Pattern forming method, method for manufacturing circuit substrate, and laminate

Abstract

The present invention provides a pattern forming method, a laminate, and applications thereof. The pattern forming method includes: a step of preparing a laminate having a first photosensitive layer, a substrate having a region transparent to an exposure wavelength, and a second photosensitive layer sequentially; a step of exposing the first photosensitive layer; a step of exposing the second photosensitive layer; a step of developing the exposed first photosensitive layer to form a first resin pattern; and a step of developing the exposed second photosensitive layer to form a second resin pattern, wherein the dominant wavelength λ1 of the exposure wavelength in the step of exposing the first photosensitive layer and the dominant wavelength λ2 of the exposure wavelength in the step of exposing the second photosensitive layer satisfy the relationship λ1≠λ2.

Description

Technical Field

[0001] This invention relates to a pattern forming method, a method for manufacturing a circuit board, and a laminate. Background Technology

[0002] For example, in the field of touch panels, a method is used to form patterns on both sides of a thin-film substrate in order to manufacture touch sensors. For example, by photolithography, resin patterns can be formed on both sides of the substrate by exposing photosensitive layers disposed on both sides of a substrate with high light-shielding properties, such as copper, and then developing the photosensitive layers.

[0003] On the other hand, if resin patterns are to be formed on both sides of a transparent conductive film substrate using the same process as the aforementioned photolithography, the following phenomenon (hereinafter referred to as "fogging") sometimes occurs during the exposure of the photosensitive layers: if the photosensitive layer disposed on one side of the transparent substrate is exposed, the photosensitive layer disposed on the other side of the transparent substrate is also exposed. If fogging occurs, it is difficult to process the photosensitive layers disposed on both sides of the transparent substrate into the desired shape.

[0004] As a technique to suppress the generation of exposure fog, for example, a pattern forming method using a photosensitive layer with optical concentration adjusted within a specific range has been proposed (see Patent Document 1).

[0005] Patent Document 1: International Publication No. 2019 / 022090 Summary of the Invention

[0006] The technical problem to be solved by the invention

[0007] The optical density of the photosensitive layer can be adjusted, for example, by adding an ultraviolet-absorbing material (e.g., carbon black) to the photosensitive layer (refer to Patent Document 1). However, for example, if an ultraviolet-absorbing material is used to increase the optical density of the photosensitive layer (i.e., if the transmittance of the photosensitive layer is reduced), it can sometimes affect the reactivity of the photosensitive layer. As a result, for example, there is a possibility of deterioration in the resolution of the obtained resin pattern or a decrease in exposure sensitivity, leading to a deterioration in process suitability.

[0008] The present invention was made in view of the above circumstances.

[0009] One objective of this invention is to provide a pattern forming method that can suppress the generation of exposure fog and form resin patterns with excellent resolution.

[0010] Another objective of the present invention is to provide a method for manufacturing a circuit board using a pattern forming method that can suppress the generation of exposure fog and form resin patterns with excellent resolution.

[0011] Another objective of the present invention is to provide a laminate capable of suppressing the generation of exposure fog and forming resin patterns with excellent resolution.

[0012] means for solving technical problems

[0013] The present invention includes the following methods.

[0014] <1> A pattern forming method includes: preparing a laminate having a first photosensitive layer, a substrate having a region transparent to an exposure wavelength, and a second photosensitive layer sequentially; exposing the first photosensitive layer; exposing the second photosensitive layer; developing the exposed first photosensitive layer to form a first resin pattern; and developing the exposed second photosensitive layer to form a second resin pattern, wherein the dominant wavelength λ1 of the exposure wavelength in the step of exposing the first photosensitive layer and the dominant wavelength λ2 of the exposure wavelength in the step of exposing the second photosensitive layer satisfy the relationship λ1≠λ2.

[0015] <2> according to <1> The pattern forming method, wherein,

[0016] The first photosensitive layer and the second photosensitive layer contain different photosensitive compounds.

[0017] <3> according to <1> or <2> The pattern forming method, wherein,

[0018] Regarding the first photosensitive layer and the second photosensitive layer mentioned above, the following relationships 1 and 2 are satisfied.

[0019] Relationship 1: 1.1 ≤ E 1r / E2

[0020] Relationship 2: 1.1≤E 2r / E1

[0021] Among them, E 1r E1 represents the maximum exposure level at which the first photosensitive layer does not react when exposed to light having the dominant wavelength λ2 from the second photosensitive layer side of the aforementioned laminate. E2 represents the exposure level at which the second photosensitive layer is exposed to light having the dominant wavelength λ2 during the process of exposing the second photosensitive layer. 2r E1 represents the maximum exposure amount at which the second photosensitive layer does not react when exposed to light having the dominant wavelength λ1 from the first photosensitive layer side of the above-mentioned laminate. E1 represents the exposure amount when the first photosensitive layer is exposed to light having the dominant wavelength λ1 during the process of exposing the first photosensitive layer.

[0022] <4> according to <1> to <3> The pattern forming method described in any one of the following statements, wherein,

[0023] Regarding the first photosensitive layer and the second photosensitive layer mentioned above, the following relationships 3 and 4 are satisfied.

[0024] Relationship 3: 3≤S 12 / S 11

[0025] Relation 4: 3≤S 21 / S 22

[0026] Among them, S 12 S represents the spectral sensitivity of the first photosensitive layer relative to the dominant wavelength λ2. 11 S represents the spectral sensitivity of the first photosensitive layer relative to the dominant wavelength λ1. 21 S represents the spectral sensitivity of the second photosensitive layer relative to the dominant wavelength λ1. 22 This indicates the spectral sensitivity of the second photosensitive layer relative to the aforementioned dominant wavelength λ2.

[0027] <5> according to <1> to <4> The pattern forming method described in any one of the following statements, wherein,

[0028] The first photosensitive layer contains a substance that absorbs light of the dominant wavelength λ2 and / or the second photosensitive layer contains a substance that absorbs light of the dominant wavelength λ1.

[0029] <6> according to <1> to <5> The pattern forming method described in any one of the following statements, wherein,

[0030] The aforementioned laminate has at least one of the following: a layer containing a substance that absorbs light of the dominant wavelength λ2 disposed between the substrate and the first photosensitive layer; a layer containing a substance that absorbs light of the dominant wavelength λ2 disposed on the substrate with the first photosensitive layer spaced apart; a layer containing a substance that absorbs light of the dominant wavelength λ1 disposed between the substrate and the second photosensitive layer; and a layer containing a substance that absorbs light of the dominant wavelength λ1 disposed on the substrate with the second photosensitive layer spaced apart.

[0031] <7> according to <5> or <6> The pattern forming method, wherein,

[0032] The substance that absorbs light with the dominant wavelength λ2 and the substance that absorbs light with the dominant wavelength λ1 have a maximum absorption wavelength λ in the wavelength region above 400 nm. max The substance.

[0033] <8> according to <1> to <7> The pattern forming method described in any one of the following statements, wherein,

[0034] A component for absorbing light of the dominant wavelength λ2 is disposed between the first photosensitive layer and the light source for exposing the first photosensitive layer, and / or a component for absorbing light of the dominant wavelength λ1 is disposed between the second photosensitive layer and the light source for exposing the second photosensitive layer.

[0035] <9> according to <8> The pattern forming method, wherein,

[0036] The component that absorbs light with the dominant wavelength λ2 and the component that absorbs light with the dominant wavelength λ1 both have a maximum absorption wavelength λ within a wavelength region of 400 nm or higher. max Components of the material.

[0037] <10> according to <1> to <9> The pattern forming method described in any one of the following statements, wherein,

[0038] Simultaneously, the process of exposing the first photosensitive layer and the process of exposing the second photosensitive layer are performed.

[0039] <11> according to <1> to <9> The pattern forming method described in any one of the following statements, wherein,

[0040] The process of exposing the first photosensitive layer and the process of exposing the second photosensitive layer are performed respectively.

[0041] <12> according to <1> to <11> The pattern forming method described in any one of the following statements, wherein,

[0042] Simultaneously, the process of developing the exposed first photosensitive layer to form a first resin pattern and the process of developing the exposed second photosensitive layer to form a second resin pattern are performed.

[0043] <13> according to <1> to <11> The pattern forming method described in any one of the following statements, wherein,

[0044] The process involves developing the exposed first photosensitive layer to form a first resin pattern and developing the exposed second photosensitive layer to form a second resin pattern.

[0045] <14> according to <1> to <13> The pattern forming method described in any one of the following statements, wherein,

[0046] The aforementioned laminate has at least one conductive layer on at least one side of the aforementioned substrate.

[0047] <15> according to <1> to <13> The pattern forming method described in any one of the following statements, wherein,

[0048] The aforementioned laminate has at least one conductive layer on each of the two sides of the aforementioned substrate.

[0049] <16> according to <1> to <13> The pattern forming method described in any one of the following statements, wherein,

[0050] The aforementioned laminate has at least one conductive layer on at least one side of the substrate, and a conductive layer having a different composition from the aforementioned conductive layer is further formed on at least a portion of the conductive layer.

[0051] <17> according to <1> to <13> The pattern forming method described in any one of the following statements, wherein,

[0052] The aforementioned laminate has at least one conductive layer on at least one side of the aforementioned substrate, and the conductive layer has two or more regions with different compositions within the substrate.

[0053] <18> according to <14> to <17> The pattern forming method described in any one of the following statements, wherein,

[0054] At least one of the aforementioned conductive layers is a layer containing a metal oxide.

[0055] <19> according to <14> to <17> The pattern forming method described in any one of the following statements, wherein,

[0056] At least one of the aforementioned conductive layers is a layer comprising at least one selected from metal nanowires and metal nanoparticles.

[0057] <20> according to <14> to <19> The pattern forming method according to any one of the above-mentioned methods further includes the step of using at least one of the first resin pattern and the second resin pattern as a mask to etch the conductive layer.

[0058] <21> according to <1> to <20> The pattern forming method described in any one of the following statements, wherein,

[0059] The aforementioned first photosensitive layer is a negative photosensitive layer whose solubility in the developing solution decreases due to exposure.

[0060] <22> according to <1> to <20> The pattern forming method described in any one of the following statements, wherein,

[0061] The aforementioned first photosensitive layer is a positive photosensitive layer whose solubility in the developer increases through exposure.

[0062] <23> according to <1> to <22> The pattern forming method described in any one of the following statements, wherein,

[0063] The aforementioned second photosensitive layer is a negative photosensitive layer whose solubility in the developing solution decreases due to exposure.

[0064] <24> according to <1> to <22> The pattern forming method described in any one of the following statements, wherein,

[0065] The aforementioned second photosensitive layer is a positive photosensitive layer whose solubility in the developing solution increases through exposure.

[0066] <25> according to <1> to <24> The pattern forming method described in any one of the following statements, wherein,

[0067] The exposure wavelength in the process of exposing the first photosensitive layer does not include wavelength 365nm.

[0068] <26> according to <25> The pattern forming method, wherein,

[0069] The exposure wavelength in the process of exposing the second photosensitive layer does not include wavelength 405nm.

[0070] <27> according to <1> to <24> The pattern forming method described in any one of the following statements, wherein,

[0071] The exposure wavelength in the process of exposing the first photosensitive layer does not include wavelength 405nm.

[0072] <28> according to <27> The pattern forming method, wherein,

[0073] The exposure wavelength in the process of exposing the second photosensitive layer does not include wavelength 365nm.

[0074] <29> A method for manufacturing a circuit board, comprising: <1> to <28> The pattern forming method described in any one of the following statements.

[0075] <30> A laminate comprising a first photosensitive layer, a substrate and a second photosensitive layer, having the following characteristics A and B.

[0076] Feature A: When the maximum sensitivity wavelength of the first photosensitive layer is set to λ m1 The maximum sensitivity wavelength of the second photosensitive layer is set to λ. m2 When λ is satisfied m1 ≠λ m2 The relationship is as follows. The maximum sensitivity wavelength refers to the minimum exposure required for the photosensitive layer to react at each wavelength of light, which is considered the wavelength with the lowest spectral sensitivity and minimum exposure.

[0077] Characteristic B: The above-mentioned substrate relative to the above-mentioned wavelength λ m1 and λ m2 The light has a transmittance of at least 50%.

[0078] <31> according to <30> The aforementioned laminate, wherein,

[0079] The above wavelength λ m1 In the range of wavelengths exceeding 395 nm but below 500 nm, the aforementioned wavelength λ m2 Within the range of 250nm and above and 395nm and below.

[0080] <32> according to <30> or <31> The aforementioned laminate, wherein,

[0081] The aforementioned first photosensitive layer contains materials that absorb the aforementioned wavelength λ. m2 The substance of light.

[0082] <33> according to <30> to <32> The laminated body described in any one of the following statements, wherein,

[0083] The aforementioned second photosensitive layer contains materials that absorb the aforementioned wavelength λ. m1 The substance of light.

[0084] <34> according to <30> to <33> The laminated body described in any one of the following statements, wherein,

[0085] Regarding the first photosensitive layer and the second photosensitive layer mentioned above, the following relationships C and D are satisfied.

[0086] Relation C: 3≤S m12 / S m11

[0087] Relation D: 3≤S m21 / S m22

[0088] Among them, S m12 This indicates that, relative to the wavelength λ mentioned above... m2 The spectral sensitivity of the first photosensitive layer mentioned above, S m11 This indicates that, relative to the wavelength λ mentioned above... m1 The spectral sensitivity of the first photosensitive layer mentioned above, S m21 This indicates that, relative to the wavelength λ mentioned above... m1 The spectral sensitivity of the aforementioned second photosensitive layer, S m22 This indicates that, relative to the wavelength λ mentioned above... m2 The spectral sensitivity of the aforementioned second photosensitive layer.

[0089] <35> according to <30> to <34> The laminated body described in any one of the following statements, wherein,

[0090] The wavelength λ in the first photosensitive layer mentioned above m2 The light transmittance is less than 70%.

[0091] <36> according to <30> to <35> The laminated body described in any one of the following statements, wherein,

[0092] The wavelength λ in the aforementioned second photosensitive layer m1 The light transmittance is less than 70%.

[0093] <37> according to <30> to <36> The laminated body described in any one of the following statements, wherein,

[0094] The substrate has at least one conductive layer on at least one side.

[0095] <38> according to <30> to <37> The laminated body described in any one of the following statements, wherein,

[0096] The substrate has at least one conductive layer on at least one side, and a conductive layer having a different composition from the conductive layer is further formed on at least a portion of the conductive layer.

[0097] <39> according to <30> to <37> The laminated body described in any one of the following statements, wherein,

[0098] The substrate has at least one conductive layer on at least one side, and the conductive layer has two or more regions with different compositions within the substrate.

[0099] <40> according to <30> to <39> The laminated body described in any one of the following statements, wherein,

[0100] The substrate has at least one conductive layer on each of its two sides.

[0101] <41> according to <37> to <40> The laminated body described in any one of the following statements, wherein,

[0102] At least one of the aforementioned conductive layers is a layer containing a metal oxide.

[0103] <42> according to <37> to <41> The laminated body described in any one of the following statements, wherein,

[0104] At least one of the aforementioned conductive layers is a layer comprising at least one selected from metal nanowires and metal nanoparticles.

[0105] <43> according to <30> to <42> The laminated body described in any one of the following statements, wherein,

[0106] The first photosensitive layer mentioned above is a negative photosensitive layer.

[0107] <44> according to <30> to <43> The laminated body described in any one of the following statements, wherein,

[0108] The aforementioned second photosensitive layer is a negative photosensitive layer.

[0109] <45> according to <30> to <42> The laminated body described in any one of the following statements, wherein,

[0110] The first photosensitive layer mentioned above is a positive photosensitive layer.

[0111] <46> according to <30> to <43> and <45> The laminated body described in any one of the following statements, wherein,

[0112] The aforementioned second photosensitive layer is a positive photosensitive layer.

[0113] <47> according to <30> to <46> The laminated body described in any one of the following statements, wherein,

[0114] The above wavelength λ m2 Within the range of 335nm and above and 395nm and below.

[0115] <48> according to <30> to <47> The laminated body described in any one of the following statements, wherein,

[0116] The above wavelength λ m1 Within the range of 396nm and above and 456nm and below.

[0117] Invention Effects

[0118] According to one aspect of the present invention, a pattern forming method is provided that can suppress the generation of exposure fog and form resin patterns with excellent resolution.

[0119] According to another aspect of the present invention, a method for manufacturing a circuit board using a pattern forming method capable of suppressing the generation of exposure fog and forming resin patterns with excellent resolution can be provided.

[0120] According to yet another aspect of the present invention, a laminate capable of suppressing the generation of exposure fog and forming resin patterns with excellent resolution can be provided. Detailed Implementation

[0121] Hereinafter, embodiments of the present invention will be described in detail. Furthermore, the present invention is not limited to any of the following embodiments, and can be implemented with appropriate modifications within the scope of the objectives of the present invention.

[0122] In this invention, the numerical range indicated by "~" refers to the range encompassed by the values ​​recorded before and after "~" as the lower and upper limits. Within the numerical ranges recorded in stages in this invention, the upper or lower limit recorded within a certain numerical range can be replaced with the upper or lower limit of another numerical range recorded in stages. Furthermore, within the numerical ranges recorded in this invention, the upper or lower limit recorded within a certain numerical range can be replaced with the values ​​shown in the embodiments.

[0123] In this invention, "(meth)acrylic acid" refers to either or both of acrylic acid and methacrylic acid, and "(meth)acrylate" refers to either or both of acrylate and methacrylate.

[0124] In this invention, when a composition contains multiple substances corresponding to each component, unless otherwise specified, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition.

[0125] In this invention, the term "process" includes not only independent processes, but also processes that achieve their intended purpose even when they cannot be clearly distinguished from other processes.

[0126] In the designation of groups (atomic groups) in this invention, the designations without indicating whether they are substituted or unsubstituted include groups without substituents and groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0127] In this invention, "mass%" and "weight%" have the same meaning, and "parts of mass" and "parts of weight" have the same meaning.

[0128] In this invention, a combination of two or more preferred methods is a more preferred method.

[0129] In this invention, chemical structural formulas are sometimes described as simplified structural formulas that omit hydrogen atoms.

[0130] In this invention, "solid component" refers to a component from which the solvent has been removed from the composition of the composition.

[0131] In this invention, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are obtained by measuring them using a gel permeation chromatography (GPC) analysis apparatus (columns: “TSKgel GMHxL, TSKgel G4000HxL” (manufactured by TOSOH CORPORATION) and “TSKgel G2000HxL” (manufactured by TOSOH CORPORATION), detector: differential spectrometer, solvent: tetrahydrofuran (THF)) and converting them using polystyrene as a standard substance.

[0132] In this invention, ordinal numbers (e.g., "first" and "second") are terms used to distinguish constituent elements, and do not limit the number of constituent elements or the quality of the constituent elements.

[0133] <Pattern Formation Methods>

[0134] The pattern forming method of the present invention includes: a step of preparing a laminate having a first photosensitive layer, a substrate having a region transparent to the exposure wavelength, and a second photosensitive layer in sequence (hereinafter, sometimes referred to as the "preparation step"); a step of exposing the first photosensitive layer (hereinafter, sometimes referred to as the "exposure step (1)"); a step of exposing the second photosensitive layer (hereinafter, sometimes referred to as the "exposure step (2)"); a step of developing the exposed first photosensitive layer to form a first resin pattern (hereinafter, sometimes referred to as the "development step (1)"); and a step of developing the exposed second photosensitive layer to form a second resin pattern (hereinafter, sometimes referred to as the "development step (2)"). The dominant wavelength λ1 of the exposure wavelength in the step of exposing the first photosensitive layer and the dominant wavelength λ2 of the exposure wavelength in the step of exposing the second photosensitive layer satisfy the relationship λ1≠λ2 (hereinafter, sometimes referred to as "specific exposure conditions").

[0135] The pattern forming method of the present invention includes the above-described steps, thereby suppressing the generation of exposure fog and forming resin patterns with excellent resolution. The reason why the pattern forming method of the present invention achieves the above-described effect is speculated as follows. As mentioned above, if, in order to suppress the generation of exposure fog, for example, an ultraviolet absorbing material is used to increase the optical concentration of the photosensitive layer, the resolution of the obtained resin pattern may deteriorate. On the other hand, the pattern forming method of the present invention includes a preparation step, an exposure step (1), an exposure step (2), a development step (1), and a development step (2), wherein the dominant wavelength λ1 of the exposure wavelength in the exposure step (1) and the dominant wavelength λ2 of the exposure wavelength in the exposure step (2) are different from each other, thereby enabling selective or preferential exposure of the first photosensitive layer and the second photosensitive layer, respectively. Therefore, the pattern forming method of the present invention can suppress the generation of exposure fog and form resin patterns with excellent resolution.

[0136] In this invention, "exposure wavelength" refers to the wavelength of light irradiated when exposing the photosensitive layer, and specifically the wavelength of light reaching the photosensitive layer. For example, when exposing the photosensitive layer via a wavelength-selective filter, the wavelength of the light before passing through the filter does not conform to the exposure wavelength. Here, "wavelength selectivity" refers to the property of transmitting light within a specific wavelength range. In this invention, the wavelength and intensity of the light are measured using a known spectrometer (e.g., RPS900-R, manufactured by International Light Technologies).

[0137] In this invention, "dominant wavelength" refers to the wavelength of light with the strongest intensity among the wavelengths of light reaching the photosensitive layer (i.e., the exposure wavelength). For example, if the light reaching the photosensitive layer has wavelengths of 365 nm and 405 nm, and the intensity of the 365 nm wavelength is greater than that of the 405 nm wavelength, then the dominant wavelength of the aforementioned exposure light is 365 nm. In this invention, "exposure light" refers to the light used to expose the photosensitive layer.

[0138] The following is a detailed description of each step in the pattern forming method involved in this invention.

[0139] Preparation Process

[0140] The pattern forming method of the present invention includes a step of preparing a laminate having a first photosensitive layer, a substrate (hereinafter sometimes simply referred to as "substrate") having a region transparent relative to the exposure wavelength, and a second photosensitive layer in sequence.

[0141] In this invention, "preparing a laminate" means setting the laminate to a usable state, which, unless otherwise specified, includes preparing a pre-manufactured laminate and manufacturing the laminate. That is, the laminate used in the pattern forming method of this invention can be a pre-manufactured laminate or a laminate manufactured in the preparation process.

[0142] In the pattern forming method of the present invention, the laminate of the present invention described later can preferably be used as the laminate.

[0143] [Substrate]

[0144] The laminate includes a substrate having a region that is transparent relative to the exposure wavelength. The substrate is disposed between a first photosensitive layer and a second photosensitive layer.

[0145] In this invention, "the region that is transparent relative to the exposure wavelength" refers to a region with a transmittance of 30% or more at the dominant wavelength of the exposure wavelength. The transmittance is preferably 50% or more, more preferably 60% or more, further preferably 80% or more, and particularly preferably 90% or more. There is no upper limit to the transmittance. For example, the transmittance can be determined as long as it is within the range of 100% or less. The transmittance is measured using a known transmittance measuring instrument (e.g., the V-700 series manufactured by JASCO Corporation).

[0146] The region that is transparent to the exposure wavelength can be disposed on the entire substrate or a portion of the substrate. Preferably, the region that is transparent to the exposure wavelength is disposed on the portion corresponding to the exposure section in the exposure process. More preferably, the region that is transparent to the exposure wavelength is disposed on the entire substrate. That is, the substrate is preferably a substrate that is transparent to the exposure wavelength.

[0147] Materials used as substrates include, for example, resin materials and inorganic materials.

[0148] Examples of resin materials include polyesters (e.g., polyethylene terephthalate and polyethylene naphthalate), polyetheretherketone, acrylic resins, cyclic olefin polymers, and polycarbonates.

[0149] Examples of inorganic materials include glass and quartz.

[0150] The substrate is preferably a resin film, and more preferably a polyethylene terephthalate film, a polyethylene naphthalate film, or a cyclic olefin polymer film.

[0151] There is no limitation on the thickness of the substrate. From the viewpoints of transportability, electrical properties, and film formation, the average thickness of the substrate is preferably 10 μm to 100 μm, more preferably 10 μm to 60 μm. The average thickness of the substrate is set as the average of the thicknesses of 10 locations measured by observing a cross-section perpendicular to the in-plane direction of the substrate using a scanning electron microscope (SEM).

[0152] [Conductive layer]

[0153] The substrate preferably has a conductive layer. Specifically, the laminate preferably has at least one conductive layer on at least one side of the substrate. More preferably, the laminate has at least one conductive layer on each of the two sides of the substrate. The conductive layer preferably has a region that is transparent relative to the exposure wavelength.

[0154] In this invention, "conductivity" refers to a volume resistivity of less than 1×10⁻⁶. 6 Ωcm. The volume resistivity, representing conductivity, is preferably less than 1 × 10⁻⁶. 4 Ωcm. Volume resistivity is measured using a known resistivity meter (e.g., the EC-80P resistivity meter, manufactured by NAPSON CORPORATION).

[0155] From the viewpoint of conductivity, the conductive layer preferably contains a metal. Examples of metals include copper, silver, tin, palladium, gold, nickel, chromium, platinum, iron, and indium. The metal can be a single metal or an alloy. Examples of alloys include copper alloys and silver alloys.

[0156] From the viewpoint of conductivity, the conductive layer preferably contains at least one metal selected from copper, silver, tin and indium.

[0157] The transparent conductive layer can contain a single metal or two or more metals.

[0158] Examples of specific conductive layers include layers comprising metal oxides, layers comprising metal nanoparticles, and layers comprising metal nanowires. In one embodiment, at least one conductive layer included in the laminate is preferably a layer comprising a metal oxide. In another embodiment, at least one conductive layer included in the laminate is preferably a layer comprising at least one selected from metal nanowires and metal nanoparticles. Examples of metal oxides include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), and IGZO (registered trademark; an oxide semiconductor comprising indium (In), gallium (Ga), zinc (Zn), and oxygen (O)). Examples of metal nanoparticles include silver nanoparticles, copper nanoparticles, gold nanoparticles, and platinum nanoparticles. Examples of metal nanowires include silver nanowires, copper nanowires, gold nanowires, and platinum nanowires. From the viewpoint of transparency, at least one component of the conductive layer is preferably ITO, silver nanoparticles, or silver nanowires.

[0159] There is no limitation on the thickness of the conductive layer. From the viewpoint of conductivity and film-forming properties, the average thickness of the conductive layer is preferably 0.001 μm to 1,000 μm, more preferably 0.005 μm to 15 μm, and particularly preferably 0.01 μm to 10 μm. The average thickness of the conductive layer is measured by the method described above for measuring the average thickness of the substrate.

[0160] There are no limitations on the method for forming the conductive layer, and known methods can be used. Examples of methods for forming the conductive layer include coating, vacuum evaporation, sputtering, and electroplating.

[0161] Furthermore, after forming the conductive layer, another layer can be formed on a localized or entire area of ​​the conductive layer. For example, another layer can be formed on the conductive layer for purposes such as stacking another conductive layer, protecting the conductive layer, controlling the adhesion to the photosensitive layer, or controlling electrical properties. This other layer can be a layer composed of organic matter, a layer composed of inorganic matter, a layer in which inorganic matter is dispersed in a matrix of organic matter, or a layer in which organic matter is dispersed in a matrix of inorganic matter. For example, forming an organic-based protective film after forming a conductive layer containing silver nanowires, or forming an adhesive layer after forming a conductive layer containing gold nanowires, are examples, but the method is not limited to these.

[0162] Furthermore, when another conductive layer is stacked, a layer with the composition described above can be stacked. For example, examples include forming a layer containing silver nanoparticles on a portion or all of the conductive layer containing silver nanowires after forming the conductive layer containing silver nanowires, or forming a layer containing copper on a portion or all of the conductive layer containing ITO after forming the conductive layer containing ITO, but these are not limited to these.

[0163] As another method for forming the aforementioned layer, known methods such as coating, vacuum evaporation, sputtering, and lamination can be used.

[0164] Furthermore, the conductive layer can contain regions with different compositions mixed within the same plane. Examples include regions containing silver nanowires and regions containing ITO, or regions containing silver nanowires and regions containing silver nanoparticles, but these are not limited to these examples. By dividing the conductive layer into regions in this way, for instance, the characteristics of the circuit formed by the conductive layer can be improved.

