Method for manufacturing a transfer film and a laminate having a conductive pattern

Abstract

To provide a transfer film which enables manufacture of a resist pattern having large thickness and a large aspect ratio, and a method for manufacturing a laminate having a conductor pattern.SOLUTION: A transfer film is provided, having a temporary support and a photosensitive composition layer, wherein average film thickness of the photosensitive composition layer is 10 μm or more, the photosensitive composition layer includes a sensitizer and resin having a weight average molecular weight of 10,000 or more, the resin includes a structural unit having a crosslinkable group, the content of the structural unit having the crosslinkable group is 30 mass% or more with respect to the total structural unit of the resin, and transmittance at a wavelength of 365 nm of the photosensitive composition layer is 40% or more.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] Because the number of steps required to obtain a predetermined pattern is small, a method is widely used in which a photosensitive composition layer is placed on any substrate using a transfer film, and the photosensitive composition layer is exposed to light through a mask and then developed.

[0003] Patent Document 1 discloses a transfer film having a temporary support and a photosensitive resin composition layer containing a binder polymer containing a predetermined repeating unit. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-060891 Summary of the Invention [Problem to be solved by the invention]

[0005] Recently, there has been a demand for resist patterns that are thick (approximately 10 μm or more) and have a large aspect ratio. The present inventors attempted to form a resist pattern using the transfer film described in Patent Document 1, but found that they were unable to form a resist pattern having the above-mentioned properties, and that further improvements were necessary.

[0006] An object of the present invention is to provide a transfer film that can produce a resist pattern that is thick and has a large aspect ratio. Another object of the present invention is to provide a method for producing a laminate having a conductor pattern. [Means for solving the problem]

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

[0008] (1) A transfer film having a temporary support and a photosensitive composition layer, The photosensitive composition layer has an average film thickness of 10 μm or more, the photosensitive composition layer contains a sensitizer and a resin having a weight average molecular weight of 10,000 or more; the resin contains a structural unit having a crosslinkable group, the content of structural units having crosslinkable groups is 30% by mass or more relative to all structural units of the resin, A transfer film, wherein the transmittance of the photosensitive composition layer at a wavelength of 365 nm is 40% or more. (2) The transfer film according to (1), wherein the mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer and having a weight-average molecular weight of less than 10,000 to the resin is 0.50 to 0.80. (3) The transfer film according to (1) or (2), which has an intermediate layer between the temporary support and the photosensitive composition layer. (4) The transfer film according to (3), wherein the intermediate layer is a water-soluble resin layer. (5) A lamination step of laminating the transfer film and the substrate so that the surface of the transfer film opposite to the temporary support according to any one of (1) to (4) contacts the metal layer of the substrate having a metal layer on its surface; an exposure step of exposing the photosensitive composition layer to light; a developing step of performing a development treatment on the exposed photosensitive composition layer to form a resist pattern; one of an etching step of etching a metal layer in an area where the resist pattern is not disposed, and a plating step of plating the metal layer; a stripping step of stripping the resist pattern; Furthermore, when a plating process step is included, a removal process is included in which the metal layer exposed by the peeling process is removed and a conductor pattern is formed on the substrate. A method for producing a laminate having a conductive pattern, further comprising a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step. (6) The method for producing a laminate having a conductive pattern according to (5), wherein the exposure step is a step of performing pattern exposure through a photomask. (7) The method for producing a laminate having a conductive pattern according to (5) or (6), wherein the exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using actinic rays onto which an image of a photomask is projected. (8) A temporary support peeling step is provided between the laminating step and the exposure step, The method for producing a laminate having a conductive pattern according to any one of (5) to (7), wherein the exposure step is a step of peeling off the temporary support and bringing the exposed surface into contact with a photomask to expose the photosensitive composition layer in a pattern. [Effects of the Invention]

[0009] According to the present invention, a transfer film can be provided that can produce a resist pattern that is thick and has a large aspect ratio. Furthermore, the present invention can provide a method for producing a laminate having a conductive pattern. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram illustrating an example of a layer structure of a transfer film according to an embodiment. 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] The following describes the meaning of each description in this specification. 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 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.

[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, the term "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, 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 the standard substance. 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 content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer. 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" is a concept that encompasses both acrylic and methacrylic, and "(meth)acryloxy group" is a concept that encompasses both acryloxy group and methacryloxy group.

[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.

[0018] 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. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0019] 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.

[0020] A feature of the transfer film of the present invention is that the photosensitive composition layer has high transmittance while using a predetermined resin. The high transmittance of the photosensitive composition layer allows light to easily penetrate into the photosensitive composition layer, resulting in the reaction of the crosslinkable group and the reaction of the polymerizable compound proceeding more easily. Furthermore, the weight-average molecular weight of the resin is a predetermined value or more, and the content of the structural unit having a crosslinkable group is a predetermined value or more, so that curing in the formed pattern proceeds more easily. As a result, a pattern with a large aspect ratio can be formed even if the pattern is thick.

[0021] <Transfer film> The transfer film of the present invention has a temporary support and a photosensitive composition layer. The transfer film may have other layers in addition to the temporary support and the photosensitive composition layer. Examples of other layers include an intermediate layer, which will be described later. The transfer film may also have other members (such as a protective film), which will be described later.

[0022] The transfer film may be embodied in the following manner (1) or (2), with the preferred embodiment being (2). (1) "Temporary support / photosensitive composition layer / protective film" (2) "Temporary support / intermediate layer / photosensitive composition layer / protective film" The transfer film preferably has an intermediate layer.

[0023] From the viewpoint of preventing the generation of bubbles in the lamination step described later, the maximum waviness width of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit of the maximum waviness width is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the undulation of the transfer film is a value measured by the following procedure. First, the transfer film is cut perpendicular to the main surface to a size of 20 cm x 20 cm to prepare a test sample. If the transfer film has a protective film, the protective film is peeled off. Next, the test sample is placed on a flat, horizontal stage with the surface of the temporary support facing the stage. After the sample is placed, a 10 cm square area in the center of the test sample is scanned with a laser microscope (e.g., Keyence VK-9700SP) to obtain a three-dimensional surface image. The minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. This procedure is performed on 10 test samples, and the arithmetic average value is taken as the "maximum waviness width of the transfer film."

[0024] When the photosensitive composition layer of the transfer film further has other composition layers on the surface of the photosensitive composition layer opposite the temporary support, the total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, of the total thickness of the photosensitive composition layer.

[0025] An example of an embodiment of the transfer film will now be described. The transfer film 10 shown in FIG. 1 has a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19, in this order. The transfer film 10 shown in FIG. 1 has an intermediate layer 13 and a protective film 19, but may not have the intermediate layer 13 or the protective film 19. In FIG. 1, each layer (for example, a photosensitive composition layer and an intermediate layer) other than the protective film 19 that can be disposed on the temporary support 11 is also referred to as a "composition layer." Each member and component of the transfer film will be described in detail below.

[0026] [Temporary support] The transfer film has a temporary support. The temporary support is a member that supports the photosensitive composition layer, and is ultimately removed by a peeling treatment.

[0027] The temporary support may have either a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. In addition, the temporary support is preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat, and is also preferably a film that is free from deformation such as wrinkles and scratches. Examples of the film include polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred.

[0028] The temporary support preferably has high transparency so that pattern exposure can be performed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. 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.

[0029] 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).

[0030] 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.

[0031] In order to improve the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that comes into contact with the photosensitive composition layer may be subjected to a surface modification treatment. Examples of surface modification treatments include treatments using UV (ultraviolet) radiation, corona discharge, plasma, and the like. 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. As long as the exposure amount is within the above range, there are no particular limitations on the lamp output and illuminance. 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.

[0032] 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 16KS40 (registered trademark) and Lumirror 16FB40 (registered trademark) (both manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0033] [Photosensitive composition layer] The transfer film has a photosensitive composition layer. The photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the formed resist pattern corresponds to a cured film.

