same reference numerals in the drawings represent the same components. Dimensional ratios in the drawings do not necessarily represent actual dimensional ratios.

[0062] In the present invention, the numerical range represented by "to" represents a range including the numerical values recorded before and after "to" as the lower limit and upper limit, respectively. In the numerical ranges recorded in stages in the present invention, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in another stage. Furthermore, in the numerical ranges recorded in the present invention, the upper limit or lower limit recorded in a certain numerical range can be replaced by the values shown in the Examples.

[0063] In the present invention, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition, unless otherwise specified.

[0064] In the present invention, the term "step" includes not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the intended purpose of the step can be achieved.

[0065] In the present invention, "mass %" and "weight %" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0066] In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

[0067] In the present invention, the term "unsubstituted" or "unsubstituted" includes both unsubstituted and substituted groups. For example, the term "alkyl" includes both unsubstituted alkyl groups (i.e., unsubstituted alkyl groups) and substituted alkyl groups (i.e., substituted alkyl groups).

[0068] In the present invention, "(meth)acrylic acid" means acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid.

[0069] In the present invention, "(meth)acryloyl" means an acryloyl group, a methacryloyl group, or both an acryloyl group and a methacryloyl group.

[0070] In the present invention, "(meth)acrylate" refers to acrylate, methacrylate, or both acrylate and methacrylate.

[0071] In the present invention, "alkali-soluble" means a property in which the solubility of sodium carbonate in an aqueous solution (100 g, sodium carbonate concentration: 1 mass %) at a liquid temperature of 22°C is 0.1 g or more.

[0072] In the present invention, chemical structural formulas may be described as structural formulas with hydrogen atoms omitted.

[0073] In the present invention, "conductive" means the property of easy flow of electric current. The required easy flow of electric current is not limited as long as it is the degree required for the purpose and use. When the conductivity is expressed by volume resistivity, the volume resistivity is preferably less than 1×10 6 Ωcm, more preferably less than 1×10 4 Ωcm or less.

[0074] In the present invention, "light" refers to electromagnetic waves including ultraviolet light, visible light, and infrared light. Light preferably has a wavelength in the range of 200 nm to 1,500 nm, more preferably in the range of 250 nm to 450 nm, and particularly preferably in the range of 300 nm to 410 nm.

[0075] In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights converted using polystyrene as a standard substance. Molecular weights were measured using a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL columns (all trade names manufactured by TOSOH CORPORATION), with the compound in THF (tetrahydrofuran) detected by differential refractometer.

[0076] In the present invention, the "solid content" refers to a component obtained by removing the solvent from the total components of an object.

[0077] In the present invention, symbols (for example, A and B) added to names are used to distinguish components and do not limit the types of components, the number of components, or the quality of components.

[0078] <Method for Manufacturing Conductive Pattern>

[0079] The method for producing a conductive pattern of the present invention includes: preparing a laminate (hereinafter sometimes referred to as a "preparation step"), the laminate comprising: a transparent substrate, a light-shielding pattern on the transparent substrate, and a negative photosensitive resin layer disposed on and in contact with the transparent substrate; irradiating light onto the surface of the transparent substrate opposite to the surface facing the light-shielding pattern (hereinafter sometimes referred to as an "exposure step"); developing the negative photosensitive resin layer to form a resin pattern in an area defined by the transparent substrate and the light-shielding pattern (hereinafter sometimes referred to as a "development step"); and forming a conductive pattern on the light-shielding pattern (hereinafter sometimes referred to as a "conductive pattern forming step"). According to the method for producing a conductive pattern of the present invention, a thick conductive pattern is formed in which the occurrence of morphological abnormalities is reduced.

[0080] The reasons for the aforementioned effects of the conductive pattern manufacturing method of the present invention are presumably as follows. As described above, conventional conductive pattern manufacturing methods (e.g., subtractive and semi-additive methods) employ a step of etching a prefabricated conductive layer into a pattern, or a step of removing a seed layer after forming the conductive pattern. Consequently, controllability of the shape and size of thick conductive patterns poses a challenge.

[0081] On the other hand, in the method for manufacturing a conductive pattern of the present invention, the occurrence of morphological abnormalities of the conductive pattern caused by, for example, side etching or removal of the seed layer can be reduced through the preparation step, exposure step, development step, and conductive pattern formation step. Figure 1 The method for producing the conductive pattern of the present invention will be described. Figure 1 This is a schematic cross-sectional view showing an example of a method for producing a conductive pattern of the present invention. Figure 1 (a) shows an example of a preparation step. Figure 1 (b) shows an example of an exposure step. Figure 1 (c) shows an example of a development step. Figure 1 (d) shows an example of a step of forming a conductive pattern. Figure 1 The laminate 100 shown in (a) comprises a transparent substrate 10, a light-shielding pattern 20, and a negative photosensitive resin layer 30. Figure 1 As shown in (b), light is irradiated onto the surface of the transparent substrate 10 opposite to the surface facing the light-shielding pattern 20 (i.e., the exposed surface 10a). Since the proportion of light passing through the light-shielding pattern 20 is small, the light incident on the exposed surface 10a of the transparent substrate 10 passes through the transparent substrate 10 and passes through the exposed portion 30a of the negative photosensitive resin layer 30. As a result, the exposed portion 30a of the negative photosensitive resin layer 30 is selectively exposed. Figure 1 As shown in (c), by developing the negative photosensitive resin layer 30, the portion other than the exposed portion 30a of the negative photosensitive resin layer 30 is removed, and a resin pattern 40 is formed in the area (i.e., the groove) defined by the transparent substrate 10 and the light-shielding pattern 20. Figure 1 As shown in (d), a conductive pattern 50 is formed on the light-shielding pattern 20. Figure 1 In (d), the conductive pattern 50 is formed in the region (i.e., the groove) defined by the light-shielding pattern 20, which functions like a mold, and the resin pattern 40. Through the above-described steps, a thick conductive pattern 50 can be easily formed. Therefore, according to the conductive pattern manufacturing method of the present invention, a thick conductive pattern with reduced morphological abnormalities can be formed.

[0082] Preparation Steps

[0083] In the preparation step, a laminate is prepared, comprising: a transparent substrate; a light-shielding pattern on the transparent substrate; and a negative photosensitive resin layer disposed on the transparent substrate and the light-shielding pattern and in contact with the transparent substrate. In the present invention, "preparation" means bringing an object into a state ready for use. The laminate may be previously manufactured. Alternatively, the laminate may be manufactured in the preparation step. That is, the preparation step may also include a step of manufacturing the laminate.

[0084] [Transparent substrate]

[0085] The laminate has a transparent substrate. In the present invention, "transparent" means that the transmittance of the exposure wavelength is 50% or more. The transmittance of the exposure wavelength specified in the term "transparent" is preferably 80% or more, more preferably 90%, and particularly preferably 95%. In the present invention, "transmittance of the exposure wavelength" refers to the transmittance of the wavelength included in the light reaching the object (e.g., transparent substrate) in the exposure step. For example, when a light source with a wavelength of 365nm is used in the exposure step, "transmittance of the exposure wavelength" refers to the transmittance at a wavelength of 365nm. In the present invention, "transmittance" refers to the ratio of the intensity of the outgoing light emitted through the measurement object to the intensity of the incident light when the light is incident in a direction perpendicular to the main surface of the measurement object (i.e., the thickness direction). The transmittance is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0086] The shape of the transparent substrate is not limited. As the transparent substrate, for example, a film-shaped or plate-shaped transparent substrate is preferably used.

[0087] As a transparent substrate, for example, a resin substrate (for example, a resin film) and a glass substrate can be mentioned. The resin substrate is preferably a resin substrate that transmits visible light. As a preferred component of a resin substrate that transmits visible light, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, polyimide resins and polycarbonate resins can be mentioned. As a more preferred component of a resin substrate that transmits visible light, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), polyimide and polycarbonate can be mentioned. The transparent substrate is preferably a polyamide film, polyethylene terephthalate film, cycloolefin polymer (COP), polyethylene naphthalate film, polyimide film or polycarbonate film, more preferably a polyethylene terephthalate film.

[0088] Examples of the transparent substrate include paper phenol, paper epoxy, glass composite, glass epoxy, polytetrafluoroethylene, and rigid-flexible materials obtained by combining hard and soft materials. The transparent substrate may also be porous. The transparent substrate may also contain fillers and additives.

[0089] The surface of the transparent substrate can be modified by, for example, alkali treatment or energy ray irradiation.

[0090] The structure of the transparent substrate can be a single layer structure or a multilayer structure. The transparent substrate can also include a functional layer. Examples of the functional layer include an adhesive layer, a hard coat layer, and a refractive index adjustment layer.

[0091] There is no limit to the thickness of the transparent substrate. The average thickness of the transparent substrate is preferably 10 μm to 200 μm, more preferably 20 μm to 120 μm, and particularly preferably 20 μm to 100 μm. The average thickness of the transparent substrate is measured by the following method. A scanning electron microscope (SEM) is used to observe a cross section in a direction perpendicular to the main surface of the transparent substrate (i.e., thickness direction). Based on the obtained observation image, the thickness of the transparent substrate is measured at 10 points. The average thickness of the transparent substrate is obtained by taking the arithmetic average of the measured values. In addition, depending on the thickness of the object, a transmission electron microscope (TEM) can also be used instead of a scanning electron microscope (SEM).

[0092] The transparent substrate preferably has a high total light transmittance. The total light transmittance of the transparent substrate is preferably 50% or higher, more preferably 80% or higher, even more preferably 90% or higher, and particularly preferably 95% or higher. There is no upper limit to the total light transmittance of the transparent substrate. The total light transmittance of the transparent substrate may be determined within a range of 100% or lower. The total light transmittance is measured using the method specified in JIS K 7361-1.

[0093] [Light-blocking pattern]

[0094] The laminate has a light-shielding pattern on a transparent substrate. Figure 1 As shown in FIG. 2 (b), the laminate 100 includes a light-shielding pattern 20, which allows selective exposure of a portion of the negative-type photosensitive resin layer 30 (i.e., the exposed portion 30a) during the exposure step. In the present invention, "light-shielding" means a transmittance of less than 50% at the exposure wavelength. The transmittance at the exposure wavelength defined in the term "light-shielding" is preferably less than 30%, more preferably less than 10%, and even more preferably less than 1%.

[0095] The light-shielding pattern is preferably conductive. The conductive light-shielding pattern can function as an electrical conductor (e.g., a seed layer) during plating in the conductive pattern formation step described later. The seed layer can function as a cathode during electroplating, for example.

[0096] As a component of the light-shielding pattern, for example, a metal can be mentioned. As a metal, for example, Nb (niobium), Al (aluminum), Ni (nickel), Zn (zinc), Mo (molybdenum), Ta (tantalum), Ti (titanium), V (vanadium), Cr (chromium), Fe (iron), Co (cobalt), W (tungsten), Cu (copper), Sn (tin) and Mn (manganese) can be mentioned. From the viewpoint of conductivity, the light-shielding pattern preferably contains a metal, more preferably contains at least one selected from Nb, Al, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn and Mn, and particularly preferably contains Cu. From the viewpoint of low resistance and low price, Cu is preferred. The light-shielding pattern may contain one metal alone or two or more metals. The metal contained in the light-shielding pattern may be a single metal or an alloy. The light-shielding pattern preferably contains Cu or a Cu alloy. When the light-shielding pattern contains a metal, the metal element contained in the light-shielding pattern may be the same as or different from the metal element contained in the conductive pattern. The light-shielding pattern preferably contains the same metal element as the metal element contained in the conductive pattern.

[0097] The light-shielding pattern may contain elements other than metal elements. Examples of elements other than metal elements include carbon (C), phosphorus (P), and boron (B). Elements other than metal elements may form alloys with metal elements.

[0098] The shape of the light-shielding pattern is not limited and may be determined according to the shape of the target conductive pattern, for example.

[0099] The structure of the light-shielding pattern may be a single-layer structure or a multi-layer structure. The components of each layer of the light-shielding pattern having a multi-layer structure may be the same or different.

[0100] There is no limit to the thickness of the light-shielding pattern. The average thickness of the light-shielding pattern is preferably 3 μm or less, more preferably 2 μm or less, further preferably 1 μm or less, and particularly preferably 0.5 μm or less. By having an average thickness of the light-shielding pattern of 3 μm or less, the formability of the light-shielding pattern can be improved. As a result, the occurrence of morphological abnormalities of the conductive pattern can be further reduced. The average thickness of the light-shielding pattern is preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.3 μm or more. By having an average thickness of the light-shielding pattern of 0.05 μm or more, the transmittance of the exposure wavelength can be reduced. Furthermore, when the light-shielding pattern is used as a seed layer, the productivity of the conductive pattern can be improved. The average thickness of the light-shielding pattern is measured by the method according to the above-mentioned method for measuring the average thickness of the transparent substrate.

[0101] There is no limit to the width of the light-shielding pattern. The width of the light-shielding pattern can be determined, for example, based on the width of the conductive pattern formed in the conductive pattern formation step. The average width of the light-shielding pattern is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 2 μm or less. The average width of the light-shielding pattern is preferably 0.1 μm or more, more preferably 0.5 μm or more. The average width of the light-shielding pattern is the arithmetic mean of the widths of the light-shielding pattern measured at five points.

[0102] The light-shielding pattern may also be in contact with the transparent substrate directly or via other layers. As other layers, for example, an adhesive layer may be mentioned. For example, the laminate may also have an adhesive layer between the transparent substrate and the light-shielding pattern. The composition of the adhesive layer is not limited. The composition of the adhesive layer may be determined, for example, based on the adhesion between the transparent substrate and the light-shielding pattern, and the stability of the conductive pattern obtained by the method for manufacturing the conductive pattern of the present invention in the use environment (for example, humidity and temperature). The adhesive layer preferably comprises at least one selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn and Mn. The adhesive layer may also further comprise at least one selected from C, O (oxygen), H (hydrogen) and N (nitrogen). The adhesive layer may also be a blackening layer. The blackening layer can suppress light reflection caused by the light-shielding pattern during the exposure step. When the adhesive layer functions as a blackening layer, the adhesive layer preferably comprises, for example, a Ni-Cu alloy. The adhesive layer functioning as a blackening layer may also comprise at least one selected from C, O, H and N. The thickness of the adhesive layer is not limited. The average thickness of the adhesive layer is preferably 3 nm to 50 nm, more preferably 3 nm to 35 nm, and particularly preferably 3 nm to 33 nm. The average thickness of the adhesive layer is measured by the method according to the above-mentioned method for measuring the average thickness of the transparent substrate.

[0103] [Negative photosensitive resin layer]

[0104] The laminate comprises a negative photosensitive resin layer disposed on a transparent substrate and a light-shielding pattern and in contact with the transparent substrate. The negative photosensitive resin layer may be in contact with the light-shielding pattern directly or via another layer. The negative photosensitive resin layer is preferably in contact with the light-shielding pattern. A known negative photosensitive resin layer can be used as the negative photosensitive resin layer.