[0165] [First photosensitive layer]

[0166] The laminate has a first photosensitive layer. There are no limitations on the first photosensitive layer, as long as it has the property of altering its solubility in the developer upon exposure. Examples of first photosensitive layers include, for instance, a positive photosensitive layer (hereinafter sometimes simply referred to as "positive photosensitive layer") whose solubility in the developer increases upon exposure, and a negative photosensitive layer (hereinafter sometimes simply referred to as "negative photosensitive layer") whose solubility in the developer decreases upon exposure.

[0167] In this invention, "increased solubility of the developer due to exposure" means that the solubility of the developer in the exposed part is relatively greater than that in the non-exposed part.

[0168] In this invention, "the solubility of the developer decreases due to exposure" means that the solubility of the developer in the exposed part is relatively smaller compared to the solubility of the non-exposed part.

[0169] From the viewpoint of resolution, the first photosensitive layer is preferably a positive photosensitive layer whose solubility in the developer increases upon exposure. From the viewpoint of the strength, heat resistance, and chemical resistance of the obtained resin pattern, the first photosensitive layer is preferably a negative photosensitive layer whose solubility in the developer decreases upon exposure. The positive and negative photosensitive layers will be described in detail below.

[0170] [Positive photosensitive layer]

[0171] There are no limitations on the type of positive photosensitive layer; any known type of positive photosensitive layer can be used. The preferred positive photosensitive layer includes an acid-degradable resin, i.e., a polymer having structural units with acid groups protected by acid-degradable groups, and a photoacid generator. Furthermore, the positive photosensitive layer can be a positive photosensitive layer containing naphthoquinone diazide compounds and phenolic varnish resin as photoreaction initiators.

[0172] The positive photosensitive layer is more preferably a chemically amplified positive photosensitive layer comprising a polymer having structural units with acid groups protected by acid-degradable groups and a photoacid-generating agent.

[0173] (Polymers possessing structural units with acid groups protected by acid-degrading groups)

[0174] The positive photosensitive layer is preferably a polymer (hereinafter, sometimes referred to as "polymer X") containing structural units (hereinafter, sometimes referred to as "structural unit A") having acid groups protected by acid-degradable groups. The positive photosensitive layer may contain a single polymer X or two or more polymer Xs.

[0175] In polymer X, acid groups protected by acid-degrading groups are converted into acid groups via a deprotection reaction under the action of an acidic substance (e.g., acid) generated through exposure in a catalytic amount. By generating acid groups in polymer X, the solubility of the positive photosensitive layer in the developer is increased.

[0176] Polymer X is preferably an addition polymer, and more preferably a polymer having structural units derived from (meth)acrylic acid or its esters.

[0177] -Structural units with acid groups protected by acid-decomposing groups-

[0178] Polymer X is preferably a structural unit (structural unit A) having an acid group protected by an acid-degradable group. By having structural unit A, the sensitivity of the positive photosensitive layer can be improved.

[0179] There are no restrictions on the type of acid group; any known acid group can be used. The preferred acid group is a carboxyl group or a phenolic hydroxyl group.

[0180] Examples of acid-degradable groups include those that are relatively easily degraded by acids and those that are relatively difficult to degrade by acids. Examples of groups that are relatively easily degraded by acids include acetal-type protecting groups (e.g., 1-alkoxyalkyl, tetrahydropyranyl, and tetrahydrofuranyl). Examples of groups that are relatively difficult to degrade by acids include tertiary alkyl groups (e.g., tert-butyl) and tertiary alkoxycarbonyl groups (e.g., tert-butoxycarbonyl). Among the above, acetal-type protecting groups are preferred.

[0181] From the viewpoint of suppressing deviations in the linewidth of the resin pattern, the molecular weight of the acid-degradable group is preferably 300 or less.

[0182] From the viewpoint of sensitivity and resolution, structural unit A is preferably a structural unit represented by formula A1, formula A2, or formula A3, and more preferably a structural unit represented by formula A3. The structural unit represented by formula A3 is a structural unit having a carboxyl group protected by an acetal-type acid decomposition group.

[0183] [Chemical Formula 1]

[0184]

[0185] In equation A1, R 11 and R 12 Each of the following can be independently represented by a hydrogen atom, alkyl group, or aryl group; R 11 and R 12 At least one of them is alkyl or aryl, R 13 R indicates alkyl or aryl. 11 Or R 12 With R 13 They can link together to form cyclic ethers, R 14 X represents a hydrogen atom or a methyl group. 1 R represents a linker base that is either a single bond or a divalent bond. 15 represents a substituent, and n represents an integer from 0 to 4.

[0186] In formula A2, R 21 and R 22 Each of the following can be independently represented by a hydrogen atom, alkyl group, or aryl group; R 21 and R 22 At least one of them is alkyl or aryl, R 23 R indicates alkyl or aryl. 21 Or R 22 With R 23 They can link together to form cyclic ethers, R 24 Each of these can be independently represented as a hydroxyl group, halogen atom, alkyl group, alkoxy group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, hydroxyalkyl group, arylcarbonyl group, aryloxycarbonyl group, or cycloalkyl group, where m represents an integer from 0 to 3.

[0187] In equation A3, R 31 and R 32 Each of the following can be independently represented by a hydrogen atom, alkyl group, or aryl group; R 31 and R 32 At least one of them is alkyl or aryl, R 33 R indicates alkyl or aryl. 31 Or R 32 With R 33 They can link together to form cyclic ethers, R 34 X represents a hydrogen atom or a methyl group. 0 It indicates a single bond or an aryl group.

[0188] In equation A3, in R 31 Or R 32 When the alkyl group is alkyl, the alkyl group with 1 to 10 carbon atoms is preferred.

[0189] In equation A3, in R 31 Or R 32 If the methyl group is aryl, phenyl is preferred.

[0190] In equation A3, R31 and R 32 Each is preferably an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0191] In equation A3, R 33 Preferably, it is an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

[0192] In equation A3, R 31 ~R 33 The alkyl and aryl groups indicated may have substituents.

[0193] In formula A3, R is preferred. 31 Or R 32 With R 33 They are linked together to form a cyclic ether. The number of rings in the above-mentioned cyclic ether is preferably 5 or 6, more preferably 5.

[0194] In equation A3, X 0 Preferably, it is a single bond. The aryl group may have substituents.

[0195] In Equation A3, from the viewpoint that the glass transition temperature (Tg) of polymer X can be further reduced, R 34 Hydrogen atoms are preferred.

[0196] Relative to the total mass of structural unit A contained in polymer X, R in equation A3 34 The content of structural units consisting of hydrogen atoms is preferably 20% by mass or more. Regarding R in structural unit A and formula A3... 34 The content of structural units for hydrogen atoms can be determined by... 13 C-NMR measurements are confirmed by the intensity ratio of peak intensities calculated using conventional methods.

[0197] As a preferred embodiment of formulas A1 to A3, reference can be made to paragraphs 0044 to 0058 of International Publication No. 2018 / 179640.

[0198] In formulas A1 to A3, from the viewpoint of sensitivity, the acid-degrading group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, even more preferably a group having a tetrahydrofuran ring structure, and especially preferably a tetrahydrofuran group.

[0199] Polymer X can have a single structural unit A, or it can have two or more structural units A.

[0200] Relative to the total mass of polymer X, the content of structural unit A is preferably 10% to 70% by mass, more preferably 15% to 50% by mass, and particularly preferably 20% to 40% by mass. By ensuring the content of structural unit A is within the above range, the resolution is further improved. When polymer X contains two or more structural units A, the above-mentioned content of structural unit A represents the total content of the two or more structural units A. The content of structural unit A can be determined by... 13 C-NMR measurements are confirmed using the intensity ratio of peak intensity calculated using conventional methods.

[0201] -Structural units with acid groups-

[0202] Polymer X may possess structural units with acid groups (hereinafter sometimes referred to as "structural unit B").

[0203] Structural unit B is a structural unit with an acid group that is not protected by an acid-degrading group, i.e., a structural unit with an acid group that does not have a protecting group. Because polymer X has structural unit B, the sensitivity during pattern formation becomes better. Furthermore, it is easily soluble in alkaline developer during the post-exposure development process, thus shortening the development time.

[0204] The acid group in structural unit B refers to a proton-dissociable group with a pKa of 12 or less. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Furthermore, the pKa of the acid group is preferably -5 or more.

[0205] Examples of acid groups include carboxyl, sulfonamide, phosphonic acid, sulfonyl, phenolic hydroxyl, and sulfonyl imide. The acid group is preferably a carboxyl or phenolic hydroxyl group, and more preferably a carboxyl group.

[0206] Polymer X can have a single structural unit B or two or more structural units B.

[0207] Relative to the total mass of polymer X, the content of structural unit B is preferably 0.01% to 20% by mass, more preferably 0.01% to 10% by mass, and particularly preferably 0.1% to 5% by mass. With the content of structural unit B within the above range, the resolution becomes better. When polymer X has two or more structural units B, the above-mentioned content of structural unit B represents the total content of the two or more structural units B. The content of structural unit B can be determined by... 13 C-NMR measurements are confirmed using the intensity ratio of peak intensity calculated using conventional methods.

[0208] -Other structural units-

[0209] Polymer X preferably has structural units other than the structural units A and B already described (hereinafter sometimes referred to as "structural unit C"). By adjusting at least one of the types and contents of structural unit C, various properties of polymer X can be adjusted. By having structural unit C, the glass transition temperature, acid value, and hydrophilicity / hydrophobicity of polymer X can be easily adjusted.

[0210] Examples of monomers that form structural unit C include styrene, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, aryl (meth)acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic anhydrides.

[0211] From the viewpoint of adhesion to the substrate, the monomer forming structural unit C is preferably an alkyl (meth)acrylate, more preferably an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms. Examples of alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0212] Structural unit C can be derived from styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, or polyethylene glycol monoacetoacetate mono(meth)acrylate. Structural unit C can also be derived from the structural units described in paragraphs 0021 to 0024 of Japanese Patent Application Publication No. 2004-264623.

[0213] From a distinguishing point of view, structural unit C is preferably a structural unit containing a base. Examples of bases include, for example, groups having a nitrogen atom. Examples of groups having a nitrogen atom include, for example, aliphatic amino groups, aromatic amino groups, and nitrogen-containing heteroaromatic ring groups. The base is preferably an aliphatic amino group.

[0214] As an aliphatic amino group, it can be any one of primary, secondary, and tertiary amino groups, but from the point of view of differentiation, secondary or tertiary amino groups are preferred.

[0215] Examples of monomers that form structural units with base groups include, for instance, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidinyl acrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 2-(diethylamino)ethyl methacrylate, 2-(diethylamino)ethyl methacrylate, N-(3-dimethylamino)propyl methacrylate, and N-(3-dimethylamino)propyl methacrylate. N-[3-(dimethylamino)propyl methacrylate, N-(3-diethylamino)propyl methacrylate, 2-(diisopropylamino)ethyl methacrylate, 2-morpholine ethyl methacrylate, 2-morpholine ethyl acrylate, N-[3-(dimethylamino)propyl]acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazolium, 2-methyl-1-vinylimidazolium, 1-allylimidazolium, and 1-vinyl-1,2,4-triazole. Preferably, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate is preferred.

[0216] Furthermore, from the viewpoint of improving electrical properties, structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton. Examples of monomers forming these structural units include styrene, α-methylstyrene, dicyclopentyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and benzyl methacrylate. Of these, cyclohexyl methacrylate is preferred.

[0217] Polymer X can have a single structural unit C or more than two structural units C.

[0218] Relative to the total mass of polymer X, the content of structural unit C is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less. Relative to the total mass of polymer X, the content of structural unit C is preferably 10% by mass or more, more preferably 20% by mass or more. With the content of structural unit C within the above range, the resolution and adhesion to the substrate are further improved. When polymer X has two or more types of structural unit C, the above-mentioned content of structural unit C represents the total content of the two or more types of structural unit C. The content of structural unit C can be determined by... 13 C-NMR measurements are confirmed using the intensity ratio of peak intensity calculated using conventional methods.

[0219] Preferred examples of polymer X are shown below. However, polymer X is not limited to the examples shown below. Furthermore, the proportions and weight-average molecular weights of the structural units in polymer X shown below are appropriately selected to obtain preferred physical properties.

[0220] [Chemical Formula 2]

[0221]

[0222] -Glass transition temperature-

[0223] The glass transition temperature (Tg) of polymer X is preferably 90°C or lower, more preferably 20°C to 60°C, and particularly preferably 30°C to 50°C. When the positive photosensitive layer is formed using the transfer material described later, the glass transition temperature of polymer X is within the above range, thereby improving the transferability of the positive photosensitive layer.

[0224] As a method for adjusting the Tg of polymer X within the aforementioned range, for example, the method using the FOX formula can be cited. According to the FOX formula, for example, the Tg of the target polymer X can be adjusted based on the Tg of the homopolymer of each structural unit in the target polymer X and the mass fraction of each structural unit.

[0225] The following explanation of the FOX type will take a copolymer having a first structural unit and a second structural unit as an example.

[0226] With the glass transition temperature of the homopolymer of the first structural unit set as Tg1, the mass fraction of the first structural unit in the copolymer set as W1, the glass transition temperature of the homopolymer of the second structural unit set as Tg2, and the mass fraction of the second structural unit in the copolymer set as W2, the glass transition temperature TgO (unit: K) of the copolymer having the first structural unit and the second structural unit can be deduced according to the following formula.

[0227] FOX equation: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)

[0228] Furthermore, the Tg of the polymer can be adjusted by adjusting the weight-average molecular weight of the polymer.

[0229] -Acid Value-

[0230] From the point of view of distinguishability, the acid value of polymer X is preferably 0 mg KOH / g to 50 mg KOH / g, more preferably 0 mg KOH / g to 20 mg KOH / g, and especially preferably 0 mg KOH / g to 10 mg KOH / g.

[0231] The acid value of a polymer indicates the mass of potassium hydroxide required to neutralize 1 gram of the polymer's acidic component. The specific measurement method is described below. First, the sample is dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran / water = 9 / 1). Using a potentiometric titration apparatus (e.g., trade name: AT-510, manufactured by KYOTOELECTRONICS MANUFACTURING CO., LTD.), the resulting solution is titrated with a 0.1 mol / L sodium hydroxide aqueous solution at 25°C. The inflection point of the pH titration curve is taken as the titration endpoint, and the acid value is calculated using the following formula.

[0232] A = 56.11 × Vs × 0.1 × f / w

[0233] A: Acid value (mgKOH / g)

[0234] Vs: The volume (mL) of 0.1 mol / L sodium hydroxide aqueous solution required for titration.

[0235] f: Titration volume of 0.1 mol / L sodium hydroxide aqueous solution

[0236] w: Mass of the measured sample (g) (conversion based on solid composition)

[0237] -weight-average molecular weight-

[0238] The weight-average molecular weight (Mw) of polymer X, converted from polystyrene, is preferably 60,000 or less. When the positive photosensitive layer is formed using the transfer material described later, the weight-average molecular weight of polymer X is 60,000 or less, thereby enabling the transfer of the positive photosensitive layer at low temperatures (e.g., 130°C or less).

[0239] The weight-average molecular weight of polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

[0240] The ratio of number-average molecular weight to weight-average molecular weight (dispersion) of polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

[0241] The weight-average molecular weight of polymer X was measured by GPC (gel permeation chromatography). Various commercially available instruments can be used as the measuring device. The method for measuring the weight-average molecular weight of polymer X based on GPC is described in detail below.

[0242] As a measuring device, HLC (registered trademark)-8220GPC (manufactured by TOSOH CORPORATION) is used.

[0243] As the tubing, a series of TSKgel (registered trademark) Super HZM-M (4.6mm ID×15cm, manufactured by TOSOH CORPORATION), Super HZ4000 (4.6mm ID×15cm, manufactured by TOSOH CORPORATION), Super HZ3000 (4.6mm ID×15cm, manufactured by TOSOH CORPORATION), and Super HZ2000 (4.6mm ID×15cm, manufactured by TOSOH CORPORATION) tubing is used.

[0244] THF (tetrahydrofuran) is used as the eluent.

[0245] Regarding the measurement conditions, the sample concentration was set to 0.2% by mass, the flow rate to 0.35 mL / min, the sample injection volume to 10 μL, and the measurement temperature to 40℃.

[0246] As the detector, a differential refractive index (RI) detector is used.

[0247] The calibration curve was prepared using any one of the following seven samples manufactured by TOSOH CORPORATION: “TSK standard, polystyrene”: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-2500” and “A-1000”.

[0248] -content-

[0249] From the viewpoint of high resolution, the content of polymer X is preferably 50% to 99.9% by mass, more preferably 70% to 98% by mass, relative to the total mass of the positive photosensitive layer.

[0250] -Manufacturing Method-

[0251] There are no limitations on the method for manufacturing polymer X, and known methods can be used. For example, polymer X can be manufactured by polymerizing monomers for forming structural unit A, and subsequently, if necessary, monomers for forming structural unit B and monomers for forming structural unit C, using a polymerization initiator in an organic solvent. Furthermore, polymer X can also be manufactured through a so-called polymer reaction.

[0252] (Other polymers)

[0253] In addition to polymer X, the positive photosensitive layer may also contain polymers that do not have structural units with acid groups protected by acid-degradable groups (hereinafter, sometimes referred to as "other polymers").

[0254] Other polymers include, for example, polyhydroxystyrene. Commercially available polyhydroxystyrene products include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA17352P, SMA 2625P and SMA 3840F manufactured by Sartomer Company, Inc.; ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 manufactured by TOAGOSEI CO., LTD.; and Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 manufactured by BASF.

[0255] Positive photosensitive layers may contain a single other polymer or two or more other polymers.

[0256] When the positive photosensitive layer contains other polymers, the content of the other polymers is preferably 50% by mass or less, more preferably 30% by mass or less, and especially preferably 20% by mass or less, relative to the total mass of the polymer components.

[0257] In this invention, "polymer composition" refers to the collective term for all polymers contained in the positive photosensitive layer. For example, if the positive photosensitive layer contains polymer X and other polymers, polymer X and other polymers are collectively referred to as "polymer composition". Furthermore, crosslinking agents, dispersants, and compounds corresponding to surfactants, even if they are polymeric compounds, are not included in the polymer composition.

[0258] The content of the polymer component relative to the total mass of the positive photosensitive layer is preferably 50% to 99.9% by mass, more preferably 70% to 98% by mass.

[0259] (Photo-acid generator)

[0260] The positive photosensitive layer preferably contains a photoacid-generating agent as a photosensitizing compound. The photoacid-generating agent is a compound that can generate acid upon irradiation by active light (e.g., ultraviolet light, far ultraviolet light, X-rays, and electron beams).

[0261] As a photoacid generator, a compound that generates acid by sensing active light with a wavelength of 300 nm or higher, preferably 300 nm to 450 nm, is preferred. Furthermore, regarding photoacid generators that do not directly sense active light with a wavelength of 300 nm or higher, if they are compounds that generate acid by sensing active light with a wavelength of 300 nm or higher when used in conjunction with a sensitizer, they can also be used in combination with the sensitizer, which is also preferred.

[0262] The photoacid-generating agent is preferably a photoacid-generating agent that produces acids with a pKa of 4 or less, more preferably a photoacid-generating agent that produces acids with a pKa of 3 or less, and particularly preferably a photoacid-generating agent that produces acids with a pKa of 2 or less. There is no limitation on the lower limit of the pKa of the acid derived from the photoacid-generating agent. For example, the pKa of the acid derived from the photoacid-generating agent is preferably -10.0 or more.

[0263] Examples of photoacid generators include ionic and nonionic photoacid generators.

[0264] Examples of ionic photoacid generators include onium salt compounds. Examples of onium salt compounds include diaryliodophosphate compounds, triarylsulfonium salt compounds, and quaternary ammonium salt compounds. Onium salt compounds are preferred as ionic photoacid generators, and at least one of triarylsulfonium salt compounds and diaryliodophosphate compounds is particularly preferred.

[0265] As an ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643 is also preferred.

[0266] Examples of nonionic photoacid generators include trichloromethyl-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. From the viewpoints of sensitivity, resolution, and adhesion to the substrate, oxime sulfonate compounds are preferred nonionic photoacid generators.

[0267] Specific examples of trichloromethyl-triazine compounds, diazomethane compounds, and imide sulfonate compounds include the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494.

[0268] As an oxime sulfonate compound, the oxime sulfonate compound described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 is preferably used.

[0269] From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from onium salt compounds and oxime sulfonate compounds, more preferably an oxime sulfonate compound.

[0270] As a preferred example of a photoacid generator, a photoacid generator having the following structure can be cited.

[0271] [Chemical Formula 3]

[0272]

[0273] As a photoacid generator that has absorption at a wavelength of 405 nm, for example, ADEKA ARKLS (registered trademark) SP-601 (manufactured by ADEKA CORPORATION) can be cited.

[0274] Positive photosensitive layers may contain a single photoacid generator or two or more photoacid generators.

[0275] From the viewpoint of sensitivity and resolution, the content of photoacid generator is preferably 0.1% to 10% by mass, more preferably 0.5% to 5% by mass, relative to the total mass of the positive photosensitive layer.

[0276] (Other additives)

[0277] In addition to the components mentioned above, the positive photosensitive layer may also contain known additives. Examples of additives include sensitizers, basic compounds, heterocyclic compounds, alkoxysilane compounds, and surfactants.

[0278] -Plasticizer-

[0279] To improve plasticity, positive photosensitive layers may contain plasticizers.

[0280] From the viewpoint of imparting plasticity, plasticizers are preferably those having alkene groups in their molecules. The alkene groups contained in the plasticizer are preferably those having the following structure.

[0281] [Chemical Formula 4]

[0282]

[0283] In the above formula, R represents an alkylene group with 2 to 8 carbon atoms, n represents an integer from 1 to 50, and * represents the bonding position with other atoms.

[0284] Furthermore, since the plasticity of the positive photosensitive layer containing the compound having the above-described alkoxy group (hereinafter referred to as "Compound X"), polymer X, and photoacid-producing agent is not improved compared to the positive photosensitive layer without Compound X, Compound X does not meet the requirements of the plasticizer in this invention. Moreover, any surfactant used is generally not used in an amount sufficient to impart plasticity to the positive photosensitive layer, and therefore does not meet the requirements of the plasticizer in this invention.

[0285] Examples of plasticizers include compounds having the following structures. However, plasticizers are not limited to the compounds described below.

[0286] [Chemical Formula 5]

[0287]

[0288] The weight-average molecular weight of the plasticizer is preferably smaller than that of polymer X. From the viewpoint of imparting plasticity, the weight-average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and particularly preferably 800 or more and less than 4,000.

[0289] Positive photosensitive layers may contain a single plasticizer or two or more plasticizers.

[0290] From the viewpoint of adhesion to the substrate, the content of plasticizer is preferably 1% to 50% by mass, more preferably 2% to 20% by mass, relative to the total mass of the positive photosensitive layer.

[0291] -Sensitizer-

[0292] The positive photosensitive layer preferably contains a sensitizer.

[0293] Sensitizers become electronically excited by absorbing active light. Contact between the electronically excited sensitizer and a photoacid generator results in electron transfer, energy transfer, and heating. Through these processes, the photoacid generator produces acid. Therefore, including a sensitizer in a positive photosensitive layer can improve exposure sensitivity.

[0294] As a sensitizer, it is preferably at least one compound selected from anthracene derivatives, acridinone derivatives, thioxanthone derivatives, coumarin derivatives, basic styrene derivatives and stilbene derivatives, more preferably anthracene derivatives.

[0295] The anthracene derivative is preferably anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene.

[0296] As sensitizers, compounds described in paragraphs 0139 to 0141 of International Publication No. 2015 / 093271 can be cited.

[0297] Positive photosensitive layers can contain a single sensitizer or two or more sensitizers.

[0298] The content of the sensitizer is preferably 0% to 10% by mass relative to the total mass of the positive photosensitive layer, more preferably 0.1% to 10% by mass.

[0299] -Alkaline compounds-

[0300] The positive photosensitive layer is preferably composed of an alkaline compound.

[0301] Examples of basic compounds include, for example, aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of basic compounds include those described in paragraphs 0204 to 0207 of Japanese Patent Application Publication No. 2011-221494, the contents of which are incorporated herein by reference.

[0302] Examples of aliphatic amines include, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.

[0303] Examples of aromatic amines include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine.

[0304] Examples of heterocyclic amines include, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazolium, 2-phenylbenzimidazole, 2,4,5-triphenylimidazolium, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-dihexabicyclo[4.3.0]-5-nonene, and 1,8-dihexabicyclo[5.3.0]-7-undecene.

[0305] Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

[0306] Examples of quaternary ammonium salts of carboxylic acids include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

[0307] From the viewpoint of the rust prevention of the conductive layer and the linearity of the conductive pattern, the alkaline compound is preferably a benzotriazole compound.

[0308] There are no restrictions on the benzotriazole compounds that have a benzotriazole skeleton, and known benzotriazole compounds can be used. Examples of benzotriazole compounds include, for instance, 1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 5-carboxybenzotriazole, 1-(hydroxymethyl)-1H-benzotriazole, 1-acetyl-1H-benzotriazole, 1-aminobenzotriazole, 9-(1H-benzotriazole-1-ylmethyl)-9H-carbazole, 1-chloro-1H-benzotriazole, 1-(2-pyridyl)benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1-(1'-hydroxyethyl)benzotriazole, 1-(2'- Hydroxyethyl benzotriazole, 1-propylbenzotriazole, 1-(1'-hydroxypropyl)benzotriazole, 1-(2'-hydroxypropyl)benzotriazole, 1-(3'-hydroxypropyl)benzotriazole, 4-hydroxy-1H-benzotriazole, 5-methyl-1H-benzotriazole, methylbenzotriazole-5-carboxylic acid ester, ethylbenzotriazole-5-carboxylic acid ester, tert-butyl-benzotriazole-5-carboxylic acid ester, cyclopentylethyl-benzotriazole-5-carboxylic acid ester, 1H-benzotriazole-1-acetonitrile, 1H-benzotriazole-1-carboxaldehyde, 2-methyl-2H-benzotriazole and 2-ethyl-2H-benzotriazole.

[0309] Positive photosensitive layers can contain a single basic compound or two or more basic compounds.

[0310] The content of alkaline compound relative to the total mass of the positive photosensitive layer is preferably 0.001% to 5% by mass, more preferably 0.005% to 3% by mass.

[0311] -Heterocyclic compounds-

[0312] Positive photosensitive layers can contain heterocyclic compounds.

[0313] Examples of heterocyclic compounds include, for instance, compounds having an epoxy or oxocyclic butyl group within the molecule, heterocyclic compounds having an alkoxymethyl group, oxygen-containing heterocyclic compounds (e.g., cyclic ethers and cyclic esters (e.g., lactones)), and nitrogen-containing heterocyclic compounds (e.g., cyclic amines and oxazolines). Heterocyclic compounds can also be heterocyclic compounds containing elements with electrons in the d orbitals (e.g., silicon, sulfur, and phosphorus).

[0314] Examples of compounds having epoxy groups within the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, cresol varnish type epoxy resin, and aliphatic epoxy resin.

[0315] Compounds containing intramolecular epoxy groups are preferably bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenolic varnish type epoxy resins, or aliphatic epoxy resins, more preferably aliphatic epoxy resins.

[0316] Compounds containing an intramolecular epoxy group can be obtained as commercially available products. Examples of commercially available products containing an intramolecular epoxy group include JER828, JER1007, JER157S70 and JER157S65 manufactured by Mitsubishi Chemical Corporation, and the commercially available products described in paragraph 0189 of Japanese Patent Application Publication No. 2011-221494.

[0317] Other commercially available products besides those mentioned above include, for example, ADEKARESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S manufactured by ADEKA CORPORATION; NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 manufactured by Nippon Kayaku Co., Ltd.; and DENACOL manufactured by Nagase ChemteX Corporation. EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, E X-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171 and EX-192, NIPPON STEEL Chemical & Material Co., Ltd. manufactures YH-300, YH-301, YH-302, YH-315, YH-324 and YH-325, and Daicel Corporation manufactures CELLOXIDE2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, SERUBINASU B0134 and B0177.