[0034] The transmittance of the photosensitive composition layer at a wavelength of 365 nm is 40% or more, preferably 45% or more, and more preferably 50% or more, in that it allows the production of a resist pattern with a larger thickness and a larger aspect ratio (hereinafter simply referred to as "the advantage of the present invention being superior"). There is no particular upper limit, and it is often 95% or less. In that the advantage of the present invention being superior, it is preferably 80% or less, and more preferably 70% or less. The transmittance of the photosensitive composition layer at a wavelength of 365 nm was measured as follows. The transfer film is laminated onto Eagle XG (manufactured by Corning, 0.7 mm thick) so that the photosensitive composition layer in the transfer film faces Eagle XG (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 1.0 MPa, linear speed 4.0 m / min). Next, the temporary support is peeled off from the obtained laminate, and the laminate is set in a spectrophotometer UV1800 (manufactured by Shimadzu Corporation) with the photosensitive composition layer surface facing the incident light side. Thereafter, the transmission spectrum is measured in an atmospheric environment in a wavelength range of 250 to 750 nm (reference: air), and the transmittance at a wavelength of 365 nm is obtained.

[0035] The average film thickness of the photosensitive composition layer is 10 μm or more. In particular, from the viewpoint of more excellent effects of the present invention, it is preferably 15 μm or more, and more preferably 17 μm or more. There is no particular upper limit, but it is often 30 μm or less, and more often 20 μm or less. The thickness of the photosensitive composition layer can be calculated, for example, as the average value of measurements taken at any five points by cross-sectional observation using a scanning electron microscope (SEM).

[0036] Each component contained in the photosensitive composition layer will be described below.

[0037] (resin) The photosensitive composition layer contains a resin (hereinafter also referred to as "resin A") having a weight-average molecular weight of 10,000 or more and containing a structural unit having a crosslinkable group. The content of the structural unit having a crosslinkable group in resin A is 30% by mass or more relative to the total structural units of resin A. First, resin A will be described in detail below.

[0038] The weight average molecular weight of Resin A is 10,000 or more. In particular, from the viewpoint of more excellent effects of the present invention, it is preferably 15,000 or more, and more preferably 18,000 or more. There is no particular upper limit, but it is often 100,000 or less, and more often 80,000 or less.

[0039] The dispersity of Resin A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. The dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight). In the present disclosure, the weight average molecular weight and the number average molecular weight are values ​​measured using gel permeation chromatography.

[0040] Resin A is preferably an alkali-soluble resin. 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, in order to suppress swelling of the photosensitive composition layer by the developer and thereby achieve better resolution. The lower limit of the acid value of Resin A 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 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 Resin A can be adjusted by adjusting the type of structural unit constituting Resin A and the content of structural units containing acid groups, which will be described later.

[0041] The glass transition temperature Tg of resin A is preferably 30 to 135°C. By using resin A having a Tg of 135°C or less, it is possible to suppress line width thickening and deterioration of resolution when the focal position is shifted during exposure. From this viewpoint, the Tg of resin A is more preferably 130°C or less, even more preferably 120°C or less, and particularly preferably 110°C or less. Furthermore, using resin A having a Tg of 30°C or more is preferable from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of resin A is more preferably 40°C or more, even more preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0042] -Structural unit having a crosslinkable group- Resin A contains a structural unit having a crosslinkable group. The crosslinkable group can connect the polymer chains constituting the resin A by a covalent bond. Examples of the crosslinkable group include a polymerizable group, and the polymerizable group is preferred. That is, the resin A preferably contains a structural unit having a polymerizable group. The polymerizable group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group. When the resin A has an ethylenically unsaturated group, the resin A preferably has a structural unit having an ethylenically unsaturated group in a 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. The ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group.

[0043] As the structural unit having a polymerizable group, a structural unit represented by formula (P) is preferred.

[0044] [ka]

[0045] In formula (P), R P represents a hydrogen atom or a methyl group. Prepresents a divalent linking group. P represents a crosslinkable group.

[0046] R P represents a hydrogen atom or a methyl group. R P is preferably a hydrogen atom.

[0047] L P represents a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -, a divalent hydrocarbon group, and a divalent group combining these. N represents a substituent. Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group. The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5. The alkylene group may have a heteroatom, and a methylene group in the alkylene group may be replaced with a heteroatom. The heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom. The cycloalkylene group may be either monocyclic or polycyclic. The cycloalkylene group preferably has 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms. The arylene group may be either monocyclic or polycyclic. The number of carbon atoms in the arylene group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The arylene group is preferably a phenylene group. The cycloalkylene group and the arylene group may have a heteroatom as a ring member atom, and the heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom. The hydrocarbon group may further have a substituent. Examples of the substituent include a halogen atom (such as a fluorine atom), a hydroxy group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkenyl group, with a hydroxy group being preferred. L P As the alkylene group, an alkylene group which may have a hetero atom is preferred.

[0048] P represents a crosslinkable group. The crosslinkable group is as described above, and is preferably a polymerizable group.

[0049] Examples of the structural unit having a polymerizable group include, but are not limited to, those shown below.

[0050] [ka]

[0051] In the above structural unit, Rx represents a hydrogen atom or a methyl group, and Ry represents a hydrogen atom or a methyl group.

[0052] Resin A may contain one type of structural unit having a crosslinkable group, or may contain two or more types. The content of the structural unit having a crosslinkable group in the resin A is 30% by mass or more relative to all structural units of the resin A. There is no particular upper limit, but it is often 50% by mass or less.

[0053] Examples of a method for introducing a crosslinkable 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 crosslinkable groups into resin A is to synthesize a polymer having carboxy groups by polymerization, and then react some of the carboxy groups of the resulting polymer with a (meth)acrylate having an epoxy group, such as glycidyl (meth)acrylate, by a polymer reaction to introduce (meth)acryloxy groups into the polymer. Another method is to synthesize a polymer having hydroxyl groups by polymerization, and then react some of the hydroxyl groups of the resulting polymer with a (meth)acrylate having an isocyanate group by a polymer reaction to introduce (meth)acryloxy groups into the polymer. By this means, a resin A having a (meth)acryloxy group on the side chain can be obtained. The polymerization reaction is preferably carried out at a temperature of 70 to 100°C, more preferably at a temperature of 80 to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo-based initiator, more preferably V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The polymerization reaction is preferably carried out at a temperature of 80 to 110°C. In the polymerization reaction, it is preferable to use a catalyst such as an ammonium salt.

[0054] -Structural unit derived from a monomer having an aromatic hydrocarbon group- Furthermore, in order to prevent line width thickening and resolution degradation caused by shifting the focal position during exposure, it is preferable that Resin A contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of structural units derived from monomers having an aromatic hydrocarbon group in Resin A is preferably 20% by mass or more, and more preferably 30% by mass or more, relative to all structural units of Resin A. There is no particular upper limit, but it is preferably 95% by mass or less, and more preferably 85% by mass or less. When multiple types of Resin A are contained, it is preferable that the average content of structural units derived from monomers having an aromatic hydrocarbon group falls within the above range.

[0055] 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, styrene dimer, styrene trimer, etc.). Among these, a monomer having an aralkyl group or styrene is preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of structural units derived from styrene is preferably 10 to 70 mass%, more preferably 15 to 65 mass%, still more preferably 20 to 60 mass%, and particularly preferably 25 to 55 mass%, relative to all structural units of resin A. When the photosensitive composition layer contains multiple types of resin A, the content of structural units having an aromatic hydrocarbon group is determined as a weight average value.

[0056] The aralkyl group includes an optionally substituted phenylalkyl group, and is preferably an optionally substituted benzyl group.

[0057] Examples of the monomer having a phenylalkyl group which may have a substituent include phenylethyl (meth)acrylate.

[0058] Examples of the monomer having a benzyl group which may have a substituent include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol, of which (meth)acrylates having a benzyl group are preferred, and benzyl (meth)acrylate is more preferred. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of the structural units derived from benzyl (meth)acrylate is preferably 10 to 70 mass%, more preferably 15 to 65 mass%, even more preferably 20 to 60 mass%, and particularly preferably 25 to 55 mass%, based on the total structural units of the resin A.

[0059] -Structural unit derived from a monomer having a carboxy group- Resin A may have a structural unit derived from a monomer having a carboxy group. Examples of the monomer having a carboxy group include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred. The content of structural units derived from monomers having a carboxy group in the resin A is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 15 to 30 mass %, based on all structural units of the resin A. A content of 5% by mass or more is preferred from the viewpoints of achieving good developability and controlling edge fusing properties, etc. A content of 50% by mass or less is preferred from the viewpoints of high resolution and foot shape of the resist pattern, as well as chemical resistance of the resist pattern.