[0105] In one embodiment, the negative photosensitive resin layer preferably comprises polymer A, polymerizable compound B, and a photopolymerization initiator. Relative to the total mass of the negative photosensitive resin layer, the negative photosensitive resin layer preferably comprises 10% to 90% by mass of polymer A, 5% to 70% by mass of polymerizable compound B, and 0.01% to 20% by mass of photopolymerization initiator. In one embodiment, the negative photosensitive resin layer preferably comprises an alkali-soluble polymer, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator. The negative photosensitive resin layer is described in detail below.

[0106] (Polymer A)

[0107] The negative photosensitive resin layer preferably contains polymer A. Polymer A is preferably an alkali-soluble polymer. Alkali-soluble polymers include polymers that are easily soluble in alkaline substances.

[0108] From the perspective of obtaining a more preferred resolution by suppressing the swelling of the negative photosensitive resin layer caused by the developer, the acid value of polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and particularly preferably less than 190 mgKOH / g. There is no restriction on the lower limit of the acid value. From the perspective of more preferred developability, the acid value of polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more. The acid value of polymer A can be adjusted, for example, by the type of structural unit constituting polymer A and the content of the structural unit containing an acid group.

[0109] In the present invention, the acid value is the mass (mg) of potassium hydroxide required to neutralize 1g of a sample. In the present invention, the unit of the acid value is mgKOH / g. The acid value can be calculated, for example, based on the average content of acid groups in the compound.

[0110] The weight average molecular weight (Mw) of polymer A is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably set to 500,000 or less. The weight average molecular weight of polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregates, the weight average molecular weight is preferably set to 5,000 or more. The weight average molecular weight of polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.

[0111] The dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In the present invention, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

[0112] From the viewpoint of suppressing thickening of line width and reduction in resolution when the focus position deviates during exposure, the polymer A preferably has a structural unit derived from a monomer having an aromatic hydrocarbon group.

[0113] Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.

[0114] The content ratio of the structural units derived from the monomer having an aromatic hydrocarbon group in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, relative to the total mass of polymer A. There is no upper limit on the content ratio of the structural units derived from the monomer having an aromatic hydrocarbon group. The content ratio of the structural units derived from the monomer having an aromatic hydrocarbon group in polymer A is preferably 95% by mass or less, more preferably 85% by mass or less, relative to the total mass of polymer A. In addition, when the negative photosensitive resin layer contains multiple types of polymers A, the content ratio of the structural units derived from the monomer having an aromatic hydrocarbon group is calculated as a weight average value.

[0115] Examples of the monomer having an aromatic hydrocarbon group 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). The monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.

[0116] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferred.

[0117] As a monomer having a phenylalkyl group, for example, phenylethyl (meth)acrylate may be mentioned.

[0118] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group (e.g., benzyl (meth)acrylate and benzyl (meth)acrylate chloride) and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol). The monomer having a benzyl group is preferably benzyl (meth)acrylate.

[0119] In one embodiment, when the structural unit derived from a monomer having an aromatic hydrocarbon group in polymer A is a structural unit derived from benzyl (meth)acrylate, the content ratio of the structural unit derived from the benzyl (meth)acrylate monomer in polymer A relative to the total mass of polymer A is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass.

[0120] In a certain embodiment, when the structural unit derived from a monomer having an aromatic hydrocarbon group in polymer A is a structural unit derived from styrene, the content ratio of the structural unit derived from styrene in polymer A is preferably 20% by mass to 55% by mass, more preferably 25% to 45% by mass, further preferably 30% to 40% by mass, and particularly preferably 30% to 35% by mass, relative to the total mass of polymer A.

[0121] In one embodiment, the polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a copolymer obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one selected from a first monomer and a second monomer described below. The copolymer comprises: a structural unit derived from a monomer having an aromatic hydrocarbon group; and at least one selected from a structural unit derived from the first monomer and a structural unit derived from the second monomer.

[0122] The polymer A may be a polymer having no structural unit derived from a monomer having an aromatic hydrocarbon group. The polymer A having no structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a polymer obtained by polymerizing at least one of the first monomers described below (excluding monomers having an aromatic hydrocarbon group), and more preferably a copolymer obtained by polymerizing at least one of the first monomers described below (excluding monomers having an aromatic hydrocarbon group) and at least one of the second monomers described below (excluding monomers having an aromatic hydrocarbon group).

[0123] In one embodiment, polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described below, and more preferably a copolymer obtained by polymerizing at least one of the first monomers described below and at least one of the second monomers described below. The copolymer has a structural unit derived from the first monomer and a structural unit derived from the second monomer.

[0124] The first monomer is a monomer having a carboxyl group and a polymerizable unsaturated group in the molecule. The first monomer may also be a monomer without an aromatic hydrocarbon group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. The first monomer is preferably (meth)acrylic acid.

[0125] The content of the structural unit derived from the first monomer in the polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass, relative to the total mass of the polymer A.

[0126] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. The second monomer may also be a monomer that does not have an aromatic hydrocarbon group in its molecule. Examples of the second monomer include (meth)acrylate compounds, vinyl alcohol ester compounds, and (meth)acrylonitrile. In the present invention, "(meth)acrylonitrile" includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.

[0127] Examples of the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0128] As the ester compound of vinyl alcohol, for example, vinyl acetate can be mentioned.

[0129] The second monomer is preferably at least one selected from methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate.

[0130] The content of the structural unit derived from the second monomer in polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 45% by mass, relative to the total mass of polymer A.

[0131] From the perspective of suppressing line width thickening and resolution degradation when the focus position deviates during exposure, the polymer A preferably contains at least one selected from a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene. For example, the polymer A is preferably at least one selected from a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene; and a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene.

[0132] Polymer A may also have any one of a straight chain structure, a branched structure and an alicyclic structure in the side chain. By using a monomer containing a group with a branched structure in the side chain or a monomer containing a group with an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of polymer A. The group with an alicyclic structure may also be a monocyclic or polycyclic ring. As a specific example of a monomer containing a group with a branched structure in the side chain, isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-pentyl (meth) acrylate, sec-pentyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and tert-octyl (meth) acrylate. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate are more preferred. Specific examples of monomers containing a group having an alicyclic structure in a side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group, and (meth)acrylates containing alicyclic hydrocarbons having 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2-(meth)acrylate), 1-adamantyl(meth)acrylate, 2-adamantyl(meth)acrylate, 3-methyl-1-adamantyl(meth)acrylate, 3,5-dimethyl-1-adamantyl(meth)acrylate, 3-ethyladamantyl(meth)acrylate, 3-methyl-5-ethyl-1-adamantyl(meth)acrylate, 3,5,8-triethyl-1-adamantyl(meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl(meth)acrylate, 2-methyl-2-adamantyl(meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate. acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentholinden-5-yl (meth)acrylate, octahydro-4,7-mentholinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecyl (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, amyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate.Among these (meth)acrylates, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, pentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecyl (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecyl (meth)acrylate is more preferred.

[0133] In one embodiment, polymer A is preferably a polymer comprising 25% to 60% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 55% by mass of structural units derived from the first monomer, and 20% to 55% by mass of structural units derived from the second monomer. Polymer A is more preferably a polymer comprising 25% to 40% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from the first monomer, and 30% to 45% by mass of structural units derived from the second monomer.

[0134] In one embodiment, the polymer A preferably contains 70% by mass to 90% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group and 10% by mass to 25% by mass of a structural unit derived from the first monomer.

[0135] The glass transition temperature (Tg) of polymer A is preferably 30°C to 135°C. In the negative photosensitive resin layer, by having polymer A with a Tg of 135°C or less, it is possible to suppress the thickening of the line width and the reduction in resolution when the focus position deviates during exposure. From the above viewpoints, the Tg of polymer A is more preferably 130°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. Furthermore, from the viewpoint of improving edge melting resistance, the Tg of polymer A is preferably 30°C or more. From the above viewpoints, the Tg of polymer A is more preferably 40°C or more, further preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0136] Polymer A can also be a commercially available product or a synthetic product. The synthesis of polymer A is preferably such as by adding a free radical polymerization initiator (for example, benzoyl peroxide or azoisobutyronitrile) appropriately to a solution obtained by diluting at least one of the above-mentioned monomers with a solvent (for example, acetone, methyl ethyl ketone or isopropanol), followed by heating and stirring. In addition, sometimes a part of the mixture is dropped into the reaction solution while being synthesized. After the reaction is completed, a solvent is sometimes added to be adjusted to the desired concentration. As a synthesis means, in addition to solution polymerization, block polymerization, suspension polymerization or emulsion polymerization can also be used.

[0137] The negative photosensitive resin layer may contain one type of polymer A alone, or may contain two or more types of polymers A.

[0138] The content of polymer A relative to the total mass of the negative photosensitive resin layer is preferably 10% to 90% by mass, more preferably 30% to 70% by mass, and particularly preferably 40% to 60% by mass. From the perspective of controlling development time, the content of polymer A relative to the negative photosensitive resin layer is preferably 90% by mass or less. On the other hand, from the perspective of improving edge melting resistance, the content of polymer A relative to the negative photosensitive resin layer is preferably 10% by mass or more.

[0139] When the negative photosensitive resin layer contains two or more polymers A, the negative photosensitive resin layer preferably contains two or more polymers A having structural units derived from a monomer having an aromatic hydrocarbon group, or preferably contains a polymer A having structural units derived from a monomer having an aromatic hydrocarbon group and a polymer A having no structural units derived from a monomer having an aromatic hydrocarbon group. In the latter case, the content ratio of the polymer A having structural units derived from a monomer having an aromatic hydrocarbon group relative to the total mass of the polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0140] (Polymerizable compound B)

[0141] The negative photosensitive resin layer preferably contains a polymerizable compound B. In the present invention, a "polymerizable compound" refers to a compound having a bond or polymerizable group that participates in a polymerization reaction and polymerizes under the action of a polymerization initiator described below. The polymerizable compound B is a compound different from the polymer A described above.

[0142] As a bond participating in the polymerization reaction in the polymerizable compound B, for example, an ethylenically unsaturated bond may be mentioned.

[0143] The polymerizable group in the polymerizable compound B is not limited as long as it is a group that participates in the polymerization reaction. Examples of the polymerizable group in the polymerizable compound B include groups containing ethylenically unsaturated bonds (e.g., vinyl, acryloyl, methacryloyl, styryl, and maleimido) and cationic polymerizable groups (e.g., epoxy and oxetane). The polymerizable group is preferably a group containing an ethylenically unsaturated bond (hereinafter sometimes referred to as an "ethylenically unsaturated group"), more preferably an acryloyl or methacryloyl group.

[0144] From the perspective of achieving superior photosensitivity in the negative photosensitive resin layer, the polymerizable compound B is preferably a compound having an ethylenically unsaturated bond, more preferably a compound having one or more ethylenically unsaturated groups per molecule (i.e., an ethylenically unsaturated compound), and particularly preferably a compound having two or more ethylenically unsaturated groups per molecule (i.e., a polyfunctional ethylenically unsaturated compound). Furthermore, from the perspective of achieving superior resolution and releasability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and particularly preferably 2 or less.

[0145] The ethylenically unsaturated compound is preferably a (meth)acrylate compound having one or more (meth)acryloyl groups in one molecule.

[0146] From the viewpoint of achieving a better balance among the photosensitivity, resolution and peelability in the negative photosensitive resin layer, the polymerizable compound B is preferably at least one selected from a compound having two ethylenically unsaturated groups in one molecule (i.e., a bifunctional ethylenically unsaturated compound) and a compound having three ethylenically unsaturated groups in one molecule (i.e., a trifunctional ethylenically unsaturated compound), and more preferably a compound having two ethylenically unsaturated groups in one molecule.

[0147] From the perspective of excellent releasability of the negative photosensitive resin layer, in the negative photosensitive resin layer, the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is 60% by mass or more, more preferably greater than 70% by mass, and particularly preferably 90% by mass or more. The upper limit of the content ratio of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is not limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the negative photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

[0148] -Polymerizable compound B1-

[0149] The negative photosensitive resin layer of the present invention preferably contains a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups in one molecule. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule of the polymerizable compound B.

[0150] From the perspective of achieving better resolution, the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B in the negative photosensitive resin layer is preferably 40% by mass or greater, more preferably 50% by mass or greater, even more preferably 55% by mass or greater, and particularly preferably 60% by mass or greater. There is no upper limit on the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B. From the perspective of releasability, the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0151] Examples of the aromatic ring in polymerizable compound B1 include aromatic hydrocarbon rings (e.g., benzene rings, naphthalene rings, and anthracene rings), aromatic heterocyclic rings (e.g., thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings), and condensed rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may also have a substituent.

[0152] From the perspective of improving resolution by suppressing swelling of the negative photosensitive resin layer caused by the developer, the polymerizable compound B1 preferably has a bisphenol structure. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (i.e., 2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (i.e., 2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (i.e., 2,2-bis(4-hydroxyphenyl)butane). The bisphenol structure is preferably a bisphenol A structure.

[0153] As the polymerizable compound B1 having a bisphenol structure, for example, there can be mentioned a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Each polymerizable group may also be directly bonded to the bisphenol structure. Each polymerizable group may also be bonded to the bisphenol structure via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, more preferably ethyleneoxy groups. There is no limit to the number of alkyleneoxy groups added to the bisphenol structure, but it is preferably 4 to 16 per molecule, more preferably 6 to 14.

[0154] Paragraphs 0072 to 0080 of JP-A-2016-224162 describe a polymerizable compound B1 having a bisphenol structure, the contents of which are incorporated herein by reference.

[0155] The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-(((meth)acryloyloxypolyalkoxy)phenyl)propane.

[0156] Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodeethoxytetrapropoxy)phenyl)propane (FA-3200MY, Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecethoxy)phenyl)propane (BPE-1300, Shin-Nakamura Chemical Co., Ltd.). Co., Ltd.), 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, Shin-Nakamura Chemical Co., Ltd.).

[0157] Examples of the polymerizable compound B1 include compounds represented by the following general formula (I).

[0158] [Chemical Formula 1]

[0159]

[0160] In the general formula (I), R1 and R2 each independently represent a hydrogen atom or a radical, A represents C2H4, B represents C3H6, n1 and n3 each independently represent an integer of 1 to 39, n1+n3 represents an integer of 2 to 40, n2 and n4 each independently represent an integer of 0 to 29, n2+n4 represents an integer of 0 to 30, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the biphenyl side. n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0. n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.

[0161] The negative photosensitive resin layer may contain one type of polymerizable compound B1 alone, or may contain two or more types of polymerizable compounds B1.