[0318] Examples of compounds having an intramolecular oxocyclic butyl group include ARON OXETANE OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ and PNOX manufactured by TOAGOSEI CO., LTD.

[0319] Furthermore, compounds having an oxetine group are preferably used alone or in combination with compounds having an epoxy group.

[0320] From the perspective of etch resistance and linewidth stability, heterocyclic compounds are preferably compounds with epoxy groups.

[0321] Positive photosensitive layers can contain a single cyclic compound or two or more cyclic compounds.

[0322] From the viewpoint of adhesion to the substrate and etch resistance, the content of heterocyclic compound is preferably 0.01% to 50% by mass, more preferably 0.1% to 10% by mass, and particularly preferably 1% to 5% by mass, relative to the total mass of the positive photosensitive layer.

[0323] -Alkoxysilane compounds-

[0324] Positive photosensitive layers may contain alkoxysilane compounds.

[0325] Examples of alkoxysilane compounds include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-methacryloyloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, and vinyltrialkoxysilane.

[0326] In the above, the alkoxysilane compound is preferably a trialkoxysilane compound, more preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloyloxypropyltrialkoxysilane, even more preferably γ-glycidoxypropyltrialkoxysilane, and especially preferably 3-glycidoxypropyltrimethoxysilane.

[0327] Positive photosensitive layers may contain a single alkoxysilane compound or two or more alkoxysilane compounds.

[0328] From the viewpoint of adhesion to the substrate and etch resistance, the content of alkoxysilane compound is preferably 0.1% to 50% by mass, more preferably 0.5% to 40% by mass, and particularly preferably 1.0% to 30% by mass, relative to the total mass of the positive photosensitive layer.

[0329] -surfactant-

[0330] From the viewpoint of uniformity of film thickness, the positive photosensitive layer preferably contains a surfactant.

[0331] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Nonionic surfactants are preferred.

[0332] Examples of nonionic surfactants include, for example, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, polysiloxane surfactants, and fluorinated surfactants.

[0333] Commercially available nonionic surfactants include, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by KYOEISHA CHEMICAL Co., Ltd.), Eftop (manufactured by JEMCO), Megaface (registered trademark) (manufactured by DIC CORPORATION), Fluorad (manufactured by Sumitomo 3M Limited), AsahiGuard (registered trademark) (manufactured by AGC Inc.), Surflon (registered trademark) (manufactured by AGC SEIMI CHEMICAL CO., Ltd.), PolyFox (manufactured by OMNOVA Solutions Inc.), and SH-8400 (manufactured by Dow Corning Toray Co., Ltd.).

[0334] Furthermore, examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solsperse 20000 (all manufactured by Japan). Lubrizol Corporation manufactures NCW-101, NCW-1001, and NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, and D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, and 440 (all manufactured by Nissin Chemical Co., Ltd.), etc.

[0335] The surfactant is preferably a copolymer containing structural units SA and SB represented by the following formula I-1, and whose weight-average molecular weight (Mw) converted from polystyrene by gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent is 1,000 or more and 10,000 or less.

[0336] [Chemical Formula 6]

[0337]

[0338] In Equation I-1, R 401 and R 403 Each can be used independently to represent a hydrogen atom or a methyl group, R 402 R represents a straight-chain alkylene group with 1 or more but less than 4 carbon atoms. 404 The symbol indicates an alkyl group with 1 or more hydrogen atoms and 4 or fewer carbon atoms; L indicates an alkylene group with 3 or more carbon atoms and 6 or fewer carbon atoms; p and q are mass percentages representing the polymerization ratio, where p represents a value of 10% or more by mass and 80% or less by mass; q represents a value of 20% or more by mass and 90% or less by mass; r represents an integer of 1 or more by mass and 18 or less; s represents an integer of 1 or more by mass and 10 or less; and * indicates a bonding position with other structures.

[0339] L is preferably a branched alkylene group represented by the following formula I-2. R in formula I-2 405 The alkyl group refers to an alkyl group with 1 or more but less than 4 carbon atoms. From the viewpoint of compatibility, an alkyl group with 1 or more but less than 3 carbon atoms is preferred, and an alkyl group with 2 or 3 carbon atoms is more preferred. The sum of p and q (p+q) is preferably p+q = 100, that is, 100% by mass.

[0340] [Chemical Formula 7]

[0341]

[0342] The weight-average molecular weight (Mw) of the copolymer comprising the structural unit SA and the structural unit SB represented by Formula I-1 above is preferably 1,500 or more and 5,000 or less.

[0343] Commercially available fluorinated surfactants include, for example, Megaface F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, and F... -565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above are from DIC) (manufactured by CORPORATION), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by Neos Corporation), etc.

[0344] Furthermore, acrylic compounds are preferably used as fluorinated surfactants. These compounds have a molecular structure containing functional groups with fluorine atoms, and when heated, the functional groups containing fluorine atoms are partially cleaved, causing the fluorine atoms to volatilize. Examples of such fluorinated surfactants include the MegafaceDS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016)), such as MegafaceDS-21.

[0345] As a fluorinated surfactant, polymers of vinyl ether compounds containing fluorinated atoms having fluorinated alkyl or fluorinated alkylene ether groups and hydrophilic vinyl ether compounds are preferred.

[0346] As a fluorinated surfactant, block polymers can also be used.

[0347] As a fluorinated surfactant, a fluorinated polymer compound can also be preferably used, which comprises: structural units derived from (meth)acrylate compounds having fluorine atoms; and structural units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxide or propoxide).

[0348] Furthermore, as a fluorinated surfactant, it can also be used on fluorinated polymers with side chains containing olefinically unsaturated bonds. Examples include Megaface RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC CORPORATION).

[0349] From the viewpoint of improving environmental adaptability, surfactants derived from alternative materials such as perfluorooctane acid (PFOA) and perfluorooctane sulfonic acid (PFOS), which have straight-chain perfluoroalkyl groups with 7 or more carbon atoms, are preferred as fluorinated surfactants.

[0350] Examples of polysiloxane surfactants include linear polymers containing siloxane bonds and modified siloxane polymers obtained by introducing organic groups into the side chains and ends.

[0351] Specific examples of polysiloxane surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all from Dow Corning Toray). (manufactured by Shin-Etsu Chemical Co., Ltd.), and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials). BYK307, BYK323, BYK330 (manufactured by BYK-Chemie Corporation), etc.

[0352] As a surfactant, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Application No. 2009-237362 can also be used.

[0353] Positive photosensitive layers can contain a single surfactant or two or more surfactants.

[0354] The surfactant content is preferably 10% by mass or less relative to the total mass of the positive photosensitive layer, more preferably 0.001% by mass to 10% by mass, and especially preferably 0.01% by mass to 3% by mass.

[0355] Plasticizers, sensitizers, basic compounds, heterocyclic compounds, alkoxysilane compounds, and surfactants are also described in paragraphs 0097 to 0127 of International Publication No. 2018 / 179640. These contents are incorporated herein by reference.

[0356] -Other ingredients-

[0357] The positive photosensitive layer may also contain components other than the additives mentioned above (hereinafter, sometimes referred to as "other components"). Examples of other components include, for instance, metal oxide particles, antioxidants, dispersants, acid proliferators, development promoters, conductive fibers, colorants, thermal free radical polymerization initiators, thermal acid-producing agents, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents. Preferred methods for using other components are described in paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-85643, the contents of which are incorporated herein by reference.

[0358] Positive photosensitive layers may contain solvents. For example, in cases where a positive photosensitive layer is formed from a composition containing a solvent, the solvent may sometimes remain in the positive photosensitive layer.

[0359] As solvents, examples include those described in paragraphs 0174 to 0178 of Japanese Patent Application Publication No. 2011-221494 and those described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640. Cyclic ether solvents such as tetrahydrofuran can also be used as solvents.

[0360] Positive photosensitive layers can contain a single solvent or two or more solvents.

[0361] The solvent content is preferably 2% by mass or less relative to the total mass of the positive photosensitive layer, more preferably 1% by mass or less, and especially preferably 0.5% by mass or less.

[0362] [Negative photosensitive layer]

[0363] There are no limitations on the type of negative photosensitive layer used; known negative photosensitive layers can be employed. From the viewpoint of pattern formation, the negative photosensitive layer is preferably composed of a polymer having acid groups, a polymerizable compound, and a photopolymerization initiator. For example, the photosensitive resin layer described in Japanese Patent Application Publication No. 2016-224162 can be used as the negative photosensitive layer.

[0364] [Polymers with acid groups]

[0365] The negative photosensitive layer is preferably a polymer containing acid groups (hereinafter, sometimes referred to as "polymer Y").

[0366] Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups. The preferred acid group is a carboxyl group.

[0367] From the viewpoint of alkali-developable properties, polymer Y is preferably an alkali-soluble resin with an acid value of 60 mg KOH / g or higher, and more preferably an acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher.

[0368] Examples of carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher include the acrylic resin containing carboxyl groups in the polymer described in paragraph 0025 of Japanese Patent Application Publication No. 2011-95716, the acrylic resin containing carboxyl groups in the polymer described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and the acrylic resin containing carboxyl groups in the adhesive polymer described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162. Here, "acrylic resin" refers to a resin containing at least one structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylate. The content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate in the acrylic resin is preferably 30% to 100% by mass, more preferably 50% to 100% by mass, relative to the total mass of the acrylic resin.

[0369] The content of acid-containing structural units in polymer Y is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and especially preferably 12% to 30% by mass, relative to the total mass of polymer Y.

[0370] Polymer Y may have reactive groups. Preferably, these reactive groups are polymerizable. Examples of polymerizable groups include olefinic unsaturated groups, condensation groups (e.g., hydroxyl and carboxyl groups), and addition-polymerizable reactive groups (e.g., epoxy and isocyanate groups).

[0371] From the viewpoint of alkaline developability, the acid value of polymer Y is preferably 60 mg KOH / g to 200 mg KOH / g, more preferably 100 mg KOH / g to 200 mg KOH / g, and especially preferably 150 mg KOH / g to 200 mg KOH / g.

[0372] The weight-average molecular weight of polymer Y is preferably 1,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 to 100,000.

[0373] Polymer Y can have structural units derived from non-acidic monomers. Examples of non-acidic monomers include (meth)acrylates, esters of vinyl alcohol, (meth)acrylonitrile, and aromatic vinyl compounds.

[0374] Examples of (meth)acrylates include, for example, 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, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate.

[0375] Examples of ester compounds of vinyl alcohol include, for instance, vinyl acetate.

[0376] Examples of aromatic vinyl compounds include, for example, styrene and styrene derivatives.

[0377] The non-acidic monomer is preferably methyl methacrylate, n-butyl methacrylate, styrene, styrene derivatives, or benzyl methacrylate. From the viewpoints of resolution, adhesion to the substrate, etch resistance, and reduction of aggregates during development, the non-acidic monomer is more preferably styrene, styrene derivatives, or benzyl methacrylate.

[0378] Polymer Y can have any of the following side chains: straight-chain, branched, or alicyclic. Branched or alicyclic structures can be introduced into the side chains of polymer A by using monomers containing groups with branched side chains or monomers containing groups with alicyclic side chains. The groups with alicyclic structures can be monocyclic or polycyclic.

[0379] Specific examples of monomers containing groups having a branched structure in their side chains include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate are preferred, and isopropyl (meth)acrylate or tert-butyl (meth)acrylate are more preferred.

[0380] Specific examples of monomers containing alicyclic groups in their side chains include monomers having monocyclic aliphatic hydrocarbon groups and monomers having polycyclic aliphatic hydrocarbon groups. Furthermore, (meth)acrylates having alicyclic hydrocarbon groups with 5 to 20 carbon atoms are also examples. More specific examples include (meth)acrylate (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate-2-methyl-2-adamantyl ester, (meth)acrylate-2-ethyl- 2-Adamantyl ester, 3-hydroxy-1-adamantyl ester of (meth)acrylate, octahydro-4,7-methyleneind-5-yl (meth)acrylate, octahydro-4,7-methyleneind-1-ylmethyl ester of (meth)acrylate, 1-menthyl ester of (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester of (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester of (meth)acrylate, (nor)bornyl ester of (meth)acrylate, isobornyl ester of (meth)acrylate, ferrous ester of (meth)acrylate, 2,2,5-trimethylcyclohexyl ester of (meth)acrylate, and cyclohexyl ester of (meth)acrylate, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, norborneol (meth)acrylate, isoborneol (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fumarate (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and more preferably cyclohexyl (meth)acrylate, norborneol (meth)acrylate, isoborneol (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.

[0381] The negative photosensitive layer can contain a single polymer Y or two or more polymer Ys.

[0382] From the viewpoint of photosensitivity, the content of polymer Y is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and especially preferably 30% to 70% by mass, relative to the total mass of the negative photosensitive layer.

[0383] [Polymerizing compounds]

[0384] The negative photosensitive layer is preferably composed of a polymeric compound.

[0385] There are no restrictions on the polymerizable compound; any known polymerizable compound can be used. The polymerizable compound is preferably an olefinically unsaturated compound. An olefinically unsaturated compound is a compound having one or more olefinically unsaturated groups. Olefinically unsaturated compounds contribute to the photosensitivity (i.e., photocurability) of the negative photosensitive layer and the strength of the cured film.

[0386] The preferred olefinic unsaturated group is (meth)acryloyl.

[0387] The olefinic unsaturated compound is preferably a (meth)acrylate compound.

[0388] Examples of olefinically unsaturated compounds include, for instance, 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.], epoxide-modified (meth)acrylate compounds [e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD.], ethoxylated glycerol triacrylate [e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.], and ARONIX (registered trademark) TO-2349 (TOAGOSEI). (manufactured by TAISEI Co., LTD.), ARONIX M-520 (manufactured by TOAGOSEI Co., LTD.), ARONIX M-510 (manufactured by TOAGOSEI Co., LTD.) and amine ester (meth) acrylate compounds [e.g., 8UX-015A (manufactured by TAISEI FINECHEMICAL Co., LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.)].

[0389] As an olefinic unsaturated compound, a polymeric compound having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 may be used.

[0390] The negative photosensitive layer is preferably a compound containing two or more olefin unsaturated groups as an olefin unsaturated compound. Hereinafter, an olefin unsaturated compound having X olefin unsaturated groups is sometimes referred to as an "X-functionalized olefin unsaturated compound".

[0391] Examples of difunctional olefinic unsaturated compounds include, for example, tricyclodecanediethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0392] As a difunctional alkene unsaturated compound, a difunctional alkene unsaturated compound having a bisphenol structure may also be preferred.

[0393] Examples of difunctional olefinic unsaturated compounds having a bisphenol structure include, for example, the compounds described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162. Furthermore, examples of difunctional olefinic unsaturated compounds having a bisphenol structure include epoxy-modified bisphenol A di(meth)acrylate.

[0394] Examples of ethylene glycol dimethacrylates modified with alkylene oxides include, for instance, ethylene glycol dimethacrylates obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A; ethylene glycol dimethacrylates obtained by adding an average of 2 moles of ethylene oxide to each end of bisphenol A; ethylene glycol dimethacrylates obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A; alkylene glycol dimethacrylates obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to each end of bisphenol A; and alkylene glycol dimethacrylates obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to each end of bisphenol A.

[0395] Specific examples of epoxy-modified bisphenol A di(meth)acrylates include 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane and 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane.

[0396] Commercially available products of epoxy-modified bisphenol A di(meth)acrylate include, for example, BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0397] Examples of olefinic unsaturated compounds with three or more functions include, for example, dipentaerythritol (tris / tetras / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and glycerol tri(meth)acrylate.

[0398] "(Tri / Tetra / Penta / Hexa)meth)acrylates" refers to the concept of including tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates, and hexa(meth)acrylates. "(Tri / Tetra)meth)acrylates" refers to the concept of including tri(meth)acrylates and tetra(meth)acrylates.

[0399] The olefinic unsaturated compound with three or more functions is preferably a tetramethacrylate obtained by adding an average of 9 moles of ethylene oxide to the hydroxyl end of pentaerythritol, a tetramethacrylate obtained by adding an average of 12 moles of ethylene oxide to the hydroxyl end of pentaerythritol, a tetramethacrylate obtained by adding an average of 15 moles of ethylene oxide to the hydroxyl end of pentaerythritol, a tetramethacrylate obtained by adding an average of 20 moles of ethylene oxide to the hydroxyl end of pentaerythritol, a tetramethacrylate obtained by adding an average of 28 moles of ethylene oxide to the hydroxyl end of pentaerythritol, or a tetramethacrylate obtained by adding an average of 35 moles of ethylene oxide to the hydroxyl end of pentaerythritol.

[0400] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200. When the polymerizable compound is a compound with a molecular weight distribution (e.g., a polymer), the weight-average molecular weight (Mw) of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0401] The negative photosensitive layer can contain a single polymeric compound or two or more polymeric compounds.

[0402] The content of the polymeric compound relative to the total mass of the negative photosensitive layer is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and especially preferably 20% to 50% by mass.

[0403] (Photopolymerization initiator)

[0404] The negative photosensitive layer preferably contains a photopolymerization initiator. The photopolymerization initiator initiates the polymerization of polymerizable compounds by receiving active light (e.g., ultraviolet and visible light). The photopolymerization initiator is a type of photoreaction initiator.

[0405] Examples of photopolymerization initiators include, for instance, photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure. Preferably, the photopolymerization initiator is selected from at least one of the following: photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, and photopolymerization initiators having an N-phenylglycine structure.

[0406] The photopolymerization initiator is preferably selected from at least one of 2,4,5-triarylimidazolium dimers and their derivatives. Furthermore, in the 2,4,5-triarylimidazolium dimers and their derivatives, the two 2,4,5-triarylimidazolium structures may be identical or different.

[0407] Preferred examples of derivatives of 2,4,5-triarylimidazolium dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0408] As a photopolymerization initiator, for example, the photopolymerization initiators described in Japanese Patent Application Publication No. 2011-95716, paragraphs 0031 to 0042, and Japanese Patent Application Publication No. 2015-14783, paragraphs 0064 to 0081, can be used.

[0409] Commercially available photopolymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Japan Ltd.), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetophenone-1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF Japan Ltd.), IRGACURE OXE-03 (manufactured by BASF Japan Ltd.), IRGACURE OXE-04 (manufactured by BASF Japan Ltd.), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins). 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV). Omnirad 651 (manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethyl-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiators (trade name: Lunar 6, manufactured by DKSH Management Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (also known as: 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (trade name: B-CIM, Hampford Research Inc.).(Manufactured) and 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0410] Furthermore, commercially available photopolymerization initiators include, for example, ADEKA ARKLSNCI-930, ADEKA ARKLSNCI-730, and ADEKA ARKLSN-1919T manufactured by ADEKA CORPORATION.

[0411] The negative photosensitive layer may contain a single photopolymerization initiator or two or more photopolymerization initiators.

[0412] The content of the photopolymerization initiator relative to the total mass of the negative photosensitive layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more. The content of the photopolymerization initiator relative to the total mass of the negative photosensitive layer is preferably 10% by mass or less, more preferably 5% by mass or less.

[0413] [Other Additives]

[0414] In addition to the components mentioned above, the negative photosensitive layer may also contain known additives. Examples of additives include polymerization inhibitors, plasticizers, sensitizers, hydrogen donors, heterocyclic compounds, and ultraviolet (UV) absorbers.

[0415] (polymerization inhibitor)

[0416] Negative photosensitive layers may contain polymerization inhibitors.

[0417] As a polymerization inhibitor, examples include the heat-inhibiting agent described in paragraph 0018 of Japanese Patent No. 4502784. Preferred inhibitors include phenothiazine, phenoxazine, hydroquinone, tetrachlorobenzoquinone, sodium indophenolate, m-aminophenol, or 4-methoxyphenol.

[0418] Negative photosensitive layers can contain a single type of polymerization inhibitor or two or more types of polymerization inhibitors.

[0419] The content of the polymerization inhibitor relative to the total mass of the negative photosensitive layer is preferably 0.01% to 3% by mass, more preferably 0.01% to 1% by mass, and particularly preferably 0.01% to 0.8% by mass.

[0420] (Plasticizer)

[0421] As a plasticizer, examples include the plasticizer described in the above-mentioned positive photosensitive layer, and the preferred plasticizer is also the same.

[0422] Negative photosensitive layers can contain a single plasticizer or two or more plasticizers.

[0423] From the viewpoint of adhesion to the substrate, the content of plasticizer is preferably 1% to 50% by mass, more preferably 2% to 20% by mass, relative to the total mass of the negative photosensitive layer.

[0424] (Sensitizer)

[0425] Negative photosensitive layers can contain sensitizers.

[0426] Examples of sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, anthocyanin compounds, xanthonesone compounds, thioxanthonesone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds, pyrazoline compounds, and aminoacridine compounds.

[0427] As sensitizers, dyes or pigments can be used. Examples of dyes or pigments include magenta, phthalocyanine green, coumarin 6, coumarin 7, coumarin 102, DOC iodide, sodium indole monocarbocyanine, auramine base, alkoxide green S, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE GREEN), basic blue 20, and diamond green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) D [AMOND GREEN GH]).

[0428] As dyes, chromogenic dyes can be used. Chromogenic dyes are compounds that exhibit color development upon light exposure. Examples of chromogenic dyes include colorless dyes and fluorescein dyes. Colorless dyes are preferred among chromogenic dyes.

[0429] The negative photosensitive layer can contain a single sensitizer or two or more sensitizers.

[0430] From the viewpoint of improving sensitivity to light sources and improving curing speed based on the balance between polymerization rate and chain transfer, the content of sensitizer is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass, relative to the total mass of the negative photosensitive layer.

[0431] (Hydrogen donor)

[0432] The negative photosensitive layer may contain a hydrogen donor. The hydrogen donor can provide hydrogen to the photopolymerization initiator.

[0433] Examples of hydrogen donors include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, thiols, and colorless crystal violet.

[0434] A negative photosensitive layer can contain a single hydrogen donor or two or more hydrogen donors.

[0435] The hydrogen donor content is preferably 0.01% to 10% by mass relative to the total mass of the negative photosensitive layer, more preferably 0.05% to 5% by mass, and especially preferably 0.1% to 2% by mass.

[0436] (Heterocyclic compounds)

[0437] Examples of heterocyclic compounds include those described in the above-described positive photosensitive layer, and the preferred heterocyclic compounds are also the same.

[0438] The negative photosensitive layer can contain a single cyclic compound or two or more cyclic compounds.

[0439] From the viewpoint of adhesion to the substrate and etch resistance, the content of heterocyclic compound is preferably 0.01% to 50% by mass, more preferably 0.1% to 10% by mass, and particularly preferably 1% to 5% by mass, relative to the total mass of the negative photosensitive layer.

[0440] (Ultraviolet (UV) absorber)

[0441] Without departing from the spirit of the invention, the negative photosensitive layer may contain a UV absorber. The UV absorber can reduce the transmittance of the negative photosensitive layer relative to the exposure wavelength.

[0442] Examples of UV absorbers include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, benzoic acid ester-based UV absorbers, salicylic acid ester-based UV absorbers, triazine-based UV absorbers, and cyanoacrylate-based UV absorbers. Preferably, the UV absorber is selected from at least one of benzotriazole-based and triazine-based UV absorbers.

[0443] Examples of benzotriazole-based UV absorbers include, for instance, 2-(2H-benzotriazole-2-yl)-p-cresol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-[5-chloro(2H)-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol, 2-(2H-benzotriazole-yl)-4,6-di-tert-pentylphenol, and 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol. Benzotriazole-based UV absorbers can be mixtures, modified forms, polymers, or derivatives of the above compounds.

[0444] Examples of triazine-based UV absorbers include, for instance, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tetrazoloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-symmetric triazine. Triazine-based UV absorbers can be mixtures, modified forms, polymers, or derivatives of the above compounds.

[0445] A negative photosensitive layer can contain a single UV absorber or two or more UV absorbers.

[0446] From the viewpoint of suppressing exposure fog and improving resolution, the content of UV absorber is preferably 0.1% to 5% by mass, more preferably 0.1% to 3% by mass, and especially preferably 0.1% to 2% by mass, relative to the total mass of the negative photosensitive layer.

[0447] (Other ingredients)

[0448] The negative photosensitive layer may also contain components other than the additives mentioned above (hereinafter, sometimes referred to as "other components"). Examples of other components include metal oxide particles, antioxidants, dispersants, acid proliferation agents, development accelerators, conductive fibers, colorants, thermal free radical polymerization initiators, thermal acid-producing agents, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents. Preferred methods for these components are described in paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-85643, the contents of which are incorporated herein by reference.

[0449] The negative photosensitive layer may contain a solvent. For example, when a negative photosensitive layer is formed from a composition containing a solvent, the solvent may sometimes remain in the negative photosensitive layer. Examples of solvents include those described in the positive photosensitive layer above.

[0450] A negative photosensitive layer can contain a single solvent or two or more solvents.

[0451] The solvent content is preferably 2% by mass or less relative to the total mass of the negative photosensitive layer, more preferably 1% by mass or less, and especially preferably 0.5% by mass or less.

[0452] The negative photosensitive layer may contain a resin other than polymer Y. Preferred examples of the aforementioned resins include polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, and polysiloxane resin. The resin other than polymer Y contained in the negative photosensitive layer may be a single type or two or more types.

[0453] [Impurities]

[0454] The first photosensitive layer is preferably free of impurities such as metallic components and residual monomer components.

[0455] 〔thickness〕

[0456] There is no limitation on the thickness of the first photosensitive layer. From the viewpoint of film thickness uniformity, the average thickness of the first photosensitive layer is preferably 0.5 μm or more, more preferably 1 μm or more. From the viewpoint of resolution, the average thickness of the first photosensitive layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The average thickness of the first photosensitive layer is measured by the method described above for measuring the average thickness of the substrate.

[0457] [Second photosensitive layer]

[0458] The laminate has a second photosensitive layer. There are no limitations on the second photosensitive layer, as long as it has the property of altering its solubility in the developer upon exposure. Examples of second photosensitive layers include positive photosensitive layers whose solubility in the developer increases upon exposure and negative photosensitive layers whose solubility in the developer decreases upon exposure.

[0459] From the viewpoint of resolution, the second photosensitive layer is preferably a positive photosensitive layer whose solubility in the developer increases upon exposure. Examples of positive photosensitive layers include those described in the section on "first photosensitive layer" above, and the preferred positive photosensitive layer is also the same.

[0460] From the viewpoint of the strength, heat resistance, and chemical resistance of the obtained resin pattern, the second photosensitive layer is preferably a negative photosensitive layer whose solubility in the developer decreases upon exposure. Examples of negative photosensitive layers include those described in the section on "first photosensitive layer" above, and the preferred negative photosensitive layer is also the same.

[0461] [Impurities]

[0462] The second photosensitive layer is preferably free of impurities such as metallic components and residual monomer components.

[0463] 〔thickness〕

[0464] There is no limitation on the thickness of the second photosensitive layer. From the viewpoint of film thickness uniformity, the average thickness of the second photosensitive layer is preferably 0.5 μm or more, more preferably 1 μm or more. From the viewpoint of resolution, the average thickness of the second photosensitive layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The average thickness of the second photosensitive layer is measured by the method described above for measuring the average thickness of the substrate.

[0465] As a combination of the type of the first photosensitive layer and the type of the second photosensitive layer, the following combinations can be cited as examples.

[0466] (1) The first photosensitive layer is a negative photosensitive layer, and the second photosensitive layer is a negative photosensitive layer.

[0467] (2) The first photosensitive layer is a positive photosensitive layer, and the second photosensitive layer is a positive photosensitive layer.

[0468] (3) The first photosensitive layer is a negative photosensitive layer and the second photosensitive layer is a positive photosensitive layer.

[0469] (4) The first photosensitive layer is a positive photosensitive layer and the second photosensitive layer is a negative photosensitive layer.

[0470] [Sensitivity of the photosensitive layer and photosensitive compounds]

[0471] The first and second photosensitive layers preferably each have specific exposure sensitivities. This effectively suppresses the formation of exposure fog.

[0472] Specifically, when the sensitivities of the first and second photosensitive layers satisfy the following relationships 1 and 2, the generation of exposure fog can be effectively suppressed.