[0060] -Non-acidic structural unit- Resin A is non-acidic and may contain a non-acidic structural unit derived from a monomer having at least one polymerizable unsaturated group in the molecule. Examples of the monomer (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.

[0061] 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 in the side chain or a monomer containing a group having 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. Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred. Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group, as well as a (meth)acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxybenzoate (meth)acrylate, and 2-hydroxybenzoate. Examples of such acrylates include 1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, and tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, and tricyclodecane (meth)acrylate are more preferred.

[0062] The resin A may be used alone or in combination of two or more. When two or more types are used, it is preferable to mix two types of resin A containing structural units derived from a monomer having an aromatic hydrocarbon group, or to mix a resin A containing structural units derived from a monomer having an aromatic hydrocarbon group with a resin A that does not contain structural units derived from a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of resin A containing structural units derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of resin A.

[0063] Resin A can be synthesized by polymerizing one or more of the above-described monomers using a radical polymerization initiator such as a peroxide-based polymerization initiator (e.g., benzoyl peroxide) and an azo-based polymerization initiator (e.g., azobisisobutyronitrile).

[0064] The resin A may be used alone or in combination of two or more. The content of resin A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, relative to the total mass of the photosensitive composition layer. A content of resin A of 90% by mass or less is preferred from the viewpoint of controlling the development time. On the other hand, a content of resin A of 10% by mass or more is preferred from the viewpoint of improving edge fuse resistance.

[0065] 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.

[0066] (sensitizer) The photosensitive composition layer contains a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, distyrylbenzene compounds, styrylpyridine compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. The compounds listed above also include derivatives of the above compounds. Among these, as the sensitizer, a dialkylaminobenzophenone compound, an anthracene compound, a distyrylbenzene compound, or a styrylpyridine compound is preferred, an anthracene compound, a distyrylbenzene compound, or a styrylpyridine compound is more preferred, and an anthracene derivative, a distyrylbenzene derivative, or a styrylpyridine derivative is even more preferred.

[0067] The sensitizers may be used alone or in combination of two or more. The content of the sensitizer in the photosensitive composition layer can be appropriately selected depending on the purpose, but from the viewpoints of improving sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content is preferably 0.001 to 5 mass %, more preferably 0.01 to 1 mass %, and even more preferably 0.01 to 0.5 mass %, relative to the total mass of the photosensitive composition layer.

[0068] (polymerizable compound) The photosensitive composition layer may contain a polymerizable compound having a polymerizable group, and the polymerizable compound is preferably an ethylenically unsaturated compound. In this specification, the term "polymerizable compound" refers to a compound that undergoes polymerization under the action of a polymerization initiator, which will be described later, and is different from the resin A described above.

[0069] The polymerizable group contained in the polymerizable compound may be any group that is involved in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group such as an epoxy group and an oxetane group. A group having an ethylenically unsaturated group is preferred, and an acryloyl group or a methacryloyl group is more preferred.

[0070] Examples of the ethylenically unsaturated group contained in the ethylenically unsaturated compound include a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group. The ethylenically unsaturated group is preferably an acryloyl group or a methacryloyl group. The polymerizable group contained in the polymerizable compound other than the ethylenically unsaturated compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having a cationically polymerizable group such as an epoxy group and an oxetane group. The ethylenically unsaturated compound will now be described.

[0071] The ethylenically unsaturated compound is preferably a compound having two or more ethylenically unsaturated groups in one molecule (a polyfunctional ethylenically unsaturated compound) in terms of superior photosensitivity. In addition, from the viewpoint of achieving better resolution and releasability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0072] In order to obtain a better balance between the photosensitivity, resolution, and peelability of the photosensitive composition layer, it is preferable to contain a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and it is more preferable to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. The content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more, from the viewpoint of excellent releasability. The upper limit is not particularly limited, and may be 100% by mass. That is, all of the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Moreover, the ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group.

[0073] -Polymerizable compound B1- The photosensitive composition layer also preferably contains, as a polymerizable compound, a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

[0074] In the photosensitive composition layer, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40 mass% or more, more preferably 50 mass% or more, even more preferably 55 mass% or more, and particularly preferably 60 mass% or more, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100 mass% or less, preferably 99 mass% or less, more preferably 95 mass% or less, even more preferably 90 mass% or less, and particularly preferably 85 mass% or less.

[0075] Examples of the aromatic ring that the polymerizable compound B1 has include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocycles such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof, and aromatic hydrocarbon rings are preferred, and benzene ring is more preferred. Note that the aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0076] The polymerizable compound B1 preferably has a bisphenol structure, since this inhibits swelling of the photosensitive composition layer due to a developer, thereby improving resolution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0077] Examples of the polymerizable compound 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 polymerizable compound B1 preferably has an alkyleneoxide-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 polymerizable compound 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.

[0078] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by 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.).

[0079] The polymerizable compound B1 is also preferably a compound represented by the following general formula (B1).

[0080] [ka]

[0081] 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.

[0082] The polymerizable compound B1 may be used alone or in combination of two or more. The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive composition layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which a photosensitive resin oozes out from the edge of a transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0083] The photosensitive composition layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1. The polymerizable compound other than the polymerizable compound B1 is not particularly limited and 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 having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0084] 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.

[0085] 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.).

[0086] 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. 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. In one embodiment, the photosensitive composition layer preferably contains the above-described polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-described polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compounds (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compounds) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0087] 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.).

[0088] 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.

[0089] The molecular weight (weight average molecular weight when the polymerizable compound (including polymerizable compound B1) has a molecular weight distribution) of preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0090] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 0 to 70% by mass, more preferably from 10 to 70% by mass, and even more preferably from 20 to 60% by mass, based on the total mass of the photosensitive composition layer. The mass ratio of the polymerizable compound other than resin A contained in the photosensitive composition layer and having a weight average molecular weight of less than 10,000 to resin A is not particularly limited, but is preferably 0.85 or less in terms of providing superior effects of the present invention. The lower limit of the mass ratio is not particularly limited, but is preferably 0.50 or more, more preferably 0.60 or more, in terms of providing superior effects of the present invention.

[0091] (Polymerization initiator) The photosensitive composition layer may contain a polymerization initiator. As the polymerization initiator, for example, a known polymerization initiator can be used depending on the type of polymerization reaction, and specific examples include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.

[0092] The photosensitive composition layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to actinic rays such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0093] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0094] In addition, from the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution, the photosensitive composition layer preferably contains, as a photoradical polymerization initiator, at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0095] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP 2011-095716 A and paragraphs

[0064] to

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

[0096] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0097] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF). BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV), BV), oxime ester photoinitiator (trade name: Lunar 6, DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (trade name: TR-PBG-305, Changzhou Qiang) Examples of suitable oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronics 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 Strong Electronics New Materials Co., Ltd.).

[0098] A cationic photopolymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. The cationic photopolymerization initiator is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but the chemical structure is not limited. Even cationic photopolymerization initiators that are not directly sensitive to actinic rays with a wavelength of 300 nm or more can be preferably used in combination with a sensitizer, as long as they respond to actinic rays with a wavelength of 300 nm or more and generate an acid when used in combination with a sensitizer. The cationic photopolymerization initiator is preferably a cationic photopolymerization initiator that generates an acid having a pKa of 4 or less, more preferably a cationic photopolymerization initiator that generates an acid having a pKa of 3 or less, and even more preferably a cationic photopolymerization initiator that generates an acid having a pKa of 2 or less. There is no particular restriction on the lower limit of the pKa, but it is preferably, for example, −10.0 or more.

[0099] Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs

[0114] to

[0133] of JP-A No. 2014-085643 may be used.

[0100] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include compounds described in paragraphs

[0083] to

[0088] of JP 2011-221494 A. Examples of oxime sulfonate compounds include compounds described in paragraphs

[0084] to

[0088] of WO 2018 / 179640 A.

[0101] The photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

[0102] The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the photosensitive composition layer.

[0103] (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 (for example, a water-soluble resin layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

[0104] 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.

[0105] Among these, from the viewpoints of the visibility of exposed and unexposed areas and resolution, 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, in terms of the visibility of exposed and unexposed areas and resolution. In addition, from the viewpoint of visibility of exposed and unexposed areas, it is preferable that dye N is a dye that develops color in response to an acid, a base, or a radical.

