Transfer film, and method for manufacturing laminate having conductor pattern

Abstract

To provide a transfer film which enables formation of a pattern excellent in resolution, and suppresses lowering of development speed.SOLUTION: A transfer film has a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer in this order, wherein the thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer having a polymerizable group, a polymerization inhibitor, and an optical decoloring compound, in the thermoplastic resin layer, a mass ratio of a content of the optical decoloring compound to a content of the polymerization initiator is 400 or less, when a laminate obtained by peeling the temporary support from the transfer film is irradiated with ultraviolet light including light at a wavelength of 365 nm from the thermoplastic resin layer side so that an irradiation amount at a wavelength of 365 nm is 1,000 mJ / cm2, a relation of expression (1) is satisfied. Expression (1): T1000 / T0≥4, where T0 is transmittance at a wavelength of 365 nm of the laminate before the irradiation, and T1000 is transmittance at a wavelength of 365 nm of the laminate after the irradiation.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a transfer film and a method for producing a laminate having a conductive pattern. [Background technology]

[0002] In display devices (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.) equipped with a touch panel such as a capacitance-type input device, conductive patterns such as an electrode pattern corresponding to a sensor in the visual recognition area, and wiring for peripheral wiring and lead-out wiring are provided inside the touch panel. In addition, wiring patterns are also formed in printed circuit board wiring and the like by etching and plating processes. The above-mentioned conductor pattern is formed by a method in which a patterned layer is formed on a conductor layer, and then the conductor layer is subjected to treatments such as etching and plating. In forming such a patterned layer, the number of steps required to obtain a desired pattern shape is small, and therefore a method in which a photosensitive composition layer is disposed on an arbitrary substrate using a transfer film, and this photosensitive composition layer is exposed to pattern exposure and then developed is widely used.

[0003] As an example of such a transfer film, Patent Document 1 discloses a transfer film having a temporary support, an intermediate layer containing a surfactant, and a photosensitive composition layer, and wherein the surface free energy of the exposed surface not containing the temporary support after peeling off the temporary support is 66.0 mJ / m 2 The following transfer film is disclosed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2023 / 210777 Summary of the Invention [Problem to be solved by the invention]

[0005] The above document discloses, as one embodiment of the transfer film, a transfer film having a predetermined thermoplastic resin layer. Recently, there has been a demand for further improvement in the resolution of the patterns to be formed, while at the same time, there is also a demand for ensuring a sufficient development speed. The present inventors have applied a photobleachable compound to the transfer film disclosed in the above-mentioned document 1 in an attempt to improve resolution, but have found that the development speed after exposure may decrease, and that the composition needs to be reconsidered.

[0006] Therefore, an object of the present invention is to provide a transfer film that can form a pattern with excellent resolution and that suppresses a decrease in development speed. Another object of the present invention is to provide a method for producing a laminate having a conductor pattern of the transfer film. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A transfer film having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer in this order, the thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer having a polymerizable group, a polymerization inhibitor, and a photo-bleachable compound; In the thermoplastic resin layer, the mass ratio of the content of the photo-decolorizable compound to the content of the polymerization inhibitor is 400 or less; The laminate obtained by peeling the temporary support from the transfer film was irradiated with ultraviolet light containing light with a wavelength of 365 nm at an irradiation dose of 1000 mJ / cm 2 at a wavelength of 365 nm. 2 When irradiated from the thermoplastic resin layer side so as to satisfy the relationship of formula (1), the transmittance of the laminate at a wavelength of 365 nm before the irradiation is T0 and the transmittance of the laminate at a wavelength of 365 nm after the irradiation is T1000. Formula (1) T1000 / T0≧4 [2] The transfer film according to [1], wherein the photosensitive composition layer contains an alkali-soluble thermoplastic resin, a monomer having a radical polymerizable group, and a radical polymerization initiator. [3] The transfer film according to [1] or [2], wherein the content of the photo-decolorizable compound is 5.00 to 40.00% by mass relative to the total mass of the thermoplastic resin layer. [4] The transfer film according to any one of [1] to [3], wherein the thermoplastic resin layer has a thickness of 1 to 15 μm. [5] The transfer film according to any one of [1] to [4], wherein the T1000 is 65% or more. [6] The transfer film according to any one of [1] to [5], wherein the intermediate layer has a thickness of 0.1 to 3 μm. [7] The transfer film according to any one of [1] to [6], wherein the intermediate layer contains polyvinyl alcohol. [8] The transfer film according to any one of [1] to [7], wherein the intermediate layer contains a photobleachable compound. [9] The molar absorption coefficient of the photobleaching compound at a wavelength of 365 nm is 8000 L mol -1 ·cm -1 The transfer film according to any one of [1] to [8] above.

[10] The transfer film according to any one of [1] to [9], wherein the transmittance of the photosensitive composition layer after the irradiation at a wavelength of 365 nm is 75% or more.

[11] The transfer film according to any one of [1] to

[10] , wherein the photosensitive composition layer has a thickness of 2 to 20 μm.

[12] A lamination step of laminating the transfer film according to any one of [1] to

[11] so that the photosensitive composition layer side is in contact with the metal layer of a substrate having a metal layer on its surface; an exposure step of pattern-exposing the photosensitive composition layer from the side opposite to the substrate side; a developing step of developing the exposed photosensitive composition layer using an alkaline developer to form a resist pattern; one of an etching process for etching the metal layer in an area where the resist pattern is not disposed to form a conductor pattern, and a plating process for plating the metal layer; a resist stripping step of stripping the resist pattern; Furthermore, when the plating treatment step is included, the method further includes a removal step of removing the metal layer exposed by the resist stripping step to form a conductor pattern on the substrate. A method for manufacturing a laminate having a conductive pattern.

[13] A method for producing a laminate having a conductive pattern according to

[12] , comprising a step of peeling off the temporary support before the exposure step. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a transfer film that can form a pattern with excellent resolution and that suppresses a decrease in the development speed of a thermoplastic resin layer. The present invention also provides a method for producing a laminate having a conductive pattern of the transfer film. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic diagram illustrating an example of the configuration of a transfer film of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0012] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In the present specification, in the numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. As used herein, a combination of two or more preferred embodiments is a more preferred embodiment.

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

[0014] In this specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0015] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured by a gel permeation chromatography (GPC) analyzer using a TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, and converted using polystyrene as a standard substance. In this specification, unless otherwise specified, the ratio of polymer structural units is a mass ratio. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0016] In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, "(meth)acryloyl" is a concept that includes both acryloyl and methacryloyl, "(meth)acrylate" is a concept that includes both acrylate and methacrylate, and "(meth)acrylamide" is a concept that includes both acrylamide and methacrylamide.

[0017] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more. As used herein, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more. For example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0018] In this specification, the "solid content" of a composition refers to components that form a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0019] In this specification, unless otherwise specified, when a group (atomic group) is represented without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups). In this specification, when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as "substituents, etc.") represented by a specific symbol, or when a plurality of substituents, etc. are simultaneously specified, it means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc.

[0020] In this specification, for compounds that may have stereoisomers, the general formula or structural formula representing the compound may be described in only one form for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to any one stereoisomer, and any one stereoisomer may be used alone, or multiple stereoisomers may be used in combination.

[0021] [Transfer film] The transfer film will be described in detail below. The transfer film of the present invention (hereinafter also simply referred to as "transfer film") is a transfer film having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer in this order, wherein the thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer having a polymerizable group, a polymerization inhibitor, and a photodecolorizable compound, and the mass ratio of the content of the photodecolorizable compound to the content of the polymerization inhibitor is 400 or less, and the temporary support is peeled off from the transfer film to obtain a laminate, and ultraviolet light including light with a wavelength of 365 nm is irradiated at an irradiation dose of 1000 mJ / cm at a wavelength of 365 nm. 2 When irradiation is performed from the thermoplastic resin layer side so that the transmittance of the laminate at a wavelength of 365 nm before the irradiation is T0 and the transmittance of the laminate at a wavelength of 365 nm after the irradiation is T1000, the relationship of formula (1) is satisfied. Formula (1) T1000 / T0≧4

[0022] The reason why the transfer film having the above-described configuration can solve the problems of the present invention is not entirely clear, but the present inventors speculate as follows. The mechanism by which the effects are obtained is not limited by the following speculation. In other words, even if the effects are obtained by a mechanism other than the one described below, it is still included in the scope of the present invention. In the transfer film of the present invention, the thermoplastic resin layer contains a photo-bleachable compound, and the transfer film satisfies the relationship of formula (1), so that the thermoplastic resin layer functions as a contrast enhancement layer (CEL). This increases the contrast of pattern light incident on the photosensitive composition layer, allowing for the formation of a pattern with excellent resolution. Furthermore, since the content ratio of the polymerization inhibitor to the photo-bleachable compound in the thermoplastic resin layer is within a predetermined range, it is presumed that the thermoplastic resin layer exhibits the function of a CEL while suppressing the reaction of the plasticizer having a polymerizable group, thereby suppressing a decrease in the development rate of the thermoplastic resin layer. Hereinafter, the ability to form a pattern with excellent resolution using a transfer film will be simply referred to as "excellent resolution," and the ability to achieve at least one of better resolution and better suppression of a decrease in development rate will be referred to as "better effects of the present invention."

[0023] FIG. 1 is a cross-sectional view showing an example of an embodiment of the transfer film of the present invention. The transfer film 10 shown in Fig. 1 has a configuration in which a temporary support 12, a thermoplastic resin layer 14, an intermediate layer 16, a photosensitive composition layer 18, and a protective film 20 are laminated in this order. Although the transfer film 10 shown in Fig. 1 has the protective film 20 arranged therein, the protective film 20 does not necessarily have to be arranged.

[0024] [Transmittance] The transfer film was prepared by irradiating a laminate obtained by peeling off the temporary support from the transfer film with ultraviolet light containing light with a wavelength of 365 nm at an irradiation dose of 1000 mJ / cm at a wavelength of 365 nm. 2 When irradiation is performed from the thermoplastic resin layer side so that the transmittance at a wavelength of 365 nm of the laminate before irradiation is T0 and the transmittance at a wavelength of 365 nm of the laminate after irradiation is T1000, the relationship of formula (1) is satisfied. Formula (1) T1000 / T0≧4

[0025] When the transfer film satisfies the relationship of the above formula (1), the transfer film can form a pattern with excellent resolution. Specifically, the T1000 and T0 can be measured using a laminate T (glass / photosensitive composition layer / intermediate layer / thermoplastic resin layer) obtained by laminating a transfer film to glass so that the photosensitive composition layer of the transfer film is in contact with the glass and peeling off the temporary support. The T1000 and T0 of the laminate (a laminate of thermoplastic resin layer / intermediate layer / photosensitive composition layer obtained by peeling off the temporary support from the transfer film of the present invention) can be obtained by excluding the transmittance of the glass from the transmittance measured for the laminate T before and after ultraviolet light irradiation. The light irradiated onto the laminate is ultraviolet light containing light with a wavelength of 365 nm. The irradiation method can be a method in which light emitted from a light source is irradiated through a 365 nm bandpass filter. The light source is not particularly limited as long as it can irradiate ultraviolet light containing light with a wavelength of 365 nm. Examples of the light source include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the 150 to 450 nm wavelength band. The exposure time is 1000 mJ / cm at a wavelength of 365 nm. 2 It can be adjusted appropriately so that The transmittance before and after the irradiation can be measured using a spectrophotometer (for example, UV-1800 manufactured by Shimadzu Corporation). The irradiation amount at a wavelength of 365 nm can be measured using a known illuminometer.