[0473] Relationship 1: 1.1 ≤ E 1r / E2

[0474] Relationship 2: 1.1≤E 2r / E1

[0475] Here, E 1rE1 represents the maximum exposure level at which the first photosensitive layer does not react when exposed to light having the dominant wavelength λ2 from the second photosensitive layer side of the laminate. E2 represents the exposure level at which the second photosensitive layer is exposed to light having the dominant wavelength λ2 during the exposure process. 2r E1 represents the maximum exposure level at which the second photosensitive layer does not react when exposed to light with a dominant wavelength λ1 from the first photosensitive layer side of the laminate. E1 represents the exposure level when the first photosensitive layer is exposed to light with a dominant wavelength λ1 during the exposure process. The units for all the above exposure levels are the same. For example, the unit for each of the above exposure levels is mJ / cm². 2 .

[0476] The above sensitivity conditions will be described in detail. In the process of exposing the first photosensitive layer and the second photosensitive layer face to face with the substrate apart (i.e., exposure step (1) and exposure step (2)), the first photosensitive layer is exposed using exposure light with a dominant wavelength λ1, and the second photosensitive layer is exposed using exposure light with a dominant wavelength λ2. Furthermore, in the above process, the first photosensitive layer is exposed from the substrate side using exposure light with a dominant wavelength λ2 that has transmitted through the second photosensitive layer and the substrate, and the second photosensitive layer is exposed from the substrate side using exposure light with a dominant wavelength λ1 that has transmitted through the first photosensitive layer and the substrate.

[0477] Therefore, the first and second photosensitive layers must not react to exposure light transmitted from the substrate side, i.e., exposure fog must not occur. If the photosensitive layers react due to exposure light transmitted from the substrate, unintended exposure patterns may form, adversely affecting the final wiring quality. To avoid exposure fog, in the case of the first photosensitive layer, the highest exposure amount E that prevents the first photosensitive layer from reacting when exposed from the second photosensitive layer side is used. 1r The exposure level should be higher than the E2 of the second photosensitive layer. The same applies to the second photosensitive layer.

[0478] As E 1r The value of / E2 and E 2r The value of / E1 is preferably 1.1 or higher, more preferably 1.15 or higher, and particularly preferably 1.2 or higher. By... 1r / E2、E 2r With / E1 set to this ratio, even slight variations in exposure can result in stable patterning without exposure haze. E 1r / E2 and E 2r There is no particular limit to the upper limit of / E1; as long as it has appropriate performance as a photosensitive layer, it can be set to any value.

[0479] In order to make E 1r / E2 and E2r The ratio / E1, as described above, can be achieved by adjusting the absorption coefficient of the photosensitive layer relative to each of the dominant wavelengths λ1 and λ2. More specifically, by appropriately selecting photoreaction-related compounds such as photoinitiators, sensitizers, and chain transfer agents for each photosensitive layer, a photosensitive layer with the properties described above can be obtained.

[0480] For example, when exposing a first photosensitive layer to light with a dominant wavelength of 405 nm and a second photosensitive layer to light with a dominant wavelength of 365 nm, reducing the absorption coefficient of the first photosensitive layer relative to a wavelength of 365 nm can prevent exposure haze caused by exposure light of 365 nm that has transmitted through the second photosensitive layer and the substrate from forming. Furthermore, for example, by introducing a compound that absorbs light of 365 nm into the second photosensitive layer, controlling the amount of light transmitted through the second photosensitive layer and the substrate can also be used as a technique to suppress the formation of exposure haze in the first photosensitive layer. On the other hand, for example, by reducing the absorption coefficient of the second photosensitive layer relative to a wavelength of 405 nm, similarly to the first photosensitive layer, the formation of exposure haze in the second photosensitive layer can be suppressed.

[0481] Regarding the sensitivity of the first and second photosensitive layers, it is also preferable to satisfy the following relationships 3 and 4.

[0482] Relationship 3: 3≤S 12 / S 11

[0483] Relation 4: 3≤S 21 / S 22

[0484] Here, S 12 S represents the spectral sensitivity of the first photosensitive layer relative to the dominant wavelength λ2. 11 S represents the spectral sensitivity of the first photosensitive layer relative to the dominant wavelength λ1. 21 S represents the spectral sensitivity of the second photosensitive layer relative to the dominant wavelength λ1. 22 This represents the spectral sensitivity of the second photosensitive layer relative to the dominant wavelength λ2. The units for all the spectral sensitivities mentioned above are the same. For example, the unit for each of the spectral sensitivities mentioned above is mJ / cm². 2 .

[0485] Spectral sensitivity refers to the minimum exposure required for a photosensitive layer to react when exposed to light of a specific wavelength. The smaller the value of the spectral sensitivity (i.e., the minimum exposure required for the photosensitive layer to react), the higher the sensitivity of the photosensitive layer. Typically, photosensitive layers have absorption coefficients that vary with each wavelength, and photoreaction initiators and sensitizers have quantum yields that vary with each wavelength; therefore, the sensitivity of the photosensitive layer typically also varies with each wavelength. After suppressing exposure haze, for example, it is desirable to achieve a certain spectral sensitivity (S) in the first photosensitive layer relative to the dominant wavelength λ2. 12 Large, meaning low sensitivity. (Through S) 12 / S 11 and S 21 / S 22 When the ratio is above a certain level, it is less likely to cause a reaction due to the exposure light transmitted from the substrate side, thus achieving good patterning performance.

[0486] As S 12 / S 11 The value of S 21 / S 22 The value of is preferably 3 or more, more preferably 4 or more, and especially preferably 5 or more. 12 / S 11 The value of S 21 / S 22 There is no particular upper limit to the value of λ; as long as the photosensitive layer has appropriate properties, it can be set to any value. A photosensitive layer with such properties can be obtained by adjusting the light absorption coefficient of the photosensitive layer relative to each of the dominant wavelengths λ1 and λ2.

[0487] In the measurement of spectral sensitivity, a specific wavelength of exposure light is applied to the photosensitive layer using a step-wedge table, followed by a development process. In a negative photosensitive layer, the lowest exposure level remaining in the exposed area can be used as the spectral sensitivity. Conversely, in a positive photosensitive layer, the lowest exposure level after removing the exposed area can be used as the spectral sensitivity.

[0488] The first and second photosensitive layers preferably contain different photosensitive compounds. By containing different photosensitive compounds in the first and second photosensitive layers, the formation of exposure fog can be further suppressed.

[0489] In this invention, "different photosensitive compounds" refers to photosensitive compounds whose molar absorptivity values ​​at different exposure wavelengths are different. In the first and second photosensitive layers, preferably, in one photosensitive layer, the molar absorptivity of the photosensitive compound at 365 nm is greater than that at 405 nm, and in the other photosensitive layer, the molar absorptivity of the photosensitive compound at 405 nm is greater than that at 365 nm.

[0490] Regarding the statement that "the molar absorptivity at wavelength 365 nm is greater than the molar absorptivity at wavelength 405 nm," the following preferred ranges are shown. When the molar absorptivity at wavelength 365 nm is set to 100%, the molar absorptivity at wavelength 405 nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. There is no lower limit to the molar absorptivity at wavelength 405 nm. When the molar absorptivity at wavelength 365 nm is set to 100%, the molar absorptivity at wavelength 405 nm can be determined, for example, as long as it is within the range of 0% or more.

[0491] Regarding the statement that "the molar absorptivity at wavelength 405 nm is greater than the molar absorptivity at wavelength 365 nm," the following preferred ranges are shown. When the molar absorptivity at wavelength 405 nm is set to 100%, the molar absorptivity at wavelength 365 nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. There is no lower limit to the molar absorptivity at wavelength 365 nm. When the molar absorptivity at wavelength 405 nm is set to 100%, the molar absorptivity at wavelength 365 nm can be determined, for example, as long as it is within the range of 0% or more.

[0492] For example, preferably, the first and second photosensitive layers, when exposed at an exposure wavelength where the intensity at 365 nm is greater than that at 405 nm, contain a photosensitive compound whose molar absorptivity at 365 nm is greater than that at 405 nm, and the photosensitive layers exposed at an exposure wavelength where the intensity at 405 nm is greater than that at 365 nm, contain a photosensitive compound whose molar absorptivity at 405 nm is greater than that at 365 nm. By including the photosensitive compound described above in the first and second photosensitive layers, the formation of exposure fog can be further suppressed.

[0493] There are no limitations on the photosensitive compound, as long as it has the property of reacting with light. Examples of photosensitive compounds include photoacid generators, photoreaction initiators, and sensitizers. The photosensitive compound is preferably a photoacid generator or a photopolymerization initiator. Examples of photoacid generators include those described in the "positive photosensitive layer" section above, and the same photoacid generator is preferred. Examples of photopolymerization initiators include those described in the "negative photosensitive layer" section above, and the same photopolymerization initiator is preferred.

[0494] [Light Absorption Properties]

[0495] The first photosensitive layer preferably has the property of absorbing light with a dominant wavelength λ2. In the process of exposing the second photosensitive layer (i.e., exposure process (2)), for example, exposure light that has sequentially transmitted through the second photosensitive layer, the substrate, and the first photosensitive layer may sometimes be reflected by components such as a wavelength-selective filter and re-reach the second photosensitive layer. If the second photosensitive layer is re-exposed by the reflected exposure light, the resolution may decrease. On the other hand, the first photosensitive layer, having the property of absorbing light with a dominant wavelength λ2, can absorb both the light with a dominant wavelength λ2 that has been transmitted through the second photosensitive layer and the substrate, and the light with a dominant wavelength λ2 that has been reflected by components such as a wavelength-selective filter. Therefore, the decrease in resolution caused by the re-exposure of the second photosensitive layer can be suppressed.

[0496] The second photosensitive layer preferably has the property of absorbing light with a dominant wavelength λ1. In the process of exposing the first photosensitive layer (i.e., the exposure process (1)), for example, the exposure light that has been transmitted sequentially through the first photosensitive layer, the substrate, and the second photosensitive layer is sometimes reflected by components such as a wavelength-selective filter and reaches the first photosensitive layer again. If the first photosensitive layer is re-exposed by the reflected exposure light, the resolution may decrease. On the other hand, the second photosensitive layer, which has the property of absorbing light with a dominant wavelength λ1, can absorb the light with a dominant wavelength λ1 that has been transmitted through the first photosensitive layer and the substrate, as well as the light with a dominant wavelength λ1 that has been reflected by components such as a wavelength-selective filter. As a result, the decrease in resolution caused by the re-exposure of the first photosensitive layer can be suppressed.

[0497] From the viewpoint of suppressing the decrease in resolution caused by reexposure, in one embodiment, it is preferable that the first photosensitive layer contains a material that absorbs light of the dominant wavelength λ2 or the second photosensitive layer contains a material that absorbs light of the dominant wavelength λ1. The above-described embodiment includes the following (1) to (3). Among the following (1) to (3), (3) is preferred.

[0498] (1) The first photosensitive layer contains a substance that absorbs light with the dominant wavelength λ2.

[0499] (2) The second photosensitive layer contains a substance that absorbs light of the dominant wavelength λ1.

[0500] (3) The first photosensitive layer contains a substance that absorbs light of the dominant wavelength λ2, and the second photosensitive layer contains a substance that absorbs light of the dominant wavelength λ1.

[0501] From the viewpoint of suppressing the resolution degradation caused by reexposure, the layer having the property of absorbing a specific dominant wavelength can be a layer other than the first photosensitive layer and the second photosensitive layer. In one embodiment, the laminate preferably has at least one of the following: a layer containing a substance that absorbs light of dominant wavelength λ2 disposed between the substrate and the first photosensitive layer; a layer containing a substance that absorbs light of dominant wavelength λ2 disposed on the substrate with the first photosensitive layer spaced apart; a layer containing a substance that absorbs light of dominant wavelength λ1 disposed between the substrate and the second photosensitive layer; and a layer containing a substance that absorbs light of dominant wavelength λ1 disposed on the substrate with the second photosensitive layer spaced apart. As a layer containing a substance that absorbs light of dominant wavelength λ1 or dominant wavelength λ2, for example, the layers described in "Other Layers" below can be cited. The layer containing a substance that absorbs light of dominant wavelength λ1 or dominant wavelength λ2 is preferably a thermoplastic resin layer or an intermediate layer, more preferably a thermoplastic resin layer. The thermoplastic resin layer and the intermediate layer will be described later.

[0502] Examples of substances that absorb light of dominant wavelength λ1 or dominant wavelength λ2 include dyes and pigments. Examples of substances that absorb light of dominant wavelength λ1 or dominant wavelength λ2 include near-ultraviolet absorbers. Examples of substances that absorb light of dominant wavelength λ1 or dominant wavelength λ2 include inorganic particles.

[0503] The material absorbing the dominant wavelength λ2 and the material absorbing the dominant wavelength λ1 are preferably materials that have absorption in the wavelength region of 400 nm or higher. Depending on the spectral distribution of the light source, such as a high-pressure mercury lamp, the exposure wavelength is typically selected with 400 nm as the boundary. For example, the exposure wavelength in either exposure step (1) or exposure step (2) is sometimes selected in the wavelength region of 400 nm or higher. In applications of the exposure wavelengths described above, in particular, the material absorbing the dominant wavelength λ2 and the material absorbing the dominant wavelength λ1 are preferably materials that have absorption in the wavelength region of 400 nm or higher.

[0504] Examples of substances that absorb wavelengths above 400 nm include dyes and pigments that absorb wavelengths above 400 nm. Examples of dyes that absorb wavelengths above 400 nm include Solvent Yellow 4, Solvent Yellow 14, Solvent Yellow 56, Methyl Yellow, Solvent Green 3, Acid Yellow 3, Acid Yellow 23, Acid Yellow 36, Acid Yellow 73, Basic Yellow 1, Basic Yellow 2, Basic Yellow 7, Acid Green 1, Acid Green 3, Acid Green 27, Acid Green 50, Acid Green A, and Basic Green 1. Examples of pigments that absorb wavelengths above 400 nm include Pigment Yellow 1, Pigment Yellow 14, Pigment Yellow 34, Pigment Yellow 93, Pigment Yellow 138, Pigment Yellow 150, Pigment Green 7, Pigment Green 36, Pigment Green 50, and Pigment Green 58. Examples of substances that absorb in wavelengths above 400 nm include near-ultraviolet absorbers and inorganic particles that absorb in wavelengths above 400 nm.

[0505] Materials that absorb in wavelengths above 400 nm are preferably those that have a maximum absorption wavelength λ in wavelengths above 400 nm. max The substance.

[0506] The preferred method for selecting a substance that absorbs light of dominant wavelength λ1 or dominant wavelength λ2 can be based on the following (1) to (4). By selecting a substance with light absorption characteristics corresponding to the target dominant wavelength, it is possible to suppress the decrease in resolution caused by reexposure.

[0507] (1) When the dominant wavelength λ1 is above 400 nm, the substance that absorbs the light of the dominant wavelength λ1 has absorption in the wavelength region above 400 nm.

[0508] (2) When the dominant wavelength λ1 is less than 400 nm, the substance that absorbs the light of the dominant wavelength λ1 has absorption in the wavelength region of less than 400 nm.

[0509] (3) When the dominant wavelength λ2 is above 400nm, the substance that absorbs the light with the dominant wavelength λ2 has absorption in the wavelength region above 400nm.

[0510] (4) When the dominant wavelength λ2 is less than 400 nm, the substance that absorbs the light with the dominant wavelength λ2 has absorption in the wavelength region less than 400 nm.

[0511] Relative to the total mass of the layer containing the aforementioned substances, the content of the substance absorbing light of dominant wavelength λ1 or dominant wavelength λ2 is preferably 30% by mass or less. By minimizing the content of the substance absorbing light of dominant wavelength λ1 or dominant wavelength λ2, damage to the original function of the layer containing the aforementioned substances can be suppressed. The lower limit of the content of the substance absorbing light of dominant wavelength λ1 or dominant wavelength λ2 can be determined based on the amount of light (hereinafter referred to as "reflected light amount") when the reflected exposure light re-reaches the photosensitive layer. Preferably, the content of the substance absorbing light of dominant wavelength λ1 or dominant wavelength λ2 is adjusted such that the ratio of reflected light amount to the amount of exposure light incident on the target photosensitive layer is 50% or less (preferably 20% or less, more preferably 10% or less). The calculation of reflected light amount is, for example, based on the absorbance and reflectivity of the photosensitive layer, the absorbance and reflectivity of the substrate, the absorbance and reflectivity of the photomask, and the absorbance of the substance absorbing light of dominant wavelength λ1 or dominant wavelength λ2.

[0512] [Other layers]

[0513] Laminated bodies may have layers other than those described above (hereinafter sometimes referred to as "other layers"). Examples of other layers include, for instance, temporary supports and protective films.

[0514] The temporary support will now be described. As will be discussed later, the temporary support is, for example, a component used when forming a photosensitive layer using a transfer material. When the laminate has a temporary support, the temporary support is generally only required to be disposed on at least one side of the laminate. Specifically, the temporary support may be disposed on the outermost layer of the side on which the first photosensitive layer is disposed with reference to the substrate. Furthermore, the temporary support may be disposed on the outermost layer of the side on which the second photosensitive layer is disposed with reference to the substrate.

[0515] Examples of temporary supports include glass substrates, resin films, and paper. From the viewpoint of strength and flexibility, resin films are preferred as temporary supports. Examples of resin films include polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Polyethylene terephthalate films are preferred as temporary supports, and biaxially stretched polyethylene terephthalate films are more preferred.

[0516] As a temporary support, a flexible film that does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat can be used. Examples of such films include polyethylene terephthalate films (e.g., biaxially stretched polyethylene terephthalate films), cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films. Among these, biaxially stretched polyethylene terephthalate films are particularly preferred as temporary supports. Furthermore, the film used as a temporary support is preferably free from deformation, scratches, or the like.

[0517] From the viewpoint of enabling pattern exposure via a temporary support, the temporary support is preferably highly transparent. The transmittance of the temporary support at 365 nm is preferably 60% or more, more preferably 70% or more.

[0518] From the viewpoint of pattern formation properties during pattern exposure via a temporary support and the transparency of the temporary support, the haze of the temporary support is preferably low. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less.

[0519] From the viewpoint of pattern formation properties during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable that the number of particles, foreign matter, and defects contained in the temporary support is low. The number of particles, foreign matter, and defects with a diameter of 1 μm or more is preferably 50 per 10 mm. 2 The following is more preferably 10 per 10mm 2 The following is a further preferred option: 3 per 10mm 2 The following is particularly preferred: 0 per 10mm 2 .

[0520] There is no particular limitation on the thickness of the temporary support, but it is preferably 5μm to 200μm, and more preferably 10μm to 150μm from the point of view of ease of handling and versatility, and even more preferably 10μm to 50μm.

[0521] Preferred methods for temporary supports are described, for example, in paragraphs 0017-0018 of Japanese Patent Application Publication No. 2014-85643, paragraphs 0019-0026 of Japanese Patent Application Publication No. 2016-27363, paragraphs 0041-0057 of International Publication No. 2012 / 081680, and paragraphs 0029-0040 of International Publication No. 2018 / 179370, the contents of which are incorporated herein by reference.

[0522] When the laminate has a protective film, the protective film is generally only required to be disposed on at least one side of the laminate. Specifically, the protective film may be disposed on the outermost layer of the side on which the first photosensitive layer is disposed with reference to the substrate. Furthermore, the protective film may be disposed on the outermost layer of the side on which the second photosensitive layer is disposed with reference to the substrate.

[0523] The protective film will now be described. Examples of protective films include resin films and paper. From the viewpoint of strength and flexibility, a resin film is preferred. Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. The resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

[0524] The protective film is preferably transparent. Because the protective film is transparent, it allows for exposure.

[0525] There is no limitation on the thickness of the protective film. The average thickness of the protective film can be determined, for example, within the range of 1 μm to 2 mm. The average thickness of the protective film is measured using the method described above for measuring the average thickness of the substrate.

[0526] Other layers include, for example, thermoplastic resin layers and intermediate layers.

[0527] The thermoplastic resin layer will now be described. The thermoplastic resin layer comprises resin. Some or all of the resin is thermoplastic resin. The thermoplastic resin layer preferably comprises thermoplastic resin.

[0528] Thermoplastic resins are preferably alkali-soluble resins. Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, 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 glycols.

[0529] From the viewpoint of developability and adhesion to adjacent layers, acrylic resin is preferred as an alkali-soluble resin. Acrylic resin refers to a resin having at least one structural unit selected from structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide. In acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide, relative to the total mass of the acrylic resin, is preferably 50% by mass or more. Specifically, the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate, relative to the total mass of the acrylic resin, is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass.

[0530] Alkali-soluble resins are preferably polymers containing acid groups. Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl groups being preferred.

[0531] From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin with an acid value of 40 mg KOH / g or higher, more preferably an acrylic resin containing carboxyl groups with an acid value of 40 mg KOH / g or higher. The acid value of the alkali-soluble resin is preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and particularly preferably 160 mg KOH / g or less.

[0532] Examples of carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher include: alkali-soluble acrylic resins with an acid value of 60 mg KOH / g or higher in the polymer described in Japanese Patent Application Publication No. 2011-095716 (paragraph 0025); alkali-soluble acrylic resins with an acid value of 60 mg KOH / g or higher in the polymer described in Japanese Patent Application Publication No. 2010-237589 (paragraphs 0033-0052); and carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher in the adhesive polymer described in Japanese Patent Application Publication No. 2016-224162 (paragraphs 0053-0068). The copolymerization ratio of carboxyl-containing structural units in the carboxyl-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 acrylic resin. As an alkali-soluble resin, from the viewpoint of developability and adhesion to adjacent layers, an acrylic resin having structural units derived from (meth)acrylic acid is particularly preferred.

[0533] Alkali-soluble resins may have reactive groups. Examples of reactive groups include those capable of addition polymerization. Examples of reactive groups include olefinic unsaturated groups, condensation groups (e.g., hydroxyl and carboxyl groups), and addition polymerization reactive groups (e.g., epoxy and (block) isocyanate groups).

[0534] 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 especially preferably 20,000 to 50,000.

[0535] Alkali-soluble resins can be used alone or in combination with two or more types.

[0536] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, further preferably 40% to 80% by mass, and especially preferably 50% to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0537] The thermoplastic resin layer preferably contains a pigment (hereinafter sometimes referred to as "pigment B") whose maximum absorption wavelength is 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength is altered by acid, alkali, or free radicals. From the viewpoint of visibility and resolution of the exposed and unexposed areas, pigment B is preferably a pigment whose maximum absorption wavelength is altered by acid or free radicals, and more preferably a pigment whose maximum absorption wavelength is altered by acid. From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both the pigment B, whose maximum absorption wavelength is altered by acid, and a compound that generates acid upon exposure to light.

[0538] Pigment B can be used alone or in combination with two or more pigments.

[0539] From the viewpoint of visibility of the exposed and non-exposed areas, the content of pigment B relative to the total mass of the thermoplastic resin layer is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, even more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.

[0540] The content of pigment B refers to the amount of pigment when all pigment B contained in the thermoplastic resin layer is in a colored state. The following describes the quantitative method for the content of pigment B, taking a pigment colored by free radicals as an example. Solutions were prepared by dissolving 0.001 g of pigment in 100 mL of methyl ethyl ketone and another solution by dissolving 0.01 g of pigment in 100 mL of methyl ethyl ketone. Irgacure OXE01 (trade name, BASF Japan Ltd.) as a photoradioactive polymerization initiator was added to each of the obtained solutions, and the solutions were irradiated with 365 nm light, thereby generating free radicals and setting all pigments to a colored state. Then, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION), and a calibration curve was created. Next, 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment, and the absorbance of the solution in which all pigments were colored was measured using the same method as above. The amount of pigment contained in the thermoplastic resin layer is calculated based on the absorbance of the obtained solution including the thermoplastic resin layer, according to the calibration curve.

[0541] The thermoplastic resin layer may contain a compound that generates acids, bases, or free radicals upon exposure to light (hereinafter, sometimes referred to as "Compound C"). Compound C is preferably a compound that generates acids, bases, or free radicals upon receiving active light such as ultraviolet and visible light. Known photoacid generators, photoalkali generators, and photoradical polymerization initiators (photoradical generators) can be used as Compound C.

[0542] From a distinguishing point of view, the thermoplastic resin layer may contain a photoacid generator. Examples of photoacid generators include, for instance, photocationic polymerization initiators.

[0543] From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution, and binding, it is more preferably to contain oxime sulfonate compounds. Furthermore, the photoacid generator preferably has the following structure.

[0544] [Chemical Formula 8]

[0545]

[0546] The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators that can be contained in the aforementioned negative photosensitive layer include photoradical polymerization initiators.

[0547] The thermoplastic resin layer may contain a photoalkali-generating agent. Examples of photoalkali-generating agents include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, and (4-morpholinobenzoyl)-1-benzyl-1-dimethyl... The compounds include methylaminopropane, 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.

[0548] Compound C can be used alone or in more than two forms.

[0549] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the content of 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.

[0550] From the viewpoints of resolvability, adhesion to adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer. The plasticizer preferably has a molecular weight (weight-average molecular weight, if it is an oligomer or polymer with a molecular weight distribution) smaller than that of the alkali-soluble resin. The molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000. There are no limitations on the plasticizer, as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has alkene oxides in its molecule, more preferably a polyalkylene glycol compound. The alkene oxides contained in the plasticizer are more preferably polyethylene oxide or polypropylene oxide structures.

[0551] Furthermore, from the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, the alkali-soluble resin is more preferably an acrylic resin, and the plasticizer contains a (meth)acrylate compound. Examples of (meth)acrylate compounds that can be used as plasticizers include the polymerizable compounds described in the aforementioned negative photosensitive layer.

[0552] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of adhesion between the thermoplastic resin layer and adjacent layers, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed portion after exposure. Furthermore, from the viewpoint of the resolvability of the thermoplastic resin layer, adhesion to adjacent layers, and developability, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups per molecule is preferred as a (meth)acrylate compound that can be used as a plasticizer. Moreover, as a (meth)acrylate compound that can be used as a plasticizer, a (meth)acrylate compound having an acid group or an amine ester (meth)acrylate compound is also preferred.

[0553] Plasticizers can be used alone or in combination with two or more.

[0554] From the viewpoints of the resolvability of the thermoplastic resin layer, its adhesion to adjacent layers, and its developability, the content of plasticizer relative to the total mass of the thermoplastic resin layer is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and particularly preferably 20% to 50% by mass.

[0555] The thermoplastic resin layer may contain a sensitizer. There are no particular limitations on the sensitizer; examples of sensitizers that may be contained in the aforementioned negative photosensitive layer are provided.

[0556] A single sensitizer can be used alone, or two or more sensitizers can be used.

[0557] The content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and unexposed parts, it 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.

[0558] In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives such as surfactants, as needed. Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-085643, the contents of which are incorporated herein by reference.

[0559] From the viewpoint of adhesion to adjacent layers, the thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. From the viewpoint of developability and resolution, the thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less.

[0560] The intermediate layer will now be described. For example, a water-soluble resin layer containing a water-soluble resin can be used as the intermediate layer. Furthermore, an oxygen-barrier layer with an oxygen-barrier function, as described as a "separation layer" in Japanese Patent Application Publication No. 5-072724, can also be used as the intermediate layer. If the intermediate layer is an oxygen-barrier layer, the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and productivity is improved. Regarding the oxygen-barrier layer that can be used as the intermediate layer, it is sufficient to appropriately select from known layers. Preferably, an oxygen-barrier layer exhibiting low oxygen permeability and dispersed or dissolved in water or an alkaline aqueous solution (e.g., a 1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0561] The intermediate layer is preferably disposed between the photosensitive layer and the thermoplastic resin layer.

[0562] The water-soluble resin layer, as one of the intermediate layers, comprises a resin. Part or all of the resin is a water-soluble resin. Examples of resins suitable for use as water-soluble resins include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins. Furthermore, copolymers of (meth)acrylic acid and vinyl compounds are also examples of water-soluble resins. Copolymers of (meth)acrylic acid and vinyl compounds are preferably copolymers of (meth)acrylic acid and allyl methacrylate, more preferably copolymers of methacrylic acid and allyl methacrylate. When the water-soluble resin is a copolymer of (meth)acrylic acid and vinyl compounds, the component ratios (mol%) are preferably 90 / 10 to 20 / 80, more preferably 80 / 20 to 30 / 70.