[0106] 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.

[0107] 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.

[0108] 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 wavelength 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).

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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 Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), and Oil Scarlet #308 (manufactured by Orient Chemical 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.

[0113] 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.

[0114] 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.

[0115] The dye N may be used alone or in combination of two or more. The content of dye N is preferably 0.1 mass % or more, more preferably 0.1 to 10 mass %, even more preferably 0.1 to 5 mass %, and particularly preferably 0.1 to 1 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.

[0116] 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. The photosensitive composition layer 3g is the same as the total solid content 3g in the photosensitive composition.

[0117] (thermal crosslinking agent) The photosensitive composition layer may contain a thermal crosslinking agent. Examples of the thermal crosslinking agent include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound or the like has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when the film obtained by curing the negative photosensitive composition layer is used as a protective film. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0118] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used, but the differential scanning calorimeter is not limited to this.

[0119] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., at least one selected from oxime compounds is preferred from the viewpoint of storage stability, for example.

[0120] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred because the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0121] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0122] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). Furthermore, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0123] [ka]

[0124] The thermal crosslinking agent may be used alone or in combination of two or more. The content of the thermally crosslinkable compound in the photosensitive composition layer is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0125] (pigment) The photosensitive composition layer may contain a pigment. When the photosensitive composition layer contains a pigment, the photosensitive composition layer corresponds to a colored resin layer. In order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is sometimes attached. A colored resin layer can be used to form such a light-shielding layer. The pigment may be appropriately selected according to the desired hue, and examples thereof include black pigments, white pigments, and pigments of chromatic colors other than black and white. When a black pattern is to be formed, the pigment is preferably a black pigment.

[0126] Examples of black pigments include known black pigments (such as organic pigments and inorganic pigments). Among these, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, or graphite is preferred as the black pigment, and carbon black is more preferred. As the carbon black, from the viewpoint of surface resistance, surface-modified carbon black, at least a part of whose surface is coated with a resin, is preferred.

[0127] The particle size (number average particle size) of the black pigment is preferably from 0.001 to 0.1 μm, more preferably from 0.01 to 0.08 μm, from the viewpoint of dispersion stability. "Particle size" refers to the diameter of a circle with the same area as the pigment particle, calculated from the area of ​​the pigment particle in a photograph taken with an electron microscope. "Number average particle size" refers to the average value obtained by calculating the particle size of 100 random particles and averaging the particle sizes of the 100 particles.

[0128] Examples of the white pigment include inorganic pigments and the white pigments described in paragraphs

[0015] and

[0114] of JP-A No. 2005-007765. As the inorganic pigment, titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferred, titanium oxide or zinc oxide is more preferred, titanium oxide is even more preferred, rutile or anatase titanium oxide is particularly preferred, and rutile titanium oxide is most preferred. The surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be treated with two or more of these, which suppresses the catalytic activity of titanium oxide and improves heat resistance and fading resistance. In order to reduce the thickness of the photosensitive composition layer after heating, it is preferable to perform at least one of alumina treatment and zirconia treatment on the surface of the titanium oxide, and it is more preferable to perform both alumina treatment and zirconia treatment.

[0129] When the photosensitive composition layer is a colored resin layer, it is also preferable that the photosensitive composition layer contains a chromatic pigment other than a black pigment and a white pigment from the viewpoint of transferability. The particle size (number average particle size) of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of superior dispersibility. The lower limit is preferably 10 nm or more. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter also referred to as "CI") 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Blue CI Pigment Red 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23, with CI Pigment Red 177 being preferred.

[0130] The pigments may be used alone or in combination of two or more. The pigment content is preferably more than 3% by mass and not more than 40% by mass, more preferably more than 3% by mass and not more than 35% by mass, even more preferably more than 5% by mass and not more than 35% by mass, and particularly preferably 10 to 35% by mass, relative to the total mass of the photosensitive composition layer.

[0131] When the photosensitive composition layer contains a pigment other than a black pigment (for example, a white pigment and a chromatic pigment), the content of the pigment other than the black pigment is preferably 30 mass % or less, more preferably 1 to 20 mass %, and even more preferably 3 to 15 mass %, relative to the total mass of the black pigment.

[0132] When the photosensitive composition layer contains a black pigment, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may be prepared by previously mixing the black pigment and the pigment dispersant, adding the resulting mixture to an organic solvent (or vehicle), and dispersing the mixture using a disperser. The pigment dispersant may be selected depending on the pigment and solvent, and for example, a commercially available dispersant may be used. The term "vehicle" refers to the medium in which the pigment is dispersed when a pigment dispersion is prepared. The vehicle is liquid and contains a binder component that keeps the black pigment dispersed, and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0133] Examples of the dispersing machine include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Alternatively, fine pulverization may be carried out by utilizing frictional force through mechanical grinding. For details of dispersers and fine pulverization, see, for example, "Encyclopedia of Pigments" (Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0134] (Other additives) The photosensitive composition layer may contain known additives in addition to the above components, if necessary. Examples of additives include radical polymerization inhibitors, antioxidants (e.g., phenidone, etc.), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles, etc.), sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazoles, etc.), pyridines (e.g., isonicotinamide, etc.), and purine bases (e.g., adenine, etc.). Examples of other additives include metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic suspending agents, and the disclosures of paragraphs

[0165] to

[0184] of JP2014-085643A, the contents of which are incorporated herein by reference. Each additive may be used alone or in combination of two or more.

[0135] The photosensitive composition layer may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive composition layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor. The content of the radical polymerization inhibitor is preferably from 0.005 to 5.0 mass %, more preferably from 0.01 to 3.0 mass %, and even more preferably from 0.01 to 1.0 mass %, based on the total mass of the polymerizable compounds.

[0136] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0137] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of carboxybenzotriazoles that can be used include commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd.).

[0138] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3 mass %, more preferably 0.05 to 1 mass %, based on the total mass of the photosensitive composition layer. When the content is 0.01 mass % or more, the storage stability of the photosensitive composition layer is improved. On the other hand, when the content is 3 mass % or less, the sensitivity is maintained and the decolorization of the dye is suppressed better.

[0139] Examples of surfactants include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of JP-A-2009-237362.

[0140] The surfactant is preferably a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant. 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, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, and EXP MFS-330, EXP.MFS-578, 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, DS-21 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Co., Ltd.), and U-120E (Unichem Co., Ltd.). Also suitable for use as fluorosurfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac DS-21. As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Furthermore, a block polymer can also be used as the fluorine-based surfactant. Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0141] From the viewpoint of improving environmental friendliness, it is preferable that the fluorine-based surfactant be a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Specific examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2, HYDROPALAT WE 3323 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), Solsperse 20000 (all manufactured by The Lubrizol Group, Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0142] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0143] Specific examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (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.), as well as X-22-4952, X-22-4272, and X-22-626. 6, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF -6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124 , KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Polymers) Examples include 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).

[0144] The surfactants may be used alone or in combination of two or more. When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.01 to 1.0 mass %, and even more preferably 0.05 to 0.80 mass %, relative to the total mass of the photosensitive composition layer.

[0145] The content of water in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of improving reliability and lamination properties.

[0146] (Impurities, etc.) The photosensitive composition layer may contain impurities. Examples of impurities include metal impurities or ions thereof, halide ions, residual organic solvents, and residual monomers.

[0147] Examples of metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof, as well as halide ions. Among these, sodium ions, potassium ions and halide ions are preferably contained in the following amounts because they are easily mixed in. Metal impurities are compounds that are different from the above-mentioned particles (for example, metal oxide particles) that may be contained in the transfer film.

[0148] The content of metal impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive composition layer. The lower limit is preferably 1 ppb by mass or more, more preferably 0.1 ppm by mass or more.

[0149] Methods for adjusting the impurity content include, for example, selecting raw materials for the photosensitive composition layer that have a low impurity content, and preventing impurities from being mixed in when forming the photosensitive composition layer and removing them by washing. The content of impurities can be determined by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0150] Examples of the remaining organic solvent include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of the residual organic solvent is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive composition layer. The lower limit is preferably 10 ppb by mass or more, more preferably 100 ppb by mass or more, relative to the total mass of the photosensitive composition layer. The amount of the residual organic solvent can be adjusted by adjusting the drying conditions in the transfer film manufacturing method described below. The amount of the residual organic solvent can be determined by a known method such as gas chromatography analysis.