[0026] In order to obtain superior resolution, the transfer film preferably satisfies the relationship T1000 / T0≧10, more preferably satisfies the relationship T1000 / T0≧50, even more preferably satisfies the relationship T1000 / T0≧500, and particularly preferably satisfies the relationship T1000 / T0≧3000. In addition, in order to suppress surface defects, the transfer film preferably satisfies the relationship T1000 / T0≦10000, and more preferably satisfies the relationship T1000 / T0≦5000. The surface defects mentioned above refer to defects such as cracks and bumps that are observed on the surface when the transfer film is transferred. The value of T1000 / T0 can be adjusted by adjusting the composition (particularly the type and content of the photobleachable compound) and layer thickness of each layer in the transfer film.

[0027] T0 is preferably 50% or less, more preferably 20% or less, and even more preferably 5% or less. The lower limit of T0 is 0% or more, often 0.001% or more, and preferably 0.01% or more. T1000 is preferably 50% or more, more preferably 65% ​​or more, and even more preferably 70% or more. The upper limit of T1000 is 100% or less, often 95% or less, and more often 90% or less.

[0028] It is preferable that the transfer film of the present invention also satisfies the above-mentioned requirement for the transmittance ratio measured at a wavelength of 405 nm using ultraviolet light containing light with a wavelength of 405 nm instead of the ultraviolet light containing light with a wavelength of 365 nm. That is, the transfer film is formed by irradiating the laminate obtained by peeling off the temporary support with ultraviolet light containing light with a wavelength of 405 nm at an irradiation dose of 1000 mJ / cm 2 at a wavelength of 405 nm. 2 When irradiation is performed so as to satisfy the following formula (1'), it is preferable that the transmittance of the laminate at a wavelength of 405 nm before irradiation is T0' and the transmittance of the laminate at a wavelength of 405 nm after irradiation is T1000'. Formula (1') T1000' / T0'≧4 The preferred values ​​of T1000' / T0', T1000', and T0' are the same as the values ​​of T1000 / T0, T1000, and T0 described above, respectively.

[0029] Each element constituting the transfer film will be described in detail below.

[0030] [Temporary support] The transfer film has a temporary support. The temporary support is a member that supports the thermoplastic resin layer, the intermediate layer, and the photosensitive composition layer, and is finally removed by a peeling treatment. The temporary support may have either a single-layer structure or a multi-layer structure. The temporary support is preferably a flexible film that does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of such films include polyethylene terephthalate (PET) films (e.g., biaxially oriented polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, with polyethylene terephthalate films being preferred. Furthermore, the temporary support is preferably free of deformations such as wrinkles and scratches.

[0031] The temporary support preferably has high transparency in order to allow pattern exposure through the temporary support. Specifically, the transmittance at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. The upper limit is preferably less than 100%. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.1% or less. The lower limit is not particularly limited, but may be 0.01% or more. From the viewpoint of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support is 50 / 10 mm. 2 Preferably less than 10 pieces / 10mm 2 Less than 3 pieces / 10mm is more preferable. 2 Less than 0 pieces / 10mm is more preferable. 2 is particularly preferred.

[0032] The thickness of the temporary support is preferably 5 μm or more, more preferably 6 μm or more, and the upper limit is preferably 200 μm or less, and from the viewpoint of ease of handling and versatility, more preferably 150 μm or less, even more preferably 50 μm or less, and particularly preferably 20 μm or less. The thickness of the temporary support is calculated as the average value of measurements taken at any five points by cross-sectional observation using an SEM (Scanning Electron Microscope).

[0033] From the viewpoint of handling, the temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0034] In order to improve the adhesion between the temporary support and the thermoplastic resin layer, the surface of the temporary support that comes into contact with the thermoplastic resin layer may be subjected to a surface modification treatment, such as UV (ultraviolet) irradiation, corona discharge, or plasma treatment. The exposure dose for UV irradiation is 10 to 2000 mJ / cm 2 is preferred, and 50 to 1000 mJ / cm 2 is more preferred. Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs), all of which emit light in the 150 to 450 nm wavelength band. As long as the exposure amount is within the above range, there are no particular limitations on the lamp output and illuminance.

[0035] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. Further, examples of temporary supports include those described in paragraphs

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

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

[0029] to

[0040] of WO 2018 / 179370 A, the contents of which are incorporated herein by reference. Commercially available temporary supports include, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0036] [Thermoplastic resin layer] The transfer film has a thermoplastic resin layer. The thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer having a polymerizable group, a polymerization inhibitor, and a photo-bleachable compound. As described above, in the transfer film of the present invention, the thermoplastic resin layer contains a photo-bleachable compound and functions as a CEL, thereby achieving excellent resolution. Furthermore, since the transfer film has a thermoplastic resin layer containing a thermoplastic resin and a plasticizer, the conformability of the transfer film to the substrate is improved in the lamination process between the transfer film and the substrate, which will be described later, and the inclusion of air bubbles between the substrate and the transfer film can be suppressed, thereby suppressing pattern defects. Each component that the thermoplastic resin layer may contain will be described in detail below.

[0037] <Alkali-soluble thermoplastic resin> Examples of the alkali-soluble thermoplastic resin layer include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0038] As the alkali-soluble thermoplastic resin, an acrylic resin is preferred from the viewpoints of developability and adhesion to adjacent layers. Here, the acrylic resin means a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. The acrylic resin preferably contains structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides in a total content of 50% by mass or more relative to the total mass of the acrylic resin. In particular, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, relative to the total mass of the acrylic resin.

[0039] The alkali-soluble thermoplastic resin preferably has an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphate group, and a phosphonate group, and the carboxy group is preferred. In particular, the alkali-soluble thermoplastic resin preferably has an acid group as a repeating unit having an acid group. From the viewpoint of developability, the alkali-soluble thermoplastic resin is preferably an alkali-soluble thermoplastic resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The lower limit of the acid value is not particularly limited, but from the viewpoint of better developability, it is more preferably 120 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more. The upper limit of the acid value of the alkali-soluble thermoplastic resin is not particularly limited, but it is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of an alkali-soluble thermoplastic resin can be adjusted by adjusting the type of structural unit that constitutes the resin (for example, the content of structural units containing acid groups).

[0040] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins. Examples include alkali-soluble thermoplastic resins that are carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A 2011-095716, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A 2016-224162. The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 70 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 55 mass %, relative to the total mass of the acrylic resin. As the alkali-soluble thermoplastic resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred from the viewpoints of developability and adhesion to adjacent layers.

[0041] The alkali-soluble thermoplastic resin may have a reactive group, which may be an addition-polymerizable group, such as an ethylenically unsaturated group, a polycondensable group such as a hydroxy group or a carboxy group, or a polyaddition-reactive group such as an epoxy group or a (blocked) isocyanate group.

[0042] The weight average molecular weight (Mw) of the alkali-soluble thermoplastic resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000. The polydispersity of the alkali-soluble thermoplastic resin is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0043] The alkali-soluble thermoplastic resin may be used alone or in combination of two or more kinds. From the viewpoint of resolution, the content of the alkali-soluble thermoplastic resin is preferably 20.00 to 80.00 mass %, more preferably 20.00 to 60.00 mass %, and even more preferably 35.00 to 60.00 mass %, relative to the total mass of the thermoplastic resin layer.

[0044] <Plasticizers having polymerizable groups> The thermoplastic resin layer contains a plasticizer having a polymerizable group. The plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or polymer and has a molecular weight distribution) than the alkali-soluble thermoplastic resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer having a polymerizable group is preferably liquid at 25° C. (1 atmosphere). The viscosity of the polymerizable group-containing plasticizer at 25°C is preferably 10,000 mPa·s or less. There is no particular lower limit to the viscosity, but it is often 3 mPa·s or more. The viscosity can be measured using a known viscometer.

[0045] The polymerizable group of the plasticizer is preferably a radically polymerizable group, more preferably an ethylenic double bond, and even more preferably a (meth)acryloyl group. Among them, from the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble thermoplastic resin is an acrylic resin and the plasticizer having a polymerizable group is a compound having a (meth)acryloyl group. The number of polymerizable groups possessed by the plasticizer is 1 or more, may be 2 or more, and preferably is 2 or more. There is no particular upper limit, but it is often 6 or less, and preferably 4 or less.

[0046] The plasticizer having a polymerizable group preferably has an alkylene oxide chain from the viewpoint of plasticity. The alkylene group in the alkylene oxide chain may be any of linear, branched, and cyclic, and is preferably linear or branched, more preferably linear. The alkylene group preferably has 1 to 6 carbon atoms, and more preferably 2 or 3 carbon atoms. The alkylene oxide chain may be a polyalkylene oxide chain in which two or more alkylene oxides are linked together. In particular, the plasticizer having a polymerizable group preferably has at least one structure selected from the group consisting of an ethylene oxide chain and a propylene oxide chain.

[0047] Examples of plasticizers having two polymerizable groups include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 2,2-bis(4-methacryloxypolyethoxyphenyl)propane. More specific examples include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol 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.).

[0048] Examples of plasticizers having three or more polymerizable groups include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0049] Examples of plasticizers having a polymerizable group include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Co., Ltd., etc.), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0050] Examples of the plasticizer having a polymerizable group include urethane (meth)acrylate (preferably tri- or higher functional urethane (meth)acrylate). Examples of the urethane (meth)acrylate compound include propylene oxide-modified urethane di(meth)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0051] The plasticizer having a polymerizable group also preferably has an acid group, such as a carboxylic acid group, or a group derived from an acid anhydride. Examples of plasticizers having an acid group and a polymerizable group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). As the plasticizer having an acid group and a polymerizable group, for example, a (meth)acrylate compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A No. 2004-239942 can also be used.

[0052] The plasticizer having a polymerizable group may be used alone or in combination of two or more kinds. The content of the plasticizer having a polymerizable group is preferably 10.00 to 50.00 mass %, more preferably 15.00 to 36.00 mass %, and even more preferably 25.00 to 36.00 mass %, relative to the total mass of the thermoplastic resin layer, from the viewpoints of resolution, adhesion to adjacent layers, and developability.

[0053] <Polymerization inhibitor> The thermoplastic resin layer contains a polymerization inhibitor. As the polymerization inhibitor, known polymerization inhibitors can be used. Specific examples of the polymerization inhibitor include phenothiazine-based compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid. phenoxazine compounds such as phenoxazine; nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate, with phenothiazine compounds being preferred.

[0054] The polymerization inhibitor may be used alone or in combination of two or more. The content of the polymerization inhibitor is preferably from 0.01 to 5.00% by mass, more preferably from 0.03 to 0.50% by mass, and even more preferably from 0.04 to 0.10% by mass, relative to the total mass of the thermoplastic resin layer.

[0055] <Photodecolorizable compound> The thermoplastic resin layer contains a photobleachable compound. The photobleachable compound is a compound that, upon exposure to light, exhibits reduced absorption at the exposure wavelength and increases transmittance (that is, is bleached). The photo-bleachable compound may be decolorized by exposure light used for patterned exposure. Specifically, the photo-bleachable compound is preferably decolorized by light having a wavelength of 190 to 500 nm, more preferably by light having a wavelength of 365 nm or 405 nm, and even more preferably by light having a wavelength of 365 nm.