[0563] The weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and particularly preferably 10,000 or more. Furthermore, the weight-average molecular weight of the water-soluble resin is preferably 200,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less. The dispersibility (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

[0564] From the viewpoint of further improving the interlayer mixing inhibition ability of the water-soluble resin layer, it is preferable that the resin in the water-soluble resin layer is a different resin from the resin contained in the layer disposed on one side of the water-soluble resin layer and the resin contained in the layer disposed on the other side.

[0565] From the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability, it is more preferable that the water-soluble resin contains polyvinyl alcohol, and more preferably it contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0566] Water-soluble resins can be used alone or in combination with two or more.

[0567] From the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability, the content of water-soluble resin relative to the total mass of the water-soluble resin layer 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. There is no upper limit to the content of water-soluble resin. The content of water-soluble resin relative to the total mass of the water-soluble resin layer is preferably 99.9% by mass or less, more preferably 99.8% by mass or less.

[0568] As needed, the intermediate layer may contain known additives such as surfactants. Examples of surfactants include those described in the section on "positive photosensitive layer" above.

[0569] The thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. If the thickness of the intermediate layer is within the above range, the oxygen barrier properties are not reduced, and the interlayer mixing suppression ability is excellent. Furthermore, it can also suppress the increase in the removal time of the intermediate layer during development.

[0570] [Manufacturing method of laminated bodies]

[0571] There are no limitations on the manufacturing method of the laminate, and known methods can be used. For example, a method in which a first photosensitive layer is formed on one side of a substrate and a second photosensitive layer is formed on the other side of the substrate can be described. The first and second photosensitive layers can be formed simultaneously or separately. Hereinafter, the first and second photosensitive layers will sometimes be collectively referred to as "photosensitive layers". Unless otherwise specified, the term "photosensitive layer" includes either the first photosensitive layer or the second photosensitive layer, or both the first and second photosensitive layers.

[0572] There are no limitations on the method for forming the photosensitive layer, and known methods can be used. Examples of methods for forming the photosensitive layer include coating and using transfer materials.

[0573] The methods for forming the first and second photosensitive layers can be the same or different. For example, the first and second photosensitive layers can be formed by coating or by using a transfer material. Furthermore, one of the photosensitive layers can be formed by coating, and the other photosensitive layer can be formed by using a transfer material.

[0574] (Coating method)

[0575] There are no limitations on the coating method, and known methods can be used. For example, a photosensitive layer can be formed by coating a photosensitive layer forming composition onto a substrate. The photosensitive layer forming composition coated on the substrate can be dried using known methods, as needed.

[0576] As a method for preparing a composition for forming a photosensitive layer, for example, a method of mixing raw materials and solvents of the target photosensitive layer in any proportion can be cited. There are no limitations on the mixing method, and known methods can be used. Furthermore, the composition for forming the photosensitive layer can be filtered using a filter with a pore size of 0.2 μm or the like.

[0577] Examples of solvents include, for example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Also included as solvents are those described in paragraphs 0174 to 0178 of Japanese Patent Application Publication No. 2011-221494 and those described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640, which are incorporated herein by reference.

[0578] As needed, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate may be added to the solvents described.

[0579] Furthermore, as a solvent, a solvent with a boiling point of 130°C or higher and less than 160°C, a solvent with a boiling point of 160°C or higher, or a mixture thereof are preferred.

[0580] Examples of solvents with boiling points above 130°C and below 160°C include propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monoethyl ether acetate (boiling point 158°C), propylene glycol methyl-n-butyl ether (boiling point 155°C), and propylene glycol methyl-n-propyl ether (boiling point 131°C).

[0581] Examples of solvents with boiling points above 160°C include ethyl 3-ethoxypropionate (boiling point 170°C), diethylene glycol methyl ethyl ether (boiling point 176°C), propylene glycol monomethyl ether propionate (boiling point 160°C), dipropylene glycol methyl ether acetate (boiling point 213°C), 3-methoxybutyl ether acetate (boiling point 171°C), diethylene glycol diethyl ether (boiling point 189°C), diethylene glycol dimethyl ether (boiling point 162°C), propylene glycol diacetate (boiling point 190°C), diethylene glycol monoethyl ether acetate (boiling point 220°C), dipropylene glycol dimethyl ether (boiling point 175°C), and 1,3-butanediol diacetate (boiling point 232°C).

[0582] The composition for forming a photosensitive layer may contain a single solvent or two or more solvents. It is preferable to use two or more solvents simultaneously in the composition for forming a photosensitive layer. When using two or more solvents simultaneously, for example, it is preferable to use propylene glycol monoalkyl ether acetates and dialkyl ethers simultaneously, diacetates and diethylene glycol dialkyl ethers simultaneously, or esters and butanediol alkyl ether acetates simultaneously.

[0583] The solvent content is preferably 50 to 1,900 parts by mass relative to 100 parts by mass of the total solids in the composition for forming the photosensitive layer, and more preferably 100 to 900 parts by mass.

[0584] Methods for applying a composition for forming a photosensitive layer include, for example, slit coating, spin coating, curtain coating, and inkjet coating. Slit coating is the preferred method for applying the composition for forming a photosensitive layer.

[0585] (Transfer printing process)

[0586] As a method of using transfer material, for example, a method of bonding a substrate to the transfer material can be cited. For example, by bonding a transfer material having a temporary support and a first photosensitive layer to a substrate, the first photosensitive layer can be transferred to the substrate.

[0587] Regarding the bonding of the substrate and the transfer material, it is preferable to perform the bonding while applying pressure and heating using rollers or the like. Regarding pressure, it is acceptable to determine a range of 1,000 N / m to 10,000 N / m for linear pressure. Regarding temperature, it is acceptable to determine a range of 40°C to 130°C for example. If at least one of the pressure and temperature is lower than the above ranges, air that may be trapped during lamination may not be sufficiently expelled from between the substrate and the photosensitive layer. If the pressure is higher than the above ranges, the photosensitive layer may deform. If the temperature is higher than the above ranges, the photosensitive layer may decompose or deteriorate due to heat, which may be an undesirable condition.

[0588] In the bonding of the substrate and the transfer material, for example, a laminator, a vacuum laminator, and an automated cutting laminator that can further improve productivity can be used. Furthermore, the bonding of the substrate and the transfer material can also be performed roller-to-roll, depending on the material of the substrate.

[0589] The transfer of the first photosensitive layer to the substrate and the transfer of the second photosensitive layer to the substrate can be performed simultaneously or separately.

[0590] The transfer material can, for example, form a photosensitive layer by coating a photosensitive layer forming composition onto a temporary support. The photosensitive layer forming composition coated onto the temporary support can be dried using known methods, if necessary. Examples of temporary supports include those described in the "Other Layers" section above, and the preferred temporary supports are also the same.

[0591] When the transfer material has a temporary support and a photosensitive layer, a protective film can be disposed on the side of the photosensitive layer opposite to the side where the temporary support is disposed. Examples of such protective films include those described in the "Other Layers" section above, and the preferred protective film is also the same.

[0592] Exposure Process (1)

[0593] The pattern forming method of the present invention includes a step of exposing a first photosensitive layer (exposure step (1)). In the exposure step (1), the solubility of the exposed first photosensitive layer (i.e., the exposed portion) in the developer changes. For example, when the first photosensitive layer is a positive photosensitive layer, the solubility of the exposed portion of the first photosensitive layer in the developer increases compared to the unexposed portion. For example, when the first photosensitive layer is a negative photosensitive layer, the solubility of the exposed portion of the first photosensitive layer in the developer decreases compared to the unexposed portion.

[0594] As a method for exposing the first photosensitive layer, for example, a method using a photomask can be employed. For instance, by placing a photomask between the first photosensitive layer and a light source, the first photosensitive layer can be exposed into a pattern via the photomask. By patterning the first photosensitive layer, exposed and unexposed areas can be formed within the first photosensitive layer.

[0595] In the exposure process (1), it is preferable to expose the first photosensitive layer by contacting it with the photomask. This method of exposing the first photosensitive layer to the photomask (also known as "contact exposure") can improve resolution.

[0596] Furthermore, in the exposure process (1), in addition to the contact exposure described above, it is also possible to appropriately select a proximity exposure method, a lens system or mirror system projection exposure method, or a direct exposure method using an exposure laser, etc. In the case of the lens system projection exposure method, an exposure machine with an appropriate lens numerical aperture (NA) can be used according to the required resolution and depth of focus. In the case of the direct exposure method, it is possible to draw directly on the photosensitive layer, or to perform reduced projection exposure on the photosensitive layer through a lens. Furthermore, exposure can be performed not only under atmospheric conditions, but also under reduced pressure or vacuum conditions, and it is also possible to expose the photosensitive layer by placing a liquid such as water between the light source and the photosensitive layer.

[0597] When a protective film is disposed on the first photosensitive layer, the first photosensitive layer can be exposed through the protective film. When exposing the first photosensitive layer by contact exposure, from the viewpoint of avoiding the influence of photomask contamination and foreign matter adhering to the photomask on the exposure, it is preferable to expose the first photosensitive layer through the protective film. After exposing the first photosensitive layer through the protective film, it is preferable to perform the development step (1) described later after removing the protective film.

[0598] When the first photosensitive layer is exposed via a protective film, the protective film used is preferably a thin film capable of transmitting light that is irradiated during exposure. For example, a protective film capable of transmitting light that is irradiated during exposure, as described in the "Other Layers" section above, can be used.

[0599] When the first photosensitive layer is exposed via a protective film, the protective film only needs to be placed on the first photosensitive layer at least before the exposure step (1).

[0600] When a temporary support is provided on the first photosensitive layer, the first photosensitive layer can be exposed via the temporary support, or it can be exposed after the temporary support has been removed from the first photosensitive layer. When exposing the first photosensitive layer by contact exposure, from the viewpoint of avoiding the influence of photomask contamination and foreign matter attached to the photomask on the exposure, it is preferable to expose the first photosensitive layer via the temporary support. When the first photosensitive layer has been exposed via the temporary support, after removing the temporary support, it is preferable to perform the development step (1) described later.

[0601] When the first photosensitive layer is exposed via a temporary support, the temporary support used is preferably a thin film capable of transmitting light that is irradiated during exposure. For example, a temporary support capable of transmitting light that is irradiated during exposure, as described in the "Other Layers" section above, can be used.

[0602] There are no limitations on the light source used for exposure, as long as it is a light source capable of illuminating light in a wavelength range (e.g., 365 nm or 405 nm) that can alter the solubility of the first photosensitive layer in the developer. Examples of light sources for exposure include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and light-emitting diodes (LEDs).

[0603] As described above, the dominant wavelength λ1 of the exposure wavelength in exposure step (1) only needs to be different from the dominant wavelength λ2 of the exposure wavelength in exposure step (2). The exposure wavelength and dominant wavelength λ1 in exposure step (1) only need to be determined in the wavelength region of 10nm to 450nm. The dominant wavelength λ1 is preferably in the range of 300nm to 400nm or 370nm to 450nm, and more preferably in the range of 300nm to 380nm or 390nm to 450nm.

[0604] The exposure wavelength in exposure step (1) is preferably excluding wavelength 365nm. In this invention, "excluding wavelength 365nm" means that when the maximum intensity of the entire exposure wavelength region (i.e., the intensity of the dominant wavelength, hereinafter the same) is set to 100%, the intensity of wavelength 365nm is 30% or less. When the maximum intensity of the entire exposure wavelength region is set to 100%, the intensity of wavelength 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. There is no limitation on the lower limit of the intensity of wavelength 365nm. When the maximum intensity of the entire exposure wavelength region is set to 100%, the intensity of wavelength 365nm can be determined, for example, as long as it is within the range of 0% or more.

[0605] When the exposure wavelength in exposure step (1) does not include wavelength 365nm, and the exposure wavelength in exposure step (1) includes the main wavelength in the wavelength region of 370nm to 450nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 365nm is preferably 30% or less. When the main wavelength is included in the wavelength region of 380nm to 430nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 365nm is more preferably 30% or less. When the main wavelength is included in the wavelength region of 390nm to 420nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 365nm is particularly preferably 30% or less. When the intensity of the main wavelength is set to 100%, the intensity of wavelength 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. There is no limitation on the lower limit of the intensity of wavelength 365nm. With the intensity of the dominant wavelength set to 100%, the intensity of the wavelength 365nm can be determined, for example, as long as it is within the range of 0% or higher.

[0606] The exposure wavelength in exposure step (1) is preferably excluding wavelength 405 nm. In this invention, "excluding wavelength 405 nm" means that when the maximum intensity of the entire exposure wavelength region is set to 100%, the intensity of wavelength 405 nm is 30% or less. When the maximum intensity of the entire exposure wavelength region is set to 100%, the intensity of wavelength 405 nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. There is no limitation on the lower limit of the intensity of wavelength 405 nm. When the maximum intensity of the entire exposure wavelength region is set to 100%, the intensity of wavelength 405 nm can be determined, for example, as long as it is within the range of 0% or more.

[0607] When the exposure wavelength in exposure step (1) does not include wavelength 405 nm, and the exposure wavelength in exposure step (1) includes the main wavelength in the wavelength region of 300 nm to 400 nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 405 nm is preferably 30% or less. When the main wavelength is included in the wavelength region of 300 nm to 380 nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 405 nm is more preferably 30% or less. When the main wavelength is included in the wavelength region of 350 nm to 380 nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 405 nm is particularly preferably 30% or less. When the intensity of the main wavelength is set to 100%, the intensity of wavelength 405 nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. There is no limitation on the lower limit of the intensity of wavelength 405 nm. With the intensity of the dominant wavelength set to 100%, the intensity of the wavelength 405nm can be determined, for example, as long as it is within the range of 0% or higher.

[0608] In one embodiment, the exposure wavelength in the exposure step (1) is preferably an exposure wavelength with an intensity of 365 nm greater than that of 405 nm (hereinafter referred to as "condition (1-1)" in this paragraph) or an exposure wavelength with an intensity of 405 nm greater than that of 365 nm (hereinafter referred to as "condition (1-2)" in this paragraph). When the intensity of 365 nm is set to 100% under condition (1-1), the intensity of 405 nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. There is no lower limit to the intensity of 405 nm under condition (1-1). When the intensity of 365 nm is set to 100% under condition (1-1), the intensity of 405 nm can be determined, for example, as long as it is within the range of 0% or more. On the other hand, when the intensity of the wavelength 405 nm is set to 100% under condition (1-2), the intensity of the wavelength 365 nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. There is no limitation on the lower limit of the intensity of the wavelength 365 nm under condition (1-2). When the intensity of the wavelength 405 nm is set to 100% under condition (1-2), the intensity of the wavelength 365 nm can be determined, for example, as long as it is within the range of 0% or more.

[0609] As a method for adjusting the exposure wavelength in the exposure process (1), examples include using a wavelength-selective filter and using a light source capable of irradiating light with a specific wavelength. For example, by exposing the first photosensitive layer via a wavelength-selective filter, the wavelength of the light reaching the first photosensitive layer can be adjusted within a specific range.

[0610] The optimal exposure level is 5 mJ / em. 2 ~1,000mJ / cm 2 More preferably 10 mJ / cm 2 ~500mJ / cm 2 The preferred value is 10 mJ / cm. 2 ~200mJ / cm 2 Exposure is determined based on the illuminance of the light source and the exposure time. Furthermore, exposure can be measured using a photometer.

[0611] In the exposure step (1), the first photosensitive layer can be exposed without using a photomask. In the case of exposing the first photosensitive layer without using a photomask (hereinafter, sometimes referred to as "maskless exposure"), for example, a direct drawing apparatus can be used to expose the first photosensitive layer. The direct drawing apparatus can directly draw an image using active energy rays. Examples of light sources in maskless exposure include lasers (e.g., semiconductor lasers, gas lasers, and solid-state lasers) and mercury short-arc lamps (e.g., ultra-high pressure mercury lamps) capable of irradiating light with wavelengths from 350 nm to 410 nm. The dominant wavelength λ1 of the exposure wavelength in maskless exposure is not limited as long as it differs from the dominant wavelength λ2 of the exposure wavelength in the exposure step (2). The preferred range of the exposure wavelength is as described above. The exposure amount is determined based on the illuminance of the light source and the transfer speed of the laminate. The drawn pattern can be controlled by a computer.

[0612] In the exposure process (1), the first photosensitive layer can be exposed from the side where the first photosensitive layer is disposed with reference to the substrate, or it can be exposed from the side where the second photosensitive layer is disposed with reference to the substrate. From the viewpoint of suppressing exposure haze, in the exposure process (1), it is preferable to expose the first photosensitive layer from the side where the first photosensitive layer is disposed with reference to the substrate.

[0613] Exposure process (2)

[0614] The pattern forming method of the present invention includes a step of exposing a second photosensitive layer (exposure step (2)). In the exposure step (2), the solubility of the exposed second photosensitive layer (exposed portion) in the developer changes. For example, when the second photosensitive layer is a positive photosensitive layer, the solubility of the exposed portion of the second photosensitive layer in the developer increases compared to the unexposed portion. For example, when the second photosensitive layer is a negative photosensitive layer, the solubility of the exposed portion of the second photosensitive layer in the developer decreases compared to the unexposed portion.

[0615] As a method for exposing the second photosensitive layer, for example, a method using a photomask can be employed. For instance, by placing a photomask between the second photosensitive layer and a light source, the second photosensitive layer can be exposed into a pattern via the photomask. By patterning the second photosensitive layer, exposed and unexposed areas can be formed within the second photosensitive layer.

[0616] In the exposure step (2), it is preferable to expose the laminate by contacting it with the photomask. This method of exposing the laminate by contacting it with the photomask (also known as "contact exposure") can improve resolution.

[0617] When a protective film is disposed on the second photosensitive layer, the second photosensitive layer can be exposed through the protective film. When exposing the second photosensitive layer by contact exposure, from the viewpoint of avoiding the influence of photomask contamination and foreign matter adhering to the photomask on the exposure, it is preferable to expose the second photosensitive layer through the protective film. After exposing the second photosensitive layer through the protective film, it is preferable to perform the development step (2) described later after removing the protective film.

[0618] As a protective film used when exposing the second photosensitive layer via the protective film, there are no limitations as long as it is a thin film capable of transmitting light irradiated during exposure. For example, a protective film capable of transmitting light irradiated during exposure, as described in the "Other Layers" section above, can be used.

[0619] When a temporary support is provided on the second photosensitive layer, the second photosensitive layer can be exposed via the temporary support, or it can be exposed after the temporary support has been removed from the second photosensitive layer. When exposing the second photosensitive layer by contact exposure, it is preferable to expose it via the temporary support, from the viewpoint of avoiding the influence of photomask contamination and foreign matter attached to the photomask on the exposure. After exposing the second photosensitive layer via the temporary support and removing the temporary support, it is preferable to perform the development process (2) described later.

[0620] When the second photosensitive layer is exposed via a temporary support, the temporary support used is preferably a thin film capable of transmitting light that is irradiated during exposure. For example, a temporary support capable of transmitting light that is irradiated during exposure, as described in the "Other Layers" section above, can be used.

[0621] There are no limitations on the light source used for exposure, as long as it is a light source capable of illuminating light in a wavelength range (e.g., 365 nm or 405 nm) that can alter the solubility of the second photosensitive layer in the developer. Examples of light sources for exposure include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and light-emitting diodes (LEDs).

[0622] As described above, the dominant wavelength λ2 of the exposure wavelength in exposure step (2) only needs to be different from the dominant wavelength λ1 of the exposure wavelength in exposure step (1). The exposure wavelength and dominant wavelength λ2 in exposure step (2) only need to be determined in the wavelength region of 10nm to 410nm. The dominant wavelength λ2 is preferably in the range of 300nm to 400nm or 370nm to 450nm. More preferably, it is in the range of 300nm to 380nm or 390nm to 450nm. For example, when the dominant wavelength λ1 in exposure step (1) is in the range of 300nm to 400nm (preferably 300nm to 380nm), the dominant wavelength λ2 in exposure step (2) is preferably in the range of 370nm to 450nm (preferably 390nm to 450nm). For example, when the dominant wavelength λ1 in the exposure process (1) is in the range of 370nm to 450nm (preferably 390nm to 450nm), the dominant wavelength λ2 in the exposure process (2) is preferably in the range of 300nm to 400nm (preferably 300nm to 380nm).

[0623] When the exposure wavelength in exposure step (1) does not include wavelength 365 nm, the exposure wavelength in exposure step (2) preferably does not include wavelength 405 nm. By using the exposure wavelengths described above in exposure steps (1) and (2), specific photosensitive layers can be exposed more selectively. When the maximum intensity in the entire exposure wavelength region is set to 100%, the intensity of wavelength 405 nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. There is no limitation on the lower limit of the intensity of wavelength 405 nm. When the maximum intensity in the entire exposure wavelength region is set to 100%, the intensity of wavelength 405 nm can be determined, for example, as long as it is within the range of 0% or more.

[0624] When the exposure wavelength in exposure step (2) does not include wavelength 405 nm, and the exposure wavelength in exposure step (2) includes the main wavelength in the wavelength region of 300 nm to 400 nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 405 nm is preferably 30% or less. When the main wavelength is included in the wavelength region of 300 nm to 380 nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 405 nm is more preferably 30% or less. When the main wavelength is included in the wavelength region of 350 nm to 380 nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 405 nm is particularly preferably 30% or less. When the intensity of the main wavelength is set to 100%, the intensity of wavelength 405 nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. There is no limitation on the lower limit of the intensity of wavelength 405 nm. With the intensity of the dominant wavelength set to 100%, the intensity of the wavelength 405nm can be determined, for example, as long as it is within the range of 0% or higher.

[0625] When the exposure wavelength in exposure step (1) does not include wavelength 405 nm, the exposure wavelength in exposure step (2) preferably does not include wavelength 365 nm. By using the exposure wavelengths described above in exposure steps (1) and (2), specific photosensitive layers can be exposed more selectively. When the maximum intensity in the entire exposure wavelength region is set to 100%, the intensity of wavelength 365 nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. There is no limitation on the lower limit of the intensity of wavelength 365 nm. When the maximum intensity in the entire exposure wavelength region is set to 100%, the intensity of wavelength 365 nm can be determined, for example, as long as it is within the range of 0% or more.

[0626] When the exposure wavelength in exposure step (2) does not include wavelength 365nm, and the exposure wavelength in exposure step (2) includes the main wavelength in the wavelength region of 370nm to 450nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 365nm is preferably 30% or less. When the main wavelength is included in the wavelength region of 380nm to 430nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 365nm is more preferably 30% or less. When the main wavelength is included in the wavelength region of 390nm to 420nm, and the intensity of the main wavelength is set to 100%, the intensity of wavelength 365nm is particularly preferably 30% or less. When the intensity of the main wavelength is set to 100%, the intensity of wavelength 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. There is no limitation on the lower limit of the intensity of wavelength 365nm. With the intensity of the dominant wavelength set to 100%, the intensity of the wavelength 365nm can be determined, for example, as long as it is within the range of 0% or higher.

[0627] When the exposure wavelength in exposure step (1) is "an exposure wavelength with an intensity greater than that of wavelength 405nm", the exposure wavelength in exposure step (2) is preferably an exposure wavelength with an intensity greater than that of wavelength 365nm (hereinafter referred to as "condition (2-1)" in this paragraph). The preferred method of condition (2-1) is the same as the preferred method of condition (1-2) described in the above-mentioned "exposure step (1)" item. On the other hand, when the exposure wavelength in exposure step (1) is "an exposure wavelength with an intensity greater than that of wavelength 405nm", the exposure wavelength in exposure step (2) is preferably an exposure wavelength with an intensity greater than that of wavelength 405nm (hereinafter referred to as "condition (2-2)" in this paragraph). The preferred method of condition (2-2) is the same as the preferred method of condition (1-1) described in the above-mentioned "exposure step (1)" item.

[0628] As a method for adjusting the exposure wavelength in the exposure step (2), examples include using a wavelength-selective filter and using a light source capable of irradiating light with a specific wavelength. For example, by exposing the second photosensitive layer via a wavelength-selective filter, the wavelength of the light reaching the second photosensitive layer can be adjusted within a specific range.

[0629] The optimal exposure level is 5 mJ / cm. 2 ~1,000mJ / cm 2 More preferably 10 mJ / cm 2 ~500mJ / cm2 The preferred value is 10 mJ / cm. 2 ~200mJ / cm 2 Exposure is determined based on the illuminance of the light source and the exposure time. Furthermore, exposure can be measured using a photometer.

[0630] The dominant wavelengths λ1 and λ2 are preferably configured as follows.

[0631] From the viewpoint of suppressing exposure fog, the aforementioned dominant wavelength λ1 is preferably in the range of more than 395 nm and less than 500 nm, and more preferably in the range of more than 396 nm and less than 456 nm.

[0632] From the viewpoint of suppressing exposure fog, the aforementioned dominant wavelength λ2 is preferably in the range of 250 nm or more and 395 nm or less, and more preferably in the range of 335 nm or more and 395 nm or less.

[0633] Furthermore, from the viewpoint of suppressing exposure fog, it is even more preferable that the dominant wavelength λ1 is in the range of more than 395 nm and less than 500 nm, and the dominant wavelength λ2 is in the range of more than 250 nm and less than 395 nm. It is particularly preferable that the dominant wavelength λ1 is in the range of more than 396 nm and less than 456 nm, and the dominant wavelength λ2 is in the range of more than 335 nm and less than 395 nm.

[0634] In the pattern forming method of the present invention, the exposure amount in the exposure step (1) and the exposure amount in the exposure step (2) may be the same or different.

[0635] In the exposure step (2), the second photosensitive layer can be exposed without using a photomask. In the case of exposing the first photosensitive layer without using a photomask (hereinafter sometimes referred to as "maskless exposure"), for example, a direct drawing apparatus can be used to expose the first photosensitive layer. The direct drawing apparatus can directly draw an image using active energy rays. Examples of light sources for maskless exposure include lasers (e.g., semiconductor lasers, gas lasers, and solid-state lasers) and mercury short-arc lamps (e.g., ultra-high pressure mercury lamps) capable of irradiating light with wavelengths from 350 nm to 410 nm. There is no limitation on the dominant wavelength λ2 of the exposure wavelength in maskless exposure, as long as it differs from the dominant wavelength λ2 of the exposure wavelength in the exposure step (1). The preferred range of the exposure wavelength is as described above. The exposure amount is determined based on the illuminance of the light source and the transfer speed of the laminate. The drawn pattern can be controlled by a computer.

[0636] In the exposure step (2), the second photosensitive layer can be exposed from the side where the second photosensitive layer is disposed with reference to the substrate, or it can be exposed from the side where the first photosensitive layer is disposed with reference to the substrate. The light irradiation direction in the exposure step (1) and the light irradiation direction in the exposure step (2) can be the same or different. From the viewpoint of suppressing exposure haze, in the exposure step (2), it is preferable to expose the second photosensitive layer from the side where the second photosensitive layer is disposed with reference to the substrate.

[0637] In one embodiment, it is preferable to have a component for absorbing light of dominant wavelength λ2 disposed between the first photosensitive layer and the light source for exposing the first photosensitive layer, or to have a component for absorbing light of dominant wavelength λ1 disposed between the second photosensitive layer and the light source for exposing the second photosensitive layer. According to the above embodiment, as explained in the "Light Absorption Characteristics" section, the resolution degradation caused by reexposure can be suppressed. That is, the component for absorbing light of dominant wavelength λ2 disposed between the first photosensitive layer and the light source for exposing the first photosensitive layer can absorb light of dominant wavelength λ2 that has been transmitted through the second photosensitive layer and the substrate, as well as light of dominant wavelength λ2 reflected by components such as wavelength-selective filters. Therefore, the resolution degradation caused by reexposure of the second photosensitive layer can be suppressed. On the other hand, the component for absorbing light of dominant wavelength λ1 disposed between the second photosensitive layer and the light source for exposing the second photosensitive layer can absorb light of dominant wavelength λ1 that has been transmitted through the first photosensitive layer and the substrate, as well as light of dominant wavelength λ1 reflected by components such as wavelength-selective filters. Therefore, the resolution degradation caused by reexposure of the first photosensitive layer can be suppressed. The above-described embodiments include the following (1) to (3). Among the following (1) to (3), (3) is preferred.

