Method for manufacturing laminate and laminate

Abstract

To provide a method for manufacturing a laminate which prevents generation of a difference in sensitivity between one end side and the other end side in a long-sized direction, suppresses generation of foreign substances and scratches between a water-soluble resin layer and a photosensitive resin layer, and enables formation of a pattern excellent in linearity when the photosensitive resin layer is transferred onto an object to be transferred and is subjected to exposure and development treatments.SOLUTION: A method for manufacturing a laminate includes steps of, in the following order: forming a water-soluble resin layer 3 on a supporting body 1 and forming a laminate A; forming a temporary protective layer in the water-soluble resin layer and forming a laminate B; winding the laminate B and forming a wound body C; winding the laminate B from the wound body C, and then peeling a temporary protective layer from the laminate B; forming a photosensitive resin layer 11 so as to be brought into contact with the exposed water-soluble resin layer and forming a laminate D; and forming a cover film so as to be brought into contact with the photosensitive resin layer, and forming a laminate E having the supporting body, the water-soluble resin layer, the photosensitive resin layer and the cover film in this order.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] The present invention relates to a method for producing a laminate and a laminate. [Background technology]

[0002] Because the number of steps required to obtain a desired pattern is small, a pattern formation method in which a photosensitive resin layer is placed on any substrate using a transfer film, and the photosensitive resin is then exposed to light through a mask and developed is widely used.

[0003] For example, Patent Document 1 discloses a photosensitive element (transfer film) having a laminated structure in which a specific support film having a resin layer containing fine particles, a water-soluble resin layer, and a photosensitive resin layer are laminated in this order. As a manufacturing method thereof, a technique is disclosed in which a water-soluble resin layer is formed by a coating method using a water-soluble resin composition on the surface of the support film having a resin layer containing fine particles opposite to the resin layer, and then a photosensitive resin layer is formed by a coating method using a photosensitive resin composition on the water-soluble resin layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2013-024913 A Summary of the Invention [Problem to be solved by the invention]

[0005] The inventors examined the transfer film manufacturing method described in Patent Document 1 and the resulting transfer film and found that a difference in sensitivity may occur between one end and the other end of the transfer film in the longitudinal direction. In addition, the transfer film is required to have the following basic performance: to prevent the occurrence of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer so as to prevent exposure defects (optical abnormalities) when the photosensitive resin layer is transferred to the substrate and subjected to exposure processing; and to be able to form a pattern with excellent linearity when the photosensitive resin layer is transferred to the substrate and subjected to exposure and development processing.

[0006] Therefore, an object of the present invention is to provide a method for manufacturing a laminate (transfer film) in which a difference in sensitivity between one end and the other end in the longitudinal direction is unlikely to occur, the occurrence of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer is suppressed, and a pattern with excellent linearity can be formed when the photosensitive resin layer is transferred to a transfer target and subjected to exposure and development treatments. Another object of the present invention is to provide a laminate. [Means for solving the problem]

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

[0008] [1] A process Xa of forming a water-soluble resin layer on a support to form a laminate A; A step Xb of forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B; A process Xc of winding the laminate B to form a wound body C; A process Xd of unwinding the laminate B from the roll C and then peeling the temporary protective layer from the laminate B between the temporary protective layer and the water-soluble resin layer; a step Xe of forming a photosensitive resin layer so as to be in contact with the exposed water-soluble resin layer to form a laminate D; and a step Xf of forming a cover film in contact with the photosensitive resin layer to form a laminate E having, in this order, the support, the water-soluble resin layer, the photosensitive resin layer, and the cover film. [2] The method for producing a laminate according to [1], wherein the arithmetic mean roughness of the surface of the temporary protective layer in contact with the water-soluble resin layer is 10 to 50 nm. [3] The method for producing a laminate according to [1] or [2], wherein neither the water-soluble resin layer nor the photosensitive resin layer contains substantially any filler. [4] The method for producing a laminate according to any one of [1] to [3], wherein the water-soluble resin layer contains polyvinyl alcohol. [5] The method for producing a laminate according to any one of [1] to [4], wherein the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. [6] The method for producing a laminate according to [5], wherein the polymerizable compound contains a compound represented by formula (B-2) described below. [7] The method for producing a laminate according to [5] or [6], wherein the polymerizable compound contains a compound represented by formula (B-3) described below. [8] The method for producing a laminate according to any one of [5] to [7], wherein the photopolymerization initiator is at least one selected from the group consisting of an acridine-based photopolymerization initiator, a benzophenone-based polymerization initiator, an oxime ester-based photopolymerization initiator, a biimidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator. [9] The method for producing a laminate according to any one of [1] to [8], wherein the photosensitive resin layer contains a polymer D containing at least one repeating unit α selected from the group consisting of a repeating unit represented by formula (A-1) described later and a repeating unit represented by formula (A-2) described later, and a repeating unit β represented by formula (B) described later.