[0056] The molar extinction coefficient of the photobleaching compound at a wavelength of 365 nm is 5000 L mol -1 ·cm -1 More than 8000 L·mol is preferable. -1 ·cm -1 More than 15,000 L·mol is preferable. -1 ·cm -1 The upper limit of the molar extinction coefficient is not particularly limited, but is preferably 40,000 L mol -1 ·cm -1 In most cases, the molar absorption coefficient at a wavelength of 365 nm is the value before exposure (i.e., before bleaching). The molar absorption coefficient at a wavelength of 365 nm can be measured using a spectrophotometer (for example, UV-3100 manufactured by Shimadzu Corporation). The difference in the molar absorption coefficient at a wavelength of 365 nm before and after bleaching of the photobleachable compound ((molar absorption coefficient at a wavelength of 365 nm before bleaching) - (molar absorption coefficient at a wavelength of 365 nm after bleaching)) is 5000 L mol -1 ·cm -1 More than 8000 L·mol is preferable. -1 ·cm -1 More than 10,000 L·mol is preferable. -1 ·cm -1 The upper limit is not particularly limited, and is 40,000 L mol -1 ·cm -1 The following cases are common:

[0057] Specific examples of the photo-bleachable compound include oxime sulfonate compounds, oxime ester compounds, acylphosphine oxide compounds, diazonium salts, stilbazolium salts, and arylnitroso salts, with oxime sulfonate compounds being preferred.

[0058] The oxime sulfonate compound is preferably an oxime sulfonate compound having an aromatic ring group, and more preferably a compound represented by formula (X1) or a compound represented by formula (X2).

[0059] [ka]

[0060] In formula (X1), R 1 represents an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group may be either linear or branched, preferably branched. The alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. The cycloalkyl group preferably has 3 to 10 carbon atoms, and more preferably 5 to 7 carbon atoms. The aryl group may be either monocyclic or polycyclic. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms. The aryl group includes a phenyl group and a naphthyl group, and the phenyl group is preferred. The alkyl group, cycloalkyl group, and aryl group may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, alkyl group (preferably having 1 to 3 carbon atoms), alkenyl group, alkynyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxy group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, nitro group, hydrazino group, and heterocyclic group. The substituent may be further substituted with the substituent. When the alkyl group has a fluorine atom as a substituent, the alkyl group may be a perfluoroalkyl group. The substituent is preferably a halogen atom or a methyl group. R 1 is preferably an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a phenyl group, and even more preferably a branched alkyl group having 3 to 6 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms. Among them, R 1 As the alkyl group, an isopropyl group, a tert-butyl group, a neopentyl group, or a cyclohexyl group is preferable, and a tert-butyl group or a cyclohexyl group is more preferable.

[0061] In formula (X1), R 2 represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group. The alkyl group may be either linear or branched, preferably branched, and preferably has 1 to 10 carbon atoms. The cycloalkyl group may have a carbonyl carbon atom as a ring member atom. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a 7,7-dimethylbicyclo[2.2.1]heptanone group. The aryl group may be either monocyclic or polycyclic, and preferably has 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, and a p-methylphenyl group (a p-toluyl group), with a phenyl group or a p-methylphenyl group being preferred. Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group. The alkyl group, cycloalkyl group, aryl group, and heteroaryl group may have a substituent. The substituent may be R 1 Examples of the substituent include the groups exemplified as the substituent that the alkyl group, cycloalkyl group, and aryl group represented by the following formula (I) may have, and an alkyl group or a halogen atom is preferred, and a methyl group or a halogen atom is more preferred. The substituent is preferably a bulky group such as a branched alkyl group, a cycloalkyl group, a cycloalkylcarbonyloxy group, a cycloalkyloxycarbonyl group, a cycloalkyloxycarbonyl group, a 7,7-dimethylbicyclo[2.2.1]heptanone group, or a decahydroisoquinolinesulfonyl group. R 2 As the group, an alkyl group, a cycloalkyl group, or an aryl group is preferable, an aryl group is more preferable, and a phenyl group or a p-methylphenyl group is even more preferable.

[0062] In formula (X1), R 3 ~R 6 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom. R 3 ~R 6 The definitions and preferred embodiments of the alkyl group, cycloalkyl group, and aryl group represented by the formula (I) are the same as those of the above-mentioned R 2 The groups are the same as those in the above. R 3 and R4 , R 4 and R 5 , or R 5 and R 6 may be bonded to each other to form a ring. The ring may be either an alicyclic ring or an aromatic ring, and is preferably an aromatic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. R 3 ~R 6 is preferably a hydrogen atom, an alkyl group, or a halogen atom (preferably a fluorine atom, a chlorine atom, or a bromine atom), and more preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, or a bromine atom. Also, R 3 and R 4 , R 4 and R 5 , and R 5 and R 6 are preferably bonded to each other to form a benzene ring, and R 5 and R 6 are more preferably bonded to each other to form a benzene ring. R 3 ~R 6 The preferred embodiments are as follows: (Aspect 1) R 3 ~R 6 At least two of the atoms are hydrogen atoms. (Embodiment 2) The total number of alkyl groups, cycloalkyl groups, aryl groups, and halogen atoms is 3 or less, preferably 1 or less. (Aspect 3) R 3 and R 4 , R 4 and R 5 , and R 5 and R 6 are bonded to each other to form a benzene ring. (Aspect 4) An aspect that satisfies the above aspects 1 and 2, and / or an aspect that satisfies the above aspects 1 and 3.

[0063] In formula (X1), X 1represents an oxygen atom or a sulfur atom, and an oxygen atom is preferred.

[0064] Examples of the compound represented by formula (X1) include the compounds shown below. Hereinafter, Ts represents a p-toluenesulfonyl group, Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] In formula (X2), R 11 represents a monovalent organic group. R 11 The definition and preferred embodiments of the monovalent organic group represented by the formula (X1) are as follows: 2 It is the same as the group exemplified as the monovalent organic group represented by the following formula: R 11 Among these, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, a benzyl group, a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group is preferred, and a phenyl group or a p-methylphenyl group is more preferred.

[0069] In formula (X2), R 12 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. However, if two or more R12 At least one of R represents an alkyl group, an aryl group, or a halogen atom. 12 At least one of represents an alkyl group, an aryl group, or a halogen atom. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms. The aryl group preferably has 6 to 30 carbon atoms. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom or a bromine atom being preferred. The alkyl group and the aryl group may have a substituent. Examples of the substituent include R 1 Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group represented by the formula (I) may have include groups exemplified above, and a halogen atom, an aryl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, or an amino group is preferred. When the alkyl group and aryl group have a substituent, it is preferred that the number of carbon atoms including the substituent satisfies the preferred range above. R exists more than once 12 may be the same or different from each other. R 12 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0070] In formula (X2), Ar 11 represents an aromatic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may be either a monocyclic ring or a polycyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, a furan ring, a thiophene ring, and a quinoline ring, with a benzene ring or a naphthalene ring being preferred, and a naphthalene ring being more preferred. The aromatic ring may have a substituent. Examples of the substituent include R 1 The groups exemplified as the substituents that the alkyl group, cycloalkyl group, and aryl group represented by the following formula (I) may have are included, and an alkyl group or alkyloxy group is preferred. The alkyl group and alkyloxy group which are the above substituents preferably have 1 to 30 carbon atoms, more preferably 1 to 6 carbon atoms. The alkyl group and alkyloxy group which are the above substituents may further have the above-mentioned substituents (preferably a halogen atom, an alkyloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, or an aminocarbonyl group). The number of substituents that the aromatic ring may have is preferably 0 to 6, more preferably 0 to 2, and even more preferably 0.

[0071] In formula (X2), X 11 represents an oxygen atom or a sulfur atom, and an oxygen atom is preferred.

[0072] In formula (X2), n represents 1 or 2, with 1 being preferred.

[0073] Examples of the compound represented by formula (X2) include the compounds shown below.

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF, and trade name: Lunar 6, DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Powerful Electronic New Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Powerful Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Powerful Electronic New Materials Co., Ltd.).

[0080] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. In addition, the acylphosphine oxide compounds described in JP-A-55-13794 and JP-A-55-15471 can also be used.

[0081] Diazonium salts include aryl diazonium salts such as 4-(N,N-dimethylamino)benzenediazonium tetrafluoroborate, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium tetrafluoroborate, and 4-chlorobenzenediazonium hexafluorophosphate.

[0082] The photo-bleachable compounds may be used alone or in combination of two or more. In the thermoplastic resin layer, the mass ratio of the content of the photo-bleachable compound to the content of the polymerization inhibitor is not more than 400. If the mass ratio exceeds 400, the plasticizer having a polymerizable group in the thermoplastic resin layer reacts, deteriorating the solubility in the developer and decreasing the development rate, which is undesirable. The mass ratio is preferably 350 or less, and more preferably 300 or less, from the viewpoint of further suppressing a decrease in development rate and further suppressing surface defects. The lower limit of the mass ratio is preferably 1 or more, more preferably 10 or more, even more preferably 20 or more, and particularly preferably 30 or more, from the viewpoint of more excellent resolution. The content of the photo-bleachable compound is preferably 1.00 to 60.00 mass %, more preferably 5.00 to 40.00 mass %, and even more preferably 8.00 to 30.00 mass %, relative to the total mass of the thermoplastic resin layer, in terms of achieving better effects of the present invention.

[0083] <Other ingredients> The thermoplastic resin layer may contain other components in addition to the above. Other ingredients include, for example, surfactants and rust inhibitors.

[0084] (surfactant) The thermoplastic resin layer may contain a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A No. 2009-237362. Of these surfactants, fluorine-based surfactants or silicone-based surfactants are preferred.

[0085] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved and the fluorine atom is volatilized. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21, etc.). The fluorosurfactant may be a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. The fluorosurfactant may be a block polymer. The fluorine-based surfactant may be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group with an ethylenically unsaturated double bond in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0086] As the fluorine-based surfactant, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred in terms of improving environmental friendliness.

[0087] Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, and F-555- A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (all manufactured by DIC); EXP.MFS-324, EXP.MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS- 579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC Corporation); PolyFox Examples include PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS); and U-120E (manufactured by Unichem).

[0088] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or terminals, and polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain. Preferred silicone surfactants are polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain. The polymers may be either random copolymers or block copolymers.

[0089] Commercially available silicone surfactants include, for example, EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2, and S-506 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, and X-22-6266. , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, K F-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-12 5, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicones Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Perform BYK Materials; BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0090] The surfactants may be used alone or in combination of two or more. The content of the surfactant is preferably from 0.01 to 5.00% by mass, more preferably from 0.05 to 1.00% by mass, based on the total mass of the thermoplastic resin layer.

[0091] (rust inhibitor) The thermoplastic resin layer also preferably contains a rust inhibitor. Examples of the rust inhibitor include heterocyclic compounds, such as triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, pyrimidine compounds, and pyridine compounds, and triazole compounds, benzotriazole compounds, and tetrazole compounds are preferred. Examples of heterocyclic compounds include compounds described in WO 2022 / 039027.

[0092] The rust inhibitors may be used alone or in combination of two or more. The content of the rust inhibitor is preferably from 0.01 to 5.00 mass %, more preferably from 0.05 to 1.00 mass %, based on the total solid content of the photosensitive composition.