[0151] The content of water in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of improving reliability and lamination properties.

[0152] [Middle layer] The transfer film preferably has an intermediate layer between the temporary support and the photosensitive composition layer. Examples of the intermediate layer include a water-soluble resin layer and an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A No. 5-072724. As the intermediate layer, an oxygen-blocking layer is preferred because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. An oxygen-blocking layer that exhibits low oxygen permeability and is dispersible or soluble in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C) is more preferred. Hereinafter, each component that may be contained in the water-soluble resin layer (intermediate layer) will be described.

[0153] The water-soluble resin layer (intermediate layer) contains a resin. The resin preferably contains a water-soluble resin as a part or the whole thereof. Examples of resins that can be used as the water-soluble resin 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. Furthermore, as the water-soluble resin, a copolymer of (meth)acrylic acid / vinyl compound can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / allyl (meth)acrylate is preferred, and a copolymer of methacrylic acid / allyl methacrylate is more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid and a vinyl compound, the composition ratio (mol %) is, for example, preferably from 90 / 10 to 20 / 80, and more preferably from 80 / 20 to 30 / 70.

[0154] 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 dispersity (Mw / Mn) of the water-soluble resin is preferably 1-10, and more preferably 1-5.

[0155] The water-soluble resins may be used alone or in combination of two or more. The content of the water-soluble resin is not particularly limited, but from the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppression ability, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the water-soluble resin layer (intermediate layer). The upper limit is not particularly limited, but for example, it is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.

[0156] The intermediate layer may contain other components in addition to the water-soluble resin. As the other component, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds are preferred, and polyhydric alcohols, phenol derivatives or amide compounds are more preferred. Other components include, for example, known surfactants.

[0157] Examples of polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. The number of hydroxy groups that the polyhydric alcohols have is preferably 2 to 10. Examples of alkylene oxide adducts of polyhydric alcohols include compounds in which an ethyleneoxy group, a propyleneoxy group, or the like is added to the above-mentioned polyhydric alcohols. The average number of alkyleneoxy groups added is preferably 1 to 100, more preferably 2 to 50, and even more preferably 2 to 20. Phenol derivatives include, for example, bisphenol A and bisphenol S. An example of the amide compound is N-methylpyrrolidone.

[0158] The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives, and amide compounds.

[0159] The molecular weight of the other component is preferably less than 5000, more preferably 4000 or less, even more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less. The lower limit is preferably 60 or more.

[0160] The other components may be used alone or in combination of two or more. The content of other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0161] The intermediate layer may contain impurities. The impurities include, for example, impurities contained in the photosensitive composition layer.

[0162] The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property is not reduced and the ability to suppress interlayer mixing is excellent. Furthermore, the increase in the time required to remove the water-soluble resin layer (intermediate layer) during development can be suppressed.

[0163] [Protection 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.

[0164] 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. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of being relatively inexpensive.

[0165] In addition, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 It is preferable that: "Fisheyes" are foreign matter, unmelted material, and oxidized degradation products of the material 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.

[0166] 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 even more preferred: This makes it possible to suppress defects caused by the transfer of irregularities due to particles contained in the protective film to the photosensitive composition layer or metal layer.

[0167] 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.

[0168] [Transfer film manufacturing method] The method for producing the transfer film is not particularly limited, and known methods can be used. Examples of methods for manufacturing the transfer film 10 include a method including the steps of applying a composition for forming an intermediate layer to the surface of the temporary support 11 to form a coating film, and then drying this coating film to form the intermediate layer 13, and applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and then drying this coating film to form the photosensitive composition layer 15.

[0169] When the transfer film 10 has a protective film 19, the protective film 19 may be pressure-bonded onto the composition layer 17 of the transfer film 10 produced by the above-mentioned production method. A preferred method for manufacturing the transfer film 10 includes a step of providing a protective film 19 in contact with the surface of the composition layer 17 opposite the temporary support 11, thereby manufacturing a transfer film 10 comprising the temporary support 11, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19. 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.

[0170] The method for producing the transfer film 10 may also be a method in which the composition layer 17 is formed on the protective film 19 .

[0171] (Water-soluble resin composition and method for forming intermediate layer (water-soluble resin layer)) The water-soluble resin composition preferably contains the various components forming the intermediate layer (water-soluble resin layer) described above and a solvent. Note that in the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the water-soluble resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, 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 solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 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.

[0172] The method for forming the water-soluble 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.).

[0173] (Photosensitive composition and method for forming a photosensitive composition layer) In terms of excellent productivity, it is desirable to form the photosensitive composition layer by a coating method using a photosensitive composition containing the components constituting the photosensitive composition layer described above (e.g., resin A, a polymerizable compound, a polymerization initiator, a sensitizer, etc.) and a solvent. Specifically, a preferred method for producing a transfer film is to apply a photosensitive composition onto an intermediate layer to form a coating film, and then to dry the coating film at a predetermined temperature to form a photosensitive composition layer.

[0174] The photosensitive composition preferably contains the various components forming the photosensitive composition layer described above and a solvent. Note that the preferred range of the content of each component in the photosensitive composition 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.

[0175] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, more preferably 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, and even more preferably a mixed solvent containing at least three of alkylene glycol ether, alkylene glycol ether acetate, and ketone solvents.

[0176] 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. Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone. As the solvent, the solvents described in paragraphs

[0092] to

[0094] of International Publication No. 2018 / 179640 and the solvents described in paragraph

[0014] of Japanese Patent Application Laid-Open No. 2018-177889 may be used, the contents of which are incorporated herein by reference. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 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.

[0177] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0178] As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred. The drying temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher. There is no particular upper limit to the drying temperature, but it is preferably 130° C. or lower, and more preferably 120° C. or lower. 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 particular upper limit, but it is preferably 450 seconds or less, and more preferably 300 seconds or less. The drying temperature is preferably 80°C or more, and more preferably 90°C or more. The upper limit is preferably 130°C or less, and more preferably 120°C or less. 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.

[0179] Furthermore, a transfer film can be produced by laminating a protective film onto the photosensitive composition layer. The method for laminating the 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.

[0180] <Method of manufacturing a laminate having a conductive pattern> The method for producing a laminate having a conductor pattern using the transfer film of the present invention is not particularly limited, but a lamination step of laminating the transfer film and the substrate so that the surface of the transfer film opposite to the temporary support side is in contact with the metal layer of the substrate having a metal layer on its surface; an exposure step of pattern-exposing the photosensitive composition layer; a developing step of subjecting the exposed photosensitive composition layer to a development treatment to form a resist pattern; one of an etching step of etching a metal layer in an area where the resist pattern is not disposed and a plating step of plating the metal layer; a stripping step of stripping the resist pattern; Furthermore, when a plating treatment step is included, the method includes a removal step of removing the metal layer exposed by the peeling step and forming a conductor pattern on the substrate, in this order; It is preferable to further include a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step. Each step will be described in detail below.

[0181] [Lamination process] The laminating step is a step of laminating the transfer film and the substrate so that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of the substrate having a metal layer on its surface. By carrying out this step, a substrate with a photosensitive composition layer can be obtained, which has a substrate, a metal layer, a photosensitive composition layer, and a temporary support in this order. In addition, when the transfer film has a protective film, the protective film is peeled off before the laminating step is carried out.

[0182] The configuration of the transfer film is as described above.

[0183] A substrate having a metal layer on its surface (substrate with a metal layer) has a substrate and a metal layer disposed on the surface of the substrate. Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate, and the substrate described in paragraph

[0140] of WO 2018 / 155193 is preferred. The resin substrate is preferably made of polyethylene terephthalate, cycloolefin polymer, or polyimide. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0184] The metal layer is a layer containing a metal, and the metal is not particularly limited, and any known metal can be used. The metal layer is preferably a conductive layer. Examples of the main component (so-called main metal) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The term "main component" refers to the metal with the largest content among the metals contained in the metal layer.

[0185] The method for forming the metal layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion liquid in which metal fine particles are dispersed and sintering the coating film, a sputtering method, and a vapor deposition method.

[0186] The thickness of the metal layer is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more, and the upper limit is preferably 2 μm or less.

[0187] One or more metal layers may be disposed on the substrate. When two or more metal layers are disposed, the two or more disposed metal layers may be the same or different, and are preferably made of different materials.