[0162] From the perspective of achieving better resolution, the content of the polymerizable compound B1 in the negative photosensitive resin layer is preferably 10% by mass or greater, and more preferably 20% by mass or greater, relative to the total mass of the negative photosensitive resin layer. There is no upper limit on the content of the polymerizable compound B1. From the perspective of transferability and edge melting resistance, the content of the polymerizable compound B1 in the negative photosensitive resin layer is preferably 70% by mass or less, and more preferably 60% by mass or less, relative to the total mass of the negative photosensitive resin layer.

[0163] The negative photosensitive resin layer may contain the polymerizable compound B1 and a polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include monofunctional ethylenically unsaturated compounds (i.e., compounds having one ethylenically unsaturated group in one molecule), difunctional ethylenically unsaturated compounds having no aromatic ring (i.e., compounds having two ethylenically unsaturated groups in one molecule without an aromatic ring), and trifunctional or higher ethylenically unsaturated compounds (i.e., compounds having three or more ethylenically unsaturated groups in one molecule).

[0164] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0165] Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0166] Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0167] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0168] Examples of the urethane di(meth)acrylate include propylene oxide-modified urethane di(meth)acrylate and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylate. Commercially available products include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Co., Ltd.).

[0169] Examples of trifunctional or higher ethylenically unsaturated compounds include dipentatriol (tri / tetra / penta / hexa) (meth)acrylate, pentatriol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, and alkylene oxide-modified compounds thereof. In the present invention, "(tri / tetra / penta / hexa) (meth)acrylate" encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. In the present invention, "(tri / tetra) (meth)acrylate" encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0170] Examples of the alkylene oxide-based trifunctional or higher ethylenically unsaturated compound include caprolactone-modified (meth)acrylate compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd., A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD.), ethoxylated glyceryl triacrylate (e.g., EPDM-106 manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethylene glycol triacrylate (e.g., EPDM-106 manufactured by Shin-Nakamura Chemical Co., Ltd.). Co., Ltd.), ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD.), ARONIX M-520 (TOAGOSEI CO., LTD.) and ARONIX M-510 (TOAGOSEI CO., LTD.).

[0171] Examples of the polymerizable compound B other than the polymerizable compound B1 include polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.

[0172] In one embodiment, the negative photosensitive resin layer preferably comprises a polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably comprises a polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In the above embodiment, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound ([total mass of the polymerizable compound B1]:[total mass of the trifunctional or higher ethylenically unsaturated compounds]) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and particularly preferably 1.5:1 to 3:1.

[0173] The molecular weight of the polymerizable compound B (when the polymerizable compound B has a molecular weight distribution, the weight average molecular weight (Mw)) is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0174] The negative photosensitive resin layer may contain one type of polymerizable compound B alone, or may contain two or more types of polymerizable compounds B.

[0175] The content of the polymerizable compound B in the negative photosensitive resin layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to the total mass of the negative photosensitive resin layer.

[0176] (Photopolymerization initiator)

[0177] The negative photosensitive resin layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives actinic rays (eg, ultraviolet rays, visible light, and X-rays) to initiate polymerization of the polymerizable compound (eg, polymerizable compound B).

[0178] The polymerization initiator is not limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include photoradical polymerization initiators and photocationic polymerization initiators, and photoradical polymerization initiators are preferred.

[0179] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0180] From the perspectives of photosensitivity, visibility of the exposed area, visibility of the unexposed area, and resolution, the negative-type photosensitive resin layer preferably contains at least one selected from 2,4,5-triarylimidazole dimers and derivatives of 2,4,5-triarylimidazole dimers as a photoradical polymerization initiator. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.

[0181] Examples of the derivatives of 2,4,5-triaryl imidazole 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.

[0182] Examples of the photoradical polymerization initiator include polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783.

[0183] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisole (p,p′-dimethoxybenzyl), and benzophenone.

[0184] Examples of commercially available photoradical polymerization initiators include TAZ-110 (Midori Kagaku Co., Ltd.), TAZ-111 (Midori Kagaku Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanedione-1-(o-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), and IRGACURE OXE-04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionitrile)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 BV), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Qmnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV), oxime ester-based photopolymerization initiator (trade name: Lunar 6, DKSH Japan KK), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (also known as 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, trade name: B-CIM, Hampford Company), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.).

[0185] A photocationic polymerization initiator (i.e., a photoacid generator) is a compound that generates an acid upon exposure to actinic radiation. Preferred photocationic polymerization initiators are compounds that are sensitive to actinic radiation having a wavelength of 300 nm or longer, preferably 300 nm to 450 nm, and generate an acid. However, the chemical structure of the photocationic polymerization initiator is not limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to actinic radiation having a wavelength of 300 nm or longer can be preferably used in combination with a sensitizer as long as they are sensitive to actinic radiation having a wavelength of 300 nm or longer and generate an acid.

[0186] The photocationic polymerization initiator preferably generates an acid having a pKa of 4 or less, more preferably generates an acid having a pKa of 3 or less, and particularly preferably generates an acid having a pKa of 2 or less. There is no lower limit for the pKa. The pKa of the acid generated by the photocationic polymerization initiator is preferably, for example, -10.0 or greater.

[0187] As the photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator may be mentioned.

[0188] Examples of the ionic photocationic polymerization initiator include onium salt compounds (eg, diaryliodonium salt compounds and triarylsulfonium salt compounds) and quaternary ammonium salt compounds.

[0189] Examples of the ionic photocationic polymerization initiator include those described in paragraphs 0114 to 0133 of JP-A-2014-85643.

[0190] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-triazine compounds, diazomethane compounds, and imide sulfonate compounds include those described in paragraphs 0083 to 0088 of JP-A-2011-221494. Examples of oxime sulfonate compounds include those described in paragraphs 0084 to 0088 of WO-2018 / 179640.

[0191] The negative photosensitive resin layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from 2,4,5-triarylimidazole dimer and a derivative of 2,4,5-triarylimidazole dimer.

[0192] The negative photosensitive resin layer may contain one type of photopolymerization initiator alone, or may contain two or more types of photopolymerization initiators.

[0193] The content of the photopolymerization initiator in the negative photosensitive resin layer is preferably 0.1% by mass or greater, more preferably 0.5% by mass or greater, and particularly preferably 1.0% by mass or greater, relative to the total mass of the negative photosensitive resin layer. There is no upper limit on the content of the photopolymerization initiator. The content of the photopolymerization initiator in the negative photosensitive resin layer is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the negative photosensitive resin layer.

[0194] (Optional ingredient)

[0195] The negative photosensitive resin layer may contain components other than the above components (hereinafter sometimes referred to as "optional components"). Examples of the optional components include pigments, surfactants, and additives other than the above components.

[0196] -pigment-

[0197] From the perspective of visibility of the exposed portion, visibility of the unexposed portion, visibility of the pattern after development, and resolution, the negative photosensitive resin layer preferably has a maximum absorption wavelength of 450 nm or greater within the wavelength range of 400 nm to 780 nm during color development, and contains a pigment (hereinafter sometimes referred to as "pigment N") whose maximum absorption wavelength changes due to acid, base, or free radicals. Although the detailed mechanism is not yet clear, the inclusion of pigment N in the negative photosensitive resin layer improves the adhesion of layers adjacent to the negative photosensitive resin layer and further improves resolution.

[0198] In the present invention, the term "the maximum absorption wavelength is changed by acid, alkali or free radicals" used in connection with the pigment can also mean any of the following: a method in which a pigment in a color-developing state is decolorized by acid, alkali or free radicals, a method in which a decolorized pigment is colored by acid, alkali or free radicals, and a method in which a pigment in a color-developing state is changed to a color-developing state of another hue.

[0199] Specifically, pigment N can be a compound that develops color by exposure from a bleached state change, or a compound that decolorizes by exposure from a bleached state change. In the above manner, pigment N can also be a pigment that makes color development or bleached state change by the effect of an acid, alkali or free radical produced by exposure. In addition, pigment N can also be a pigment that makes color development or bleached state change by changing the state (such as pH) in the negative photosensitive resin layer by an acid, alkali or free radical produced by exposure. On the other hand, pigment N can also be a pigment that makes color development or bleached state change by directly receiving an acid, alkali or free radical as a stimulus without exposure.

[0200] From the viewpoint of visibility of the exposed portion, visibility of the unexposed portion, and resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to acid or radicals, and more preferably a dye whose maximum absorption wavelength changes due to radicals.

[0201] From the viewpoint of visibility of the exposed portion, visibility of the unexposed portion, and resolution, the negative photosensitive resin layer preferably contains, as the dye N, both a dye whose maximum absorption wavelength changes due to radicals and a photoradical polymerization initiator.

[0202] From the viewpoint of visibility of the exposed portion and visibility of the unexposed portion, the dye N is preferably a dye that develops color by acid, alkali, or radicals.

[0203] As an example of the coloring mechanism of the pigment N, there can be cited a method in which a radical-reactive pigment, an acid-reactive pigment or an alkali-reactive pigment (e.g., a colorless pigment) is colored by exposing a negative photosensitive resin layer containing a photoradical polymerization initiator, a photocationic polymerization initiator (i.e., a photoacid generator) or a photobase generator, and the radicals, acids or bases generated by the photoradical polymerization initiator, the photocationic polymerization initiator or the photobase generator.

[0204] From the perspective of visibility of the exposed portion and the unexposed portion, in the pigment N, the maximum absorption wavelength within the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or more, more preferably 550 nm to 700 nm, and particularly preferably 550 nm to 650 nm.

[0205] Furthermore, the pigment N may have one or more maximum absorption wavelengths within the wavelength range of 400 nm to 780 nm during color development. When the pigment N has two or more maximum absorption wavelengths within the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or longer.

[0206] The maximum absorption wavelength of pigment N was measured by measuring the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, SHIMADZU CORPORATION) in an atmospheric atmosphere. The wavelength at which the light intensity is minimized (maximum absorption wavelength) was detected.

[0207] Examples of pigments that develop or discolor upon exposure include colorless compounds. Examples of pigments that discolor upon exposure include colorless compounds, diarylmethane pigments, oxazine pigments, xanthene pigments, iminonaphthoquinone pigments, azomethine pigments, and anthraquinone pigments. From the perspective of visibility of the exposed portion and the unexposed portion, the pigment N is preferably a colorless compound.

[0208] Examples of the colorless compound include colorless compounds having a triarylmethane skeleton (triarylmethane-based dyes), colorless compounds having a spiropyran skeleton (spiropyran-based dyes), colorless compounds having a fluoran skeleton (fluoran-based dyes), colorless compounds having a diarylmethane skeleton (diarylmethane-based dyes), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), colorless compounds having an indolylphthalide lactone skeleton (indolylphthalide lactone-based dyes), and colorless compounds having a colorless auramine skeleton (colorless auramine-based dyes). The colorless compound is preferably a triarylmethane-based dye or a fluoran-based dye, and more preferably a colorless compound having a triphenylmethane skeleton (triphenylmethane-based dye) or a fluoran-based dye.

[0209] From the viewpoint of the visibility of the exposure portion and the visibility of the unexposed portion, the colorless compound preferably has a lactone ring, sulindane or sultone ring. By reacting the lactone ring, sulindane or sultone ring contained in the colorless compound with the free radical produced by the photoradical polymerization initiator, or the acid produced by the photocationic polymerization initiator, the colorless compound can be made to become a closed loop state and decolorize, or the colorless compound is made to become an open loop state and develop the color. The colorless compound is preferably provided with a lactone ring, sulindane or sultone ring, and the compound that makes the lactone ring, sulindane or sultone ring open and develop the color by free radical or acid, more preferably with a lactone ring, and the compound that makes the lactone ring open and develop the color by free radical or acid.

[0210] Specific examples of colorless compounds include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco-methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-phenylamino-3-methyl-6-(N-ethyl-p-tolyl)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl 7-aminofluoran, 3-(N,N-diethylamino)-6-methyl-7-phenylaminofluoran, 3-(N,N-diethylamino)-6-methyl-7-dimethylanilinefluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chlorophenylamino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-(4-chlorophenylamino)fluoran, N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-phenylaminofluoran, 3-(N,N-dibutylamino)-6-methyl-7-dimethylanilinefluoran, 3-piperidino-6-methyl-7-phenylaminofluoran, 3-pyrrolidinyl-6-methyl-7-phenylaminofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1- n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0211] Examples of the pigment N include dyes. Specific examples of the dye include brilliant green, ethyl violet, methyl green, crystal violet, basic carmine, methyl violet 2B, Kinaldine red, Bengal red, m-methyl yellow, Timorsulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurine 4B, α-naphthyl red, Nile Blue 2B, Nile Blue A, methyl violet, malachite green, Parafusin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue #603 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Pink #312 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red 5B (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Scarlet #308 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red OG (ORIENT CHEMICAL INDUSTRIES CO., LTD.), and others. CO., LTD.), Oil Red RR (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Green #502 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol violet, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyphenylamino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0212] From the viewpoints of visibility of the exposed portion, visibility of the unexposed portion, and pattern visibility and resolution after development, the dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals.

[0213] The pigment N is preferably leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate.

[0214] The negative photosensitive resin layer may contain one type of dye N alone, or may contain two or more types of dyes N.

[0215] From the viewpoint of visibility of the exposed portion, visibility of the unexposed portion, visibility of the pattern after development, and resolution, the content ratio of the pigment N relative to the total mass of the negative photosensitive resin layer is preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, further preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %.

[0216] The content ratio of pigment N refers to the content ratio of the pigment when all the pigments N contained in the negative photosensitive resin layer become the color development state. Below, the quantitative method of the content ratio of pigment N is explained by taking the pigment that develops color by free radicals as an example. Two solutions are prepared by dissolving pigment (0.001g) and pigment (0.01g) in methyl ethyl ketone (100mL) respectively. IRGACURE OXE-01 (BASF) is added to each resulting solution as a photoradical polymerization initiator, and then free radicals are generated by irradiation with 365nm light, and all the pigments are made into the color development state. Then, under atmospheric atmosphere, a spectrophotometer (UV3100, SHIMADZU CORPORATION) is used to measure the absorbance of each solution with a liquid temperature of 25°C to prepare a calibration curve. Then, a negative photosensitive resin layer (3g) is dissolved in methyl ethyl ketone instead of the pigment. In addition, the absorbance of the solution that makes all the pigments develop color is measured by the same method as above. The content of the pigment contained in the negative photosensitive resin layer was calculated based on the absorbance of the obtained solution containing the negative photosensitive resin layer according to the calibration curve.

[0217] -Surfactants-

[0218] From the viewpoint of thickness uniformity, the negative photosensitive resin layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.

[0219] Examples of the nonionic surfactant include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkylphenyl ether compounds, higher fatty acid diester compounds of polyoxyethylene glycol, silicone-based nonionic surfactants, and fluorine-based nonionic surfactants.