[0093] <Properties of the thermoplastic resin layer> The thickness of the thermoplastic resin layer is preferably from 1 to 15 μm, more preferably from 3 to 15 μm, and even more preferably from 8 to 13 μm, from the viewpoints of resolution and development speed. The thickness of each layer in the transfer film can be measured using a white light interferometer (NewView7200) manufactured by Zygo.

[0094] [Middle class] The transfer film has an intermediate layer. By having the transfer film have an intermediate layer, it is possible to suppress mixing of components between the thermoplastic resin layer and the photosensitive composition layer, and to suppress a decrease in the development speed of the thermoplastic resin layer. The intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin. Alternatively, an oxygen-blocking layer having an oxygen-blocking function, as described in JP-A-5-072724 as a "separation layer," can also be used as the intermediate layer. The oxygen-blocking intermediate layer is preferred because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. The oxygen-blocking layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, an oxygen-blocking layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0095] <Water-soluble resin> Examples of the water-soluble resin contained in the water-soluble resin layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

[0096] The lower limit of the weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more, and the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The polydispersity of the water-soluble resin is preferably from 1.0 to 10.0, more preferably from 1.0 to 5.0.

[0097] The water-soluble resin preferably contains polyvinyl alcohol, more preferably both polyvinyl alcohol and polyvinylpyrrolidone, in order to further improve the oxygen barrier property and the ability to inhibit interlayer mixing. The water-soluble resin also preferably contains a cellulose-based resin.

[0098] The water-soluble resin may be used alone or in combination of two or more kinds. The content of the water-soluble resin is preferably 50.00% by mass or more, more preferably 70.00% by mass or more, and even more preferably 80.00% by mass or more, based on the total mass of the intermediate layer. There is no particular upper limit to the content of the water-soluble resin, but it is often 99.90% by mass or less, and preferably 99.80% by mass or less, based on the total mass of the intermediate layer.

[0099] <Photodecolorizable compound> In terms of achieving better resolution, it is also preferable that the intermediate layer further contains a photobleachable compound. By including a photobleachable compound in the intermediate layer, the intermediate layer also functions as a CEL, resulting in better resolution. Examples of the photo-discolorable compound that the intermediate layer may contain include the photo-discolorable compounds contained in the thermoplastic resin layer described above. When the intermediate layer contains a photo-discolorable compound, the photo-discolorable compound contained in the intermediate layer may be the same as or different from the photo-discolorable compound contained in the thermoplastic resin layer.

[0100] The photo-bleachable compounds may be used alone or in combination of two or more. The content of the photo-bleachable compound is preferably from 1.00 to 50.00% by mass, and more preferably from 5.00 to 20.00% by mass, based on the total mass of the intermediate layer.

[0101] In addition to the above components, the intermediate layer may contain other known components such as a surfactant. Examples of the surfactant that may be contained in the intermediate layer include the surfactants that may be contained in the thermoplastic resin layer described above. The surfactants may be used alone or in combination of two or more. The content of the surfactant is preferably 0.01 to 10.00% by mass, and more preferably 0.10 to 1.00% by mass, based on the total mass of the intermediate layer.

[0102] <Properties of the middle layer> The thickness of the intermediate layer is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm.

[0103] [Photosensitive composition layer] The transfer film has a photosensitive composition layer. In terms of resolution, the photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed by exposure corresponds to a cured layer.

[0104] The negative photosensitive composition layer preferably contains a resin A which is an alkali-soluble thermoplastic resin, a monomer having a radical polymerizable group, and a radical polymerization initiator.

[0105] <Alkali-soluble thermoplastic resin (Resin A)> Examples of resin A include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol. The acid value of Resin A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g, from the viewpoint of suppressing swelling of the photosensitive composition layer by an alkaline developer and thereby achieving better resolution. The lower limit of the acid value is not particularly limited, but from the viewpoint of achieving better developability, it is more preferably 120 mgKOH / g or more, and even more preferably 150 mgKOH / g or more.

[0106] The weight-average molecular weight of resin A is not particularly limited, but from the viewpoints of resolution and developability, it is preferably 500,000 or less, more preferably 100,000 or less, and even more preferably 60,000 or less. Furthermore, from the viewpoints of the edge fusing property and cut-chip property of the transfer film, it is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. Edge fusing property refers to the degree to which the photosensitive composition layer easily protrudes from the edge of the roll when the transfer film is wound into a roll. Cut-chip property refers to the degree to which chips fly off when an unexposed film is cut with a cutter. If these chips adhere to the top surface of the photosensitive composition layer, they may be transferred to a mask in a subsequent exposure process, resulting in defective products. The polydispersity of Resin A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0107] From the viewpoint of resolution, Resin A preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include an optionally substituted phenyl group and an optionally substituted aralkyl group. Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer), and a monomer having an aralkyl group or styrene is preferred. The aralkyl group includes an optionally substituted phenylalkyl group, and is preferably an optionally substituted benzyl group. Examples of the monomer having an aralkyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol; and (meth)acrylates having a phenylalkyl group other than a benzyl group, such as phenylethyl (meth)acrylate. Of the aralkyl group-containing monomers, benzyl (meth)acrylate is preferred.

[0108] Resin A may have one type of structural unit based on a monomer having an aromatic hydrocarbon group, or may have two or more types of structural units based on a monomer having an aromatic hydrocarbon group. The content of the structural units based on the monomer having an aromatic hydrocarbon group is preferably 20 to 80 mass %, more preferably 25 to 70 mass %, and even more preferably 30 to 65 mass %, based on all structural units of the resin A.

[0109] From the viewpoint of alkaline developability, it is preferable that the resin A has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphate group, and a phosphonate group, and the carboxy group is preferred. As a monomer that provides a structural unit having an acid group, a (meth)acrylate having a carboxy group or (meth)acrylic acid is preferred, and (meth)acrylic acid is more preferred.

[0110] Resin A may have one type of structural unit having an acid group, or two or more types. The content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) is preferably 10 to 50 mass %, and more preferably 15 to 40 mass %, of all structural units of the resin A, from the viewpoints of developability and resolution.

[0111] From the viewpoint of resolution, the resin A preferably has a reactive group, and more preferably has a structural unit having a reactive group. The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group, and more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.

[0112] [ka]

[0113] Resin A may have one type of structural unit having a reactive group, or may have two or more types of structural units. From the viewpoint of resolution, the content of the structural unit having a reactive group is preferably from 5 to 70 mass %, more preferably from 10 to 50 mass %, and even more preferably from 20 to 40 mass %, based on all structural units of the resin A.

[0114] Examples of a method for introducing a reactive group into Resin A include a method of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic acid anhydride. A preferred example of a method for introducing a reactive group into resin A is to synthesize a polymer having a carboxy group by polymerization, and then react some of the carboxy groups of the resulting polymer with glycidyl (meth)acrylate by a polymer reaction to introduce a (meth)acryloxy group into the polymer. This method allows for the production of a resin having a (meth)acryloxy group in its side chain.

[0115] Resin A may contain structural units derived from non-acidic monomers. Examples of the non-acidic monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred. The content of structural units derived from non-acidic monomers in Resin A is preferably 0.5 to 60 mass %, more preferably 1 to 50 mass %, and even more preferably 1 to 30 mass %, based on all structural units in Resin A.

[0116] Resin A may have a linear structure, a branched structure, or an alicyclic structure in the side chain. In this specification, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branching off from the main chain. By using a monomer containing a group having a branched structure or an alicyclic structure in the side chain, it is possible to introduce a branched structure or an alicyclic structure into the side chain of Resin A. The group having an alicyclic structure may be monocyclic or polycyclic. Examples of monomers containing a group having a branched structure in the side chain include the monomers described in paragraph

[0064] of WO 2021 / 166719, the contents of which are incorporated herein by reference.

[0117] The resin A may be used alone or in combination of two or more. The content of the resin A is preferably from 20.00 to 80.00% by mass, more preferably from 30.00 to 70.00% by mass, and even more preferably from 40.00 to 65.00% by mass, relative to the total mass of the photosensitive composition layer.

[0118] The photosensitive composition layer may contain a resin other than the resin A described above. Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0119] <Monomers with radical polymerizable groups> The photosensitive composition layer preferably contains a monomer having a radically polymerizable group (hereinafter, also simply referred to as "radical polymerizable monomer"). The radical polymerizable group is preferably an ethylenic double bond such as a vinyl group, a (meth)acryloyl group, a styryl group, or a maleimide group, and more preferably a (meth)acryloyl group. The radical polymerizable monomer is a compound different from the above-mentioned resin A, and preferably has a molecular weight (weight average molecular weight) of 200 to 2,000.

[0120] From the viewpoint of resolution, the radical polymerizable monomer is preferably a polyfunctional radical polymerizable monomer having two or more radical polymerizable groups in one molecule. The number of radically polymerizable groups that the radically polymerizable monomer has in one molecule is preferably 6 or less, and more preferably 3 or less.

[0121] (Radical polymerizable monomer B1) The radical polymerizable monomer preferably comprises a radical polymerizable monomer B1 having an aromatic ring and two ethylenically unsaturated groups. Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring, aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring, and condensed rings thereof, and the aromatic hydrocarbon ring is preferred, and the benzene ring is more preferred. The aromatic ring may have a substituent. The radical polymerizable monomer B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0122] The radical polymerizable monomer B1 preferably has a bisphenol structure, since this inhibits swelling of the photosensitive composition layer due to a developer and provides better resolution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0123] Examples of the radical polymerizable monomer B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two ends of the bisphenol structure and the two polymerizable groups may be bonded directly or via one or more alkyleneoxy groups, and preferably via one or more alkyleneoxy groups. That is, the radical polymerizable monomer B1 preferably has an alkylene oxide-modified bisphenol structure. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy or propyleneoxy groups, more preferably ethyleneoxy groups. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The radical polymerizable monomer B1 having a bisphenol structure is described in paragraphs

[0072] to

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

[0124] The radical polymerizable monomer B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane. (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated bisphenol A dimethacrylate (BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0125] The radical polymerizable monomer B1 is also preferably a compound represented by the following general formula (B1).

[0126] [ka]

[0127] In general formula (B1), R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the -(AO)- and -(BO)- structural units may be random or in a block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0128] The radical polymerizable monomer B1 may be used alone or in combination of two or more. The content of the radical polymerizable monomer B1 is preferably 10.00 to 70.00 mass %, more preferably 20.00 to 60.00 mass %, and even more preferably 25.00 to 50.00 mass %, relative to the total mass of the photosensitive composition layer, in terms of better resolution.

[0129] The radical polymerizable monomer may include a radical polymerizable monomer other than the radical polymerizable monomer B1. The polymerizable compound other than the radical polymerizable monomer B1 can be appropriately selected from known compounds, such as a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound without an aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0130] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0131] Examples of the difunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene Examples of the acrylate copolymer include glycol dimethacrylate (4G, 9G, 14G, 23G, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) M-220 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-240 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-270 (manufactured by Toagosei Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0132] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof.

[0133] Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ethoxylated trimethylolpropane triacrylate (SR454, SR499, and SR502 manufactured by Tomoe Engineering Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel-Allnex Corporation, etc.), and the like. 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), and Aronix M-510 (manufactured by Toagosei Co., Ltd.).