[10] The method for producing a laminate according to any one of [1] to [9], wherein the water-soluble resin layer in the laminate E has a depression of 1 nm or more and less than 100 nm on the surface on the photosensitive resin layer side.

[11] A process Ya of forming a water-soluble resin layer on a support to form a laminate A; A process Yb of forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B; A process Yc of winding the laminate B to form a wound body C; A method for producing a laminate, comprising a step Yd of unwinding the laminate B from the roll C, peeling the temporary protective layer from the laminate B between the temporary protective layer and the water-soluble resin layer, and laminating the photosensitive resin layer of a transfer film comprising a temporary support and a photosensitive resin layer to the exposed surface of the laminate B, thereby obtaining a laminate F comprising the support, the water-soluble resin layer, the photosensitive resin layer, and the temporary support.

[12] The method for producing a laminate according to

[11] , further comprising a step Ye of peeling the temporary support from the laminate F between the temporary support and the photosensitive resin layer, and laminating a cover film on the exposed surface of the laminate F to form a laminate G having the support, the water-soluble resin layer, the photosensitive resin layer, and the cover film in this order.

[13] Furthermore, before the above-mentioned step Yd, A process Yf of forming a photosensitive resin layer on a temporary support to form a laminate H; a step Yg of forming a temporary protective layer in contact with the photosensitive resin layer to form a laminate I; A process Yh of winding the laminate I to form a wound body J; A method for producing a laminate according to

[11] or

[12] , comprising a step Yi of unwinding the laminate I from the roll J, and peeling the temporary protective layer from the laminate I between the temporary protective layer and the photosensitive resin layer to obtain a transfer film comprising the temporary support and the photosensitive resin layer.

[14] The method for producing a laminate according to any one of

[11] to

[13] , wherein the arithmetic mean roughness of the surface of the temporary protective layer in contact with the water-soluble resin layer is 10 to 50 nm.

[15] The method for producing a laminate according to

[13] , wherein the temporary protective layer has an arithmetic mean roughness of a surface in contact with the photosensitive resin layer of 10 to 50 nm.

[16] In the laminate F, the water-soluble resin layer has a depression of 1 nm or more and less than 100 nm on the surface facing the photosensitive resin layer, and The method for producing a laminate according to any one of

[11] to

[15] , wherein the photosensitive resin layer has a depression of 1 nm or more and less than 100 nm on the surface on the water-soluble resin layer side.

[17] The method for producing a laminate according to any one of

[11] to

[16] , wherein neither the water-soluble resin layer nor the photosensitive resin layer contains substantially any filler.

[18] The method for producing a laminate according to any one of

[11] to

[17] , wherein the water-soluble resin layer contains polyvinyl alcohol.

[19] The method for producing a laminate according to any one of

[11] to

[18] , wherein the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

[20] The method for producing a laminate according to

[19] , wherein the polymerizable compound contains a compound represented by formula (B-2) described below.

[21] The method for producing a laminate according to

[19] or

[20] , wherein the polymerizable compound contains a compound represented by formula (B-3) described below.

[22] The method for producing a laminate according to any one of

[19] to

[21] , wherein the photopolymerization initiator is at least one selected from the group consisting of an acridine-based photopolymerization initiator, a benzophenone-based polymerization initiator, an oxime ester-based photopolymerization initiator, a biimidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator.

[23] The method for producing a laminate according to any one of

[11] to

[22] , wherein the photosensitive resin layer contains a polymer D containing at least one repeating unit α selected from the group consisting of a repeating unit represented by formula (A-1) described later and a repeating unit represented by formula (A-2) described later, and a repeating unit β represented by formula (B) described later.

[24] A laminate having, in this order, a support, a water-soluble resin layer, a photosensitive resin layer disposed in contact with the water-soluble resin layer, and a cover film, The water-soluble resin layer has a depression of 1 nm or more and less than 100 nm on the surface on the photosensitive resin layer side. Effect of the Invention

[0009] According to the present invention, a method for manufacturing a laminate (transfer film) can be provided in which a difference in sensitivity between one end and the other end in the longitudinal direction is unlikely to occur, the occurrence of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer is suppressed, and a pattern with excellent linearity can be formed when the photosensitive resin layer is transferred to a transfer target and subjected to exposure and development treatments. The present invention also provides a laminate. [Brief description of the drawings]

[0010] [Figure 1] FIG. 4 is a schematic diagram for explaining step Xa of the first production method. [Diagram 2] FIG. 4 is a schematic diagram for explaining step Xb of the first production method. [Diagram 3] FIG. 13 is a schematic diagram for explaining step Xe of the first manufacturing method. [Figure 4] FIG. 4 is a schematic diagram for explaining step Xf of the first manufacturing method. [Diagram 5] FIG. 13 is a schematic diagram for explaining a step Yd of the second manufacturing method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below. 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 stepwise, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical ranges described in the present specification, the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0012] In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0013] In this specification, unless otherwise specified, 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.