[0638] (1) A component for absorbing light with a dominant wavelength λ2 is disposed between the first photosensitive layer and the light source for exposing the first photosensitive layer.

[0639] (2) A component for absorbing light of the dominant wavelength λ1 is disposed between the second photosensitive layer and the light source used to expose the second photosensitive layer.

[0640] (3) A component for absorbing light of dominant wavelength λ2 is disposed between the first photosensitive layer and the light source for exposing the first photosensitive layer, and a component for absorbing light of dominant wavelength λ1 is disposed between the second photosensitive layer and the light source for exposing the second photosensitive layer.

[0641] The component absorbing light of dominant wavelength λ1 is preferably a material containing light that absorbs dominant wavelength λ1. The component absorbing light of dominant wavelength λ2 is preferably a material containing light that absorbs dominant wavelength λ2. For example, the material described in the "Light Absorption Characteristics" section above can be cited as a material absorbing dominant wavelength λ1 or dominant wavelength λ2. The preferred method for the material absorbing dominant wavelength λ1 or dominant wavelength λ2 is the same as the preferred method described in the "Light Absorption Characteristics" section above. Furthermore, either the component absorbing dominant wavelength λ2 or the component absorbing dominant wavelength λ1 is preferably a component containing a material that has absorption in the wavelength region of 400 nm or higher. For example, the material described in the "Light Absorption Characteristics" section above can be cited as a material having absorption in the wavelength region of 400 nm or higher. The preferred method for a substance having absorption in the wavelength region above 400 nm is the same as the preferred method for a substance having absorption in the wavelength region above 400 nm described in the "Light Absorption Characteristics" section above.

[0642] The content of the substance that absorbs light of dominant wavelength λ1 or dominant wavelength λ2 is determined, for example, within a range that will not affect the exposure sensitivity. The lower limit of the content of the substance that absorbs light of dominant wavelength λ1 or dominant wavelength λ2 is determined, for example, within the range described in the "Light Absorption Characteristics" section above.

[0643] In the pattern forming method of the present invention, the exposure step (1) and the exposure step (2) can be performed simultaneously. Alternatively, the exposure step (1) and the exposure step (2) can be performed separately. The exposure step (2) can be performed before the exposure step (1). Furthermore, the exposure step (2) can be performed after the exposure step (1). From a productive point of view, it is preferable that the exposure step (1) and the exposure step (2) are performed simultaneously.

[0644] In this invention, "the process of simultaneously exposing the first photosensitive layer (exposure process (1)) and the process of exposing the second photosensitive layer (exposure process (2))" is not limited to the case where the exposure of the first photosensitive layer and the exposure of the second photosensitive layer are performed completely simultaneously, and also includes the case where the period of exposing the first photosensitive layer and the period of exposing the second photosensitive layer are repeated.

[0645] In this invention, “the process of exposing the first photosensitive layer (exposure process (1)) and the process of exposing the second photosensitive layer (exposure process (2))” means that the first photosensitive layer and the second photosensitive layer are exposed separately within a range in which the exposure period of the first photosensitive layer and the exposure period of the second photosensitive layer do not overlap.

[0646] Developing Process (1)

[0647] The pattern forming method of the present invention includes a step of developing an exposed first photosensitive layer to form a first resin pattern (developing step (1)). In the developing step (1), for example, the first resin pattern can be formed by removing a portion of the exposed first photosensitive layer that is relatively soluble in the developer.

[0648] In this invention, "the first photosensitive layer that has been exposed" refers to the first photosensitive layer that has undergone the exposure process (1), and is not limited to the exposed part of the first photosensitive layer.

[0649] There are no restrictions on the development method; known methods can be used. For example, a developing solution can be used to develop the first photosensitive layer.

[0650] There are no limitations on the developer used; any known developer can be used. For example, the developer described in Japanese Patent Application Publication No. 5-72724 can be cited as an example. For example, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 can be cited as a preferred developer.

[0651] The developer is preferably an alkaline aqueous solution containing a compound with a pKa of 7 to 13. In the above-mentioned alkaline aqueous solution developer, the concentration of the compound with a pKa of 7 to 13 is preferably 0.05 mol / L to 5 mol / L.

[0652] The developer may contain, for example, an organic solvent that is miscible with water and a surfactant as other components besides those mentioned above.

[0653] The preferred temperature for the developer is 20℃ to 40℃.

[0654] There are no restrictions on the development method, and known methods can be used. Examples of development methods include spin-dip development, spray development, spray and spin development, and immersion development.

[0655] As an example of a development method, spray development will be explained. For example, when the first photosensitive layer is a negative photosensitive layer, spray development solution is applied to the exposed first photosensitive layer, thereby removing the unexposed areas of the first photosensitive layer. Furthermore, after development, it is preferable to remove development residue while spraying cleaning agent or the like and wiping with a brush.

[0656] The developing process (1) may include a process of heat-treating the first resin pattern (also known as "post-drying").

[0657] The heat treatment is preferably carried out in an environment of 8.1 kPa to 121.6 kPa, more preferably in an environment of 8.1 kPa to 114.6 kPa, and especially preferably in an environment of 8.1 kPa to 101.3 kPa.

[0658] The preferred temperature for heat treatment is 20℃ to 250℃, more preferably 30℃ to 170℃, and especially preferably 50℃ to 150℃.

[0659] The heat treatment time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and especially preferably 2 minutes to 4 minutes.

[0660] Heat treatment can be carried out in an air environment or in a nitrogen-substituted environment.

[0661] Developing Process (2)

[0662] The pattern forming method of the present invention includes a step of developing an exposed second photosensitive layer to form a second resin pattern (developing step (2)). In the developing step (2), for example, the second resin pattern can be formed by removing a portion of the exposed second photosensitive layer that is relatively soluble in the developer.

[0663] In this invention, "the exposed second photosensitive layer" refers to the second photosensitive layer after the exposure process (2), and is not limited to the exposed part of the second photosensitive layer.

[0664] There are no restrictions on the development method; known methods can be used. For example, a developing solution can be used to develop the second photosensitive layer.

[0665] There are no limitations on the developer used; any known developer can be used. For example, the developer described in Japanese Patent Application Publication No. 5-72724 can be cited as an example. For example, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 can be cited as a preferred developer.

[0666] The developer is preferably an alkaline aqueous solution containing a compound with a pKa of 7 to 13. In the above-mentioned alkaline aqueous solution developer, the concentration of the compound with a pKa of 7 to 13 is preferably 0.05 mol / L to 5 mol / L.

[0667] The developer may contain, for example, an organic solvent that is miscible with water and a surfactant as other components besides those mentioned above.

[0668] The preferred temperature for the developer is 20℃ to 40℃.

[0669] There are no restrictions on the development method, and known methods can be used. Examples of development methods include spin-dip development, spray development, spray and spin development, and immersion development.

[0670] As an example of a development method, spray development will be explained. For example, when the second photosensitive layer is a negative photosensitive layer, spray development solution is applied to the exposed second photosensitive layer, thereby removing the unexposed areas of the second photosensitive layer. Furthermore, after development, it is preferable to remove development residue while spraying cleaning agent or the like with a brush.

[0671] The developing process (2) may include a process of heat-treating the second resin pattern (also known as "post-drying").

[0672] The heat treatment is preferably carried out in an environment of 8.1 kPa to 121.6 kPa, more preferably in an environment of 8.1 kPa to 114.6 kPa, and especially preferably in an environment of 8.1 kPa to 101.3 kPa.

[0673] The preferred temperature for heat treatment is 20℃ to 250℃, more preferably 30℃ to 170℃, and especially preferably 50℃ to 150℃.

[0674] The heat treatment time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and especially preferably 2 minutes to 4 minutes.

[0675] Heat treatment can be carried out in an air environment or in a nitrogen-substituted environment.

[0676] In the pattern forming method of the present invention, the developing step (1) and the developing step (2) can be performed simultaneously. Alternatively, the developing step (1) and the developing step (2) can be performed separately. The developing step (2) can be performed before the developing step (1). Furthermore, the developing step (2) can be performed after the developing step (1). From a productive point of view, it is preferable that the developing step (1) and the developing step (2) are performed simultaneously.

[0677] In this invention, "simultaneously performing the process of developing the first exposed photosensitive layer to form a first resin pattern (development process (1)) and the process of developing the second exposed photosensitive layer to form a second resin pattern (development process (2))" is not limited to the case where the development of the first photosensitive layer and the development of the second photosensitive layer are performed completely simultaneously, including the case where the period of developing the first photosensitive layer and the period of developing the second photosensitive layer are repeated.

[0678] In this invention, “the process of developing the first exposed photosensitive layer to form a first resin pattern (development process (1)) and the process of developing the second exposed photosensitive layer to form a second resin pattern (development process (2))” means that the first photosensitive layer and the second photosensitive layer are developed separately within a range where the period of developing the first photosensitive layer and the period of developing the second photosensitive layer do not overlap.

[0679] In one embodiment, it is preferable to perform the exposure process (1) and the exposure process (2) simultaneously, and to perform the development process (1) and the development process (2) simultaneously. By performing the exposure process (1) and the exposure process (2) simultaneously, and to perform the development process (1) and the development process (2) simultaneously, the time and environment from exposure to the start of development can be the same, thus making it easier to stabilize product quality. In addition, it can shorten the process length and reduce process costs. On the other hand, in one embodiment, it is preferable to perform the exposure process (1) and the exposure process (2) separately, or to perform the development process (1) and the development process (2) separately. For example, when the reaction speeds of the first photosensitive layer and the second photosensitive layer after exposure are significantly different, or when different exposure light sources need to be arranged far away from the photosensitive layer, it is preferable to perform the exposure process (1) and the exposure process (2) separately. Furthermore, for example, when the developing solution used for developing the first photosensitive layer is different from the developing solution used for developing the second photosensitive layer, it is preferable to perform the development process (1) and the development process (2) separately.

[0680] Etching Process

[0681] When a conductive layer is disposed on at least one side of a substrate, the pattern forming method according to the present invention preferably includes a step of etching the conductive layer using at least one of a first resin pattern and a second resin pattern as a mask (hereinafter, sometimes referred to as an "etching step"). By including the etching step in the pattern forming method according to the present invention, a conductive pattern can be formed on at least one side of the substrate. For example, when the conductive layer is etched using the first resin pattern as a mask, the conductive layer covered by the first resin pattern remains on the substrate as a conductive pattern. On the other hand, the conductive layer not covered by the first resin pattern is removed.

[0682] For example, dry etching and wet etching can be cited as etching methods. Since no vacuum process is required and the process is simple, wet etching is preferred. As an example of etching, the method described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155 can also be cited.

[0683] Examples of etching solutions used in wet etching include acidic and alkaline etching solutions.

[0684] Examples of acidic etching solutions include aqueous solutions containing acidic components (e.g., hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and phosphoric acid) and aqueous solutions containing acidic components and salts (e.g., ferric chloride, ammonium fluoride, ferric nitrate, and potassium permanganate). Acidic etching solutions may contain a single acidic component or two or more acidic components. Acidic etching solutions may contain a single salt or two or more salts.

[0685] Examples of alkaline etching solutions include, for instance, aqueous solutions containing alkaline components (e.g., sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide)) and aqueous solutions containing both alkaline components and salts (e.g., potassium permanganate). Alkaline etching solutions may contain a single alkaline component or two or more alkaline components. Alkaline etching solutions may contain a single salt or two or more salts.

[0686] From the viewpoint of controlling the etching rate, the etching solution may contain a rust inhibitor. Examples of rust inhibitors include nitrogen-containing compounds. Examples of nitrogen-containing compounds include triazole compounds, imidazole compounds, and tetraazole compounds.

[0687] From the perspective of controlling the etching rate, the etching solution may contain surfactants, organic solvents, chelating agents, antioxidants, pH adjusters, etc.

[0688] The temperature of the etching solution is preferably below 45°C.

[0689] In the pattern forming method of the present invention, it is preferable that the first resin pattern, which can be used as a mask, and the second resin pattern, which can be used as a mask, both exhibit excellent resistance to etching solutions at temperatures below 60°C. Because the first and second resin patterns possess the aforementioned resistance, it is possible to prevent their removal during the etching process. As a result, portions of the conductive layer lacking the first and second resin patterns are selectively etched.

[0690] When conductive layers are disposed on both sides of a substrate, the conductive layer on one side of the substrate can be etched first, and then the conductive layer on the other side of the substrate can be etched, or the conductive layers on both sides of the substrate can be etched simultaneously. From a production point of view, it is preferable to etch the conductive layers on both sides of the substrate simultaneously when conductive layers are disposed on both sides of the substrate.

[0691] Cleaning and drying processes

[0692] In the pattern forming method of the present invention, from the viewpoint of preventing contamination of the production line, a cleaning process and a drying process may be included as needed after the above-mentioned etching process.

[0693] In the cleaning process, for example, the substrate can be cleaned with pure water at room temperature (e.g., 25°C). The cleaning time can be appropriately set in the range of 10 seconds to 300 seconds.

[0694] In the drying process, for example, a blower can be used to dry the substrate. The blower pressure is preferably 0.1 kg / cm². 2 ~5kg / cm 2 .

[0695] Full-area exposure process

[0696] The pattern forming method of the present invention may include a step of exposing at least one of a first resin pattern and a second resin pattern to a full-surface area (hereinafter, sometimes referred to as the "full-surface exposure step"). The full-surface exposure step is preferably performed before the removal step described later. By including the full-surface exposure step in the pattern forming method of the present invention, the removability of the resin pattern in the subsequent removal step can be improved, and the reactivity of the residual pattern after development can be further improved. For example, by performing full-surface exposure on a resin pattern formed using a positive photosensitive layer, the removability in the subsequent removal step is further improved. For example, by performing full-surface exposure on a resin pattern formed using a negative photosensitive layer, curing is further advanced, and the resistance of the resin pattern to the process is improved.

[0697] In the full-surface exposure process, it is sufficient to expose at least one of the first resin pattern and the second resin pattern. For example, when the first resin pattern is fully exposed, the portion without the first resin pattern may or may not be exposed. Similarly, when the second resin pattern is fully exposed, the portion without the second resin pattern may or may not be exposed.

[0698] In the whole-surface exposure process, from the point of view of simplicity, it is preferable to expose the entire surface of the substrate.

[0699] There are no restrictions on the light source used for exposure; any known light source can be used. Examples of light sources for exposure include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and light-emitting diodes (LEDs).

[0700] From the viewpoint of removal, the exposure wavelength is preferably 365 nm or 405 nm.

[0701] From the perspective of removal, the preferred exposure level is 5 mJ / cm. 2~1,000mJ / cm 2 More preferably 10 mJ / cm 2 ~800mJ / cm 2 The preferred value is 100 mJ / cm. 2 ~500mJ / cm 2 .

[0702] From the viewpoint of removal, the exposure amount is preferably greater than the exposure amount in at least one of the exposure steps (1) and (2), and more preferably greater than the exposure amount in at least one of the exposure steps (1) and (2).

[0703] The optimal exposure illuminance is 5mW / cm². 2 ~25,000mW / cm 2 More preferably 20mW / cm 2 ~20,000mW / cm 2 The preferred value is 30mW / cm. 2 ~15,000mW / cm 2 The time required for full-area exposure can be shortened by increasing the illuminance.

[0704] Heating Process

[0705] In the pattern forming method of the present invention, at least one of the first resin pattern and the second resin pattern may be heated (hereinafter, sometimes referred to as the "heating step") between full-area exposure steps and before the full-area exposure step and the removal step described later. By including the heating step in the pattern forming method of the present invention, the first resin pattern and the second resin pattern can be easily removed. For example, in resin patterns formed using a positive photosensitive layer, the reaction rate of the photoacid generator and the reaction rate of the acid with the positive photosensitive composition can be increased, thus improving removal performance.

[0706] There are no limitations on the heating device; any known heating device can be used. Examples of heating devices include infrared heaters, hot blowers, and convection ovens.

[0707] From the viewpoint of removal, the heating temperature is preferably 30°C to 100°C, more preferably 30°C to 80°C, and especially preferably 30°C to 60°C.

[0708] From the viewpoint of removability, the heating time is preferably 1 to 600 seconds, more preferably 1 to 120 seconds, and particularly preferably 5 to 60 seconds. Here, "heating time" refers to the time calculated from when the substrate surface reaches the set temperature, excluding the time during the heating period.

[0709] The heating atmosphere is preferably air (relative humidity: 10%RH to 90%RH). The heating atmosphere can also be a non-reactive gas (e.g., nitrogen and argon).

[0710] The preferred pressure is atmospheric pressure.

[0711] In cases where a large amount of water adheres to the substrate, from the viewpoint of improving heating efficiency, a process of blowing away excess water using an air knife or the like can be combined at least one of the above-mentioned heating processes, before and during the heating process.

[0712] Removal Process

[0713] The pattern forming method of the present invention may include a step of removing at least one of a first resin pattern and a second resin pattern (hereinafter, sometimes referred to as a "removal step"). Hereinafter, the first resin pattern and the second resin pattern are sometimes collectively referred to as "resin pattern". Unless otherwise specified, the term "resin pattern" includes either the first resin pattern or the second resin pattern, or both the first resin pattern and the second resin pattern.

[0714] One method for removing resin patterns is, for example, using chemicals. When using chemicals to remove resin patterns, the resin pattern can be dissolved in the chemicals or dispersed within them.

[0715] The preferred method for removing resin patterns is to use a removal solution. For example, the resin pattern can be removed by immersing the substrate with the resin pattern in the removal solution.

[0716] The temperature of the removal liquid is preferably 30℃~80℃, more preferably 50℃~80℃.

[0717] The soaking time in the removal solution is preferably 1 to 30 minutes.

[0718] From the viewpoint of removal, the removal liquid preferably contains 30% by mass or more of water, more preferably 50% by mass or more of water, and especially preferably 70% by mass or more of water.

[0719] The removal solution preferably contains an inorganic base or an organic base. Examples of inorganic bases include sodium hydroxide and potassium hydroxide. Examples of organic bases include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0720] From the viewpoint of removal, the removal solution preferably contains an organic base component, and more preferably contains an amine compound.

[0721] From the viewpoint of removal, the content of organic base components is preferably 0.01% to 20% by mass, more preferably 0.1% to 10% by mass, relative to the total mass of the removal liquid.

[0722] From the viewpoint of removal, the removal solution preferably contains a surfactant. There are no limitations on the surfactant used; known surfactants can be employed.

[0723] From the viewpoint of removal, the surfactant content is preferably 0.1% to 10% by mass relative to the total mass of the removal liquid.

[0724] The removal solution preferably contains a water-soluble organic solvent. Examples of water-soluble organic solvents include dimethyl sulfoxide, lower alcohols, ethylene glycol ethers, and N-methylpyrrolidone.

[0725] Methods for bringing the removal liquid into contact with the resin pattern during the removal process include, for example, spraying, spraying and immersion.

[0726] As a removal liquid, the stripping liquids described in Japanese Patent Application Publication No. 11-021483, Japanese Patent Application Publication No. 2002-129067, Japanese Patent Application Publication No. 07-028254, Japanese Patent Application Publication No. 2001-188363, Japanese Patent Application Publication No. 04-048633 and Japanese Patent No. 5318773 can also be used.

[0727] The removal of the first resin pattern and the removal of the second resin pattern can be performed simultaneously or separately. From a production point of view, it is preferable to remove the first resin pattern and the second resin pattern simultaneously.

[0728] Roll-to-roll method

[0729] The pattern forming method of the present invention is preferably performed by a roll-to-roll method. There are no limitations on the roll-to-roll method, and known roll-to-roll methods can be used. For example, in the pattern forming method of the present invention, at least one step of unwinding the substrate and at least one step of winding the substrate are respectively provided before and after at least one step, thereby enabling processing while the substrate is being transported.

[0730] Other processes

[0731] The pattern forming method of the present invention may include steps other than those described above. Examples of steps other than those described above include the following.

[0732] [Process for reducing visible light reflectivity]

[0733] When the substrate has a conductive layer, the pattern forming method according to the present invention may include a step of performing a process to reduce the visible light reflectivity of part or all of the conductive layer.

[0734] As a method to reduce visible light reflectivity, oxidation is an example. For instance, when the conductive layer contains copper, oxidizing the copper to produce copper oxide can reduce the visible light reflectivity of the conductive layer.

[0735] Preferred methods for reducing visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, and these contents are incorporated herein by reference.

[0736] <Manufacturing Method of Circuit Board>

[0737] The method for manufacturing a circuit board according to the present invention includes the pattern forming method according to the present invention. The method for manufacturing a circuit board according to the present invention has the above-described structure, thereby enabling the use of a pattern forming method that can suppress the generation of exposure fog and form resin patterns with excellent resolution. For example, by using the resin pattern as an etching mask, a highly fine conductive pattern can be formed. Furthermore, for example, the resin pattern can also be used as a protective film for a conductive layer.

[0738] Regarding the pattern forming method used in the manufacturing method of the circuit board involved in this invention, as described in the above-mentioned "pattern forming method" item, the preferred embodiment is also the same.

[0739] Examples of circuit boards include printed circuit boards and touch panel sensors.

[0740] <Layered Body>

[0741] The laminate involved in this invention comprises a first photosensitive layer, a substrate, and a second photosensitive layer in sequence, and has the following characteristics A and B.

[0742] Feature A: When the maximum sensitivity wavelength of the first photosensitive layer is set to λ m1 The maximum sensitivity wavelength of the second photosensitive layer is set to λ. m2 When λ is satisfied m1 ≠λ m2 The relationship is as follows. The maximum sensitivity wavelength refers to the minimum exposure required for the photosensitive layer to react at each wavelength of light, which is considered the wavelength with the lowest spectral sensitivity and minimum exposure.

[0743] Characteristic B: The above-mentioned substrate relative to the above-mentioned wavelength λ m1and λ m2 The light has a transmittance of at least 50%.

[0744] Furthermore, the maximum sensitivity wavelength can be determined, for example, as follows: When the photosensitive layer is irradiated with light of a specific wavelength using a Stouffer 4105 step exposure meter, the minimum exposure amount at which the photosensitive material reacts is set as Emin. By changing the irradiated wavelength, a spectral sensitivity curve can be obtained. Emin varies for each wavelength, therefore the wavelength at which the minimum value is taken is the maximum sensitivity wavelength.

[0745] In a negative photosensitive layer, the lowest exposure level remaining in the exposed area can be defined as Emin. On the other hand, in a positive photosensitive layer, the lowest exposure level after the exposed area is removed can be defined as Emin.

[0746] Furthermore, when the light source, such as a high-pressure mercury lamp, has a discrete light intensity distribution (e.g., gamma rays, h-rays, i-rays), and when filters are used to control the wavelength of the irradiated light, the wavelength with the highest sensitivity among the light actually incident on the photosensitive material is set as the maximum sensitivity wavelength. For example, the minimum value in the spectral sensitivity curve of a photosensitive material is at 290 nm, and the second value is at 365 nm (i-rays). Since a high-pressure mercury lamp practically emits almost no light at 290 nm, 365 nm becomes the maximum sensitivity wavelength when exposing the photosensitive material using a high-pressure mercury lamp.

[0747] The laminate involved in this invention is in the manner described above, thereby suppressing the generation of exposure fog and forming resin patterns with excellent resolution.

[0748] The reason why the laminate involved in this invention achieves the above-mentioned effect is speculated as follows. As mentioned above, if ultraviolet absorbing materials are used to increase the optical concentration of the photosensitive layer in order to suppress the generation of exposure fog, the resolution of the obtained resin pattern may be degraded. On the other hand, the pattern forming method involved in this invention includes a preparation step, an exposure step (1), an exposure step (2), and a development step (1), wherein the maximum sensitivity wavelength λ of the first photosensitive layer is... m1 With the maximum sensitivity wavelength λ of the second photosensitive layer m2 They are different from each other, therefore even if the above-mentioned substrates are relative to the above-mentioned wavelength λ m1 and λ m2 The light has a transmittance of at least 50%, and the first and second photosensitive layers can be selectively or preferentially exposed, respectively. Therefore, the laminate of the present invention can suppress the formation of exposure fog and form resin patterns with excellent resolution.

[0749] Except as described below, the preferred embodiments of the first photosensitive layer, the substrate, and the second photosensitive layer in the laminate are the same as those of the preferred embodiments of the first photosensitive layer, the substrate, and the second photosensitive layer in the pattern forming method.

[0750] Furthermore, in addition to the following description, the aforementioned wavelength λ in the laminate... m1 and λ m2 The preferred method is to replace the main wavelengths λ1 and λ2 with the aforementioned wavelengths λ in the preferred method of the pattern forming method. m1 and λ m2 The preferred method is the same.

[0751] From the perspective of suppressing exposure haze, the aforementioned wavelength λ m1 Preferably, it is in the range of more than 395nm and less than 500nm, more preferably in the range of more than 396nm and less than 456nm.

[0752] From the perspective of suppressing exposure haze, the aforementioned wavelength λ m2 Preferably, it is in the range of 250nm or more and 395nm or less, more preferably in the range of 335nm or more and 395nm or less.

[0753] Furthermore, from the viewpoint of suppressing exposure fog, the aforementioned wavelength λ is even more preferred. m1 Within the range of wavelengths exceeding 395 nm but below 500 nm, and the aforementioned wavelength λ m2 In the range of 250 nm and above to 395 nm, the above-mentioned wavelength λ is particularly preferred. m1 Within the range of 396 nm and 456 nm, and the aforementioned wavelength λ m2 Within the range of 335nm and above and 395nm and below.

[0754] From the viewpoint of suppressing exposure haze and improving resolution, the aforementioned first photosensitive layer is preferably composed of a layer that absorbs the aforementioned wavelength λ. m2 The substance of light.

[0755] Furthermore, from the viewpoint of suppressing exposure haze and improving resolution, the wavelength λ in the aforementioned first photosensitive layer... m2 The light transmittance is preferably 70% or less, more preferably 50% or less, even more preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. Furthermore, the lower limit of the above transmittance is 0%.

[0756] From the viewpoint of suppressing exposure haze and improving resolution, the second photosensitive layer is preferably composed of a layer that absorbs the wavelength λ. m1 The substance of light.

[0757] Furthermore, from the viewpoint of suppressing exposure haze and improving resolution, the wavelength λ in the aforementioned second photosensitive layer... m1 The light transmittance is preferably 70% or less, more preferably 50% or less, even more preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. Furthermore, the lower limit of the above transmittance is 0%.

[0758] As the absorption wavelength λ mentioned above m2 The light-emitting material and its absorption at the wavelength λ mentioned above. m1 The light-absorbing material is the same as the light-absorbing material with dominant wavelength λ2 and the light-absorbing material with dominant wavelength λ1 mentioned above, and the preferred method is also the same.

[0759] Regarding the first photosensitive layer and the second photosensitive layer mentioned above, from the viewpoint of suppressing exposure haze and improving resolution, it is preferable to satisfy the following relationships C and D.

[0760] Relation C: 3≤(S) m12 / S m11 )

[0761] Relation D: 3≤(S) m21 / S m22 )

[0762] Among them, S m12 This indicates that, relative to the wavelength λ mentioned above... m2 The spectral sensitivity of the first photosensitive layer mentioned above, S m11 This indicates that, relative to the wavelength λ mentioned above... m1 The spectral sensitivity of the first photosensitive layer mentioned above, S m21 This indicates that, relative to the wavelength λ mentioned above... m1 The spectral sensitivity of the aforementioned second photosensitive layer, S m22 This indicates that, relative to the wavelength λ mentioned above... m2 The spectral sensitivity of the aforementioned second photosensitive layer.

[0763] As S m12 / S m11 The value of S m21 / S m22 The value of is preferably 3 or more, more preferably 4 or more, and especially preferably 5 or more. m12 / S m11 The value of S m21 / S m22 There is no particular upper limit to the value of λ; as long as the photosensitive layer possesses appropriate properties, it can be set to any value. A photosensitive layer with such properties can be adjusted relative to the aforementioned wavelength λ. m1 and the aforementioned wavelength λ m2 The absorption coefficient of each photosensitive layer is obtained by measuring its light absorption coefficient.

[0764] Example

[0765] The present invention will now be described in detail through examples. Unless otherwise specified, "parts" and "%" refer to quantities based on quality.