[0220] From the perspective of achieving better resolution, the negative photosensitive resin layer preferably contains a fluorinated nonionic surfactant. It is believed that the inclusion of a fluorinated nonionic surfactant in the negative photosensitive resin layer inhibits the penetration of the etching solution into the negative photosensitive resin layer, thereby reducing side etching. Commercially available fluorinated nonionic surfactants include, for example, MEGAFAC (registered trademark) F-551 (DIC Corporation), MEGAFAC F-552 (DIC Corporation), and MEGAFAC F-554 (DIC Corporation).

[0221] Examples of the surfactant include the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784, and the surfactants described in paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362.

[0222] The negative photosensitive resin layer may contain one type of surfactant alone, or may contain two or more types of surfactants.

[0223] The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, relative to the total mass of the negative photosensitive resin layer.

[0224] -additive-

[0225] Examples of additives include radical inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazole compounds, carboxybenzotriazole compounds, resins other than polymer A, and solvents. The negative photosensitive resin layer may contain one additive alone or two or more additives.

[0226] The negative-type photosensitive resin layer may also contain a free radical inhibitor. Examples of free radical inhibitors include the thermal inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Preferred free radical inhibitors include phenothiazine, phenoxazine, or 4-methoxyphenol. Examples of free radical inhibitors other than those listed above include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine. To minimize the sensitivity of the negative-type photosensitive resin layer, nitrosophenylhydroxylamine aluminum salt is preferably used as the free radical inhibitor.

[0227] The negative photosensitive resin layer may also contain a benzotriazole compound. Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0228] The negative photosensitive resin layer may also contain a carboxybenzotriazole compound. Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminovinylcarboxybenzotriazole. Examples of commercially available carboxybenzotriazole compounds include CBT-1 (JOHOKU CHEMICAL CO., LTD.).

[0229] The total content of the radical inhibitor, benzotriazole compound, and carboxybenzotriazole compound is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass, relative to the total mass of the negative photosensitive resin layer. To ensure storage stability of the negative photosensitive resin layer, the total content of these components is preferably 0.01% by mass or greater. On the other hand, to maintain sensitivity and suppress dye discoloration, the total content of these components is preferably 3% by mass or less.

[0230] The negative photosensitive resin layer may also contain a sensitizer. There are no limitations on the sensitizer, and known sensitizers can be used. Dyes and pigments may also be used as sensitizers. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0231] The negative photosensitive resin layer may contain only one type of sensitizer, or may contain two or more types of sensitizers.

[0232] When the negative photosensitive resin layer contains a sensitizer, the content ratio of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer, the content ratio of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the negative photosensitive resin layer.

[0233] The negative photosensitive resin layer may also contain at least one selected from a plasticizer and a heterocyclic compound. Examples of the plasticizer and heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0234] The negative photosensitive resin layer may contain a resin other than polymer A. Examples of the resin other than polymer A include acrylic resins, styrene-acrylic acid copolymers (however, limited to copolymers having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0235] The negative photosensitive resin layer may contain a solvent. When a negative photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain in the negative photosensitive resin layer. The solvent will be described later.

[0236] The negative photosensitive resin layer may also contain, as an additive, at least one selected from the group consisting of metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors. Such additives are described, for example, in paragraphs 0165 to 0184 of JP-A-2014-85643. The contents of this publication are incorporated herein by reference.

[0237] (impurities, etc.)

[0238] The negative photosensitive resin layer may also contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among the above, halide ions, sodium ions, and potassium ions are easily incorporated as impurities, and therefore are preferably set to the following content.

[0239] The impurity content in the negative photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less, based on mass. The impurity content in the negative photosensitive resin layer may be 1 ppb or more or 0.1 ppm or more, based on mass.

[0240] Examples of methods for controlling the impurity content within the above range include selecting a raw material with a low impurity content as the raw material for the negative photosensitive resin layer, preventing the incorporation of impurities during formation of the negative photosensitive resin layer, and cleaning the manufacturing equipment to remove impurities. These methods can control the impurity content within the above range.

[0241] Impurities can be quantified by known methods, such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

[0242] The content of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the negative photosensitive resin layer is preferably low. The content of these compounds in the negative photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass. The content of these compounds in the negative photosensitive resin layer can be 10 ppb or more or 100 ppb or more, based on mass. The content of these compounds can be suppressed using the same methods as for the metal impurities described above. Furthermore, they can be quantified using known measurement methods.

[0243] From the viewpoint of improving reliability and lamination properties, the water content in the negative photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass.

[0244] (thickness)

[0245] The thickness of the negative photosensitive resin layer may be determined, for example, based on the thickness of the resin pattern formed in the development step described below. The thickness of the negative photosensitive resin layer may be determined, for example, within a range of 1 μm to 100 μm.

[0246] (Transmittance)

[0247] In the negative photosensitive resin layer, the transmittance of light at a wavelength of 365 nm is preferably 10% or greater, more preferably 30% or greater, and particularly preferably 50% or greater, from the perspective of achieving superior adhesion. There is no upper limit on the transmittance. In the negative photosensitive resin layer, the transmittance of light at a wavelength of 365 nm is preferably 99.9% or less.

[0248] [Method for producing laminate]

[0249] As described above, the preparation step may also include the step of producing a laminate. When the preparation step includes the step of producing a laminate, the preparation step preferably includes: preparing a laminate precursor comprising the transparent substrate and a light-shielding pattern on the transparent substrate; and forming the negative-type photosensitive resin layer on the transparent substrate and the light-shielding pattern. In the step of forming the negative-type photosensitive resin layer, the negative-type photosensitive resin layer is preferably formed using a photosensitive transfer material.

[0250] When the preparation step includes the step of manufacturing a laminate, the preparation step preferably includes: preparing a transparent substrate; forming a light-shielding pattern on the transparent substrate; and forming a negative-type photosensitive resin layer on the transparent substrate and the light-shielding pattern. The step of forming the light-shielding pattern preferably includes: forming a light-shielding layer on the transparent substrate; forming a photosensitive resin layer on the light-shielding layer; forming a resist pattern by exposing and developing the photosensitive resin layer; and removing the portion of the light-shielding layer not covered by the resist pattern. In the step of forming the negative-type photosensitive resin layer, the negative-type photosensitive resin layer is preferably formed using a photosensitive transfer material.

[0251] The method for producing the laminate will be described in detail below, but the method for producing the laminate is not limited as long as it can produce a laminate having the above-mentioned constituent elements.

[0252] As a method for producing a laminate, for example, there can be mentioned a method comprising the steps of: preparing a transparent substrate; forming a light-shielding pattern on the transparent substrate; and forming a negative photosensitive resin layer on the transparent substrate and the light-shielding pattern. In the above-mentioned method for producing a laminate, the transparent substrate is used as a starting material.

[0253] Examples of methods for producing a laminate include: preparing a laminate precursor comprising a transparent substrate and a light-shielding layer on the transparent substrate; forming a light-shielding pattern from the light-shielding layer; and forming a negative photosensitive resin layer on the transparent substrate and the light-shielding pattern. In these methods for producing a laminate, a laminate precursor comprising a transparent substrate and a light-shielding layer is used as a starting material. The light-shielding layer is a layer of material that forms the light-shielding pattern. Examples of methods for producing a laminate precursor comprising a transparent substrate and a light-shielding layer include forming the light-shielding layer on the transparent substrate.

[0254] Examples of methods for producing a laminate include: preparing a laminate precursor comprising a transparent substrate and a light-shielding pattern formed on the transparent substrate; and forming the negative photosensitive resin layer on the transparent substrate and the light-shielding pattern. In these methods for producing a laminate, the laminate precursor comprising a transparent substrate and a light-shielding pattern is used as a starting material. Examples of methods for producing a laminate precursor comprising a transparent substrate and a light-shielding pattern include methods in which the light-shielding pattern is formed on the transparent substrate.

[0255] (Method for Forming Light-Shielding Pattern)

[0256] The following describes a method for forming a light-shielding pattern. For example, a method of forming a light-shielding layer on a transparent substrate and then processing the light-shielding layer into a pattern is exemplified.

[0257] As a method for forming a light-shielding layer, for example, sputtering and plating can be cited. In sputtering, for example, a layer (light-shielding layer) containing Cu, Ti or Ni can be formed on a transparent substrate. Among the above metals, Cu, which has low resistance and is inexpensive, is preferred. The composition of the layer (light-shielding layer) formed by sputtering can also be Ni, Al, Nb, W, Ni-P or Ni-B. As plating, for example, electroless plating can be cited. As a method for electroless plating, a well-known method can be used. For example, in electroless copper plating, copper can be precipitated on a transparent substrate by the reaction of copper ions and a reducing agent. The catalyst used in electroless plating is preferably a palladium-tin mixed catalyst. The primary particle size of the mixed catalyst is preferably 10 nm or less. The plating solution used for electroless plating preferably contains hypophosphorous acid as a reducing agent. As plating, for example, the plating described in the following "Step of Forming a Conductive Pattern" section can also be cited. The structure of the light-shielding layer can be a single-layer structure or a multilayer structure. By forming a multilayer light-shielding layer, a multilayer conductive pattern can be formed. Methods for forming each layer included in the multilayer light-shielding layer include, for example, electroless plating, sputtering, vapor deposition, and coupling agent coating.

[0258] As a method for processing the light-shielding layer into a pattern, for example, photolithography can be used. As the photolithography, known photolithography methods can be used. For example, a photosensitive resin layer is formed on the light-shielding layer, and then a resist pattern is formed by exposing and developing the photosensitive resin layer. The light-shielding layer not covered by the resist pattern is then removed, thereby forming a light-shielding pattern.

[0259] There is no limitation on the type of photosensitive resin layer formed on the light-shielding layer. The photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer. As a negative photosensitive resin layer, for example, the negative photosensitive resin layer described in the above-mentioned "Negative photosensitive resin layer" section can be cited. As a method for forming a photosensitive resin layer, for example, a method using a photosensitive resin composition and a method using a photosensitive transfer material can be cited. As a method using a photosensitive resin composition, for example, a method of coating a photosensitive resin composition on a photosensitive layer and then drying the photosensitive resin composition can be cited. The photosensitive resin composition is a composition of a material containing a photosensitive resin layer. As a method using a photosensitive transfer material, for example, a method of configuring a photosensitive resin layer on the light-shielding layer by laminating a photosensitive transfer material having a photosensitive resin layer to the light-shielding layer can be cited. For the method of forming a negative photosensitive resin layer, reference can be made to the following "Method for forming a negative photosensitive resin layer" section.

[0260] The method for exposing the photosensitive resin layer is not limited as long as it can form exposed and unexposed areas in the photosensitive resin layer. Known methods can be used as exposure methods. The area of the photosensitive resin layer to be exposed can be determined based on the shape of the desired light-shielding pattern. For details on exposure conditions, refer to the "Exposure Step" section below.

[0261] The method for developing the photosensitive resin layer is not limited as long as it can be used to process the photosensitive resin layer into a pattern by removing the exposed or unexposed portions of the photosensitive resin layer. In developing a negative-type photosensitive resin layer, the unexposed portions of the negative-type photosensitive resin layer are removed. In developing a positive-type photosensitive resin layer, the exposed portions of the positive-type photosensitive resin layer are removed. Known development methods can be used. For development conditions, refer to the "Development Step" section below.

[0262] As a method for removing the light-shielding layer not covered by the resist pattern (i.e., the exposed light-shielding layer), a known method can be used. For example, when the light-shielding layer contains a metal, the light-shielding layer not covered by the resist pattern can be removed by etching. As etching, for example, wet etching and dry etching can be mentioned. Etching is preferably wet etching. Wet etching is etching using a chemical called an etching solution. As an etching solution, for example, a sulfuric acid-hydrogen peroxide aqueous solution can be mentioned. The composition of the sulfuric acid-hydrogen peroxide aqueous solution is not limited. As the sulfuric acid-hydrogen peroxide aqueous solution, for example, a sulfuric acid-hydrogen peroxide aqueous solution having a concentration of 1% to 10% by volume of sulfuric acid and a concentration of 1% to 10% by volume of hydrogen peroxide can be mentioned. The temperature of the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 20°C to 35°C. The immersion time in the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 1 minute to 10 minutes. When the light-shielding layer contains copper, a sulfuric acid-hydrogen peroxide aqueous solution can be used until the concentration of copper dissolved in the sulfuric acid-hydrogen peroxide aqueous solution reaches, for example, 50 g / L. As an etching solution, for example, a copper chloride solution can also be mentioned. The composition of the copper chloride solution is not limited. As the copper chloride solution, for example, a solution containing 20% to 35% by mass of copper chloride and 1% to 7% by mass of chlorine can be preferably used. However, the etching conditions are not limited to the above conditions. For example, the temperature of the etching solution and the immersion time in the etching solution can be determined according to the composition of the light-shielding layer, the thickness of the light-shielding layer, and the type of etching solution.

[0263] In the method for producing a laminate having an adhesive layer between a transparent substrate and a light-shielding pattern, for example, the adhesive layer may be formed on the transparent substrate before forming the light-shielding pattern. Examples of methods for forming the adhesive layer include electroless plating, sputtering, and vapor deposition. Examples of methods for forming the adhesive layer include applying a metal fine particle dispersion containing dispersed metal fine particles, drying, and sintering the dispersion.

[0264] In the method for producing a laminate, the surface of the transparent substrate may be roughened by a decontamination treatment as needed before forming the adhesive layer and the light-shielding pattern. Examples of the decontamination treatment liquid (oxidative roughening liquid) include a chromium / sulfuric acid roughening liquid, an alkaline permanganate roughening liquid (e.g., sodium permanganate roughening liquid), and a sodium fluoride / chromium / sulfuric acid roughening liquid.

[0265] (Method for Forming Negative Photosensitive Resin Layer)

[0266] Hereinafter, a method for forming a negative-type photosensitive resin layer will be described. Examples of the method for forming a photosensitive resin layer include a method using a photosensitive resin composition and a method using a photosensitive transfer material.

[0267] -Photosensitive resin composition-

[0268] As a method of using the photosensitive resin composition, for example, a method of applying the photosensitive resin composition on a transparent substrate and a light-shielding pattern and then drying the photosensitive resin composition may be mentioned.

[0269] The composition of the photosensitive resin composition can be determined based on the desired composition of the negative-type photosensitive resin layer. Preferred components of the photosensitive resin composition include, for example, those described in the "Negative-Type Photosensitive Resin Layer" section above. Examples of photosensitive resin compositions include compositions comprising polymer A, polymerizable compound B, and a photopolymerization initiator. The photosensitive resin composition preferably contains a solvent to adjust its viscosity and facilitate formation of the photosensitive resin layer.