[0188] In the above lamination, it is preferable that the photosensitive composition layer side of the transfer film (the surface opposite to the temporary support side) is brought into contact with the metal layer on the substrate and pressure-bonded. 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 metal layer, 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.

[0189] [Exposure process] The exposure step is a step of pattern-exposing the photosensitive composition layer. "Pattern exposure" refers to a form of patterned exposure in which exposed areas and unexposed areas exist. The positional relationship between the exposed portion (exposed region) and the unexposed portion (unexposed region) in the pattern exposure can be appropriately adjusted. Exposure is preferably carried out from the photosensitive composition layer side.

[0190] Examples of the exposure method in the exposure step include mask exposure, direct imaging exposure, and projection exposure, with mask exposure or projection exposure being preferred. That is, the exposure step is preferably a step of performing pattern exposure through a photomask. The exposure step is also preferably a step of pattern-exposing the photosensitive composition layer through a lens using actinic rays onto which an image of a photomask is projected.

[0191] When the temporary support peeling step described later is carried out between the laminating step and the exposure step, the exposure step is preferably an exposure step in which the temporary support is peeled off and the exposed surface is brought into contact with a photomask, and pattern exposure is performed.In other words, an exposure step in which the exposed surface of the laminate from which the temporary support is peeled off is brought into contact with a photomask, and pattern exposure is performed on the photosensitive composition layer is preferably performed.In addition, when the transfer film has a three-layer structure consisting of a temporary support, an intermediate layer, and a photosensitive composition layer, the exposed surface corresponds to the surface of the intermediate layer. By employing such an exposure process, a resist pattern with higher resolution can be obtained, and ultimately, a conductor pattern with higher resolution can be obtained. Such an exposure step is preferably employed particularly when a temporary support peeling step, which will be described later, is carried out between the laminating step and the exposure step. In addition, when the temporary support peeling process described below is carried out between the exposure process and the development process, the exposure process is preferably an exposure process in which a photomask is brought into contact with the surface of the transfer film opposite to the side having the substrate in the laminate of the substrate and the transfer film obtained by the lamination process, and pattern exposure is carried out.

[0192] In the exposure step of pattern exposure, a curing reaction of components contained in the photosensitive composition layer can occur in the exposed regions of the photosensitive composition layer (regions corresponding to the openings of the photomask). By carrying out a development step after exposure, the unexposed regions of the photosensitive composition layer are removed, forming a pattern.

[0193] The method of the present invention preferably includes a photomask stripping step between the exposure step and the development step, in which the photomask used in the exposure step is stripped off. The photomask peeling step may be, for example, a known peeling step.

[0194] 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 greatest intensity.

[0195] 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.

[0196] Preferred embodiments of the light source, exposure dose, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

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

[0197] [Temporary support peeling process] Between the laminating step and the exposure step, or between the exposure step and the development step, a temporary support peeling step is carried out. In particular, it is preferable to have a peeling step between the laminating step and the exposure step. The peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with the metal layer. The temporary support can be peeled off by any known peeling method, for example, including the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A No. 2010-072589.

[0198] [Development process] The development step is a step of carrying out a development treatment on the exposed photosensitive composition layer to form a resist pattern. The photosensitive composition layer can be developed using a developer. The developer is preferably an alkaline aqueous solution. Examples of alkaline compounds that can be contained in the alkaline aqueous solution 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).

[0199] The temperature of the developer during development is preferably from 10 to 50°C, more preferably from 15 to 40°C, and even more preferably from 20 to 35°C. The pH of the developer used in development is preferably 9 or higher, more preferably 10 or higher, and even more preferably 11 or higher. The upper limit is preferably 14 or lower, more preferably less than 13. The pH can be measured using a known pH meter according to the method in accordance with JIS Z8802-1984. The pH is measured at 25°C.

[0200] The content of water in the developer is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass, based on the total mass of the developer. The content of the alkaline compound in the developer is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 10% by mass, based on the total mass of the developer.

[0201] Examples of the development method include puddle development, shower development, spin development, and dip development.

[0202] 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.

[0203] After development, it is also preferable to carry out a rinsing treatment to remove any remaining developer from the metal layer-formed substrate before proceeding to the next step. Water or the like can be used for the rinsing treatment. After the development and / or rinsing treatment, a drying treatment may be carried out to remove excess liquid from the substrate with the metal layer.

[0204] The position and size of the resist pattern formed on the metal layer-formed substrate are not particularly limited, but a thin line shape is preferred. Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is often 1.0 μm or more.

[0205] [Post-exposure process and post-bake process] The method of the present invention may include a step of exposing the resist pattern obtained by the above-mentioned development step (post-exposure step) and / or a step of heating the resist pattern (post-bake step). When both the post-exposure step and the post-bake step are included, it is preferable to carry out post-bake after the post-exposure. The exposure dose of the post-exposure is 100 to 5000 mJ / cm. 2 is preferred, and 200 to 3000 mJ / cm 2 The post-baking temperature is preferably 80 to 250° C., more preferably 90 to 160° C. The post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[0206] [Etching process] The method for producing the laminate having the conductive pattern includes an etching step or a plating step described below. When the etching step is performed, the metal layer is removed in the openings of the resist pattern, and the metal layer has the same pattern shape as the resist pattern, so that a laminate having a conductor pattern is obtained by the etching step. 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.

[0207] 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. It is preferable that the etching solution does not dissolve the resist pattern. The developer used in the developing step may also serve as the etching solution used in the etching treatment, in which case the developing step and the etching step may be carried out simultaneously.

[0208] After the etching treatment, it is also preferable to carry out a rinsing treatment to remove the etching solution remaining on the substrate with the metal layer before proceeding to the next step. Water or the like can be used for the rinsing treatment. After the etching treatment and / or rinsing treatment, a drying treatment may be carried out to remove excess liquid from the substrate with the metal layer.

[0209] [Plating process] The plating step is a step of plating the metal layer in the area where the resist pattern is not disposed. By carrying out this step, a plating layer is formed on the metal layer in the area where the resist pattern is not arranged.

[0210] 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 metal layer.

[0211] 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.

[0212] 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.

[0213] [Protective layer formation process] It is also preferable to have a protective layer forming step between the plating step and the peeling step described below. The protective layer laminating step is a step of forming a protective layer on the plating layer. The protective layer is preferably made of a material that is resistant to the stripping solution and / or etching solution used in the stripping and / or removal steps, such as metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, alloys thereof, and resins, with nickel or chromium being preferred.

[0214] Examples of methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0215] The thickness of the protective layer is preferably 0.3 μm or more, more preferably 0.5 μm or more, and the upper limit is preferably 3.0 μm or less, more preferably 2.0 μm or less.

[0216] [Peeling process] The stripping step is a step of stripping the resist pattern. The method for removing the remaining resist pattern is not particularly limited, but examples thereof include a method of removing it by chemical treatment, and a method of removing it using a remover is preferred. Alternatively, the film may be removed by a known method such as a spray method, a shower method, or a puddle method using a stripping solution.

[0217] Examples of the stripping solution include a stripping solution in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution 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. Examples of the alkaline organic compound include tetramethylammonium hydroxide or an alkanolamine compound. It is also preferable that the stripping solution does not dissolve the metal layer.

[0218] The resist pattern can be removed by immersing the substrate with the remaining resist pattern in a stirring stripping solution having a liquid temperature of preferably 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0219] The pH of the stripping solution used in the stripping treatment is preferably 11 or higher, more preferably 12 or higher, and even more preferably 13 or higher. The upper limit is preferably 14 or lower, more preferably 13.8 or lower. The pH can be measured using a known pH meter according to a method in accordance with JIS Z8802-1984. The pH measurement temperature is 25°C. The temperature of the stripping solution during the stripping treatment is preferably higher than the temperature of the developer during the development treatment. Specifically, the value obtained by subtracting the temperature of the developer from the temperature of the stripping solution (temperature of the stripping solution - temperature of the developer) is preferably 10°C or higher, more preferably 20°C or higher. The upper limit is preferably 100°C or lower, more preferably 80°C or lower. The pH of the stripping solution used in the stripping treatment is preferably higher than the pH of the developer used in the development treatment. Specifically, the value obtained by subtracting the pH of the developer from the pH of the stripping solution (pH of the stripping solution - pH of the developer) is preferably 1 or higher, more preferably 1.5 or higher. The upper limit is preferably 5 or lower, more preferably 4 or lower.