[0766] <Terminology>

[0767] The following abbreviations represent the following compounds.

[0768] "MAA": Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0769] "MMA": Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0770] “PGMEA”: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[0771] "St": Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0772] “V-601”: 2,2'-Azobis(2-methylpropionic acid)dimethyl (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0773] <Synthesis of Polymer B-1>

[0774] Propylene glycol monomethyl ether acetate (PGMEA, SHOWA DENKO KK, 116.5 parts by mass) was placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. Over 2 hours, a solution containing St (52.0 parts by mass), MMA (19.0 parts by mass), MAA (29.0 parts by mass), V-601 (4.0 parts by mass), and PGMEA (116.5 parts by mass) was added dropwise to the solution in the three-necked flask, which was maintained at 90°C ± 2°C. After the addition was complete, the mixture was stirred at 90°C ± 2°C for 2 hours to obtain polymer B-1 (solid content concentration: 30% by mass, molecular weight: 70,000, glass transition temperature: 131°C, acid value: 189 mg KOH / g).

[0775] <Examples 1 to 12 and Comparative Example 1>

[0776] Resin patterns were formed on both sides of the substrate using the following method.

[0777] [Preparation of transfer materials]

[0778] Using a slit nozzle, a photosensitive layer forming composition having the composition described in Table 1 was coated onto a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%). A photosensitive layer was formed by drying the photosensitive layer forming composition on the temporary support in a convection oven at 100°C for 2 minutes. A transfer material was prepared by laminating a protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) onto the photosensitive layer. The amounts (addition amounts) of each component described in Table 1 are in parts by mass.

[0779] [Creating Layered Objects]

[0780] After the transfer material selected according to Table 2 was cut into 50cm squares, the protective film was peeled off from the transfer material. Next, under lamination conditions of a roller temperature of 90°C, a linear pressure of 0.8MPa, and a linear speed of 3.0m / min, the transfer material was bonded to both sides of a substrate (polyethylene terephthalate film, thickness: 40μm). Specifically, the transfer material for forming the first photosensitive layer was bonded to one side of the substrate, and the transfer material for forming the second photosensitive layer was bonded to the other side of the substrate. A laminate was fabricated through these steps.

[0781] [Pattern Formation]

[0782] Without peeling off the temporary support, glass masks (duty ratio 1:1) with line and spatial patterns of 3μm to 40μm linewidth are respectively abutted against both sides of the laminate. Glass masks are positioned on both sides of the laminate such that the line patterns of the glass masks are orthogonal when viewed from above. Next, the first photosensitive layer and the second photosensitive layer are simultaneously exposed. During simultaneous exposure of the first and second photosensitive layers, the first photosensitive layer is exposed from the side where it is positioned relative to the substrate, and the second photosensitive layer is exposed from the side where it is positioned relative to the substrate.

[0783] The exposure conditions for each layer are determined as follows.

[0784] First photosensitive layer: After the first photosensitive layer is exposed through the glass mask under exposure conditions excluding 365nm, it is left to stand for 1 hour after exposure. During development, the exposure amount is set to be such that the residual pattern width is in the range of 49.0 micrometers to 51.0 micrometers in the patterned area with a line width of 50 micrometers and a space width of 50 micrometers.

[0785] Second photosensitive layer: After the second photosensitive layer is exposed through the glass mask under exposure conditions excluding 405nm, it is left to stand for 1 hour after exposure. During development, the exposure amount is set to be such that the residual pattern width is in the range of 49.0 micrometers to 51.0 micrometers in the patterned area with a line width of 50 micrometers and a space width of 50 micrometers.

[0786] In addition, the meanings of the above statements "excluding exposure conditions at 365nm" and "excluding exposure conditions at 405nm" are as follows.

[0787] "Exposure conditions excluding 365nm": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIO INC.) via a short-wavelength cutoff filter (model: LUO400, cutoff wavelength: 400nm, manufactured by Asahi Spectra Co., Ltd.). The dominant wavelength was 405nm. With the dominant wavelength intensity set to 100%, the intensity at wavelength 365nm was less than 0.5%.

[0788] "Exposure conditions excluding 405nm": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIO INC.) via a mercury exposure bandpass filter (model: HB0365, center wavelength: 365nm, manufactured by Asahi Spectra Co., Ltd.). The dominant wavelength was 365nm. With the dominant wavelength intensity set to 100%, the intensity at wavelength 405nm was less than 0.5%.

[0789] Furthermore, excluding the 365nm exposure condition, the exposure amount was measured using a lux meter (UIT-250, manufactured by USHIO INC.) with a 405nm photodetector (UVD-C405, manufactured by USHIO INC.) and via the aforementioned LU0400 cutoff filter. Excluding the 405nm exposure condition, the exposure amount was measured using a lux meter with a 365nm photodetector (UVD-C365, manufactured by USHIO INC.) and via the aforementioned bandpass filter (HB0365).

[0790] After exposure and a one-hour resting period, the temporary support was peeled off, and then a resin pattern was formed through development. For development, a 1.0% potassium carbonate aqueous solution (developer) at 28°C was used for spray development for 30 seconds. Both the first and second photosensitive layers were developed simultaneously.

[0791] <Evaluation>

[0792] Using substrates with resin patterns prepared in Examples 1 to 12 and Comparative Example 1, resolution and exposure haze were evaluated respectively. The evaluation results are shown in Table 2.

[0793] [Discrimination]

[0794] The linewidth of the highest resolution pattern in the resin pattern was set to achieve the required resolution. Resolution was evaluated based on the following criteria according to the achieved resolution. Furthermore, resolution was not possible in cases where the sidewalls of the pattern were severely rough, or where obvious folds were present and connected to adjacent line patterns.

[0795] (Benchmark)

[0796] A: Below 20μm

[0797] B: Greater than 20μm and less than 30μm

[0798] C: Exceeding 30μm or unable to be resolved

[0799] [Exposure Fog]

[0800] The non-exposed areas on the surface of the substrate with the resin pattern (limited to the exposed portion of the substrate surface on the side opposite to the non-exposed area; the same applies hereafter) were observed, and exposure haze was evaluated according to the following criteria. If exposure haze occurs, residue originating from the photosensitive layer is observed in the aforementioned non-exposed areas.

[0801] (Benchmark)

[0802] A: When observed using an optical microscope with a magnification of 50x, no residue was observed on either the side with the first photosensitive layer arranged relative to the substrate or the side with the second photosensitive layer arranged relative to the substrate.

[0803] B: When observed using an optical microscope with a magnification of 50x, residue is observed on at least one of the sides on which the first photosensitive layer is disposed with reference to the substrate and the side on which the second photosensitive layer is disposed with reference to the substrate.

[0804] <Sensitivity Measurement>

[0805] [E 1r / E2 and E 2r / E1]

[0806] For a laminate produced according to the method described above in [Fabrication of Laminated ... 1r Based on the obtained E 1r E was calculated from the exposure amount E2 of the second photosensitive layer recorded in Table 2. 1r / E2. In the same manner, E was also calculated for the second photosensitive layer. 2r / E1. The measurement results are shown in Table 2.

[0807] [S 12 / S 11 and S 21 / S22 ]

[0808] For the laminate produced according to the method described above in [Fabrication of Laminates], the spectral sensitivity was determined by exposing it under the following conditions using a 15-step exposure tablet (manufactured by FUJIFILM Corporation).

[0809] S 11 The minimum exposure required to produce a residual film after development following exposure of the first photosensitive layer under conditions excluding 365nm.

[0810] S 12 The minimum exposure level required to produce a residual film after development following exposure of the first photosensitive layer under conditions excluding 405nm.

[0811] S 21 The minimum exposure required to produce a residual film after development following exposure of the second photosensitive layer under conditions excluding 365nm.

[0812] S 22 The minimum exposure required to produce a residual film after development following exposure of the second photosensitive layer under conditions excluding 405nm.

[0813] Calculate S based on the obtained value. 12 / S 11 and S 21 / S 22 The measurement results are shown in Table 2.

[0814] <Example 13>

[0815] [Preparation of thermoplastic resin composition 1]

[0816] Thermoplastic resin composition 1 was prepared by mixing the following components.

[0817] • A propylene glycol monomethyl ether acetate solution of a copolymer of benzyl methacrylate, methacrylic acid, and acrylic acid (solid content concentration: 30.0% by weight, Mw: 30,000, acid value: 153 mg KOH / g): 42.85 parts by weight

[0818] • NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.): 5.03 parts by weight

[0819] • 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO., LTD.): 2.31 parts by weight

[0820] • ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.): 0.77 parts by weight

[0821] Megaface F-552 (manufactured by DIC CORPORATION): 0.03 parts by weight

[0822] • Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.): 39.50 parts by weight

[0823] • Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK): 9.51 parts by weight

[0824] [Preparation of thermoplastic resin composition 2]

[0825] Thermoplastic resin composition 2 was prepared by mixing the following components.

[0826] • A propylene glycol monomethyl ether acetate solution of a copolymer of benzyl methacrylate, methacrylic acid, and acrylic acid (solid content concentration: 30.0% by weight, Mw: 30,000, acid value: 153 mg KOH / g): 42.85 parts by weight

[0827] • NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.33 parts by weight

[0828] • 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO., LTD.): 2.31 parts by weight

[0829] • ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.): 0.77 parts by weight

[0830] Megaface F-552 (manufactured by DIC CORPORATION): 0.03 parts by weight

[0831] • Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.): 39.50 parts by weight

[0832] • Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK): 9.51 parts by weight

[0833] • The following compound (a photoacid generator, a compound synthesized according to the method described in paragraph 0227 of Japanese Patent Application Publication No. 2013-47765): 0.32 parts by mass

[0834] [Chemical Formula 9]

[0835]

[0836] • Compounds with the structure shown below (pigments that develop color via acid): 0.08 parts by mass

[0837] [Chemical Formula 10]

[0838]

[0839] Solvent Yellow 56 (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.3 parts by weight

[0840] [Preparation of the Intermediate Layer Composition]

[0841] The following components were mixed to prepare the intermediate layer composition.

[0842] • KURARAY POVAL PVA-205 (manufactured by KURARAY CO., LTD.): 3.22 parts by weight

[0843] • Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.): 1.49 parts by weight

[0844] Megaface F-444 (manufactured by DIC CORPORATION): 0.0015 parts by weight

[0845] • Ion-exchanged water: 38.12 parts by weight

[0846] • Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.): 57.17 parts by weight

[0847] [Production of Transfer Material 6A]

[0848] Thermoplastic resin composition 1 was coated onto a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The resulting thermoplastic resin composition coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer. An intermediate layer composition was coated onto the resulting thermoplastic resin layer using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition coating was dried at 80°C for 40 seconds to form an intermediate layer. The photosensitive layer composition 4A described in Table 1 was coated onto the resulting intermediate layer using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The photosensitive layer was formed by drying in a convection oven at 100°C for 2 minutes. Transfer material 6A was fabricated by laminating a protective film (polypropylene film, thickness: 12μm, haze: 0.2%) onto the photosensitive layer.

[0849] [Making of Transfer Material 4B]

[0850] Thermoplastic resin composition 2 was coated onto a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The resulting thermoplastic resin composition coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer. An intermediate layer composition was coated onto the formed thermoplastic resin layer using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition coating was dried at 80°C for 40 seconds to form an intermediate layer. The photosensitive layer composition 3B described in Table 1 was coated onto the formed intermediate layer using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm, and dried in a convection oven at 100°C for 2 minutes to form a photosensitive layer. Transfer material 4B was fabricated by laminating a protective film (polypropylene film, thickness: 12μm, haze: 0.2%) onto the photosensitive layer.

[0851] [Creation, Pattern Formation, and Evaluation of Layered Objects]

[0852] Using transfer materials 6A and 4B, a substrate with a resin pattern was fabricated according to the methods described in the "Fabrication of Laminated Body" and "Pattern Formation" sections above. The resolution and exposure haze described in the "Evaluation" section above were evaluated using the obtained substrate with the resin pattern. The evaluation results are shown in Table 2.

[0853] [Sensitivity Measurement]

[0854] The sensitivity was measured according to the method described in the "Sensitivity Measurement" section above. The measurement results are shown in Table 2.

[0855] [Table 1]

[0856]

[0857] The following shows the details of each component listed in Table 1.

[0858] (polymer)

[0859] "Copolymer of benzyl methacrylate and methacrylic acid": Solid content concentration 30%, PGMEA solution

[0860] (Photoradical generator)

[0861] “B-CIM”: 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer (manufactured by Hampford Research Inc.)

[0862] "OXE-01": IRGACURE OXE-01 (manufactured by BASF Japan Ltd.)

[0863] "OXE-02": IRGACURE OXE-02 (manufactured by BASF Japan Ltd.)

[0864] "379EG": Omnirad 379EG (manufactured by IGM Resins BV)

[0865] "907": Omnirad 907 (manufactured by IGM Resins BV)

[0866] (Sensitizer)

[0867] "Sensitizer A": A compound represented by the following structural formula

[0868] [Chemical Formula 11]

[0869]

[0870] Sensitizer B: Coumarin 7 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0871] Sensitizer C: 4,4'-bis(dimethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0872] "Sensitizer D": 10-Butyl-2-chloroacridone (manufactured by KUROGANE KASEI Co., Ltd.)

[0873] "Sensitizer E": KAYACURE DETX-S (product name) (manufactured by Nippon Kayaku Co., Ltd.)

[0874] (Chain transfer agent)

[0875] "Chain Transfer Agent A": N-Phenylenocarbamoylmethyl-N-Carboxymethylaniline (manufactured by FUJIFILM Wako PureChemical Corporation)

[0876] [Polymerizing compounds]

[0877] “ARONIX M250”: Product name (manufactured by TOAGOSEI CO., LTD.)

[0878] "NK Ester BPE-500": Product name (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0879] (polymerization inhibitor)

[0880] "1-Phenylon-3-pyrazolone": Manufactured by FUJIFILM Wako Pure Chemical Corporation

[0881] Phenothiazine: Manufactured by FUJIFILM Wako Pure Chemical Corporation

[0882] (solvent)

[0883] “MEK”: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0884] “MeOH”: Methanol (manufactured by Mitsui Chemicals, Inc.)

[0885] (color material)

[0886] “LCV”: Colorless Crystal Violet (pigment, manufactured by YAMADA CHEMICAL CO., LTD.)

[0887] (UV absorber)

[0888] "UV Absorber A": Diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD.)

[0889] (Carbon black)

[0890] "Carbon Black Dispersion": Solid content concentration of 38% (manufactured by TOKYO PRINTING INK MFG CO., LTD.)

[0891] (surfactant)

[0892] "Megaface F552": Product Name (Manufactured by DIC CORPORATION)

[0893] "Megaface F551A": Product Name (Manufactured by DIC CORPORATION)

[0894] [Table 2]

[0895]

[0896] The laminates of Examples 1 to 13 satisfy characteristics A and B.

[0897] In Table 2, the following terms and symbols recorded in the "Exposure Conditions" column have the following meanings.

[0898] "Excluding 365nm": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIO INC.) via a short-wavelength cutoff filter (model: LUO400, cutoff wavelength: 400nm, manufactured by Asahi Spectra Co., Ltd.). The dominant wavelength was 405nm. With the dominant wavelength intensity set to 100%, the intensity at wavelength 365nm was less than 0.5%.

[0899] "Excluding 405nm": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIO INC.) via a mercury exposure bandpass filter (model: HB0365, center wavelength: 365nm, manufactured by Asahi Spectra Co., Ltd.). The dominant wavelength was 365nm. With the dominant wavelength intensity set to 100%, the intensity at wavelength 405nm was less than 0.5%.

[0900] "-": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIO INC.) without using a wavelength-selective filter.

[0901] In Examples 1 to 13, the dominant wavelengths of the exposure wavelengths in the process of exposing the first photosensitive layer and the second photosensitive layer are different from each other. On the other hand, in Comparative Example 1, the dominant wavelengths of the exposure wavelengths when exposing the first photosensitive layer and the second photosensitive layer are the same. Furthermore, in Comparative Example 1, both the first and second photosensitive layers contain carbon black as an ultraviolet absorbing material.

[0902] According to Table 2, in Examples 1 to 13, compared with Comparative Example 1, the generation of exposure fog can be suppressed and resin patterns with excellent resolution can be formed.

[0903] <Examples 14 to Examples 27>

[0904] [abbreviation]

[0905] The following abbreviations represent the following compounds.

[0906] "A-1": Propylene glycol monomethyl ether acetate solution of a copolymer of styrene / methacrylic acid / methyl methacrylate (solids concentration: 30.0% by mass, monomer ratio: 52% by mass / 29% by mass / 19% by mass, Mw: 70,000)

[0907] "A-2": Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid copolymer (solid content concentration: 30.0% by mass, monomer ratio: 80% by mass / 20% by mass, Mw: 30,000, acid value: 153 mg KOH / g)

[0908] "A-3": KURARAY POVAL PVA-205 (manufactured by KURARAY CO., LTD.)

[0909] “A-4”: Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.)

[0910] "B-1": BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0911] "B-2": M-270 (manufactured by TOAGOSEI CO., LTD.)

[0912] "B-3": NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0913] "B-4": 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO., LTD.)

[0914] “B-5”: ARONIXTO-2349 (manufactured by TOAGOSEI CO., LTD.)

[0915] "B-6": Manufactured by KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

[0916] "C-1": B-CIM (manufactured by KUROGANE KASEI Co., Ltd.)

[0917] "C-2": Omnirad 379EG (manufactured by IGM Resins BV)

[0918] "C-3": Irgacure OXE-01 (manufactured by BASF Japan Ltd.)

[0919] “C-4”: Sensitizer A

[0920] "C-5": Coumarin 7 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0921] “C-6”: 4,4'-bis(dimethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0922] “C-7”: 10-Butyl-2-chloroacridone (manufactured by KUROGANE KASEI Co., Ltd.)

[0923] "C-8": Irgacure OXE-02 (manufactured by BASF Japan Ltd.)

[0924] "D-1": TDP-G (manufactured by Kawaguchi Chemical Industry Co., LTD.)

[0925] “D-2”: 1-Phenylon-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0926] "E-1": Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0927] “E-2”: N-Phenylenocarbamoylmethyl-N-Carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0928] "E-3": Solvent Yellow 56 (manufactured by Tokyo Chemical Industry Co., Ltd., a substance that absorbs light at 405nm)

[0929] "E-4": Diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., a substance that absorbs light at 365nm).

[0930] "E-5": CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD)

[0931] "E-6": F-552 (manufactured by DIC CORPORATION)

[0932] "E-7": F-444 (manufactured by DIC CORPORATION)

[0933] "F-1": Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0934] "F-2": Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[0935] "F-3": Ion-exchanged water

[0936] "F-4": Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

[0937] [Preparation of thermoplastic resin compositions]

[0938] Thermoplastic resin compositions 1a to 3a were prepared by mixing the compounds selected according to the description in Table 3.

[0939] [Table 3]

[0940] Thermoplastic resin composition 1a 2a 3a A-2 42.85 42.02 42.15 B-3 5.03 5.03 5.03 B-4 2.31 2.31 2.31 B-5 0.77 0.77 0.77 E-3 - 0.25 - E-4 - - 0.10 E-6 0.03 0.03 0.03 F-1 39.50 40.08 40.10 F-2 9.51 9.51 9.51

[0941] [Preparation of the Intermediate Layer Composition]

[0942] Intermediate layer composition 2 was prepared by mixing the following compounds.

[0943] • A-3: 3.22 parts by weight

[0944] • A-4: 1.49 parts by weight

[0945] E-7: 0.0015 parts by weight

[0946] F-3: 38.12 parts by weight

[0947] F-4: 57.17 parts by weight

[0948] [Preparation of compositions for forming photosensitive layers]

[0949] Photosensitive resin compositions 6A-10A and 4B-8B were prepared by mixing the compounds selected according to the description in Table 4.

[0950] [Table 4]

[0951]

[0952] [Preparation of transfer materials]

[0953] According to Table 5, a thermoplastic resin composition was coated onto the surface of a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The thermoplastic resin composition was dried at 80°C for 40 seconds to form a thermoplastic resin layer.

[0954] Using a slit nozzle, intermediate layer composition 2 was applied to the surface of the thermoplastic resin layer with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. Intermediate layer composition 2 was dried at 80°C for 40 seconds to form the intermediate layer.

[0955] According to Table 5, a photosensitive resin composition was coated onto the surface of the intermediate layer using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The photosensitive resin composition was dried at 100°C for 2 minutes to form a photosensitive layer.

[0956] A protective film (polypropylene film, thickness: 12μm, haze: 0.2%) is disposed on the surface of the photosensitive layer.

[0957] The transfer material was prepared using the steps described above (see Table 5).

[0958] [Creating Layered Objects]

[0959] After the transfer material selected according to Table 5 was cut into 50cm squares, the protective film was peeled off from the transfer material. Next, under lamination conditions of a roller temperature of 90°C, a linear pressure of 0.8MPa, and a linear speed of 3.0m / min, the transfer material was bonded to both sides of a substrate (polyethylene terephthalate film, thickness: 40μm). Specifically, the transfer material for forming the first photosensitive layer (i.e., the first transfer material) was bonded to one side of the substrate, and the transfer material for forming the second photosensitive layer (i.e., the second transfer material) was bonded to the other side of the substrate. A laminate was fabricated through these steps.

[0960] [Pattern Formation]

[0961] A substrate with a resin pattern was produced according to the method described in the "Pattern Formation" section above.

[0962] [evaluate]

[0963] Resolution and exposure haze were evaluated using a substrate with a resin pattern. The evaluation results are shown in Table 5.

[0964] (Discrimination)

[0965] The linewidth of the highest resolution pattern in the resin pattern is set to achieve the resolution. Based on the achieved resolution, the resolution was evaluated according to the following criteria. Furthermore, in cases where the sidewalls of the pattern are severely rough or where obvious folds are formed and connected to adjacent line patterns, the resolution is set to E. As an evaluation, D is preferred, C is more preferred, B is even more preferred, and A is particularly preferred.

[0966] (Benchmark)

[0967] A: Below 10μm

[0968] B: More than 10μm and less than 18μm

[0969] C: More than 18μm and less than 20μm

[0970] D: Greater than 20μm and less than 30μm

[0971] E: Exceeding 30μm or unable to be resolved

[0972] [Sensitivity Measurement]

[0973] The sensitivity was measured according to the method described in the "Sensitivity Measurement" section above. The measurement results are shown in Table 5.

[0974] [Table 5]

[0975]

[0976] The laminates of Examples 14 to 27 satisfy characteristics A and B.

[0977] As shown in Table 5, in Examples 14 to 27, the generation of exposure fog can be suppressed, and resin patterns with excellent resolution can be obtained.

[0978] <Example 28>

[0979] [Construction of Absorption Filter A]

[0980] A composition for absorption filter A was prepared by mixing the following compounds. Additionally, the abbreviations shown below have the same meaning as those already described.

[0981] • A-2: 25.2 parts by weight

[0982] B-6: 5.2 parts by weight

[0983] •C-8: 0.10 parts by weight

[0984] E-3: 0.13 parts by weight

[0985] F-1: 60.9 parts by weight

[0986] F-2: 8.4 parts by weight

[0987] The composition for absorption filter A was spin-coated onto a glass substrate (EagleXG, manufactured by Corning Incorporated) to achieve a dried film thickness of 3.6 μm, and then pre-baked at 80°C for 120 seconds. Next, the composition for absorption filter A was exposed to 100 mJ using a high-pressure mercury lamp and then dried at 140°C for 30 minutes to obtain absorption filter A.

[0988] [Construction of Absorption Filter B]

[0989] A composition for absorption filter B was prepared by mixing the following compounds. Additionally, the abbreviations shown below have the same meaning as those already described.

[0990] • A-2: 25.2 parts by weight

[0991] B-6: 5.2 parts by weight

[0992] •C-8: 0.10 parts by weight

[0993] E-4: 0.13 parts by weight

[0994] F-1: 60.9 parts by weight

[0995] F-2: 8.4 parts by weight

[0996] The composition for absorption filter B was spin-coated onto a glass substrate (EagleXG, manufactured by Corning Incorporated) to achieve a dried film thickness of 3.0 μm, and then pre-baked at 80°C for 120 seconds. Next, the composition for absorption filter B was exposed to 100 mJ using a high-pressure mercury lamp and then dried at 140°C for 30 minutes to obtain absorption filter B.

[0997] [evaluate]

[0998] In the pattern formation of Embodiment 25 described above, an absorption filter B was disposed between the glass mask on the first photosensitive layer side and the short-wavelength cutoff filter (LUO400), and an absorption filter A was disposed between the glass mask on the second photosensitive layer side and the mercury exposure bandpass filter (HB0365). The first and second photosensitive layers were then exposed. Otherwise, a substrate with a resin pattern was fabricated using the same steps as in Embodiment 25. The obtained substrate with the resin pattern was evaluated in the same way as in Embodiment 25. Both the "resolution on the first transfer material side" and the "resolution on the second transfer material side" were rated A. This result is considered to be because: by distributing the absorption filter A, which absorbs the light exposing the first photosensitive layer, the re-exposure of the first photosensitive layer by the exposure light reflected by the mercury exposure bandpass filter (HB0365) was suppressed; and by distributing the absorption filter B, which absorbs the light exposing the second photosensitive layer, the re-exposure of the second photosensitive layer by the exposure light reflected by the short-wavelength cutoff filter (LU0400) was suppressed. Furthermore, the evaluation result for "exposure fog" is A.

[0999] In addition, the laminate of Example 28 satisfies characteristics A and characteristic B.

[1000] <Examples 29-50>

[1001] [abbreviation]

[1002] The following abbreviations represent the following compounds.

[1003] "AA-1": Propylene glycol monomethyl ether acetate solution of a copolymer of styrene / methacrylic acid / methyl methacrylate (solid content concentration: 30.0% by mass, monomer ratio: 52% by mass / 29% by mass / 19% by mass, Mw: 70,000)

[1004] "AA-2": Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid copolymer (solid content concentration: 30.0% by mass, monomer ratio: 80% by mass / 20% by mass, Mw: 30,000, acid value: 153 mg KOH / g)

[1005] "AA-3": KURARAY POVAL PVA-205 (manufactured by KURARAY CO., LTD.)

[1006] "AA-4": Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.)

[1007] "AB-1": BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1008] "AB-2": M-270 (manufactured by TOAGOSEI CO., LTD.)

[1009] "AB-3": NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1010] "AB-4": 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO., LTD.)

[1011] “AB-5”: ARONIXTO-2349 (manufactured by TOAGOSEI CO., LTD.)

[1012] "AB-6": Manufactured by KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

[1013] "AB-7": NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1014] "AB-8": NK Ester A-GLY-3E (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1015] "AC-1": B-CIM (manufactured by KUROGANE KASEI Co., Ltd.)

[1016] "AC-2": Omnirad 379EG (manufactured by IGM Resins BV)

[1017] "AC-3": Irgacure OXE-01 (manufactured by BASF Japan Ltd.)

[1018] "AC-4": The above-mentioned sensitizer A

[1019] "AC-5": Coumarin 7 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1020] "AC-6": 4,4'-bis(dimethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1021] "AC-7": 10-Butyl-2-chloroacridone (manufactured by KUROGANE KASEI Co., Ltd.)

[1022] "AD-1": TDP-G (manufactured by Kawaguchi Chemical Industry Co., LTD.)

[1023] "AD-2": 1-Phenylon-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1024] "AE-1": Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1025] "AE-2": N-Phenylenocarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1026] "AE-3": Solvent Yellow 56 (manufactured by Tokyo Chemical Industry Co., Ltd., a substance that absorbs light at 405nm)

[1027] "AE-4": Solvent Yellow 4 (manufactured by Tokyo Chemical Industry Co., Ltd., a substance that absorbs light at 405nm)

[1028] "AE-5": Solvent Green 3 (manufactured by Tokyo Chemical Industry Co., Ltd., a substance that absorbs light at 405nm)

[1029] "AE-6": Acid Yellow 3 (manufactured by Tokyo Chemical Industry Co., Ltd., a substance that absorbs light at 405nm)

[1030] "AE-7": MACROLEX (registered trademark) Yellow E2R (manufactured by Lanxess AG, a material that absorbs light at 405nm).