[0270] The solvent is not limited as long as it can dissolve or disperse the components of the photosensitive resin composition (e.g., polymer A, polymerizable compound B, and polymerization initiator), and a known solvent can be used. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

[0271] The photosensitive resin composition preferably contains at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. More preferably, the photosensitive resin composition contains at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least one solvent selected from a ketone solvent and a cyclic ether solvent. The photosensitive resin composition particularly preferably contains at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.

[0272] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0273] Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0274] As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of Japanese Patent Application Laid-Open No. 2018-177889 can also be used. These contents are incorporated into this specification by reference.

[0275] The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvents.

[0276] The content of the solvent in the photosensitive resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.

[0277] The method for preparing the photosensitive resin composition is not limited. Examples of methods for preparing the photosensitive resin composition include preparing a solution by dissolving each component in a solvent and mixing the resulting solutions in predetermined proportions. The photosensitive resin composition is preferably filtered using a filter with a pore size of 0.2 to 30 μm before forming the negative photosensitive resin layer.

[0278] The method for applying the photosensitive resin composition is not limited, and a known method can be used. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0279] -Photosensitive transfer material-

[0280] As a method for using a photosensitive transfer material, for example, a method can be exemplified by laminating a photosensitive transfer material having a negative photosensitive resin layer to a transparent substrate having a light-shielding pattern, thereby arranging the negative photosensitive resin layer on the transparent substrate and the light-shielding pattern. In the method of laminating the photosensitive transfer material having a negative photosensitive resin layer to the transparent substrate having a light-shielding pattern, it is preferred to superimpose the photosensitive transfer material and the transparent substrate and apply pressure and heat using a roller or other means. Laminating can be performed using a laminator, a vacuum laminator, or an automatic cutting laminator, which can further improve productivity. The components of the photosensitive transfer material are described below.

[0281] [Photosensitive resin layer]

[0282] The photosensitive transfer material has a negative photosensitive resin layer, which is as described above in the section "Negative photosensitive resin layer".

[0283] [Temporary support]

[0284] The photosensitive transfer material preferably has a temporary support. The temporary support is a support that can be peeled off from the photosensitive transfer material. The temporary support is capable of supporting at least the negative photosensitive resin layer. The temporary support may be peeled off before the exposure step. During the exposure step, the temporary support may be peeled off after irradiation with light without peeling off the temporary support. By irradiating with light without peeling off the temporary support during the exposure step, the effects of dust and dirt in the exposure environment can be avoided.

[0285] As the temporary support, a temporary support having light transmittance can be used. In the present invention, "having light transmittance" means that the light transmittance at the wavelength used in the pattern exposure is 50% or more. From the perspective of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a light transmittance of 60% or more, more preferably 70% or more, at the wavelength used in the pattern exposure (preferably a wavelength of 365 nm).

[0286] Examples of the temporary support include a glass substrate, a resin film, and paper. From the viewpoint of strength, flexibility, and light transmittance, the temporary support is preferably a resin film.

[0287] Examples of the resin film include polyethylene terephthalate film (ie, PET film), cellulose triacetate film, polystyrene film, and polycarbonate film. The resin film is preferably a PET film, more preferably a biaxially stretched PET film.

[0288] There is no limit to the thickness of the temporary support. The average thickness of the temporary support can be determined, for example, based on the strength, light transmittance, material of the temporary support, and the flexibility required when the photosensitive transfer material is bonded to the transparent substrate. The average thickness of the temporary support is preferably 5 μm to 100 μm. Moreover, from the viewpoint of ease of handling and versatility, the average thickness of the temporary support is preferably 5 μm to 50 μm, more preferably 5 μm to 20 μm, further preferably 10 μm to 20 μm, and particularly preferably 10 μm to 16 μm.

[0289] The arithmetic mean roughness Ra of the surface of the temporary support on the side where the negative photosensitive resin layer is disposed is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.02 μm or less. There is no lower limit for the arithmetic mean roughness Ra. The arithmetic mean roughness Ra of the surface of the temporary support on the side where the negative photosensitive resin layer is disposed can be determined, for example, within a range of 0 μm or greater.

[0290] The arithmetic mean roughness Ra is measured by the following method. A three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation) is used to obtain the surface profile of the measured object under the following conditions. As measurement and analysis software, the Microscope Application of MetroPro ver8.3.2 is used. Next, the Surface Map screen is displayed using the above software, and histogram data is obtained in the Surface Map screen. The arithmetic mean roughness Ra of the surface of the measured object is obtained from the obtained histogram data. In addition, when the surface of the measured object contacts the surface of other layers, the arithmetic mean roughness Ra of the exposed surface of the measured object can be measured by peeling the measured object from the other layers.

[0291] The temporary support (particularly the resin film) is preferably free from deformation (e.g., fine lines), damage, and defects. From the perspective of transparency of the temporary support, it is preferred that the number of particles, foreign matter, defects, and precipitates contained in the temporary support is small. In the temporary support, the number of particles, foreign matter, and defects with a diameter of 1 μm or more is preferably 50 / 10 mm. 2 Less than 10 pieces / 10mm, more preferably 10 pieces / 10mm 2 Below, more preferably 3 / 10mm 2 Below, particularly preferably 0 / 10mm 2 .

[0292] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Application Laid-Open No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Application Laid-Open No. 2016-27363, paragraphs 0041 to 0057 of International Publication No. 2012 / 081680, paragraphs 0029 to 0040 of International Publication No. 2018 / 179370, and paragraphs 0012 to 0032 of Japanese Patent Application Laid-Open No. 2019-101405. The contents of these publications are incorporated herein by reference.

[0293] [Cover film]

[0294] The photosensitive transfer material may also include a cover film (also referred to as a protective film). The cover film can protect the surface of the layer in contact with the cover film (e.g., the negative photosensitive resin layer). The photosensitive transfer material preferably includes a temporary support, a negative photosensitive resin layer, and a cover film in this order. The photosensitive transfer material preferably includes a cover film that contacts the surface of the negative photosensitive resin layer opposite to the side on which the temporary support is disposed.

[0295] Examples of the cover film include resin films and paper. From the viewpoint of strength and flexibility, the cover film is preferably a resin film.

[0296] Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. The resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

[0297] The thickness of the cover film is not limited. The average thickness of the cover film is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and particularly preferably 10 μm to 20 μm.

[0298] From the perspective of achieving better resolution, the arithmetic average roughness Ra of the surface of the cover film on the side where the negative photosensitive resin layer is arranged is preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. By having the arithmetic average roughness of the surface of the cover film on the side where the negative photosensitive resin layer is arranged be within the above range, the uniformity of the thickness of the negative photosensitive resin layer and the resin pattern formed is improved. There is no restriction on the lower limit of the arithmetic average roughness Ra. The arithmetic average roughness Ra of the surface of the cover film on the side where the negative photosensitive resin layer is arranged is preferably 0.001 μm or more. The arithmetic average roughness Ra of the surface of the cover film on the side where the negative photosensitive resin layer is arranged is measured by following the method for measuring the arithmetic average roughness Ra described in the above-mentioned "temporary support body" section.

[0299] [Thermoplastic resin layer]

[0300] The photosensitive transfer material of the present invention may also include a thermoplastic resin layer. The photosensitive transfer material preferably includes a thermoplastic resin layer between the temporary support and the negative photosensitive resin layer. This is because the presence of a thermoplastic resin layer between the temporary support and the negative photosensitive resin layer improves the photosensitive transfer material's ability to conform to the adherend, suppresses the incorporation of air bubbles between the adherend and the photosensitive transfer material, and, as a result, improves interlayer adhesion.

[0301] The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

[0302] Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0303] From the perspective of developability and adhesion to the layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is preferably an acrylic resin. Here, "acrylic resin" refers to a resin having at least one selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from a (meth)acrylate, and a structural unit derived from a (meth)acrylic amide.

[0304] In the acrylic resin, the total content of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylate, and the structural units derived from (meth)acrylic acid amide is preferably 50% by mass or more relative to the total mass of the acrylic resin. In the acrylic resin, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylate is preferably 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass relative to the total mass of the acrylic resin.

[0305] Furthermore, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxyl group is preferred.

[0306] From the perspective of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or greater, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or greater. There is no upper limit on the acid value. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

[0307] As the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, there is no limitation, and known resins can be appropriately selected and used. As the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, for example, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraph 0025 of Japanese Patent Application Laid-Open No. 2011-95716, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs 0033 to 0052 of Japanese Patent Application Laid-Open No. 2010-237589, and the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the binder polymer described in paragraphs 0053 to 0068 of Japanese Patent Application Laid-Open No. 2016-224162 can be exemplified.

[0308] The content of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass, relative to the total mass of the carboxyl group-containing acrylic resin.

[0309] From the viewpoint of developability and adhesion with a layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid.

[0310] The alkali-soluble resin may also have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Examples of the reactive group include ethylenically unsaturated groups, condensation-polymerizing groups (e.g., hydroxyl groups and carboxyl groups), and complex addition-reactive groups (e.g., epoxy groups and (blocked) isocyanate groups).

[0311] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.

[0312] The thermoplastic resin layer may contain one kind of alkali-soluble resin alone, or may contain two or more kinds of alkali-soluble resins.

[0313] From the viewpoint of developability and adhesion with the layer adjacent to the thermoplastic resin layer, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, further preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass, relative to the total mass of the thermoplastic resin layer.

[0314] The thermoplastic resin layer is preferably a pigment (hereinafter sometimes referred to as "pigment B") having a maximum absorption wavelength of 450 nm or more within a wavelength range of 400 nm to 780 nm when developing color, and a maximum absorption wavelength that changes by acid, alkali, or free radicals. A preferred embodiment of pigment B will be described later, and otherwise, is the same as a preferred embodiment of pigment N.

[0315] From the viewpoint of visibility of the exposed portion, visibility of the unexposed portion, and resolution, the dye B is preferably a dye whose maximum absorption wavelength changes due to acid or radicals, and more preferably a dye whose maximum absorption wavelength changes due to acid.

[0316] From the viewpoint of visibility of the exposed portion, visibility of the unexposed portion, and resolution, the thermoplastic resin layer preferably contains a dye whose maximum absorption wavelength is changed by acid as the dye B and a compound that generates acid by light as described later.

[0317] The thermoplastic resin layer may contain one type of dye B alone, or may contain two or more types of dyes B.

[0318] From the viewpoint of visibility of the exposed portion and the unexposed portion, the content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, further preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass, relative to the total mass of the thermoplastic resin layer.

[0319] Here, the content ratio of pigment B refers to the content ratio of the pigment when all pigments B contained in the thermoplastic resin layer become color development state. Below, as an example of the pigment by free radical color development, the quantitative method of the content ratio of pigment B is described. By respectively dissolving pigment (0.001g) and pigment (0.01g) in methyl ethyl ketone (100mL) to prepare 2 kinds of solutions. IRGACURE OXE-01 (BASF company) is added to each solution obtained as a light free radical polymerization initiator, and then free radicals are generated by irradiation of 365nm light, and all pigments are made into color development state. Then, under atmospheric atmosphere, the absorbance of each solution with a liquid temperature of 25 ℃ is measured using a spectrophotometer (UV3100, SHIMADZU CORPORATION) to make a calibration curve. Then, the thermoplastic resin layer (0.1g) is dissolved in methyl ethyl ketone instead of the pigment. In addition, the absorbance of the solution in which all the pigments are color developed is measured by the same method as above. The amount of the pigment contained in the thermoplastic resin layer is calculated based on the absorbance of the solution containing the obtained thermoplastic resin layer and the calibration curve.

[0320] The thermoplastic resin layer may also contain a compound that generates an acid, base, or free radical by light (hereinafter sometimes referred to as "compound C"). Compound C is preferably a compound that generates an acid, base, or free radical by receiving actinic rays (e.g., ultraviolet rays and visible light). Examples of compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

[0321] From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the photocationic polymerization initiator that may also be contained in the negative photosensitive resin layer. Preferred embodiments are the same except for the points described below.

[0322] From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one selected from an onium salt compound and an oxime sulfonate compound. From the viewpoint of sensitivity, resolution, and adhesion, it more preferably contains an oxime sulfonate compound.

[0323] Furthermore, the photoacid generator preferably has the following structure.

[0324] [Chemical Formula 2]

[0325]

[0326] The thermoplastic resin layer may also contain a photobase generator. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, o-carbamoylhydroxyamide, o-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexyl 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylthiobenzoyl)-1-methyl-1-morpholinoethane, and the like. The present invention also contains 2,4-dihydro-1,4-dinitrophenyl-3,5-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0327] The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiator that may be contained in the negative photosensitive resin layer, and the preferred embodiments are the same.

[0328] The thermoplastic resin layer may contain one type of compound C alone, or may contain two or more types of compounds C.

[0329] From the viewpoint of visibility of the exposed portion, visibility of the unexposed portion, and resolution, the content of the compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0330] From the viewpoints of resolution, adhesion with a layer adjacent to the thermoplastic resin layer, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0331] The molecular weight of the plasticizer (the molecular weight of an oligomer or polymer is referred to as the weight average molecular weight (Mw). The same shall apply to this paragraph.) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

[0332] The plasticizer is not limited as long as it is compatible with the alkali-soluble resin and exhibits plasticity. From the perspective of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0333] From the perspectives of resolution and storage stability, the plasticizer preferably comprises a (meth)acrylate compound. From the perspectives of compatibility, resolution, and adhesion to layers adjacent to the thermoplastic resin layer, it is more preferred that the alkali-soluble resin is an acrylic resin and the plasticizer comprises a (meth)acrylate compound.

[0334] Examples of the (meth)acrylate compound used as a plasticizer include the (meth)acrylate compounds described in the "Polymerizable Compound B" section above. In a photosensitive transfer material, when a thermoplastic resin layer is disposed in direct contact with a negative-type photosensitive resin layer, the thermoplastic resin layer and the negative-type photosensitive resin layer preferably each contain the same (meth)acrylate compound. This is because when the thermoplastic resin layer and the negative-type photosensitive resin layer each contain the same (meth)acrylate compound, interlayer diffusion of components is suppressed, thereby improving storage stability.

[0335] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferred that the (meth)acrylate compound does not polymerize even in the exposed portion after exposure, from the viewpoint of adhesion with a layer adjacent to the thermoplastic resin layer.

[0336] In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

[0337] In one embodiment, the (meth)acrylate compound used as the plasticizer is preferably a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group.

[0338] The thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizers.

[0339] From the viewpoints of resolution, adhesion with the layer adjacent to the thermoplastic resin layer, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0340] From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants that may be contained in the negative photosensitive resin layer, and the preferred embodiments are the same.

[0341] The thermoplastic resin layer may contain one type of surfactant alone, or may contain two or more types of surfactants.

[0342] The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, relative to the total mass of the thermoplastic resin layer.

[0343] The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizers that may be contained in the negative photosensitive resin layer.