[0220] After the resist pattern is removed with the remover, it is also preferable to carry out a rinse treatment to remove the remover remaining on the substrate. Water or the like can be used for the rinse treatment. After the resist pattern is stripped and / or rinsed with the stripping solution, a drying process may be carried out to remove excess liquid from the substrate.

[0221] [Removal process] The removal step is a step of removing the metal layer exposed in the peeling step and forming a conductive pattern on the substrate. In the removal process, the plating layer formed in the plating process is used as an etching resist, and the metal layer located in the non-pattern formation area (in other words, the area not protected by the plating layer) is etched.

[0222] The method for removing a portion of the metal 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.

[0223] When the removal step is carried out, the metal 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.

[0224] 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.

[0225] [Other processes] 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 of reducing visible light reflectance as described in paragraph

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

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

[0226] -Process to reduce 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 metal layers of the substrate. An example of a treatment for reducing the visible light reflectance is oxidation treatment. When the substrate has a metal layer containing copper, the visible light reflectance of the metal layer can be reduced by oxidizing the copper to copper oxide and blackening the metal 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.

[0227] - A process for forming an insulating film, and a process for forming a new metal layer on the surface of the insulating film - The method for producing a laminate having a conductor pattern preferably includes the steps of forming an insulating film on the surface of the circuit wiring, and forming a new metal 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.

[0228] A preferred method for producing a laminate having a conductive pattern is to use a substrate having a plurality of metal layers on both surfaces of a base material, and to sequentially or simultaneously form circuits on the metal layers formed on both surfaces of the base material. This configuration allows the formation of a touch panel circuit wiring 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 such a touch panel circuit wiring from both surfaces of the base material using a roll-to-roll process.

[0229] <Uses of laminates having conductive patterns> The method for manufacturing a laminate having a conductive pattern can be applied to the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic wave shielding materials, and light control films; the manufacture of printed wiring boards and semiconductor packages; the manufacture of pillars and pins for interconnection between semiconductor chips and packages; the manufacture of metal masks; and the manufacture of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding). The touch panel may be a capacitive touch panel. The method for manufacturing a laminate according to the present invention can be used to form a conductive film or peripheral circuit wiring in a touch panel. The touch panel can be applied to display devices such as organic electroluminescence (EL) display devices and liquid crystal display devices. [Example]

[0230] The features of the present invention will be explained in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, treatment details, and treatment procedures 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 specific examples shown below. In the following examples, the weight average molecular weight of the resin is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene, and the acid value is the theoretical acid value.

[0231] <Materials used to make the transfer film> The materials (photosensitive composition and intermediate layer-forming composition) used in the preparation of the transfer film used in the examples will be described below.

[0232] (Components of the Photosensitive Composition) The photosensitive composition layer of the transfer film was formed using a photosensitive composition. The components used in preparing the photosensitive compositions are as follows. The components shown below were mixed in the proportions shown in Tables 2 to 5 below to obtain the photosensitive compositions used in the examples and comparative examples.

[0233] [resin] Resins A1 to A10 containing structural units derived from the compounds shown in Table 1 were prepared. Table 1 shows the amount (mass %) of the structural units of each synthesized resin, the acid value, the glass transition temperature (Tg), and the weight average molecular weight (Mw). In Table 1, the abbreviations are as follows: ·MAA: methacrylic acid St: Styrene MMA: Methyl methacrylate BzMA: Benzyl methacrylate DCPMA: dicyclopentanyl methacrylate GMA-MAA: A structural unit obtained by adding glycidyl methacrylate to a structural unit derived from methacrylic acid. The repeating unit represented by GMA-MAA above is represented by the following formula:

[0234] [ka]

[0235] [Table 1]

[0236] As shown in the table above, for example, resin A1 is a resin having a structural unit based on methacrylic acid, a structural unit based on styrene, a structural unit based on methacrylic acid, and a structural unit obtained by adding glycidyl methacrylate to a structural unit derived from methacrylic acid, in a mass ratio of 20:46:2:32, respectively.

[0237] [Polymerizable compound] B1: BPE-900 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B2: BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B3: BPE-100 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B4: FA-024M (a compound represented by the following general formula: R = methyl group, P = propylene group, E = ethylene group, m 3 = 6 (average value), n 2 +n 3 = 12 (average value, manufactured by Hitachi Chemical Co., Ltd.)

[0238] [ka]

[0239] B5: M-270 (polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.) B6: M-114 (4-normal nonylphenoxy octaethylene glycol acrylate, manufactured by Toagosei Co., Ltd.) B7: A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B8: A-DCP (tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B9: 8UX-015A (15-functional urethane acrylate, manufactured by Taisei Fine Chemical Co., Ltd.) B10: Aronix TO-2349 (acid-modified multifunctional acrylate, manufactured by Toagosei Co., Ltd.) B11: A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B12: DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

[0240] [Polymerization initiator] B-CIM (2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, manufactured by Hampford Irgacure OXE-02 (BASF) ·Ominirad 907 (IGM Resins B.V company)

[0241] [Sensitizer] ·SB-PI 701 (manufactured by Sanyo Trading Co., Ltd.) DBA (9,10-dibutoxyanthracene, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0242] [Pigment] Leuco Crystal Violet (Tokyo Chemical Industry Co., Ltd.)

[0243] [Additives] N-phenylcarbamoylmethyl-N-carboxymethylaniline (Fujifilm Wako Pure Chemical Industries, Ltd.) TDP-G (Kawaguchi Chemical Co., Ltd.) CBT-1: Carboxybenzotriazole (manufactured by Johoku Chemical Co., Ltd.) 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) Karenz AOI-BM (Showa Denko) N-phenylglycine (Junsei Chemical Co., Ltd.) 1,2,4-triazole (Otsuka Glass Co., Ltd.) Megafac F-552 (DIC) Megafac F-551A (DIC)

[0244] [solvent] PGMEA: Propylene glycol monomethyl ether acetate MEK: Methyl ethyl ketone MFG: Propylene glycol monomethyl ether MeOH: Methanol

[0245] When preparing the photosensitive composition, a solution of each of the resins A1 to A10 dissolved in a mixed solvent of PGMEA / MFG=50:50 was used, and the values ​​in the "Resin" column in Table 2 represent the parts by mass of the resin in the photosensitive composition. In addition, the numerical values ​​in the columns for each component other than the resin in Tables 2 to 5 indicate the amount (parts by mass) of each component used.

[0246] [Table 2]

[0247] [Table 3]

[0248] [Table 4]

[0249] [Table 5]

[0250] (Components of composition for forming intermediate layer) The following components were mixed to prepare a composition for forming an intermediate layer: The amount of each component is expressed in parts by mass. Ion-exchanged water: 38.12 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical Co., Inc.): 57.17 parts by mass Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.17 parts by mass Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts by mass Metolose 60SH03 (hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.05 parts by mass Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0035 parts by mass

[0251] <Preparation of transfer film> For Examples 1 to 25 and Comparative Examples 1 to 4, transfer films were produced in the following manner. First, each photosensitive composition shown in Tables 6 to 7 was applied onto a temporary support (a polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm, haze: 0.6%) using a bar coater so that the thickness after drying would be the average film thickness shown in Tables 6 to 7, and the coating was then dried in an oven at 80°C to form a photosensitive composition layer. A 16 μm thick polyethylene terephthalate film (16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded onto the resulting photosensitive composition layer as a protective film to prepare a transfer film.

[0252] In addition, for Example 26, a transfer film was prepared in the following manner. First, the composition for forming an intermediate layer was applied onto a temporary support (a polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm (16 μm), haze: 0.6%) using a bar coater so that the thickness after drying would be 1.0 μm, and the composition was dried in an oven at 90°C to form an intermediate layer. Furthermore, the photosensitive compositions shown in Tables 6 to 7 were applied onto the intermediate layer using a bar coater so that the thickness after drying would be the average film thickness shown in Tables 6 to 7, and then dried in an oven at 80°C to form photosensitive composition layers (negative photosensitive composition layers). A 16 μm thick polyethylene terephthalate film (16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded onto the resulting photosensitive composition layer as a protective film to prepare a transfer film.