[0134] Furthermore, a polymerizable compound having an acid group (such as a carboxy group) may be used as the polymerizable compound. The acid group may form an acid anhydride group. Examples of polymerizable compounds having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). As the polymerizable compound having an acid group, for example, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A No. 2004-239942 may be used.

[0135] The radical polymerizable monomers may be used alone or in combination of two or more. The content of the radical polymerizable monomer is preferably from 10.00 to 70.00% by mass, more preferably from 20.00 to 60.00% by mass, and even more preferably from 30.00 to 50.00% by mass, relative to the total mass of the photosensitive composition layer.

[0136] <Radical polymerization initiator> The photosensitive composition layer preferably contains a radical polymerization initiator. As the radical polymerization initiator, known radical polymerization initiators can be used, and a photoradical polymerization initiator is preferred. The photoradical polymerization initiator is a polymerization initiator that generates radicals when exposed to actinic rays such as ultraviolet rays, visible light, and X-rays, and is preferably a compound that generates radicals when exposed to ultraviolet rays.

[0137] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a photopolymerization initiator having a bistriarylimidazole structure. A photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an N-phenylglycine structure, or a photopolymerization initiator having a triarylbiimidazole structure is preferred, and a photopolymerization initiator having a triarylbiimidazole structure is more preferred. As the photopolymerization initiator having a triarylbiimidazole structure, 2,4,5-triarylimidazole dimer and derivatives thereof are preferred, and specific examples thereof include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A No. 2011-95716 and paragraphs

[0064] to

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

[0138] Specific examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Chemical Co., Ltd.), 1-[4-(phenylthio)]phenyl-1,2-octanedione-2-(O-benzoyloxime) (IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), and IRGACURE OXE-04 (manufactured by BASF). OXE-04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Omnirad 379EG, IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, IGM Resins BV)Co., Ltd.), oxime ester photoinitiator (Lunar 6, DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (B-CIM, Hampford Chemical Industry Co., Ltd.), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305, Changzhou Power Electric Co., Ltd.), Examples of suitable oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.).

[0139] The radical polymerization initiator may be used alone or in combination of two or more. The content of the radical polymerization initiator is preferably from 1.00 to 15.00% by mass, and more preferably from 3.00 to 10.00% by mass, based on the total mass of the photosensitive composition layer.

[0140] The photosensitive composition layer may contain components other than those described above.

[0141] <Sensitizer> From the viewpoint of resolution, the photosensitive composition layer preferably contains a sensitizer. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole, etc.), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. Dialkylaminobenzophenone compounds, anthracene compounds, distyrylbenzene compounds, and styrylpyridine compounds are preferred, and dialkylaminobenzophenone compounds are more preferred.

[0142] The sensitizers may be used alone or in combination of two or more. The content of the sensitizer is preferably from 0.001 to 5.00% by mass, more preferably from 0.01 to 1.00% by mass, and even more preferably from 0.01 to 0.50% by mass, relative to the total mass of the photosensitive composition layer.

[0143] <Dye> From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the photosensitive composition layer preferably contains a dye (also referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. When dye N is contained, adhesion to adjacent layers is improved, resulting in superior resolution, although the detailed mechanism is unknown.

[0144] In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, an embodiment in which a dye in a decolorized state develops color in response to an acid, a base, or a radical, and an embodiment in which a dye in a colored state changes to a colored state of another hue. Specifically, dye N may be a compound that changes from a decolorized state to develop a color upon exposure, or a compound that changes from a colored state to decolorize upon exposure. In this case, the dye may be one whose color-developing or decolorizing state changes when an acid, base, or radical is generated and acts within the photosensitive composition layer upon exposure, or one whose color-developing or decolorizing state changes when the state (e.g., pH) within the photosensitive composition layer changes due to an acid, base, or radical. Alternatively, the dye may be one whose color-developing or decolorizing state changes upon direct stimulation by an acid, base, or radical without exposure.

[0145] In particular, from the viewpoint of the visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains, as dye N, both a dye whose maximum absorption wavelength changes in response to radicals and a photoradical polymerization initiator, from the viewpoints of the visibility of exposed and unexposed areas and resolution. From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0146] An example of the color-developing mechanism of dye N is an embodiment in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the cationic photopolymerization initiator, or the photobase generator.

[0147] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm upon color development, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one or two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or longer.

[0148] The maximum absorption wavelength of dye N can be obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer UV3100 (Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0149] Examples of dyes that develop or lose color upon exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferred from the viewpoint of visibility of exposed and unexposed areas.

[0150] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0151] From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby converting the leuco compound into a ring-closed state and thereby discoloring, or converting the leuco compound into a ring-open state and thereby developing a color. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which develops a color upon ring-opening of the lactone ring, the sultine ring, or the sultone ring by a radical or an acid, and more preferably a compound having a lactone ring, which develops a color upon ring-opening of the lactone ring by a radical or an acid.

[0152] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue naphthalene sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), and Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.). Examples of suitable anti-inflammatory agents include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0153] Specific examples of the leuco compounds among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-di 3-(N,N-Diethylamino)-7-benzylaminofluoran, 3-(N,N-Diethylamino)-7,8-benzofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-xylidinofluoran, 3-Piperidino-6-methyl-7-anilinofluoran, 3-Pyrrolidino-6-methyl-7-anilinofluoran, 3,3-Bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-Bis(1-n-butyl-2- 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0154] From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals. As dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate is preferred.

[0155] The dye N may be used alone or in combination of two or more. The content of dye N is preferably 0.10 to 10.00 mass %, more preferably 0.10 to 5.00 mass %, and even more preferably 0.10 to 1.00 mass %, relative to the total mass of the photosensitive composition layer, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. The content of dye N means the content of dye when all of dye N contained in the total mass of the photosensitive composition layer is in a color-developing state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (BASF Japan Ltd.) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dyes have developed is measured in the same manner as above, except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye. The content of the dye contained in the photosensitive composition layer is calculated based on the absorbance of the solution containing the photosensitive composition layer obtained and a calibration curve.

[0156] <Rust inhibitor> The photosensitive composition layer preferably contains a rust inhibitor, such as the rust inhibitors that may be contained in the thermoplastic resin layer. The rust inhibitors may be used alone or in combination of two or more. The content of the rust inhibitor is preferably from 0.001 to 5.00% by mass, more preferably from 0.01 to 1.00% by mass, and even more preferably from 0.01 to 0.50% by mass, relative to the total mass of the photosensitive composition layer.

[0157] <Polymerization inhibitor> The photosensitive composition layer preferably contains a polymerization inhibitor, such as the polymerization inhibitors that may be contained in the thermoplastic resin layer. The polymerization inhibitor may be used alone or in combination of two or more. The content of the polymerization inhibitor is preferably from 0.001 to 5.00% by mass, more preferably from 0.01 to 1.00% by mass, and even more preferably from 0.01 to 0.50% by mass, relative to the total mass of the photosensitive composition layer.

[0158] <Surfactant> The photosensitive composition layer preferably contains a surfactant, such as the surfactants that may be contained in the thermoplastic resin layer. The surfactants may be used alone or in combination of two or more. The content of the surfactant is preferably from 0.001 to 5.00% by mass, more preferably from 0.01 to 1.00% by mass, and even more preferably from 0.01 to 0.50% by mass, relative to the total mass of the photosensitive composition layer.

[0159] <Hydrogen donor compounds> The photosensitive composition layer may contain a hydrogen donor compound, which has the effects of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen. Examples of hydrogen donor compounds include amines and amino acid compounds.

[0160] Examples of amines include compounds described in M.R. Sander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), JP-B-44-020189, JP-A-51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure No. 33825. More specific examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among these, at least one amine selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferred in terms of achieving better effects of the present invention.

[0161] Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred as the amino acid compound in that it provides a more excellent effect of the present invention.

[0162] Further, examples of the hydrogen donor compound include organometallic compounds (such as tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (such as trithiane) described in JP-A-6-308727.

[0163] The hydrogen donor compounds may be used alone or in combination of two or more. The content of the hydrogen donor compound is preferably 0.01 to 10.00 mass%, more preferably 0.01 to 8.00 mass%, and even more preferably 0.03 to 5.00 mass%, relative to the total mass of the photosensitive composition layer, from the viewpoint of improving the curing rate through a balance between the polymerization growth rate and chain transfer.

[0164] The photosensitive composition layer may contain known additives in addition to the above components, if necessary. Examples of additives include chain transfer agents, polymerization inhibitors, antioxidants (e.g., phenidone, etc.), plasticizers, and particles (e.g., metal oxide particles). Other components include other additives described in paragraphs

[0058] to

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

[0165] <Properties of the Photosensitive Composition Layer> The thickness of the photosensitive composition layer is preferably from 1 to 30 μm, more preferably from 2 to 20 μm, from the viewpoint of resolution.

[0166] UV light containing light with a wavelength of 365 nm is used, and the irradiation dose at the wavelength of 365 nm is 1000 mJ / cm 2 The transmittance of the photosensitive composition layer after irradiation so as to satisfy the above condition (hereinafter also referred to as "resist transmittance") is preferably 60% or more, more preferably 75% or more, and even more preferably 85% or more. The upper limit is 100% or less. The resist transmittance can be measured by the following method. The transfer film was attached to glass, and the temporary support was peeled off to obtain a laminate T. The laminate T was irradiated with ultraviolet light containing light with a wavelength of 365 nm at an irradiation dose of 1000 mJ / cm at a wavelength of 365 nm. 2 The thermoplastic resin layer is irradiated so as to obtain a laminate T after ultraviolet light irradiation. The thermoplastic resin layer and the intermediate layer are removed from the irradiated laminate T using an alkaline developer, and the transmittance of the resulting photosensitive composition layer is measured using a spectrophotometer. The ultraviolet light irradiation method can be the same as the above-mentioned method for measuring T1000 / T0 of the transfer film.

[0167] [Protective film] The transfer film may have a protective film on the photosensitive composition layer. As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Furthermore, a resin film made of the same material as the temporary support may be used as the protective film. Among these, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0168] From the viewpoints of mechanical strength and economy, the thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm.

[0169] In addition, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 The following is preferable: "Fisheyes" are foreign matter, unmelted matter, oxidized degradation products, etc., that are trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0170] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The following is more preferable: This can suppress defects caused by the transfer of irregularities due to particles contained in the protective film to the photosensitive composition layer or metal layer.

[0171] In order to provide good winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, and is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. In order to prevent defects during transfer, the surface roughness Ra of the protective film on the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, and is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0172] [Method for manufacturing transfer film] The method for producing the transfer film is not particularly limited, and known methods can be used. Examples of a method for manufacturing the transfer film 10 shown in Figure 1 include a method including the steps of applying a thermoplastic resin layer-forming composition to the surface of the temporary support 12 to form a coating film, and then drying this coating film to form the thermoplastic resin layer 14, applying an intermediate layer-forming composition to form a coating film, and then drying this coating film to form the intermediate layer 16, and applying a photosensitive composition layer-forming composition to the surface of the intermediate layer 16 to form a coating film, and then drying this coating film to form the photosensitive composition layer 18. By the above steps, a transfer film 10 can be produced in which the temporary support 12, the thermoplastic resin layer 14, the intermediate layer 16, and the photosensitive composition layer 18 are laminated in this order. When the transfer film 10 has a protective film 20, the protective film 20 may be pressure-bonded onto the photosensitive composition layer 18 of the transfer film 10 produced by the above-mentioned production method. After the transfer film 10 is produced by the above-described production method, the transfer film 10 may be wound up to produce and store a roll of transfer film. The roll of transfer film 10 can be provided as is to the lamination step with a substrate in a roll-to-roll system, which will be described later.