[0344] The thermoplastic resin layer may contain one type of sensitizer alone, or may contain two or more types of sensitizers.

[0345] From the viewpoint of improving sensitivity to light sources, visibility of exposed areas, and visibility of unexposed areas, the content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the thermoplastic resin layer.

[0346] In addition to the above-mentioned components, the thermoplastic resin layer may contain known additives as needed.

[0347] The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643, the contents of which are incorporated herein by reference.

[0348] The thickness of the thermoplastic resin layer is not limited. From the perspective of adhesion with adjacent layers, the average thickness of the thermoplastic resin layer is preferably 1 μm or greater, more preferably 2 μm or greater. There is no upper limit to the average thickness of the thermoplastic resin layer. From the perspective of developability and resolution, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

[0349] The method for forming the thermoplastic resin layer is not limited as long as it can form a layer containing the above-mentioned components. As a method for forming the thermoplastic resin layer, for example, a method of applying a thermoplastic resin composition on the surface of a temporary support and drying the coating of the thermoplastic resin composition can be mentioned.

[0350] Examples of the thermoplastic resin composition include compositions containing the above-mentioned components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate formation of a thermoplastic resin layer.

[0351] The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. The solvent may be the solvent that can also be contained in the above-mentioned photosensitive resin composition, and the preferred embodiments are the same.

[0352] The thermoplastic resin composition may contain one type of solvent alone or two or more types of solvents.

[0353] The content of the solvent in the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the thermoplastic resin composition.

[0354] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be carried out according to the above-mentioned methods for preparing the photosensitive resin composition and forming the negative photosensitive resin layer. For example, a solution of the components contained in the thermoplastic resin layer is prepared by dissolving them in a solvent, and the resulting solutions are mixed in predetermined proportions to prepare the thermoplastic resin composition. The resulting thermoplastic resin composition is then applied to the surface of a temporary support, and the coating of the thermoplastic resin composition is dried to form the thermoplastic resin layer. Alternatively, the thermoplastic resin layer can be formed on the surface of the negative photosensitive resin layer after forming the negative photosensitive resin layer on the cover film.

[0355] [Middle layer]

[0356] The photosensitive transfer material preferably has an intermediate layer between the thermoplastic resin layer and the negative photosensitive resin layer. The intermediate layer can suppress mixing of components during formation and storage of multiple layers.

[0357] From the perspective of developability and preventing mixing of components during coating of multiple layers and storage after coating, the intermediate layer is preferably a water-soluble layer. In the present invention, "water-soluble" means a solubility of 0.1 g or more in 100 g of water at a liquid temperature of 22°C and a pH of 7.0.

[0358] As an intermediate layer, for example, an oxygen barrier layer having an oxygen blocking function described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-72724 can be cited. Since the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and as a result, productivity is improved. The oxygen barrier layer used as the intermediate layer can be appropriately selected from known layers. The oxygen barrier layer used as the intermediate layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0359] The intermediate layer preferably contains a resin. Examples of the resin contained in the intermediate layer include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylic acid amide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. The resin contained in the intermediate layer is preferably a water-soluble resin.

[0360] From the viewpoint of suppressing mixing of components between multiple layers, the resin contained in the intermediate layer is preferably a resin different from either the polymer A contained in the negative photosensitive resin layer or the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0361] From the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinyl pyrrolidone.

[0362] The intermediate layer may contain one type of resin alone, or may contain two or more types of resins.

[0363] From the viewpoint of oxygen blocking properties and suppression of mixing of components during coating of multiple layers and storage after coating, the content ratio of the resin in the intermediate layer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass, relative to the total mass of the intermediate layer.

[0364] Furthermore, the intermediate layer may contain additives as needed. Examples of the additives include surfactants.

[0365] The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within this range, mixing of components during formation of multiple layers and during storage can be prevented without compromising oxygen barrier properties. Furthermore, the time required to remove the intermediate layer during development can be reduced.

[0366] The method for forming the intermediate layer is not limited as long as it can form a layer containing the above-mentioned components. Examples of the method for forming the intermediate layer include a method of applying an intermediate layer composition to the surface of a thermoplastic resin layer or a negative photosensitive resin layer and then drying the coating film of the intermediate layer composition.

[0367] Examples of intermediate layer compositions include compositions comprising a resin and any additives. The intermediate layer composition preferably contains a solvent to adjust its viscosity and facilitate intermediate layer formation. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least one selected from water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0368] Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

[0369] [Average thickness]

[0370] The average thickness of the photosensitive transfer material is preferably 5 to 55 μm, more preferably 10 to 50 μm, and particularly preferably 20 to 40 μm. The average thickness of the photosensitive transfer material is measured using the method for measuring the average thickness of the transparent substrate described above.

[0371] 〔shape〕

[0372] The shape of the photosensitive transfer material is not limited. From the perspective of versatility and transportability, the photosensitive transfer material of the present invention is preferably in the form of a roll. By winding the photosensitive transfer material, the photosensitive transfer material can be made into a roll shape.

[0373] [Manufacturing method]

[0374] There are no restrictions on the method for producing the photosensitive transfer material. As an example of a method for producing the photosensitive transfer material, there can be mentioned a method comprising the following steps: forming a negative photosensitive resin layer by coating a photosensitive resin composition on a temporary support; and disposing a cover film on the negative photosensitive resin layer. In the above method, the photosensitive resin composition coated on the temporary support can also be dried as needed. There are no restrictions on the drying method, and a known drying method can be used. As a method for disposing a cover film on the negative photosensitive resin layer, for example, there can be mentioned a method of pressing the cover film on the negative photosensitive resin layer.

[0375] Exposure Steps

[0376] In the exposure step, light is irradiated to the surface of the transparent substrate opposite to the surface facing the light-shielding pattern. In the present invention, "the surface of the transparent substrate facing the light-shielding pattern" refers to the surface of the transparent substrate facing the light-shielding pattern. For example, Figure 1 In (b), the "surface of the transparent substrate facing the light-shielding pattern" refers to the surface of the transparent substrate 10 that contacts the light-shielding pattern 20, that is, the surface facing the side opposite to the exposed surface 10a. Figure 1As shown in (b), if light is irradiated to the surface of the transparent substrate 10 opposite to the surface facing the light-shielding pattern 20 (i.e., the exposed surface 10a), a portion of the light that reaches the negative photosensitive resin layer 30 through the light-shielding pattern 20 is blocked, thereby selectively exposing a portion of the negative photosensitive resin layer 30 (i.e., the exposed portion 30a). The solubility of the exposed portion of the negative photosensitive resin layer in the developer is reduced. Moreover, by irradiating light to the surface of the transparent substrate opposite to the surface facing the light-shielding pattern, the curing of the negative photosensitive resin layer located near the transparent substrate can be promoted, compared to the case where light is irradiated from the negative photosensitive resin layer toward the transparent substrate. As a result, the resolution of the resin pattern can be improved in the development step described later. In addition, a resin pattern with a highly linear sidewall can be formed.

[0377] The light source used in the exposure step may be any light source that emits light of a wavelength capable of exposing the negative photosensitive resin layer (e.g., 365 nm or 405 nm). Specific light sources include, for example, ultrahigh-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (light emitting diodes).

[0378] The light irradiated in the exposure step preferably has a wavelength included in the wavelength range of 200nm to 1,500nm, more preferably has a wavelength included in the wavelength range of 250nm to 450nm, more preferably has a wavelength included in the wavelength range of 300nm to 410nm, and more preferably has a wavelength including 365nm.

[0379] The exposure dose is preferably 5 mJ / cm 2 ~200mJ / cm 2 , more preferably 10 mJ / cm 2 ~100mJ / cm 2 .

[0380] Since a portion of the negative photosensitive resin layer can be selectively exposed by the light-shielding pattern, light can be irradiated onto the entire surface of the transparent substrate opposite to the surface facing the light-shielding pattern.

[0381] Development Steps

[0382] In the development step, the negative photosensitive resin layer is developed to form a resin pattern in the area defined by the transparent substrate and the light-shielding pattern. Figure 1 As shown in (c), in the development step, the unexposed portion of the negative photosensitive resin layer 30 is removed, thereby forming a resin pattern 40 having a shape corresponding to the shape of the exposed portion 30 a of the negative photosensitive resin layer 30 .

[0383] As a developing method, a known method can be used. Development of the negative photosensitive resin layer can be performed using, for example, a developer. The type of developer is not limited as long as it can remove the unexposed portions of the negative photosensitive resin layer. As a developer, a known developer (for example, a developer described in Japanese Patent Application Laid-Open No. 5-72724) can be used.

[0384] The developer is preferably an aqueous alkaline solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L. The developer may also contain a water-soluble organic solvent and / or a surfactant. The developer described in paragraph 0194 of International Publication No. 2015 / 093271 is also preferred.

[0385] The developing method is not particularly limited and can be any of spin immersion developing, spray developing, spray and spin developing, and immersion developing. Spray developing refers to a developing process in which a developer is sprayed onto the exposed photosensitive resin layer to remove the exposed or unexposed areas.

[0386] After the development step, it is preferred to apply a cleaning agent by spraying and remove the development residue while rubbing with a brush.

[0387] The liquid temperature of the developer is not limited, but is preferably 20°C to 40°C.

[0388] The average thickness of the resin pattern is preferably greater than the average thickness of the light-shielding pattern. By making the average thickness of the resin pattern greater than the average thickness of the light-shielding pattern, a thick conductive pattern can be formed. The ratio of the average thickness of the resin pattern to the average thickness of the light-shielding pattern ([average thickness of the resin pattern] / [average thickness of the light-shielding pattern]) is preferably 1.1 or more, more preferably 1.5 or more, and particularly preferably 3 or more. The ratio of the average thickness of the resin pattern to the average thickness of the light-shielding pattern may also be 4, 5, or 10. The average thickness of the resin pattern is measured by the method according to the above-mentioned method for measuring the average thickness of the transparent substrate.

[0389] The average thickness of the resin pattern is preferably 1 μm or greater, more preferably 2 μm or greater, and particularly preferably greater than 2 μm. Furthermore, the average thickness of the resin pattern is preferably 3 μm or greater, more preferably 5 μm or greater, and particularly preferably 10 μm or greater. There is no upper limit on the thickness of the resin pattern. For example, the average thickness of the resin pattern can be determined within a range of 100 μm or less.

[0390] The average width of the resin pattern is preferably 50 μm or less, more preferably 5 μm or less. The average width of the resin pattern is preferably 0.3 μm or more, more preferably 0.5 μm or more. The average width of the resin pattern is measured by the method for measuring the average width of the light-shielding pattern.

[0391] Conductive pattern formation steps

[0392] In the step of forming the conductive pattern, the conductive pattern is formed on the light-shielding pattern. Figure 1 As shown in (d), in the conductive pattern forming step, the conductive pattern 50 is formed in the region defined by the light-shielding pattern 20 and the resin pattern 40 .

[0393] As a method for forming a conductive pattern, a known method can be used. As the material of the conductive pattern, a material having a conductivity suitable for the intended use can be used. The material of the conductive pattern preferably comprises Cu or a Cu alloy. The Cu alloy is preferably an alloy of Cu and at least one selected from Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W. The conductive pattern formed using the above materials contains the above-mentioned metal elements. The conductive pattern obtained in the conductive pattern forming step may also be a conductive pattern containing Cu.

[0394] As a method for forming the light-shielding pattern, a known method can be used. In the step of forming the conductive pattern, the conductive pattern is preferably formed by plating. As the plating method, known plating methods can be used. Examples of plating methods include electroplating and electroless plating. The plating method is preferably electroplating, and more preferably copper electroplating.

[0395] In electroplating, for example, a light-shielding pattern that can function as a seed layer is used as a cathode, and a metal is stacked on the light-shielding pattern, whereby a conductive pattern can be formed on the light-shielding pattern.

[0396] As a component of the plating solution used in electroplating, for example, a water-soluble copper salt can be mentioned. As the water-soluble copper salt, a commonly used water-soluble copper salt can be used as a component of the plating solution. The water-soluble copper salt is preferably, for example, at least one selected from inorganic copper salts, alkanesulfonic acid copper salts, alkanolsulfonic acid copper salts, and organic acid copper salts. Examples of inorganic copper salts include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of copper aluminate sulfonates include copper methanesulfonate and copper propanesulfonate. Examples of copper alkanolsulfonic acid salts include copper hydroxyethyl sulfonate and copper propanesulfonate. Examples of organic acid copper salts include copper acetate, copper citrate, and copper tartrate.

[0397] The plating solution may also contain sulfuric acid. When the plating solution contains sulfuric acid, the pH and sulfate ion concentration of the plating solution can be adjusted.

[0398] The electroplating method and conditions are not limited. For example, by feeding the transparent substrate after the development step into a plating tank containing a plating solution, a conductive pattern can be formed on the light-shielding pattern. During electroplating, for example, the conductive pattern can be formed by controlling the current density and the transport speed of the transparent substrate.

[0399] The temperature of the plating solution used in electroplating is usually 70°C or lower, preferably 10°C to 40°C. The current density in electroplating is usually 0.1 A / dm 2 ~100A / dm 2 , preferably 0.5A / dm 2 ~20A / dm 2 By increasing the current density, the productivity of the conductive pattern can be improved. By reducing the current density, the thickness uniformity of the conductive pattern can be improved.

[0400] In the method of forming a conductive pattern by electroplating, a variety of metals can be plated continuously. For example, in a conductive pattern formed by a metal such as copper, the decrease in visibility or aesthetics due to reflection can sometimes become a problem. As a method for reducing the reflectivity of the surface of the conductive pattern, for example, oxidation treatment, sulfurization treatment, nitriding treatment, chlorination treatment, blackening layer film formation and black plating can be cited. For example, by performing chromium plating after copper plating, a layer containing a black material can be formed on the surface of the conductive pattern. The method for reducing the reflectivity of the surface of the conductive pattern is preferably oxidation treatment or sulfurization treatment. Oxidation treatment can obtain a more excellent anti-glare effect, and is also preferred from the perspective of the simplicity of waste liquid treatment and environmental safety.

[0401] After forming the conductive pattern, a post-baking step may be performed. This step can improve insulation reliability, curing properties, and plating adhesion by completely curing any unreacted thermosetting components. The heating temperature is preferably 80°C to 240°C, and the heating time is preferably 5 to 120 minutes.

[0402] After forming the conductive pattern, the surface of the conductive pattern can be protected by a resin layer. For example, after forming the conductive pattern, the surface of the conductive pattern can be protected by forming a resin layer on the conductive pattern. Examples of the resin layer include acrylic resins, polyester resins, polyvinyl acetal resins, polyimide resins, and epoxy resins. Examples of methods for forming the resin layer include coating and thermocompression bonding.

[0403] The conductive pattern may have a single-layer structure or a multi-layer structure. The components of each layer of the conductive pattern having a multi-layer structure may be the same or different.