[1031] "AE-8": Diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., a substance that absorbs light at 365nm).

[1032] “AE-9”: Tinuvin 477 (manufactured by BASF Japan Ltd., a substance that absorbs light at 365nm)

[1033] "AE-10": Tinuvin 477-DW(N) (manufactured by BASF Japan Ltd., a substance that absorbs light at 365nm)

[1034] "AE-11": Tinuvin 360 (manufactured by BASF Japan Ltd., a substance that absorbs light at 365nm).

[1035] "AE-12": CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD)

[1036] "AE-13": F-552 (manufactured by DIC CORPORATION)

[1037] "AE-14": F-444 (manufactured by DIC Corporation)

[1038] "AF-15": Bonasorb UA-3911 (an indole compound, manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD., a substance that absorbs light at 405 nm).

[1039] "AE-16": Bonasorb UA-3912 (an indole compound, manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD., a substance that absorbs light at 405nm).

[1040] "AE-17": FDB-009 (manufactured by YAMADA CHEMICAL CO., LTD., a substance that absorbs light at 405nm)

[1041] "AE-18": A compound represented by the following structural formula (a substance that absorbs light at 405 nm).

[1042] [Chemical Formula 12]

[1043]

[1044] "AE-19": A compound represented by the following structural formula (a substance that absorbs light at 405 nm).

[1045] Additionally, t-Bu represents tert-butyl, and Et represents ethyl.

[1046] [Chemical Formula 13]

[1047]

[1048] "AE-20": A compound represented by the following structural formula (a substance that absorbs light at 405 nm).

[1049] [Chemical Formula 14]

[1050]

[1051] "AE-21": A compound represented by the following structural formula (a substance that absorbs light at 405 nm).

[1052] [Chemical Formula 15]

[1053]

[1054] "AE-22": A compound represented by the following structural formula (a substance that absorbs light at 405 nm).

[1055] [Chemical Formula 16]

[1056]

[1057] "AE-23": A compound represented by the following structural formula (a substance that absorbs light at 405 nm).

[1058] [Chemical Formula 17]

[1059]

[1060] "AF-1": Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[1061] "AF-2": Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[1062] "AF-3": Ion-exchanged water

[1063] "AF-4": Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

[1064] [Preparation of thermoplastic resin compositions]

[1065] Thermoplastic resin compositions A1a to A15a were prepared by mixing the compounds selected according to Table 6.

[1066] [Table 6]

[1067]

[1068] [Preparation of the Intermediate Layer Composition]

[1069] Intermediate layer compositions 1b to 3b were prepared by mixing the compounds selected according to the description in Table 7.

[1070] [Table 7]

[1071]

[1072] [Preparation of compositions for forming photosensitive layers]

[1073] Photosensitive resin compositions 1c-8c and 1d-9d were prepared by mixing the compounds selected according to Table 8.

[1074]

[1075] [Preparation of transfer materials]

[1076] Using a slit nozzle, the thermoplastic resin composition described in Table 9 was coated onto the surface of a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The thermoplastic resin composition was dried at 80°C for 40 seconds to form a thermoplastic resin layer.

[1077] Using a slit nozzle, the intermediate layer composition described in Table 9 was applied to the surface of the thermoplastic resin layer with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition 2 was dried at 80°C for 40 seconds to form the intermediate layer.

[1078] Using a slit nozzle, the photosensitive resin composition described in Table 9 was coated onto the surface of the intermediate layer with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The photosensitive resin composition was dried at 100°C for 2 minutes to form a photosensitive layer.

[1079] A protective film (polypropylene film, thickness: 12μm, haze: 0.2%) is disposed on the surface of the photosensitive layer.

[1080] The transfer material was prepared using the steps described above (see Table 9).

[1081] [Creating Layered Objects]

[1082] After the transfer material selected according to Table 9 was cut into 50cm squares, the protective film was peeled off from the transfer material. Next, under lamination conditions of a roller temperature of 90°C, a linear pressure of 0.8MPa, and a linear speed of 3.0m / min, the transfer material was bonded to both sides of a substrate (polyethylene terephthalate film, thickness: 40μm). Specifically, the transfer material for forming the first photosensitive layer (i.e., the first transfer material) was bonded to one side of the substrate, and the transfer material for forming the second photosensitive layer (i.e., the second transfer material) was bonded to the other side of the substrate. A laminate was fabricated through these steps.

[1083] [Pattern Formation]

[1084] A substrate with a resin pattern was produced according to the method described in the "Pattern Formation" section above.

[1085] [evaluate]

[1086] Using a substrate with a resin pattern, resolution and exposure haze were evaluated according to the evaluation method described above. The evaluation results are shown in Table 9.

[1087] [Table 9]

[1088]

[1089] The laminates of Examples 29 to 50 satisfy characteristics A and B.

[1090] As shown in Table 9, in Examples 29 to 50, the generation of exposure fog can be suppressed, and resin patterns with excellent resolution can be obtained.

[1091] <Example 51>

[1092] (Production of PET film)

[1093] A UV-absorbing polyethylene terephthalate film (hereinafter referred to as "PET(A)") was produced using the method described in paragraph 0060 of Japanese Patent Application Publication No. 6-306192. As the UV absorber, AE-11 was used instead of the dye described in the aforementioned publication, and the absorbing material was adjusted to achieve a transmittance of 30% for light with wavelengths from 350 nm to 380 nm.

[1094] Furthermore, a colored polyethylene terephthalate film (hereinafter referred to as "PET(B)") was produced by means of the method described in paragraph 0060 of Japanese Patent Application Publication No. 6-306192. As the coloring dye, AE-7 was used instead of the dye described in the aforementioned publication, and the amount of dye was adjusted to produce a film with a transmittance of 30% for light with wavelengths from 405 nm to 440 nm.

[1095] (Production of photosensitive transfer materials)

[1096] Thermoplastic resin composition A1a was coated onto PET(A) using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The resulting thermoplastic resin composition coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer.

[1097] Using a slit nozzle, an intermediate layer composition 1b was applied to the surface of the formed thermoplastic resin layer with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition coating was dried at 80°C for 40 seconds to form the intermediate layer.

[1098] Using a slit nozzle, a photosensitive resin composition 1c was coated onto the surface of the intermediate layer with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The coating was then dried at 100°C for 2 minutes to form a photosensitive layer. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was then laminated onto the photosensitive layer to produce a photosensitive transfer material A.

[1099] Thermoplastic resin composition A1a was coated onto PET(B) using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The resulting thermoplastic resin composition coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer.

[1100] Using a slit nozzle, an intermediate layer composition 1b was applied to the surface of the formed thermoplastic resin layer with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition coating was dried at 80°C for 40 seconds to form the intermediate layer.

[1101] Using a slit nozzle, a photosensitive resin composition was coated onto the surface of the intermediate layer for 1 day with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The coating was then dried at 100°C for 2 minutes to form a photosensitive layer. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was then laminated onto the photosensitive layer to produce photosensitive transfer material B.

[1102] In the obtained photosensitive transfer materials, photosensitive transfer material A is equivalent to the first photosensitive material (exposed using light excluding 365nm), and photosensitive transfer material B is equivalent to the second photosensitive material (exposed using light excluding 405nm).

[1103] The performance was evaluated using photosensitive transfer materials A and B in the same manner as in Example 29. Good results were obtained for both exposure haze and resolution of photosensitive transfer materials A and B.

[1104] In addition, the laminate of Example 51 satisfies characteristics A and characteristic B.

[1105] <Examples 52-73>

[1106] Using the same laminates as in Examples 29 to 50, and under the evaluation conditions shown in Table 10, resolution and exposure haze were evaluated according to the evaluation method described above. The results are shown in Table 10.

[1107] [Table 10]

[1108]

[1109] The laminates of Examples 52 to 73 satisfy characteristics A and B.

[1110] In addition, the meanings of the above statements "excluding wavelengths below 405nm" and "excluding wavelengths above 405nm" are as follows.

[1111] "Exposure conditions excluding wavelengths below 405nm": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIOINC.) via a short-wavelength cutoff filter (model: LU0422, cutoff wavelength: 422nm, manufactured by Asahi Spectra Co., Ltd.). The dominant wavelength was 436nm. With the dominant wavelength intensity set to 100%, the intensity at wavelength 365nm was less than 0.5%.

[1112] "Excluding wavelengths above 405nm": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIO INC.) via a mercury exposure bandpass filter (model: HB0365, center wavelength: 365nm, manufactured by Asahi Spectra Co., Ltd.). The dominant wavelength was 365nm. With the dominant wavelength intensity set to 100%, the intensities at wavelengths of 405nm and 436nm were less than 0.5%.

[1113] Furthermore, excluding exposure conditions at wavelengths below 405 nm, exposure was measured using a lux meter (UIT-250, manufactured by USHIO INC.) with a 405 nm photodetector (UVD-C405, manufactured by USHIO INC.) and via the aforementioned LU0422 cutoff filter. Excluding exposure conditions at wavelengths above 405 nm, exposure was measured using a lux meter with a 365 nm photodetector (UVD-C365, manufactured by USHIO INC.) and via the aforementioned bandpass filter (HB0365).

[1114] As shown in Table 10, even with changes in evaluation conditions, the laminate involved in this invention can still achieve good exposure haze and resolution performance.

[1115] <Examples 74 to 107>

[1116] [abbreviation]

[1117] The following abbreviations represent the following compounds.

[1118] "BA-1": Propylene glycol monomethyl ether acetate solution of a copolymer of styrene / methacrylic acid / methyl methacrylate (solid content concentration: 30.0% by mass, monomer ratio: 52% by mass / 29% by mass / 19% by mass, Mw: 70,000)

[1119] "BB-1": BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1120] "BB-2": NK Ester HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1121] "BB-3": NK Ester NOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1122] "BB-4": NK Ester A-HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1123] "BB-5": NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1124] "BB-6": Sartomer SR454 (manufactured by Arkema)

[1125] "BB-7": NK Ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1126] "BB-8": A dimethacrylate of polyethylene glycol obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A.

[1127] "BB-9": NK Ester A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1128] "BC-1": B-CIM (manufactured by KUROGANE KASEI Co., Ltd.)

[1129] "BC-2": SB-PI 701 (obtained from SANYO TRADING CO., LTD.)

[1130] "BC-3": 4,4'-bis(dimethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1131] "BC-4": 2-Isopropylthioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1132] "BC-5": Coumarin 7 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1133] "BC-6": 7-(diethylamino)coumarin-3-carboxylic acid hexyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1134] "BC-7": Coumarin 314 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1135] "BC-8": Coumarin 521T (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1136] “BC-9”: Coumarin 334 (manufactured by Sigma-Aldrich Japan)

[1137] "BC-10": 3-Acetyl-7-(diethylamino)coumarin (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1138] "BD-1": TDP-G (manufactured by Kawaguchi Chemical Industry Co., LTD.)

[1139] “BD-2”: 1-Phenylon-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1140] "BE-1": Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1141] "BE-2": N-Phenylenocarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1142] "BE-5": CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD)

[1143] "BE-6": F-552 (manufactured by DIC CORPORATION)

[1144] “BF-1”: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[1145] "BF-2": Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[1146] “BF-4”: Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

[1147] [Preparation of compositions for forming photosensitive layers]

[1148] Photosensitive resin compositions 1e-14e and 1f-11f were prepared by mixing compounds selected according to the descriptions in Table 11 or Table 12.

[1149] [Table 11]

[1150]

[1151] [Table 12]

[1152]

[1153] [Preparation of transfer materials]

[1154] Using a slit nozzle, the thermoplastic resin compositions described in Table 13 or Table 14 were coated onto the surface of a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The thermoplastic resin compositions were dried at 80°C for 40 seconds to form a thermoplastic resin layer.

[1155] Using a slit nozzle, the intermediate layer composition described in Table 13 or Table 14 was applied to the surface of the thermoplastic resin layer with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition 2 was dried at 80°C for 40 seconds to form the intermediate layer.

[1156] Using a slit nozzle, the photosensitive resin composition described in Table 13 or Table 14 was coated onto the surface of the intermediate layer with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The photosensitive resin composition was dried at 100°C for 2 minutes to form a photosensitive layer.

[1157] A protective film (polypropylene film, thickness: 12μm, haze: 0.2%) is disposed on the surface of the photosensitive layer.

[1158] The transfer material was prepared using the steps described above (refer to Table 13 or Table 14).

[1159] [Creating Layered Objects]

[1160] After the transfer material selected according to Table 13 or Table 14 was cut into 50cm squares, the protective film was peeled off from the transfer material. Next, under lamination conditions of a roller temperature of 90°C, a linear pressure of 0.8MPa, and a linear speed of 3.0m / min, the transfer material was bonded to both sides of a substrate (polyethylene terephthalate film, thickness: 40μm). Specifically, the transfer material for forming the first photosensitive layer (i.e., the first transfer material) was bonded to one side of the substrate, and the transfer material for forming the second photosensitive layer (i.e., the second transfer material) was bonded to the other side of the substrate. A laminate was fabricated through these steps.

[1161] [Pattern Formation]

[1162] A substrate with a resin pattern was produced according to the method described in the "Pattern Formation" section above.

[1163] [evaluate]

[1164] Using a substrate with a resin pattern, resolution and exposure haze were evaluated according to the evaluation method described above. The evaluation results are shown in Table 13 or Table 14.

[1165] [Table 13]

[1166]

[1167] [Table 14]

[1168]

[1169] The laminates of Examples 74 to 107 satisfy characteristics A and B.

[1170] In addition, the meanings and exposure conditions of "excluding wavelengths below 405nm", "excluding wavelengths above 405nm", "excluding 365nm" and "excluding 405nm" are the same as those mentioned above.

[1171] As shown in Tables 13 and 14, the laminates involved in this invention can achieve good exposure haze and resolution performance.

[1172] <Preparation of thermoplastic resin compositions, intermediate layer compositions, and photosensitive resin compositions>

[1173] Thermoplastic resin compositions, intermediate layer compositions, and photosensitive resin compositions were prepared by mixing the components listed in Tables 15 to 17.

[1174] In addition, the abbreviations of the ingredients listed in Tables 15 to 17 and below are as follows.

[1175] EA-1: Propylene glycol monomethyl ether acetate solution of styrene / methacrylic acid / methyl methacrylate = 52 / 29 / 19 (wt%) copolymer (solids concentration 30.0%, Mw 70,000)

[1176] EA-2: A propylene glycol monomethyl ether acetate solution of benzyl methacrylate, methacrylic acid and acrylic acid copolymer (solid content concentration 30.0%, Mw 30000, acid value 153 mg KOH / g).

[1177] EA-3: KURARAY POVAL PVA-205 (manufactured by KURARAY CO., LTD.)

[1178] EA-4: Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.)

[1179] EB-1: NK Ester BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1180] EB-2: NK Ester HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1181] EB-3: NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1182] EB-4: 8UX-015A (Manufactured by TAISEI FINE CHEMICAL CO., LTD.): 2.31 copies

[1183] EB-5: ARONIXTO-2349 (manufactured by TOAGOSEI CO., LTD.)

[1184] EB-6: Light Acrylate DPE-6A (manufactured by KyoEisha Chemical Co., Ltd.)

[1185] EC-1: B-CIM (manufactured by KUROGANE KASEI Co., Ltd.)

[1186] EC-2: SB-PI 701 (obtained from SANYO TRADING CO., LTD.)

[1187] EC-3: 3-Acetyl-7-(Diethylamino)coumarin (manufactured by FUJIFILM Wako Pute Chemical Corporation)

[1188] EC-4: Irgacure OXE02 (manufactured by BASF Japan Ltd.)

[1189] ED-1: TDP-G (manufactured by Kawaguchi Chemical Industry Co., LTD.)

[1190] ED-2: 1-Phenylon-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1191] EE-1: Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1192] EE-2: N-Phenylenocarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1193] EE-3: Solvent Yellow 56 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1194] EE-4: CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD)

[1195] EE-5: Diethylamino-phenylsulfonyl UV absorber (manufactured by DAITO CHEMICAL CO., LTD.)

[1196] EE-6: Tinuvin 970 (manufactured by BASF Japan Ltd.)

[1197] EE-7: Megaface F-552 (manufactured by DIC CORPORATION)

[1198] EE-8: Megaface F-444 (manufactured by DIC CORPORATION)

[1199] EF-1: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[1200] EF-2: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[1201] EF-3: Ion-exchanged water

[1202] EF-4: Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

[1203] [Table 15]

[1204] Thermoplastic resin composition B1a B2a B3a B4a EA-2 42.85 42.02 42.15 41.82 EB-3 5.03 5.03 5.03 5.03 EB-4 2.31 2.31 2.31 2.31 EB-5 0.77 0.77 0.77 0.77 EE-3 - 0.25 - - EE-5 - - 0.10 0.10 EE-6 - - - 0.10 EE-7 0.03 0.03 0.03 0.03

[1205] [Table 16]

[1206] Intermediate layer composition B1b EA-3 3.22 EA-4 1.49 EE-8 0.00 EF-3 38.12 EF-4 57.17

[1207] [Table 17]

[1208]

[1209] In addition, the values ​​of each component in Tables 15 to 17 represent mass ratios.

[1210] (Example 108)

[1211] <Preparation of Photosensitive Transfer Materials>

[1212] The thermoplastic resin composition described in Table 18 was applied to the surface of a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The resulting thermoplastic resin composition coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer.

[1213] Using a slit nozzle, the intermediate layer composition described in Table 18 was applied to the surface of the formed thermoplastic resin layer with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition coating was dried at 80°C for 40 seconds to form the intermediate layer.

[1214] Using a slit nozzle, the photosensitive layer forming composition described in Table 18 was coated onto the surface of the formed intermediate layer with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The photosensitive layer was then formed by drying in a convection oven at 100°C for 2 minutes. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was then laminated onto the photosensitive layer to produce photosensitive transfer material 108A.

[1215] In addition, the compositions listed in Table 18 were used, and a photosensitive transfer material 108B comprising a thermoplastic resin layer, an intermediate layer, and a photosensitive layer was prepared in the same manner as described above.

[1216] <Creating Layered Objects>

[1217] After the photosensitive transfer material 108A selected according to Table 18 was cut into 50cm squares, the protective film was peeled off from the photosensitive transfer material 108A. Next, under lamination conditions of a roller temperature of 90°C, a linear pressure of 0.8MPa, and a linear speed of 3.0m / min, the photosensitive transfer material 108A with the protective film peeled off was bonded to both sides of a substrate (a thin film on both sides of a substrate including a polyethylene terephthalate film, on which a conductive layer of silver nanowires dispersed in resin is laminated; trade name: ClearOhm, manufactured by Cambrios). Specifically, the photosensitive transfer material 108A (i.e., the first transfer material) for forming the first photosensitive layer was bonded to one side of the substrate, and the photosensitive transfer material 108B (i.e., the second transfer material) for forming the second photosensitive layer was bonded to the other side of the substrate. A laminate was fabricated through these steps.

[1218] <Construction of Wiring Circuit>

[1219] Without peeling off the temporary support, the glass mask depicting the wiring pattern is made to fit tightly against both sides of the laminate. Under the conditions described in Table 18, the first photosensitive layer and the second photosensitive layer are exposed simultaneously. When exposing the first and second photosensitive layers simultaneously, the first photosensitive layer is exposed from the side where it is disposed relative to the substrate, and the second photosensitive layer is exposed from the side where it is disposed relative to the substrate.

[1220] In addition, the meanings of “excluding wavelengths below 405nm” and “excluding wavelengths above 405nm” in Table 18 are as follows.

[1221] "Exposure conditions excluding wavelengths below 405nm": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIOINC.) via a short-wavelength cutoff filter (model: LU0422, cutoff wavelength: 422nm, manufactured by Asahi Spectra Co., Ltd.). The dominant wavelength was 436nm. With the dominant wavelength intensity set to 100%, the intensity at wavelength 365nm was less than 0.5%.

[1222] "Excluding wavelengths above 405nm": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by USHIO INC.) via a mercury exposure bandpass filter (model: HB0365, center wavelength: 365nm, manufactured by Asahi Spectra Co., Ltd.). The dominant wavelength was 365nm. With the dominant wavelength intensity set to 100%, the intensities at wavelengths of 405nm and 436nm were less than 0.5%.

[1223] Furthermore, excluding exposure conditions at wavelengths below 405 nm, exposure was measured using a lux meter (UIT-250, manufactured by USHIO INC.) with a 405 nm photodetector (UVD-C405, manufactured by USHIO INC.) and via the aforementioned LU0422 cutoff filter. Excluding exposure conditions at wavelengths above 405 nm, exposure was measured using a lux meter with a 365 nm photodetector (UVD-C365, manufactured by USHIO INC.) and via the aforementioned bandpass filter (HB0365).

[1224] After exposure and a one-hour resting period, the temporary support was peeled off, and then a resin pattern was formed through development. For development, a 1.0% potassium carbonate aqueous solution (developer) at 28°C was used for spray development for 30 seconds. Both the first and second photosensitive layers were developed simultaneously.

[1225] For the obtained photoresist pattern, the silver nanowires in the areas where the photoresist pattern was not formed were removed by wet etching. For etching, a 40% ferric(III) nitrate aqueous solution at 40°C was used for spray etching for 60 seconds.

[1226] After etching, the remaining photoresist pattern was removed by spraying a 2.38% TMAH aqueous solution at 60°C, thereby obtaining the wiring pattern. The obtained wiring pattern exhibits good electrical properties on both sides of the substrate.

[1227] (Examples 109 to 111)

[1228] The photosensitive transfer material described in Table 18 was used, except that the wiring pattern was formed in the same manner as in Example 108. A wiring pattern with good electrical properties was obtained in the same manner as in Example 108.

[1229] (Example 112)

[1230] <Preparation of Photosensitive Transfer Materials>

[1231] The thermoplastic resin composition described in Table 18 was applied to the surface of a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The resulting thermoplastic resin composition coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer.

[1232] Using a slit nozzle, the intermediate layer composition described in Table 18 was applied to the surface of the formed thermoplastic resin layer with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition coating was dried at 80°C for 40 seconds to form the intermediate layer.

[1233] Using a slit nozzle, the photosensitive layer forming composition described in Table 18 was coated onto the surface of the formed intermediate layer with a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The photosensitive layer was then formed by drying in a convection oven at 100°C for 2 minutes. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was then laminated onto the photosensitive layer to produce a photosensitive transfer material 112A.

[1234] In addition, the compositions listed in Table 18 were used, and a photosensitive transfer material 112B comprising a thermoplastic re...

Claims

1. A method for forming a pattern, comprising: The process of preparing a laminate having a first photosensitive layer, a substrate having a region transparent to the exposure wavelength, and a second photosensitive layer in sequence; The process of exposing the first photosensitive layer; The process of exposing the second photosensitive layer; The process of developing the exposed first photosensitive layer to form a first resin pattern; and The process of developing the exposed second photosensitive layer to form a second resin pattern. The dominant wavelength λ1 of the exposure wavelength in the process of exposing the first photosensitive layer and the dominant wavelength λ2 of the exposure wavelength in the process of exposing the second photosensitive layer satisfy the relationship that λ1≠λ2. A component for absorbing light of the dominant wavelength λ2 is disposed between the first photosensitive layer and the light source for exposing the first photosensitive layer, and / or a component for absorbing light of the dominant wavelength λ1 is disposed between the second photosensitive layer and the light source for exposing the second photosensitive layer. A filter that transmits the dominant wavelength λ1 and reflects the dominant wavelength λ2 is provided between the light source used to expose the first photosensitive layer and the component that absorbs the light of the dominant wavelength λ2, and a filter that transmits the dominant wavelength λ2 and reflects the dominant wavelength λ1 is provided between the light source used to expose the second photosensitive layer and the component that absorbs the light of the dominant wavelength λ1.

2. The pattern forming method according to claim 1, wherein, The first photosensitive layer and the second photosensitive layer contain different photosensitive compounds.

3. The pattern forming method according to claim 1, wherein, Regarding the first photosensitive layer and the second photosensitive layer, the following relationships 1 and 2 are satisfied. Relationship 1: 1.1 ≤ E 1r / E2 Relationship 2: 1.1≤E 2r / E1 Among them, E 1r E1 represents the maximum exposure level at which the first photosensitive layer does not react when exposed to light having the dominant wavelength λ2 from the second photosensitive layer side of the laminate. E2 represents the exposure level at which the second photosensitive layer is exposed to light having the dominant wavelength λ2 during the exposure process. 2r E1 represents the maximum exposure amount at which the second photosensitive layer does not react when exposed to light having the dominant wavelength λ1 from the first photosensitive layer side of the laminate. E1 represents the exposure amount when the first photosensitive layer is exposed to light having the dominant wavelength λ1 during the process of exposing the first photosensitive layer.

4. The pattern forming method according to claim 1, wherein, Regarding the first photosensitive layer and the second photosensitive layer, the following relationships 3 and 4 are satisfied. Relationship 3: 3≤S 12 / S 11 Relation 4: 3≤S 21 / S 22 Among them, S 12 S represents the spectral sensitivity of the first photosensitive layer relative to the dominant wavelength λ2. 11 S represents the spectral sensitivity of the first photosensitive layer relative to the dominant wavelength λ1. 21 S represents the spectral sensitivity of the second photosensitive layer relative to the dominant wavelength λ1. 22 This represents the spectral sensitivity of the second photosensitive layer relative to the dominant wavelength λ2.

5. The pattern forming method according to claim 1, wherein, The first photosensitive layer contains a substance that absorbs light of the dominant wavelength λ2 and / or the second photosensitive layer contains a substance that absorbs light of the dominant wavelength λ1.

6. The pattern forming method according to claim 1, wherein, The laminate has at least one of the following: a layer containing a substance that absorbs light of the dominant wavelength λ2 disposed between the substrate and the first photosensitive layer; a layer containing a substance that absorbs light of the dominant wavelength λ2 disposed on the substrate with the first photosensitive layer spaced apart; a layer containing a substance that absorbs light of the dominant wavelength λ1 disposed between the substrate and the second photosensitive layer; and a layer containing a substance that absorbs light of the dominant wavelength λ1 disposed on the substrate with the second photosensitive layer spaced apart.

7. The pattern forming method according to claim 5, wherein, The substance that absorbs light of the dominant wavelength λ2 and the substance that absorbs light of the dominant wavelength λ1 have a maximum absorption wavelength λ in the wavelength region above 400 nm. max The substance.

8. The pattern forming method according to claim 1, wherein, The component that absorbs light of the dominant wavelength λ2 and the component that absorbs light of the dominant wavelength λ1 both have a maximum absorption wavelength λ within a wavelength region above 400 nm. max Components of the material.

9. The pattern forming method according to claim 1, wherein, The laminate has at least one conductive layer on at least one side of the substrate.

10. The pattern forming method according to claim 1, wherein, The laminate has at least one conductive layer on each of the two sides of the substrate.

11. The pattern forming method according to claim 1, wherein, The laminate has at least one conductive layer on at least one side of the substrate, and a conductive layer having a different composition from the conductive layer is further formed on at least a portion of the conductive layer.

12. The pattern forming method according to claim 1, wherein, The laminate has at least one conductive layer on at least one side of the substrate, and the conductive layer has two or more regions with different compositions within the substrate.

13. The pattern forming method according to claim 9, wherein, At least one of the conductive layers is a layer containing a metal oxide.

14. The pattern forming method according to claim 9, wherein, At least one of the conductive layers is a layer comprising at least one selected from metal nanowires and metal nanoparticles.

15. The pattern forming method according to claim 9, further comprising the step of using at least one of the first resin pattern and the second resin pattern as a mask to etch the conductive layer.

16. The pattern forming method according to claim 1, wherein, The first photosensitive layer and the second photosensitive layer respectively contain a polymer with acid groups, a polymerizable compound, and a photopolymerization initiator.

17. The pattern forming method according to claim 16, wherein, The polymeric compound comprises epoxide-modified bisphenol A di(meth)acrylate.

18. The pattern forming method according to claim 16, wherein, The photopolymerization initiator comprises a 2,4,5-triarylimidazolium dimer.

19. The pattern forming method according to claim 16, wherein, The first photosensitive layer also contains a sensitizer.

20. The pattern forming method according to claim 19, wherein, The sensitizer contains a coumarin compound.

21. A method for manufacturing a circuit board, comprising the pattern forming method according to any one of claims 1 to 20.

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