[0173] <Composition for forming thermoplastic resin layer and method for forming thermoplastic resin layer> The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and any known method can be used. For example, the thermoplastic resin layer can be formed by applying a composition for forming a thermoplastic resin layer on the temporary support and drying it as necessary. The thermoplastic resin layer-forming composition preferably contains the various components for forming the thermoplastic resin layer described above and a solvent. Note that, in the thermoplastic resin layer-forming composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the thermoplastic resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the components other than the solvent, and any known solvent can be used. Examples of the solvent include the same solvents as those contained in the composition for forming a photosensitive composition layer described below, and preferred embodiments are also the same. The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solid content of the composition.

[0174] The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0175] <Composition for forming an intermediate layer and method for forming an intermediate layer> The composition for forming an intermediate layer preferably contains the various components for forming the intermediate layer described above and a solvent. Note that, in the composition for forming an intermediate layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the intermediate layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0176] The method for forming the composition for forming an intermediate layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0177] <Photosensitive composition layer-forming composition and method for forming photosensitive composition layer> In terms of excellent productivity and ease of forming the above-mentioned photosensitive composition layer, the photosensitive composition layer is desirably formed by a coating method using a photosensitive composition layer-forming composition containing the components constituting the above-mentioned photosensitive composition layer (e.g., an alkali-soluble thermoplastic resin, a monomer having a radical polymerizable group, and a radical polymerization initiator, etc.) and a solvent.

[0178] The composition for forming a photosensitive composition layer preferably contains the various components for forming the photosensitive composition layer described above and a solvent. Note that, in the composition for forming a photosensitive composition layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive composition layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and any known solvent can be used. Specific examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0179] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0180] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As the solvent, the solvents described in paragraphs 0092 to 0094 of WO 2018 / 179640 and the solvents described in paragraph 0014 of JP 2018-177889 A may be used, the contents of which are incorporated herein by reference. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0181] Examples of methods for applying the photosensitive composition layer-forming composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (ie, slit coating).

[0182] The method for drying the coating film of the composition for forming the photosensitive composition layer is preferably heating drying or drying under reduced pressure. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no upper limit, but the drying time is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0183] Furthermore, a transfer film can be produced by laminating a protective film to the photosensitive composition layer. The method for laminating a protective film to the photosensitive composition layer is not particularly limited, and known methods can be used. Examples of a device for laminating the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0184] [Application] The transfer film of the present invention can be used in a variety of applications. For example, it can be used as an electrode protective film, an insulating film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an anti-reflection film, an etching resist, and a plating member. More specific examples include a protective film or insulating film for a touch panel electrode, a protective film or insulating film for a printed wiring board, a protective film or insulating film for a TFT substrate, a color filter, an overcoat film for a color filter, an etching resist and a plating resist for forming wiring, and a metal mask with minute through-holes used in the manufacture of an OLED (organic light-emitting diode), etc.

[0185] The transfer film of the present invention is preferably used in the production of a laminate having a conductive pattern, and more specifically, is preferably used to form an etching resist or plating resist for forming a conductive pattern.

[0186] [Method of manufacturing a laminate having a conductive pattern] The method for producing a laminate having a conductive pattern is not particularly limited as long as it is a method that uses the transfer film of the present invention, but the following method is preferred. a lamination step of laminating the transfer film of the present invention described above to a substrate having a metal layer on its surface so that the photosensitive composition layer side is in contact with the metal layer; an exposure step of pattern-exposing the photosensitive composition layer from the side opposite to the substrate side; a developing step of developing the exposed photosensitive composition layer using an alkaline developer to form a resist pattern; one of an etching process for etching the metal layer in an area where the resist pattern is not disposed to form a conductor pattern, and a plating process for plating the metal layer; a resist stripping step of stripping the resist pattern; Furthermore, when the plating step is included, the method further includes a removal step of removing the metal layer exposed in the resist stripping step to form a conductive pattern on the substrate. The specific steps of the above manufacturing method will be described in detail below.

[0187] [Peeling process] When the transfer film has a protective film, the above-mentioned production method preferably includes a peeling step of peeling the protective film from the transfer film before the laminating step, whereby the surface of the photosensitive composition layer of the transfer film is exposed. The method for peeling off the protective film is not particularly limited, and can be any known method. For example, the protective film can be peeled off while being wound into a roll.

[0188] [Lamination process] The laminating step is a step of laminating the transfer film so that the photosensitive composition layer side is in contact with the metal layer of the substrate having a metal layer on its surface. By carrying out the laminating step, a laminate (substrate with a photosensitive composition layer) having, in this order, the substrate, the conductive layer, the thermoplastic resin layer, the intermediate layer, the photosensitive composition layer, and the temporary support is obtained.

[0189] The substrate having a conductive layer has a conductive layer on a substrate, and may have any layer formed thereon as necessary. That is, the substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0190] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the substrate is described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference. Preferred materials for the resin substrate are cycloolefin polymers and polyimides. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0191] From the viewpoints of conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Furthermore, only one conductive layer may be disposed on the substrate, or two or more conductive layers may be disposed on the substrate. When two or more conductive layers are disposed, it is preferable that the conductive layers are made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph

[0141] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0192] The conductive layer may be a transparent conductive layer that can be used to form a transparent electrode through the process described below. The transparent conductive layer is preferably made of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a metal mesh or a metal thin wire such as a metal nanowire. Examples of the thin metal wires include thin wires of silver, copper, etc. Among these, conductive silver materials such as silver mesh and silver nanowires are preferred.

[0193] The thickness of the conductive layer is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more, and the upper limit is preferably 10 μm or less, more preferably 2 μm or less.

[0194] In the lamination, it is preferable to press the conductive layer and the photosensitive composition layer together so that they come into contact with each other. The pressure-bonding method is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferable to place the surface of the photosensitive composition layer on a substrate having a conductive portion, and then apply pressure and heat with a roll or the like. For lamination, a known laminator such as a vacuum laminator or an auto-cut laminator can be used. The lamination temperature is not particularly limited, but is preferably 70 to 130°C, for example.

[0195] [Exposure process] The exposure step is a step of pattern-exposing the photosensitive composition layer from the side opposite to the substrate side. By performing the exposure step and the development step described below, a resist pattern that protects at least a part of the conductive layer on the substrate is formed. Here, the term "pattern exposure" refers to a form of patterned exposure, that is, exposure in a form in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and may be adjusted as appropriate.

[0196] The light source for pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range (e.g., 365 nm or 405 nm) that can at least cure the photosensitive composition layer. In particular, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity. Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose is 5 to 200 mJ / cm 2 is preferred, and 10 to 200 mJ / cm 2 is more preferred.

[0197] Examples of the exposure method include mask exposure, direct imaging exposure, and projection exposure, with projection exposure being preferred. A preferred embodiment of the light source, exposure dose, and exposure method used for exposure is described, for example, in paragraphs

[0146] to

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

[0198] [Temporary support peeling step] The above-mentioned manufacturing method preferably includes a temporary support peeling step of peeling off the temporary support. The temporary support peeling step is carried out between the laminating step and the exposure step, or between the exposure step and the developing step described below, and is preferably carried out before the exposure step (specifically, between the laminating step and the exposure step). The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

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

[0199] [Development process] The developing step is a step of developing the exposed photosensitive composition layer with an alkaline developer to form a resist pattern. When the photosensitive composition layer is a negative photosensitive composition layer, the unexposed portions of the photosensitive composition layer are removed with the alkaline developer, and the exposed photosensitive composition layer is formed as a resist pattern. In addition, it is preferable that the thermoplastic resin layer and the intermediate layer are removed by the developing step. The alkaline developer is preferably an alkaline aqueous solution. Examples of alkaline compounds that can be contained in the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0200] Examples of the development method include puddle development, shower development, spin development, and dip development.

[0201] In the present specification, examples of the developer that can be suitably used include the developer described in paragraph

[0194] of WO 2015 / 093271, and examples of the development method that can be suitably used include the development method described in paragraph

[0195] of WO 2015 / 093271.

[0202] After development, it is also preferable to carry out a rinse treatment to remove any developer remaining on the conductive layer-formed substrate before proceeding to the next step. Water or the like can be used for the rinse treatment. After the development and / or rinsing treatment, a drying treatment may be carried out to remove excess liquid from the substrate with the conductive layer.

[0203] In the method for manufacturing a laminate having a conductive pattern, either an etching step or a plating step is carried out.

[0204] [Etching process] The etching process is a process of etching the metal layer in the area where the resist pattern is not disposed, to form a conductive pattern. As the etching method, known methods can be applied, and examples thereof include the method described in paragraphs

[0209] to

[0210] of JP 2017-120435 A, the method described in paragraphs

[0048] to

[0054] of JP 2010-152155 A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.

[0205] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched. Examples of acidic etching solutions include aqueous solutions of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and aqueous solutions of a mixture of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions of alkaline components selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), as well as aqueous solutions of mixtures of alkaline components and salts (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0206] [Plating process] The plating step is a step of plating the conductive layer in the area where the resist pattern is not disposed. Examples of plating methods include electrolytic plating and electroless plating, with electrolytic plating being preferred from the standpoint of productivity. When the plating step is carried out, a plated layer having a pattern similar to that of the area where the resist pattern is not arranged (openings of the resist pattern) is obtained on the substrate with the conductive layer. When a plating process is carried out, the conductive layer is preferably a metal layer.

[0207] Examples of the metal contained in the plating layer include known metals. Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals. In particular, the plating layer preferably contains copper or an alloy thereof, since this provides a conductive pattern with better electrical conductivity.Furthermore, the plating layer preferably contains copper as a main component, since this provides a conductive pattern with better electrical conductivity.

[0208] The thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm or more, and the upper limit is preferably 20 μm or less.

[0209] [Resist Stripping Process] The above-described method for manufacturing a laminate having a conductive pattern includes a resist stripping step after the etching step or plating step. The resist stripping step is a step of stripping off the remaining resist pattern. The method for removing the resist pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a remover is preferred. The removal method includes immersing the substrate having the remaining resist pattern in a stirring remover solution having a liquid temperature of preferably 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes. Examples of the removal solution include a removal solution obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, the removal may be carried out by a known method such as a spray method, a shower method, or a puddle method using a removal solution.

[0210] [Removal process] In the method for manufacturing a laminate, when a plating treatment step is performed, a removal step is included in which the metal layer exposed in the resist stripping step is removed to form a conductor pattern on the substrate.

[0211] The method for removing a portion of the conductive layer is not particularly limited, but it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixed solution, and phosphoric acid-hydrogen peroxide mixed solution.

[0212] When the removal step is carried out, the conductive layer exposed on the surface of the substrate is removed, and a plated layer having a pattern shape (conductor pattern) remains, thereby obtaining a laminate having a conductor pattern.

[0213] The upper limit of the line width of the conductor pattern to be formed is preferably 8 μm or less, more preferably 6 μm or less, and the lower limit is not particularly limited, but is often 1 μm or more.