[0404] There is no limit to the thickness of the conductive pattern. The thickness of the conductive pattern can be determined, for example, according to the intended use. When the conductive pattern is used as wiring, the average thickness of the conductive pattern can be determined, for example, according to the magnitude of the current supplied to the wiring and the wiring width. From the perspective of conductivity, the average thickness of the conductive pattern is preferably 0.5 μm or more, more preferably 1 μm or more, and particularly preferably 2 μm or more. Moreover, the average thickness of the conductive pattern is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The average thickness of the conductive pattern is measured by the method according to the above-mentioned method for measuring the average thickness of the transparent substrate.

[0405] The width of the conductive pattern is preferably narrow. Specifically, the average width of the conductive pattern is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 2 μm or less. By having an average width of the conductive pattern of 5 μm or less, the visibility of the conductive pattern can be reduced in, for example, a device that is sensitive to visibility such as a touch panel. From the perspective of conductivity, the average width of the conductive pattern is preferably 0.1 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. The average width of the conductive pattern is measured by the method according to the above-mentioned method for measuring the average width of the light-shielding pattern.

[0406] The surface resistance of the conductive pattern is preferably less than 0.2 Ω / □, more preferably less than 0.15 Ω / □. The surface resistance of the conductive pattern is measured using a four-probe method. When the pattern size is fine and measurement is difficult, the surface resistance of the conductive layer can also be measured before pattern formation.

[0407] During the step of forming the conductive pattern, the interface between the conductive pattern and the light-shielding pattern may not be clearly observed. For example, when the light-shielding pattern is used as a seed layer and the conductive pattern is formed by plating, the interface between the light-shielding pattern and the conductive pattern may not be clearly observed. However, the inability to clearly observe the interface between the conductive pattern and the light-shielding pattern does not hinder the purpose of the present invention.

[0408] Removal Steps

[0409] After the conductive pattern forming step, the resin pattern remaining on the transparent substrate does not need to be removed. The resin pattern can be used as a permanent film. For example, when the conductive pattern is used for an application that does not require a resin pattern, the resin pattern remaining on the transparent substrate can be removed. In one embodiment, the method for producing a conductive pattern of the present invention preferably includes a step of removing the resin pattern after the conductive pattern forming step.

[0410] Examples of methods for removing the resin pattern include chemical treatment. A preferred method for removing the resin pattern is a method using a removal liquid. Examples of methods using a removal liquid include immersing the transparent substrate having the resin pattern in a stirring removal liquid preferably at a temperature of 30°C to 80°C, more preferably 50°C to 80°C, for 1 to 30 minutes.

[0411] Examples of the removal liquid include those obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0412] The method of removing the resin pattern using the removing liquid is not limited to the dipping method, and a known method other than the dipping method (for example, a spraying method, a shower method, and a liquid coating method) may be used.

[0413] "use"

[0414] The conductive pattern obtained by the method for producing a conductive pattern of the present invention can be applied to various applications. As applications of the conductive pattern obtained by the method for producing a conductive pattern of the present invention, for example, touch sensors, electromagnetic wave shielding parts, antennas, wiring substrates, and conductive heating elements can be mentioned. In the above applications, the conductive pattern obtained by the method for producing a conductive pattern of the present invention can, for example, function as an electrical conductor. Furthermore, in the above applications, the conductive pattern obtained by the method for producing a conductive pattern of the present invention can exhibit various functions depending on the characteristics of the conductive pattern.

[0415] <Touch Sensor>

[0416] The touch sensor of the present invention has a conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. In the touch sensor of the present invention, the conductive pattern can be, for example, a transparent electrode or a frame wiring. The constituent elements of the touch sensor of the present invention are not limited except that they include the conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. As constituent elements other than the conductive pattern, constituent elements contained in known touch sensors can be used. For touch sensors, for example, they are described in Patent Gazette No. 6486341 and Japanese Patent Application Laid-Open No. 2016-155978. The above-mentioned gazettes are incorporated into this specification by reference. The method for manufacturing the touch sensor of the present invention is not limited as long as it uses a method for obtaining a conductive pattern by the method for manufacturing a conductive pattern of the present invention.

[0417] <Electromagnetic wave shielding parts>

[0418] The electromagnetic wave shielding device of the present invention has a conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. In the electromagnetic wave shielding device of the present invention, the conductive pattern can be used as an electromagnetic wave shielding device body, for example. The components of the electromagnetic wave shielding device of the present invention are not limited except that they include the conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. As components other than the conductive pattern, components contained in known electromagnetic wave shielding devices can be used. For example, the electromagnetic wave shielding device is described in Japanese Patent Gazette No. 6486382 and Japanese Patent Application Laid-Open No. 2012-163951. The above-mentioned gazettes are incorporated into this specification by reference. The method for manufacturing the electromagnetic wave shielding device of the present invention is not limited as long as a method using a conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention is used.

[0419] <Antenna>

[0420] The antenna of the present invention is an antenna having a conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. In the antenna of the present invention, the conductive pattern can be used as a transmitting / receiving part or a transmission line part, for example. The constituent elements of the antenna of the present invention are not limited except that they include the conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. As constituent elements other than the conductive pattern, constituent elements contained in known antennas can be used. For example, the antenna is described in Japanese Patent Application Laid-Open No. 2016-219999. The above-mentioned publication is incorporated into this specification by reference. The method for manufacturing the antenna of the present invention is not limited as long as it uses a method for obtaining a conductive pattern by the method for manufacturing a conductive pattern of the present invention.

[0421] <Wiring Board>

[0422] The wiring substrate of the present invention has a conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. In the wiring substrate of the present invention, the conductive pattern can be used as a wiring of a printed wiring board, for example. The constituent elements of the wiring substrate of the present invention are not limited except that they include the conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. As constituent elements other than the conductive pattern, constituent elements contained in known wiring substrates can be used. For example, the wiring substrate is described in Patent Gazette No. 05774686 and Japanese Patent Application Laid-Open No. 2017-204538. The above-mentioned gazette is incorporated into this specification by reference. The method for manufacturing the wiring substrate of the present invention is not limited as long as a method for using the conductive pattern obtained by the method for manufacturing the conductive pattern of the present invention is used.

[0423] <Conductive Heating Element>

[0424] The conductive heating element of the present invention has a conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. In the conductive heating element of the present invention, the conductive pattern can be used as a heating element, for example. The constituent elements of the conductive heating element of the present invention are not limited except that they include the conductive pattern obtained by the method for manufacturing a conductive pattern of the present invention. As constituent elements other than the conductive pattern, constituent elements contained in known conductive heating elements can be used. The conductive heating element is described in, for example, Japanese Laid-Open Patent Publication No. 6486382. The above-mentioned publication is incorporated into this specification by reference. The method for manufacturing the conductive heating element of the present invention is not limited as long as it uses a method for obtaining a conductive pattern by the method for manufacturing a conductive pattern of the present invention.

[0425] <Structure A>

[0426] A structure of one embodiment of the present invention comprises: a transparent substrate; a light-shielding pattern on the transparent substrate; and a resin pattern, which is arranged adjacent to the light-shielding pattern on the transparent substrate and in contact with the transparent substrate, wherein the average thickness of the light-shielding pattern is less than 2 μm, and the average thickness of the resin pattern is greater than 2 μm.

[0427] According to the above embodiment, a structure useful as a material for forming a thick conductive pattern with reduced morphological abnormalities is provided. For example, by using the structure of the above embodiment, Figure 1 As shown in (d), a conductive pattern 50 is formed. Hereinafter, the structure of the above embodiment is referred to as "structure A".

[0428] Reference Figure 2 The structure A of the present invention will be described. Figure 2 This is a schematic cross-sectional view showing an example of the structure of the present invention. Figure 2 The structure 200 shown includes a transparent substrate 11, a light-shielding pattern 21, and a resin pattern 41. The light-shielding pattern 21 is disposed on the transparent substrate 11. The light-shielding pattern 21 is in contact with the transparent substrate 11. However, as described later, the light-shielding pattern 21 may be in contact with the transparent substrate 11 via another layer. The resin pattern 41 is disposed on the transparent substrate 11 adjacent to the light-shielding pattern 21 and in contact with the transparent substrate 11.

[0429] Transparent Substrate

[0430] The structure A of the present invention comprises a transparent substrate. Examples of the transparent substrate include those described in the "Method for Producing a Conductive Pattern" section above. Preferred embodiments of the transparent substrate are the same as those described in the "Method for Producing a Conductive Pattern" section above.

[0431] Light-blocking pattern

[0432] The structure A of the present invention has a light-shielding pattern on a transparent substrate. The average thickness of the light-shielding pattern is 2 μm or less. Examples of the light-shielding pattern include those described in the "Method for Producing a Conductive Pattern" section above. Preferred embodiments of the light-shielding pattern are the same as those described in the "Method for Producing a Conductive Pattern" section above.

[0433] The light-shielding pattern may be in contact with the transparent substrate directly or via another layer. Examples of the other layer include an adhesive layer. Examples of the adhesive layer include those described in the "Method for Producing a Conductive Pattern" section above. Preferred embodiments of the adhesive layer are the same as those described in the "Method for Producing a Conductive Pattern" section above.

[0434] Resin Pattern

[0435] The structure A of the present invention comprises a resin pattern, which is arranged adjacent to the light-shielding pattern on a transparent substrate and in contact with the transparent base material. The average thickness of the resin pattern exceeds 2 μm. Examples of the resin pattern include those described in the "Method for Producing a Conductive Pattern" section above. Preferred embodiments of the resin pattern are the same as those described in the "Method for Producing a Conductive Pattern" section above.

[0436] Manufacturing Method

[0437] The method for producing the structure A of the present invention is not limited as long as it can produce a structure having the above-mentioned constituent elements. For example, the structure A can be produced by the method described in the "Method for Producing a Conductive Pattern" above, which includes a preparation step, an exposure step, and a development step.

[0438] <Structure B>

[0439] Another embodiment of the present invention provides a structure comprising: a transparent substrate; a conductive pattern on the transparent substrate; and a resin pattern, which is arranged adjacent to the conductive pattern on the transparent substrate and in contact with the transparent substrate, wherein the average thickness of the conductive pattern is greater than 2 μm and less than the average thickness of the resin pattern, and the average thickness of the resin pattern is greater than 2 μm.

[0440] According to the above embodiment, a structure having a thick conductive pattern with reduced occurrence of morphological abnormalities is provided. Hereinafter, the structure of the above embodiment is referred to as "structure B."

[0441] Reference Figure 3 The structure B of the present invention will be described. Figure 3This is a schematic cross-sectional view showing an example of the structure of the present invention. Figure 3 The structure 210 shown includes a transparent substrate 12, a conductive pattern 51, and a resin pattern 42. The conductive pattern 51 is disposed on the transparent substrate 12. The conductive pattern 51 is in contact with the transparent substrate 12. However, as described later, the conductive pattern 51 may be in contact with the transparent substrate 12 via another layer. The resin pattern 42 is disposed on the transparent substrate 12 adjacent to the conductive pattern 51 and in contact with the transparent substrate 12.

[0442] Transparent Substrate

[0443] The structure B of the present invention comprises a transparent substrate. Examples of the transparent substrate include those described in the "Method for Producing a Conductive Pattern" section above. Preferred embodiments of the transparent substrate are the same as those described in the "Method for Producing a Conductive Pattern" section above.

[0444] Conductive Pattern

[0445] The structure B of the present invention has a conductive pattern on a transparent substrate. The average thickness of the conductive pattern is 2 μm or greater and less than the average thickness of the resin pattern. Examples of the conductive pattern include those described in the "Method for Producing a Conductive Pattern" section above. Preferred embodiments of the conductive pattern are the same as those described in the "Method for Producing a Conductive Pattern" section above.

[0446] The conductive pattern may also be in contact with the transparent substrate directly or via another layer. The other layer may be a conductive layer. For example, when the structure B is produced using the method described in the "Method for Producing a Conductive Pattern" section above, which includes a preparation step, an exposure step, a development step, and a conductive pattern formation step, the other layer may be, for example, the light-shielding pattern described in the "Method for Producing a Conductive Pattern" section. Preferred embodiments of the light-shielding pattern are the same as those described in the "Method for Producing a Conductive Pattern" section above.

[0447] Resin Pattern

[0448] The structure B of the present invention comprises a resin pattern, which is arranged adjacent to the conductive pattern on a transparent substrate and in contact with the transparent base material. The average thickness of the resin pattern is 2 μm or greater. Examples of the resin pattern include those described in the "Method for Producing a Conductive Pattern" section above. Preferred embodiments of the resin pattern are the same as those described in the "Method for Producing a Conductive Pattern" section above.

[0449] Manufacturing Method

[0450] The method for producing structure B is not limited as long as it can produce a structure having the above-mentioned components. Structure B can be produced, for example, by the method described in the "Method for Producing a Conductive Pattern" section above, including the preparation step, exposure step, development step, and conductive pattern formation step.

[0451] Example

[0452] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

[0453] <Synthesis of Polymer A-1>

[0454] Propylene glycol 1-monomethyl ether (75.0 g) was placed in a three-necked flask, and the liquid temperature was raised to 90°C under a nitrogen atmosphere. A solution containing styrene (32.0 g), methacrylic acid (28.0 g), methyl methacrylate (40.0 g), 2,2'-azobis(isobutyronitrile) (0.8 g), and propylene glycol 1-monomethyl ether (75.0 g) was added dropwise over 2 hours to the liquid in the three-necked flask maintained at 90°C ± 2°C. After the addition was completed, the mixed solution was stirred at 90°C ± 2°C for 2 hours to obtain a solution containing polymer A-1 (solid content concentration: 40.0% by mass). The weight average molecular weight of polymer A-1 was 40,000.

[0455] <Synthesis of Polymer A-2>

[0456] A solution containing polymer A-2 (solid content concentration: 40.0% by mass) was obtained by the same method as polymer A-1 except that the amount of monomer used was changed as follows. The weight average molecular weight of polymer A-2 was 60,000.

[0457] (1) Styrene: 52.0 g

[0458] (2) Methacrylic acid: 29.0 g

[0459] (3) Methyl methacrylate: 19.0 g

[0460] <Synthesis of Polymer A-3>

[0461] A solution containing polymer A-3 (solids concentration: 40.0% by mass) was obtained by the same method as for polymer A-1, except that the monomers used in the synthesis of polymer A-1 (styrene, methacrylic acid, and methyl methacrylate) were changed to the following monomers. The weight average molecular weight of polymer A-3 was 40,000.