[0253] <Manufacturing of laminate> The protective film of the prepared transfer film was peeled off, and the exposed surface was laminated (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 1.0 MPa, linear speed 4.0 m / min) onto a substrate having a metal layer (100 nm thick) sputtered onto polyimide to obtain a laminate. The laminate had a substrate, metal layer, photosensitive composition layer, and temporary support in this order. Next, a photomask having a line (μm) / space (μm) pattern of 1 / 1 was attached to the surface of the photosensitive composition layer in the obtained laminate opposite the substrate side. The photosensitive composition layer was exposed to light at an arbitrary exposure dose using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dai-Nippon Kaken Co., Ltd., dominant wavelength: 365 nm). A pattern was then formed by shower development for 60 seconds using an aqueous sodium carbonate solution at a liquid temperature of 30°C. The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope, and the width of the upper surface of the pattern where the pattern width was ±5% of the mask width was evaluated as the resolution. The results are shown in the "Resolution" column of Tables 6 and 7. The aspect ratio of the obtained pattern (pattern height / width of the upper surface of the pattern) was calculated and evaluated according to the following criteria. A: Aspect ratio of 4.0 or more B: Aspect ratio is 3.5 or more and less than 4.0 C: Aspect ratio is 3.0 or more and less than 3.5 D: Aspect ratio less than 3.0

[0254] In Tables 6 and 7, the "Type" column in the "Photosensitive Composition Layer" column indicates the type of photosensitive composition layer used to produce the photosensitive composition layer of the transfer film produced in each Example and Comparative Example. For example, in Example 1, the photosensitive composition layer was produced using Photosensitive Composition 1 in Table 2. In Tables 6 and 7, the column "Presence or Absence of Sensitizer" indicates that a sensitizer is contained in the photosensitive composition layer, with "Present," and that a sensitizer is not contained, with "Absent." In Tables 6 and 7, the column "Crosslinkable group content (mass %)" indicates the content (mass %) of structural units having a crosslinkable group relative to all structural units of the resin. In Tables 6 and 7, the column "Transmittance at 365 nm (%)" indicates the transmittance (%) of the photosensitive composition layer at a wavelength of 365 nm. In Tables 6 and 7, the column "B / A" indicates the mass ratio of the polymerizable compound other than resin A contained in the photosensitive composition layer and having a weight average molecular weight of less than 10,000 to resin A. In Tables 6 and 7, the column "presence or absence of intermediate layer" indicates "present" if the transfer film includes an intermediate layer, and "absent" if it does not. In Tables 6 and 7, the column "Average film thickness (μm) of photosensitive composition layer" indicates the average film thickness (μm) of the photosensitive composition layer in the transfer film.

[0255] [Table 6]

[0256] [Table 7]

[0257] As shown in the table, it was confirmed that the transfer film of the present invention can provide the desired effects. A comparison between Examples 12 and 13 confirmed that a more excellent effect could be obtained when the transmittance at a wavelength of 365 nm was 80% or less. A comparison of Examples 14 to 18 confirmed that better effects were obtained when B / A was 0.50 to 0.80 (preferably 0.55 to 0.80).

[0258] Example 27 A copper layer having a thickness of 200 nm was formed on a PET substrate having a thickness of 0.1 mm by vapor deposition to prepare a substrate with a copper layer. After peeling off the protective film from the transfer film of Example 1, the film was laminated onto the above-mentioned copper layer-bearing substrate so that the copper layer and the photosensitive composition layer were in contact with each other under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. Next, a photomask having a line / space pattern of 3 μm / 5 μm was used, and the temporary support was peeled off, followed by irradiation with 70 mJ / cm 2 The exposure was carried out. Next, shower development was carried out with a 1% aqueous solution of sodium carbonate at a liquid temperature of 30° C., followed by rinsing with water, to form a predetermined pattern on the copper layer. The substrate on which the pattern was arranged was subjected to electrolytic plating using a copper sulfate bath to form a Cu plating pattern with a thickness of 12 μm. Next, the pattern was removed from the obtained laminate using a remover, and then the copper layer was removed using an etching solution to obtain a laminate having a conductive thin line pattern of L / S=4 μm / 4 μm.

[0259] Example 28 A copper layer having a thickness of 200 nm was formed on a PET substrate having a thickness of 0.1 mm by vapor deposition to prepare a substrate with a copper layer. After peeling off the protective film from the transfer film of Example 1, the film was laminated onto the above-mentioned copper layer-bearing substrate so that the copper layer and the photosensitive composition layer were in contact with each other under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. Next, a photomask having a line / space pattern of 5 μm / 3 μm was used to peel off the temporary support, and 80 mJ / cm 2 The exposure was carried out. Next, shower development was carried out with a 1% aqueous solution of sodium carbonate at a liquid temperature of 30° C., followed by rinsing with water, to form a predetermined pattern on the copper layer. For the substrate on which the pattern was disposed, an etching solution was used to remove the copper layer located in the area on which the pattern was not disposed. Next, the pattern was removed from the obtained laminate using a remover to obtain a laminate having a conductive thin line pattern of L / S=4 μm / 4 μm. [Explanation of symbols]

[0260] 10 Transfer film 11 Temporary support 13 Middle class 15 Photosensitive composition layer 17 Composition layer 19 Protective film

Claims

1. A transfer film having a temporary support and a photosensitive composition layer, the photosensitive composition layer has an average film thickness of 10 μm or more; the photosensitive composition layer contains a sensitizer and a resin having a weight average molecular weight of 10,000 or more, the resin contains a structural unit having a crosslinkable group, the content of the structural unit having a crosslinkable group is 30% by mass or more relative to all structural units of the resin, the photosensitive composition layer has a transmittance of 40% or more at a wavelength of 365 nm; the sensitizer is a dialkylaminobenzophenone compound, the crosslinkable group is an ethylenically unsaturated group, A transfer film, wherein the photosensitive composition layer does not contain a pigment.

2. 2. The transfer film according to claim 1, wherein the mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer and having a weight average molecular weight of less than 10,000 to the resin is 0.50 to 0.

80.

3. The transfer film according to claim 1 or 2, wherein the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer.

4. The transfer film according to claim 3 , wherein the intermediate layer is a water-soluble resin layer.

5. A lamination process of laminating the transfer film and the substrate so that a surface of the transfer film opposite to the temporary support, the surface of the transfer film having a temporary support and a photosensitive composition layer, is in contact with the metal layer of the substrate having a metal layer on its surface; an exposure step of exposing the photosensitive composition layer to light; a development step of developing the exposed photosensitive composition layer to form a resist pattern. A method for producing a laminate having a conductive pattern, further comprising a temporary support peeling step of peeling off the temporary support between the laminating step and the exposure step, or between the exposure step and the development step, the photosensitive composition layer has an average film thickness of 10 μm or more; the photosensitive composition layer contains a sensitizer and a resin having a weight average molecular weight of 10,000 or more, the resin contains a structural unit having a crosslinkable group, the content of the structural unit having a crosslinkable group is 30% by mass or more and 50% by mass or less with respect to all structural units of the resin, the photosensitive composition layer has a transmittance of 40% or more at a wavelength of 365 nm; the sensitizer is a dialkylaminobenzophenone compound, the crosslinkable group is an ethylenically unsaturated group, A method for producing a laminate having a conductor pattern, wherein the photosensitive composition layer does not contain a pigment.

6. 6. The method for producing a laminate having a conductor pattern according to claim 5, wherein a mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer and having a weight average molecular weight of less than 10,000 to the resin is 0.50 to 0.

80.

7. The method for producing a laminate having a conductor pattern according to claim 5 or 6, wherein the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer.

8. The method for producing a laminate having a conductive pattern according to any one of claims 5 to 7, wherein the intermediate layer is a water-soluble resin layer.

9. The method for producing a laminate having a conductor pattern according to any one of claims 5 to 8, wherein the exposure step is a step of performing pattern exposure through a photomask.

10. The method for producing a laminate having a conductor pattern according to any one of claims 5 to 9, wherein the exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using actinic rays onto which an image of a photomask is projected.

11. a temporary support peeling step between the laminating step and the exposing step, The method for producing a laminate having a conductor pattern according to any one of claims 5 to 10, wherein the exposure step is a step of peeling off the temporary support and bringing the exposed surface into contact with a photomask to expose the photosensitive composition layer in a pattern.

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