[0214] [Other steps] The method for manufacturing a laminate having a conductive pattern may include any steps (other steps) other than the steps described above. For example, examples include a process for reducing visible light reflectance described in paragraph

[0172] of WO 2019 / 022089, and a process for forming a new conductive layer on an insulating film described in paragraph

[0172] of WO 2019 / 022089, but are not limited to these processes.

[0215] <Step of reducing visible light reflectance> The method for producing a laminate having a conductive pattern may include a step of performing a treatment to reduce the visible light reflectance of some or all of the plurality of conductive layers of the substrate. An example of a treatment for reducing the visible light reflectance is oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer. Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

[0216] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for producing a laminate having a conductive pattern preferably includes the steps of forming an insulating film on the surface of the conductive pattern, and forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and may include a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0217] A preferred method for producing a laminate having a conductive pattern is to use a substrate having multiple conductive layers on both surfaces of a base material, and to sequentially or simultaneously form circuits on the conductive layers formed on both surfaces of the base material. This configuration allows for the formation of a laminate having a conductive pattern for a touch panel, in which a first conductive pattern is formed on one surface of the base material and a second conductive pattern is formed on the other surface. It is also preferred to form a laminate having a conductive pattern for a touch panel having such a configuration from both sides of the base material using a roll-to-roll process.

[0218] [Uses of laminates having conductive patterns] The laminate having a conductive pattern produced by the above-mentioned production method can be applied to various devices. Examples of devices including the laminate having a conductive pattern produced by the above-mentioned production method include a display device, a printed wiring board, a semiconductor package, and an input device (e.g., a touch panel), with a printed wiring board or a semiconductor package being preferred. The input device can also be applied to a display device such as an organic electroluminescence (EL) display device or a liquid crystal display device. [Example]

[0219] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0220] In the following examples, unless otherwise specified, "parts" and "%" are by mass. In the following examples, the acid value used is a theoretical acid value.

[0221] [Transfer film manufacturing] The composition and components of each layer used in producing the transfer film will be described below.

[0222] [Photosensitive composition layer] The composition of each photosensitive composition layer in each transfer film described below is shown in Table 1. The numerical value of each component is the content (mass %) relative to the total solid content.

[0223] [Table 1]

[0224] Details of each component are as follows:

[0225] <Resin> Resins A1 to A3 were synthesized by known methods. Table 2 below shows the types and mass ratios (mass%) of the monomers used to synthesize Resins A1 to A3, as well as the weight average molecular weights. The weight average molecular weights (Mw) of the synthesized resins A1 to A3 were measured by GPC under the following conditions.

[0226] Apparatus: Tosoh high-speed GPC apparatus HLC-8420GPC (product name), manufactured by Tosoh Corporation Guard column: Tosoh Corporation, HZ-L Separation column: Three columns of TSK gel Super HZM-N (product name) manufactured by Tosoh Corporation connected in series Measurement temperature: 40℃ Eluent: THF (tetrahydrofuran) Flow rate: Sample pump 0.35 mL / min, reference pump 0.175 mL / min Injection volume: 10μL Detector: differential refractometer GPC column calibration standard solution: Standard polystyrene manufactured by Tosoh Corporation

[0227] [Table 2]

[0228] The following abbreviations represent the following compounds: St: Styrene (Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) MAA-GMA: A structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid

[0229] The acid value of Resin A1 was 160 mgKOH / g. A solution containing Resin A1 at a solid content concentration of 30 mass % (solvent: propylene glycol monomethyl ether acetate (PGMEA)) was prepared as Resin A1 solution. The acid value of Resin A2 was 160 mgKOH / g. A solution containing Resin A2 at a solid content concentration of 30 mass % (solvent: PGMEA) was prepared as Resin A2 solution. The acid value of Resin A3 was 160 mgKOH / g. A solution containing Resin A3 at a solid content concentration of 30 mass % (solvent: PGMEA) was prepared as Resin A3 solution. The above-mentioned resin A1 to A3 solutions were used to prepare compositions for forming a photosensitive composition layer, which will be described later. The resin contents in Table 1 above are the amounts of solid content.

[0230] <Other ingredients> Details of each component other than the resin in Table 1 are as follows: (Radical polymerizable monomer) BPE-500: 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. BPE-100: 2,2-bis(4-(methacryloylethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. (Polymerization initiator) B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford (sensitizer) SB-PI 701: 4,4′-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd. (chain transfer agent) Compound A: N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (dye) LCV: Leuco Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd. (rust inhibitor) CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd. (polymerization inhibitor) TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd. (surfactant) EXP.S-315, manufactured by DIC Corporation Megafac (registered trademark) F-552, manufactured by DIC Corporation

[0231] <Preparation of Photosensitive Composition Layer-Forming Composition> The above-mentioned components were mixed to obtain the composition shown in Table 1, and then methyl ethyl ketone (MEK) was added to prepare a composition for forming a photosensitive composition layer with a solid content concentration of 15% by mass.

[0232] [Middle class] The composition of each intermediate layer in each transfer film described below is shown in Table 3. The numerical value of each component is the content (mass %) relative to the total solid content.

[0233] [Table 3]

[0234] Details of each component are as follows: (resin) PVA: Polyvinyl alcohol, product name "Kuraray Poval PVA-205", manufactured by Kuraray Co., Ltd. PVP: Polyvinylpyrrolidone, product name "Polyvinylpyrrolidone K-30", manufactured by Nippon Shokubai Co., Ltd. HPMC: Hydroxypropyl methylcellulose, product name "Metolose 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd. (surfactant) BYK-345: BYK Japan (photodecolorable compound) 4-(N,N-dimethylamino)benzenediazonium tetrafluoroborate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0235] <Preparation of composition for forming intermediate layer> After mixing the components to obtain the composition shown in Table 3, a solvent (a mixed solvent of ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.) in a mixing ratio (ion-exchanged water / methanol [mass ratio]) of 40 / 60) was added to prepare a composition for forming an intermediate layer with a solids concentration of 5% by mass.

[0236] [Thermoplastic resin layer] The composition of each thermoplastic resin layer in each transfer film described below is shown in Table 4. The numerical value of each component is the content (mass %) relative to the total solid content.

[0237] [Table 4]

[0238] Details of each component are as follows:

[0239] <Resin> The types and mass ratios (mass%) of the monomers used to synthesize Resin A4, as well as the weight-average molecular weight, are shown in Table 5. The weight-average molecular weight was measured in the same manner as for Resins A1 to A3 described above.

[0240] [Table 5]

[0241] The following abbreviations represent the following compounds: BzMA: benzyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) AA: Acrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0242] <Other ingredients> Details of each component other than the resin in Table 4 are as follows: (Plasticizers having polymerizable groups) A-DCP: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. 8UX-015: Multifunctional urethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd. TO-2349: Polyfunctional acrylate compound with carboxyl groups, manufactured by Toagosei Co., Ltd. (rust inhibitor) CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd. (polymerization inhibitor) TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd. (photodecolorable compound) Compound 1: Compound with the structure shown below, molar absorption coefficient 15,000 L mol -1 ·cm -1

[0243] [ka]

[0244] -Synthesis of Compound 1- Compound 1 was synthesized according to the following procedure. 15.0 g of 1-nitroso-2-naphthol (Tokyo Chemical Industry Co., Ltd.), 130.5 g of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.), 150 g of distilled water, and 37.7 g of sodium hydrosulfite (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed and stirred for 4 hours at 25° C. After cooling with ice, distilled water was added and the mixture was filtered to obtain 13.1 g of intermediate 1-A. 4.8 g of Intermediate 1-A was mixed with 6.3 g of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 5.3 g of methyl pivaloylacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred for 4 hours at 140° C. After cooling, methanol was added, the mixture was cooled on ice, and filtered to obtain 5.8 g of Intermediate 1-B. Intermediate 1-B, 15.1 g of toluene, and 0.77 g of p-toluenesulfonic acid monohydrate (Fujifilm Wako Pure Chemical Industries, Ltd.) were added and stirred for 2 hours at 120° C. After cooling, distilled water and ethyl acetate were added, and the organic phase was separated to obtain a solution of intermediate 1-C. 11.8 g of the intermediate 1-C solution was mixed with 14.9 g of THF, and then 4.0 g of 2 M hydrochloric acid and then 2.5 g of isopentyl nitrite (Fujifilm Wako Pure Chemical Industries, Ltd.) were added dropwise under ice cooling, and the mixture was heated to room temperature (25°C) and stirred for 2 hours. Water and ethyl acetate were added to the resulting reaction mixture, and the mixture was separated. The organic phase was washed with water, dried over magnesium sulfate, filtered, and concentrated to obtain intermediate 1-D. Intermediate 1-D was mixed with acetone (18 mL), and triethylamine (Fujifilm Wako Pure Chemical Industries, Ltd.) (4.9 g) and p-toluenesulfonyl chloride (Tokyo Chemical Industry Co., Ltd.) (5.9 g) were added under ice cooling. The mixture was then warmed to room temperature and stirred for 1 hour. Water was added to the resulting reaction mixture, which was then crystallized, filtered, and washed with water to obtain crude compound 1. Ethyl acetate and THF were added to 3.4 g of crude compound 1, and the mixture was heated to 50°C to dissolve. Methanol was then added, the mixture was ice-cooled, stirred for 1 hour, filtered, and dried to obtain 2.9 g of compound 1.

[0245] Compound 2: The compound shown below was synthesized according to the method described in

[0227] of JP 2013-47765 A. Molar absorption coefficient: 7900 L·mol -1 ·cm -1

[0246] [ka]

[0247] 4-(N,N-dimethylamino)benzenediazonium tetrafluoroborate, molar extinction coefficient 10000 L mol -1 ·cm -1 BAPO: The compound with the structure shown below, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, with a molar absorption coefficient of 9000 L mol -1 ·cm -1

[0248] [ka]

[0249] (surfactant) EXP.S-315, manufactured by DIC Corporation

[0250] <Preparation of Thermoplastic Resin Layer-Forming Composition> The components were mixed to obtain the composition shown in Table 5, and then a solvent (MEK, PGMEA) was added to prepare a composition for forming a thermoplastic resin layer with a solid content concentration of 25% by mass.

[0251] [Production of transfer film] Each transfer film was prepared so as to have the configuration shown in Tables 6 to 8 below, and was composed of a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive composition layer. Specifically, the following applies: First, a composition for forming a thermoplastic resin layer shown in the table below was applied onto a temporary support (thickness 16 μm, 16KS40 manufactured by Toray Industries, Inc.) using a slit nozzle so that the coating width after drying would be 1.0 m and the film thickness after drying would be the values ​​shown in Tables 6 to 8. The film was then passed through a drying zone at 80°C for 40 seconds to form a thermoplastic resin layer. Next, the composition for forming an intermediate layer shown in Tables 6 to 8 was applied onto the thermoplastic resin layer using a slit nozzle so that the application width after drying would be 1.0 m and the film thickness after drying would be the value shown in Tables 6 to 8, and the coating was passed through a drying zone at 80°C for 40 seconds to form an intermediate layer. Furthermore, a composition for forming a photosensitive composition layer shown in Tables 6 to 8 was applied onto the intermediate layer using a slit nozzle so that the coating width after drying would be 1.0 m and the film thickness after drying would be the value shown in Tables 6 to 8, and the coating was passed through a drying zone at 80°C for 40 seconds to form a photosensitive composition layer. A 16 μm thick polyethylene terephthalate film (16KS40, manufactured by Toray Industries, Inc.) was pressed onto the film as a protective film to prepare a transfer film, which was then wound up into a roll.