[0462] (1) Benzyl methacrylate (81.0 g)

[0463] (2) Methacrylic acid (19.0 g)

[0464] <Synthesis of Bifunctional Methacrylate>

[0465] Bisphenol A (22.83 g, 0.1 mol), toluene (30 g) as a solvent, and triethylamine (0.3 g) as a catalyst were added to a 500 mL pressure-resistant reaction vessel. After replacing the interior of the pressure-resistant reaction vessel with nitrogen, the nitrogen pressure was adjusted to 0.2 kg / cm 2 , and the temperature was raised to 80°C while stirring the mixture. The temperature was raised to 150°C while introducing ethylene oxide (132.15 g, 3.0 mol) and propylene oxide (23.24 g, 0.4 mol) in sequence to maintain a pressure of about 2 kg / cm 2 pressure. The mixture was maintained at 150°C for 1 hour and then cooled. The mixture was neutralized with oxalic acid, and then ion exchange water (50g) was added to the mixture and stirred, and then the mixture was allowed to stand to extract the separated organic layer. The obtained organic layer was washed 3 times with ion exchange water (50g), and then the pressure was reduced to 30Torr at 50°C to remove the solvent, thereby obtaining a divalent alcohol (105.1g). In a three-necked flask with a content of 1L, diol (100.0g, 0.044mol), methacrylic acid (11.5g), 70% by mass methanesulfonic acid aqueous solution (0.9g), hydroquinone (0.2g) and toluene (200mL) were added, and then esterification was carried out under toluene reflux for 8 hours. The water generated in the reaction was removed by a Dean-Stark trap. After the reaction, the mixture was cooled to room temperature, and the resulting organic layer was washed once with a 5% aqueous sodium hydroxide solution (50 g), and then three times with ion-exchanged water (50 g). Hydroquinone monomethyl ether (0.09 g) was added to the organic layer, and the pressure was reduced to 30 Torr at 50°C to remove the solvent, thereby obtaining polyethylene glycol dimethacrylate (90.0 g) having an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A.

[0466] <Preparation of Negative Photosensitive Resin Composition>

[0467] After mixing the components selected according to the description in Table 1, methyl ethyl ketone was added to prepare a negative photosensitive resin composition (solid content concentration: 25% by mass).

[0468] [Table 1]

[0469]

[0470] In Table 1, “-” indicates that the amount used was 0 parts by mass.

[0471] In Table 1, "difunctional methacrylate" refers to polyethylene glycol dimethacrylate obtained by adding an average of 15 mol of ethylene oxide and an average of 2 mol of propylene oxide to both ends of bisphenol A.

[0472] In Table 1, "B-CIM" represents 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0473] In Table 1, the "mixture of two benzotriazole compounds" represents a mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole. The mass ratio of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole to 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole is 1:1.

[0474] <Example 1>

[0475] [Production of photosensitive transfer material]

[0476] As a temporary support, a polyethylene terephthalate (PET) film (TORAY INDUS TRIES, INC., Lumirror 16KS40, thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm) was prepared. A negative photosensitive resin composition was applied to the surface of the temporary support using a slit nozzle so that the coating width was 1.0 m and the thickness after drying became the value described in Table 2. The type of negative photosensitive resin composition was selected according to the description in Table 2. The formed coating film of the negative photosensitive resin composition was dried at 90° C. for 100 seconds to form a negative photosensitive resin layer. A photosensitive transfer material was prepared by pressing a polyethylene film (TAMAPOLY CO., LTD., GF-818, thickness: 19 μm) as a cover film on the surface of the formed negative photosensitive resin layer. By winding the obtained photosensitive transfer material, a roller-type photosensitive transfer material was prepared.

[0477] [Formation of Light-Shielding Pattern (Copper Pattern)]

[0478] A copper layer having a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby producing a PET film with a copper layer. After peeling off the cover film from the photosensitive transfer material, the photosensitive transfer material was bonded to the PET film with the copper layer. The bonding step was carried out under the conditions of a roller temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 1.0 m / min. Next, a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Japan Science Engineering Co., Ltd., main wavelength: 365 nm) was used to irradiate light through a mask, thereby exposing the negative photosensitive resin layer. After peeling off the temporary support, the negative photosensitive resin layer was spray-developed for 30 seconds using an aqueous sodium carbonate solution having a liquid temperature of 25°C, thereby forming a resin pattern (line / space = 5.5 μm / 4.5 μm). The copper layer not covered by the resin pattern was etched using an etching solution (Cu-02 manufactured by KANTO CHEMICAL CO., INC.). The remaining resin pattern was removed using a stripping solution (10% by mass sodium hydroxide aqueous solution). Through the above steps, a PET film with a copper pattern (line / space = 5 μm / 5 μm) was produced. The copper pattern functions as a light-shielding pattern. Table 2 shows the average thickness of the copper pattern.

[0479] [Formation of Conductive Pattern (Copper Pattern)]

[0480] After peeling off the covering film from the photosensitive transfer material, the PET film with the copper pattern and the photosensitive transfer material 1 were bonded. The bonding step was carried out under the conditions of a roller temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 1.0 m / min. The resulting laminated body sequentially comprises a PET film, a copper pattern (light-shielding pattern), a negative photosensitive resin layer, and a temporary support. A high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Japan Science Engineering Co., Ltd., main wavelength: 365 nm) was used to irradiate light on the side opposite to the surface of the PET film facing the copper pattern (light-shielding pattern). The exposure amount is shown in Table 2. After peeling off the temporary support, the photosensitive resin layer was spray-developed for 30 seconds using an aqueous sodium carbonate solution having a liquid temperature of 25°C to form a resin pattern. The spatial portion (i.e., groove) of the copper pattern (light-shielding pattern) is filled with the resin pattern. Table 2 shows the average thickness of the resin pattern. Copper was deposited on the copper pattern (light-shielding pattern) not covered by the resin pattern by copper electroplating. The current density in the copper electroplating was 1.8 ASD. The treatment time in the copper electroplating was 6 minutes. The PET film after copper electroplating was heated at 130°C for 30 minutes. Through the above steps, a structure having a copper pattern (line / space = 5 μm / 5 μm) was produced. Table 2 shows the average thickness of the copper pattern (conductive pattern) deposited by copper electroplating.

[0481] <Examples 2 to 6>

[0482] A structure having a copper pattern was produced by the same procedures as in Example 1, except that the type of photosensitive transfer material, the average thickness of the light-shielding pattern (copper pattern), and the average thickness of the conductive pattern (copper pattern) deposited by copper electroplating were appropriately changed according to the description in Table 2. The average thickness of copper deposited by copper electroplating can be increased by extending the treatment time.

[0483] <Comparative Example 1>

[0484] A structure having a copper pattern was attempted to be produced by the same steps as in Example 1, except that the light irradiation method was changed in the steps described in the "Formation of Conductive Pattern (Copper Pattern)" section. Specifically, in a laminate having a PET film, a copper pattern (light-shielding pattern), a negative photosensitive resin layer, and a temporary support, a mask was brought into contact with the surface of the temporary support opposite to the surface on which the negative photosensitive resin layer was disposed, and then light was irradiated onto the negative photosensitive resin layer through the mask. However, during the light irradiation step, misalignment of the copper pattern (light-shielding pattern) was observed, which was believed to be caused by the shrinkage of the PET film, making it difficult to align the position of the mask opening with the space of the copper pattern (light-shielding pattern). As a result, a resin pattern could not be formed in the space of the copper pattern (light-shielding pattern).

[0485] <Evaluation>

[0486] [Conductive pattern formability]

[0487] Observe any 100 fields of view of the structure having a conductive pattern using an optical microscope. Each field of view was set to 200 μm × 200 μm. The formability of the conductive pattern was evaluated according to the following criteria based on the number of fields in which abnormalities were observed in the conductive pattern. Abnormalities refer to areas in the conductive pattern where morphological abnormalities such as cracking, peeling, and fragmentation are observed. The evaluation results are shown in Table 2.

[0488] A: The field number at which the abnormal part is observed is less than 20.

[0489] B: The number of fields where the abnormal portion is observed is 20 or more.

[0490] [Preventing the inclusion of air bubbles during lamination]

[0491] The PET film with a copper pattern produced in each embodiment and the photosensitive transfer material used in each embodiment were laminated according to the following conditions. Specifically, under the conditions of a roller temperature of 100°C and a linear pressure of 1.0 MPa, the line speed was changed from 1.0 m / min to 5.0 m / min, and the PET film with a copper pattern and the photosensitive transfer material were laminated at the same time. The number of bubbles entrained in the area surrounded by the steps (i.e., the light-shielding pattern) of the resulting laminate was observed using an optical microscope. The degree of bubble mixing in the laminating step was evaluated according to the following standards. In addition, the following standard is one of the indicators that represent the productivity of the laminating step.

[0492] A: No bubbles were observed under any of the conditions of the line speed of 1.0 m / min and the line speed of 5.0 m / min.

[0493] B: No bubbles were observed at a line speed of 1.0 m / min, but bubbles were mixed at a line speed of 5.0 m / min.

[0494] [Table 2]

[0495]

[0496] The results shown in Table 2 indicate that in Examples 1 to 6, conductive patterns having a thickness that reduces the occurrence of morphological abnormalities were formed.

[0497] The disclosure of Japanese Patent Application No. 2020-034129, filed on February 28, 2020, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

[0498] Explanation of symbols

[0499] 10, 11, 12-transparent substrate, 10a-exposed surface, 20, 21-light-shielding pattern, 30-negative photosensitive resin layer, 30a-exposed portion, 40, 41, 42-resin pattern, 50, 51-conductive pattern, 100-laminated body, 200, 210-structure.

Claims

1. A method for manufacturing a conductive pattern, comprising: a step of preparing a laminate comprising: a transparent substrate, a light-shielding pattern on the transparent substrate, and a negative photosensitive resin layer disposed on the transparent substrate and the light-shielding pattern and in contact with the transparent substrate; irradiating light onto a surface of the transparent substrate opposite to the surface facing the light-shielding pattern; forming a resin pattern in an area defined by the transparent substrate and the light-shielding pattern by developing the negative photosensitive resin layer; as well as forming a conductive pattern on the light-shielding pattern, The average thickness of the resin pattern is greater than 10 μm, The negative photosensitive resin layer comprises an alkali-soluble polymer, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator. The compound having an ethylenically unsaturated bond comprises a bifunctional ethylenically unsaturated compound having a bisphenol A structure, The photopolymerization initiator includes at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and a derivative of 2,4,5-triarylimidazole dimer.

2. The method for producing a conductive pattern according to claim 1, wherein: In the step of forming the conductive pattern, the conductive pattern is formed by plating.

3. The method for producing a conductive pattern according to claim 2, wherein: The plating is electroplating.

4. The method for producing a conductive pattern according to claim 2, wherein: The plating is electroplating copper.

5. The method for producing a conductive pattern according to any one of claims 1 to 4, wherein: The light-shielding pattern is conductive.

6. The method for producing a conductive pattern according to any one of claims 1 to 4, wherein: The light-shielding pattern has an average thickness of 2 μm or less.

7. The method for producing a conductive pattern according to any one of claims 1 to 4, wherein: The step of preparing the laminate includes: preparing a laminate precursor having the transparent substrate and a light-shielding pattern on the transparent substrate; and forming the negative photosensitive resin layer on the transparent substrate and the light-shielding pattern.

8. The method for producing a conductive pattern according to any one of claims 1 to 4, wherein: The step of preparing the laminate includes: preparing the transparent substrate; forming a light-shielding pattern on the transparent substrate; and forming the negative photosensitive resin layer on the transparent substrate and the light-shielding pattern.

9. The method for producing a conductive pattern according to claim 8, wherein: The step of forming the light-shielding pattern includes: forming a light-shielding layer on the transparent substrate; forming a photosensitive resin layer on the light-shielding layer; forming an anti-etching pattern by exposing and developing the photosensitive resin layer; and removing the light-shielding layer not covered by the anti-etching pattern.

10. The method for manufacturing a conductive pattern according to claim 7, wherein: In the step of forming the negative photosensitive resin layer, the negative photosensitive resin layer is formed using a photosensitive transfer material. 11 . The method for manufacturing a conductive pattern according to claim 1 , further comprising removing the resin pattern after forming the conductive pattern.

12. The method for producing a conductive pattern according to any one of claims 1 to 4, 9, and 10, wherein: An average thickness of the resin pattern is greater than an average thickness of the light-shielding pattern.

13. The method for producing a conductive pattern according to any one of claims 1 to 4, 9, and 10, wherein: The light-shielding pattern has an average width of 5 μm or less.

14. The method for producing a conductive pattern according to any one of claims 1 to 4, 9, and 10, wherein: The average width of the resin pattern is 5 μm or less.

15. The method for producing a conductive pattern according to any one of claims 1 to 4, 9, and 10, wherein: The light comprises a wavelength of 365 nm. 16 . A touch sensor comprising a conductive pattern obtained by the method for producing a conductive pattern according to claim 1 . 17 . An electromagnetic shielding device comprising a conductive pattern obtained by the method for producing a conductive pattern according to claim 1 . 18 . An antenna comprising a conductive pattern obtained by the method for producing a conductive pattern according to claim 1 . 19 . A wiring board comprising a conductive pattern obtained by the method for producing a conductive pattern according to claim 1 . 20 . A conductive heating element comprising a conductive pattern obtained by the method for producing a conductive pattern according to claim 1 .

21. A structure comprising: Transparent substrate; a light-shielding pattern on the transparent substrate; as well as a resin pattern disposed adjacent to the light-shielding pattern on the transparent substrate and in contact with the transparent substrate, The average thickness of the light-shielding pattern is 2 μm or less. The average thickness of the resin pattern is greater than 10 μm, The resin pattern is formed by curing a negative photosensitive resin layer. The negative photosensitive resin layer comprises an alkali-soluble polymer, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator. The compound having an ethylenically unsaturated bond comprises a bifunctional ethylenically unsaturated compound having a bisphenol A structure, The photopolymerization initiator includes at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and a derivative of 2,4,5-triarylimidazole dimer.

22. The structure according to claim 21, wherein The light-shielding pattern has an average width of 5 μm or less, and the resin pattern has an average width of 5 μm or less.

23. A structure comprising: Transparent substrate; a conductive pattern on the transparent substrate; and a resin pattern disposed adjacent to the conductive pattern on the transparent substrate and in contact with the transparent substrate, The average thickness of the conductive pattern is greater than or equal to 2 μm and less than or equal to the average thickness of the resin pattern. The average thickness of the resin pattern is greater than 10 μm, The resin pattern is formed by curing a negative photosensitive resin layer. The negative photosensitive resin layer comprises an alkali-soluble polymer, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator. The compound having an ethylenically unsaturated bond comprises a bifunctional ethylenically unsaturated compound having a bisphenol A structure, The photopolymerization initiator includes at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and a derivative of 2,4,5-triarylimidazole dimer.

24. The structure according to claim 23, wherein The conductive pattern has an average width of 5 μm or less, and the resin pattern has an average width of 5 μm or less.

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