[0252] [Measurement of transfer film properties] [T1000 / T0] The T1000 / T0 value was measured by the following procedure. Each of the prepared transfer films was laminated onto glass so that the photosensitive composition layer side was in contact with the glass, and the temporary support was peeled off to obtain a glass / photosensitive composition layer / intermediate layer / thermoplastic resin layer laminate T. The transmittance T0 of the laminate T at 365 nm before exposure was measured using a spectrophotometer. Next, the laminate T was irradiated from the thermoplastic resin layer side with ultraviolet light containing 365 nm light using a high-pressure mercury lamp as a light source, with an illuminance of 1000 mJ / cm at 365 nm. 2 The laminate T after exposure was measured for transmittance T1000 at 365 nm using a spectrophotometer. The value of T1000 / T0 was calculated from the obtained values ​​of T0 and T1000. The spectrophotometer used was an ultraviolet-visible spectrophotometer UV-1800 manufactured by Shimadzu Corporation.

[0253] [Resist transmittance] The resist transmittance was measured by the following method. The exposed laminate T used in the measurement of T1000 was subjected to a development treatment to remove the thermoplastic resin layer and the intermediate layer, thereby obtaining an exposed photosensitive composition layer. The transmittance of the exposed photosensitive composition layer at 365 nm was measured using a spectrophotometer. The development was carried out by spray development using a 30° C. aqueous sodium carbonate solution (sodium carbonate content: 1% by mass relative to the total mass of the aqueous sodium carbonate solution) as the developer for 2.0 times the shortest development time.

[0254] [evaluation] [Resolution] The resolution of the pattern formed by the transfer film was evaluated according to the following procedure. A Cu sputtering treatment was performed on the surface of a silicon wafer with a thickness of 0.7 mm to a thickness of 200 nm to obtain a substrate having a metal layer. The transfer film of each example was laminated onto the substrate so that the photosensitive composition layer was in contact with the conductor layer, and then pressed using a 100°C heat roll at a pressure of 0.7 MPa and a speed of 2 m / min (lamination step). Next, the temporary support was peeled off, and a mask containing a wiring pattern (L = 1-2 μm, 0.1 μm intervals, 10 lines) with a line (L) / space (S) = 1 / 1 (width ratio) was used to perform pattern exposure using a projection exposure system with a theoretical resolution of 1.5 μm and a high-pressure mercury lamp as a light source. The exposure dose was set to such that when exposed using a Stouffer 41-step tablet and developed in 2.0 times the shortest development time, the remaining step number would be 13. A 30°C aqueous sodium carbonate solution (the sodium carbonate content was 1% by mass relative to the total mass of the aqueous sodium carbonate solution) was used as the developer, and spray development was carried out for a time 2.0 times the shortest development time. The unexposed areas were removed, and a resist pattern was formed on the surface of the metal layer, thereby obtaining a patterned laminate. After the development, the minimum pattern L / S (μm / μm) without residue or peeling was defined as the resist resolution. In practice, it is preferable that the minimum L / S is 1.4 / 1.4 (μm / μm) or less.

[0255] [Developability] The ability to suppress a decrease in the development rate (developability) was evaluated according to the following procedure. A patterned laminate was produced in the same manner as in the evaluation of [Resolution] above, except that the development time was 1.5 times the shortest development time. The resulting pattern was observed for the smallest L / S pattern without residue or peeling, as obtained in the evaluation of [Resolution] above, and the developability was evaluated according to the following evaluation criteria.

[0256] A: No residue was observed. B: Residue was observed in the space.

[0257] [Surface failure] The lamination process was carried out in the same manner as in the above-mentioned [Resolution]. Next, the temporary support was peeled off, and the exposed surface was subjected to a visual field of 0.25 mm2 in five randomly selected areas (1 mm x 1 mm) on the surface. 2 The specimen was observed using an optical microscope (OLYMPUS, industrial inspection microscope MX63) and evaluated for surface defects according to the following evaluation criteria.

[0258] A: No lumps or cracks were observed. B: At least one of lumps and cracks was observed.

[0259] [result] Tables 6 to 8 show the configurations of each transfer film and the evaluation results. In the table, "photosensitive composition layer," "intermediate layer," and "thermoplastic resin layer" respectively indicate the type of each layer constituting each transfer film. For example, the transfer film of Example 1 has 1 photosensitive composition layer, 1 intermediate layer, and 1 thermoplastic resin layer. In the table, the column "Photo-bleachable compound / polymerization inhibitor" indicates the mass ratio of the content of the photo-bleachable compound to the content of the polymerization inhibitor in the thermoplastic resin layer.

[0260] [Table 6]

[0261] [Table 7]

[0262] [Table 8]

[0263] From the results shown in the above table, it was confirmed that the transfer film of the present invention is capable of forming a pattern with excellent resolution and that a decrease in the development rate is suppressed.

[0264] From a comparison of Examples 1 to 3, it was confirmed that when the thickness of the thermoplastic resin layer was 3 μm or more, the resolution was superior, and when the thickness was 8 μm or more, the resolution was even superior. Comparison of Examples 1 to 3 and 11 to 20 confirmed that the resolution was better when T1000 / T0≧10, even better when T1000 / T0≧50, and particularly better when T1000 / T0≧500. It was also confirmed that planar defects could be suppressed when T1000 / T0≦5000. Comparison of Examples 11 to 20 confirmed that when the mass ratio of the content of the photo-bleachable compound to the content of the polymerization inhibitor is 350 or less, surface defects can be further suppressed, and when it is 300 or less, a decrease in the development rate can be further suppressed. Furthermore, it was confirmed that when the mass ratio is 10 or more, the resolution is better, and when it is 30 or more, the resolution is even better. Comparison of Examples 11 to 20 confirmed that when the content of the photo-bleaching compound is 5.00% by mass or more relative to the total mass of the thermoplastic resin layer, the resolution is better, and when it is 8.00% by mass or more, the resolution is even better. Also, when the content of the photo-bleaching compound is 40.00% by mass or less relative to the total mass of the thermoplastic resin layer, it was confirmed that surface defects could be further suppressed. From a comparison of Examples 11 to 20, it was confirmed that when the content of the polymerization inhibitor was 0.04% by mass or more relative to the total mass of the thermoplastic resin layer, the decrease in the development rate could be further suppressed. Comparison between Example 11 and Example 18 confirmed that when the intermediate layer contained a photobleachable compound, the resolution was superior.

[0265] [Production of a laminate having a conductor pattern] A laminate having a conductor pattern was produced using the transfer film of each example by the following method. A Cu sputtering treatment was performed on the surface of a silicon wafer with a thickness of 0.7 mm to a thickness of 200 nm to obtain a substrate having a metal layer. The transfer film of each example was laminated onto the substrate so that the photosensitive composition layer was in contact with the conductor layer, and then pressed using a 100°C heat roll at a pressure of 0.7 MPa and a speed of 2 m / min (lamination step). Using a mask having a predetermined pattern, a projection exposure apparatus with a high-pressure mercury lamp as a light source was used to perform pattern exposure at the following exposure dose (exposure step): The exposure dose was set so that when a 41-step tablet manufactured by Stouffer was used and development was performed for 2.0 times the shortest development time, the number of remaining steps would be 13. A 1% by mass aqueous solution of sodium carbonate at 30° C. was used as a developer, and spray development was carried out for a time 2.0 times the shortest development time to remove the unexposed areas and form a resist pattern (development step). The conductive layer in the area where the resist pattern was not formed was subjected to electrolytic plating using a copper sulfate plating solution to form a copper plating layer with a thickness of 2 μm (plating process).The resist pattern was then stripped using a stripping solution (resist stripping process).The conductive layer exposed by the stripping of the resist pattern was subjected to an etching process (removal process) to form a conductive pattern layer.

[0266] Furthermore, a laminate having a conductive pattern was produced using the transfer film of Example 12 in the same manner, except that a step of peeling off the temporary support was added between the laminating step and the exposure step. [Explanation of symbols]

[0267] 10 Transfer film 12 Temporary support 14 Thermoplastic resin layer 16 Middle class 18 Photosensitive composition layer 20 Protective Film

Claims

1. A temporary support; a thermoplastic resin layer; The middle class and A transfer film having, in this order, a photosensitive composition layer, the thermoplastic resin layer contains an alkali-soluble thermoplastic resin, a plasticizer having a polymerizable group, a polymerization inhibitor, and a photobleachable compound; In the thermoplastic resin layer, a mass ratio of the content of the photo-decolorizable compound to the content of the polymerization inhibitor is 400 or less; The laminate obtained by peeling the temporary support from the transfer film was irradiated with ultraviolet light containing light with a wavelength of 365 nm at an irradiation dose of 1000 mJ / cm at a wavelength of 365 nm. ２ When irradiated from the thermoplastic resin layer side so as to satisfy the relationship of formula (1), the transmittance of the laminate at a wavelength of 365 nm before the irradiation is T0 and the transmittance of the laminate at a wavelength of 365 nm after the irradiation is T1000. Formula (1) T1000 / T0≧4

2. The transfer film according to claim 1 , wherein the photosensitive composition layer comprises an alkali-soluble thermoplastic resin, a monomer having a radical polymerizable group, and a radical polymerization initiator.

3. 3. The transfer film according to claim 1, wherein the content of the photo-decolorizable compound is 5.00 to 40.00% by mass with respect to the total mass of the thermoplastic resin layer.

4. 3. The transfer film according to claim 1, wherein the thermoplastic resin layer has a thickness of 1 to 15 μm.

5. The transfer film according to claim 1 or 2, wherein the T1000 is 65% or more.

6. 3. The transfer film according to claim 1, wherein the intermediate layer has a thickness of 0.1 to 3 μm.

7. The transfer film according to claim 1 or 2, wherein the intermediate layer comprises polyvinyl alcohol.

8. The transfer film according to claim 1 or 2, wherein the intermediate layer contains a photobleachable compound.

9. The photobleachable compound has a molar absorption coefficient of 8000 L mol at a wavelength of 365 nm. －１ ・cm －１ The transfer film according to claim 1 or 2.

10. The transfer film according to claim 1 or 2, wherein the transmittance of the photosensitive composition layer after the irradiation at a wavelength of 365 nm is 75% or more.

11. 3. The transfer film according to claim 1, wherein the photosensitive composition layer has a thickness of 2 to 20 μm.

12. a lamination step of laminating the transfer film according to claim 1 or 2 to a substrate having a metal layer on its surface so that the photosensitive composition layer side is in contact with the metal layer; an exposure step of pattern-exposing the photosensitive composition layer from the side opposite to the substrate side; a developing step of developing the exposed photosensitive composition layer using an alkaline developer to form a resist pattern; one of an etching process for etching the metal layer in an area where the resist pattern is not disposed to form a conductor pattern, and a plating process for plating the metal layer; a resist stripping step of stripping the resist pattern; Furthermore, when the plating treatment step is included, the method further includes a removal step of removing the metal layer exposed by the resist stripping step to form a conductor pattern on the substrate. A method for manufacturing a laminate having a conductive pattern.

13. The method for producing a laminate having a conductive pattern according to claim 12 , further comprising a step of peeling off the temporary support before the exposure step.

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