[0014] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​converted using polystyrene as a standard substance measured with a gel permeation chromatography (GPC) analyzer using a TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all of which are product names manufactured by Tosoh Corporation) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a 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.

[0015] In this specification, "(meth)acrylic" is a concept that includes both acrylic and methacrylic, "(meth)acryloyloxy" is a concept that includes both acryloyloxy and methacryloyloxy, "(meth)acrylamide" is a concept that includes both acrylamide and methacrylamide, "(meth)acrylate" is a concept that includes both acrylate and methacrylate, and (meth)acrylonitrile is a concept that includes both acrylonitrile and methacrylonitrile.

[0016] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0017] In this specification, "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. Thus, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0018] The "solid content" of a composition means the components that form a composition layer (e.g., a photosensitive resin layer or a water-soluble resin layer) formed using the composition, and when the composition contains a solvent (e.g., an organic solvent and water, etc.), it means all components excluding the solvent. In addition, liquid components that form a composition layer are also considered to be solid contents.

[0019] The thickness of each layer is calculated as the average value of any five points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0020] [Method for producing the first laminate] The first laminate manufacturing method of the present invention (hereinafter also referred to as the "first manufacturing method") includes the following steps Xa, Xb, Xc, Xd, Xe, and Xf in this order. Step Xa: A step of forming a water-soluble resin layer on a support to form a laminate A Step Xb: A step of forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B. Step Xc: A step of winding the laminate B to form a wound body C. Step Xd: A step of unwinding the laminate B from the roll C, and then peeling the temporary protective layer from the laminate B between the temporary protective layer and the water-soluble resin layer. Step Xe: A step of forming a photosensitive resin layer so as to be in contact with the exposed water-soluble resin layer to form a laminate D. Step Xf: A step of forming a cover film so as to be in contact with the photosensitive resin layer to form a laminate E having the support, the water-soluble resin layer, the photosensitive resin layer, and the cover film in this order.

[0021] The laminate obtained by the first manufacturing method is unlikely to have a difference in sensitivity between one end side and the other end side in the longitudinal direction, and the occurrence of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer can be suppressed. Moreover, the pattern obtained by transferring the laminate obtained by the first manufacturing method to a transfer target and subjecting it to an exposure treatment and a development treatment has excellent linearity.

[0022] The mechanism by which the first production method provides the above-mentioned effects is not clear, but the present inventors speculate as follows. The first manufacturing method involves first forming a roll C by winding up a laminate B including a support, a water-soluble resin layer, and a temporary protective layer, then unwinding the laminate B from the roll C, peeling off the temporary protective layer from the laminate B, and then laminating a photosensitive resin layer on the water-soluble resin layer. In other words, the first manufacturing method is a manufacturing method that first goes through the above-mentioned roll C, rather than forming the photosensitive resin layer continuously after forming the water-soluble resin layer, and this makes it easy to set different manufacturing conditions for the photosensitive resin layer and the water-soluble resin layer.

[0023] Since the photosensitive resin layer and the water-soluble resin layer typically have different optimal manufacturing conditions (conveying speed, heat drying temperature, etc.) for each layer, it is desirable that at least one of the conveying speed and heat drying temperature can be set to different conditions for each layer when forming each layer. On the other hand, for example, when preparing a long laminate having a support, a water-soluble resin layer, and a photosensitive resin layer, if the photosensitive resin layer is continuously formed under the same manufacturing conditions as the water-soluble resin layer after the formation of the water-soluble resin layer, the degree of component penetration between the photosensitive resin layer and the water-soluble resin layer (for example, the amount of component of the water-soluble resin layer permeated into the photosensitive resin layer, the amount of component of the photosensitive resin layer permeated into the water-soluble resin layer, etc.) will be different between the start and end regions of the winding of the obtained long laminate, and as a result, a sensitivity difference may occur between the start and end regions of the winding of the laminate. To give a more specific example, for example, when the optimal drying and heating temperature of the photosensitive resin layer is higher than the optimal drying and heating temperature of the water-soluble resin layer, and when the water-soluble resin layer and the photosensitive resin layer are continuously formed on one conveying line, it is often necessary to make the drying and heating temperature of the photosensitive resin layer the same as the drying and heating temperature of the water-soluble resin layer due to manufacturing issues. If the drying and heating temperature of the photosensitive resin layer is made the same as the drying and heating temperature of the water-soluble resin layer, volatile solvent is likely to accumulate in the dryer for the photosensitive resin layer, and in the later stages of conveying, a situation is likely to occur in which drying in the dryer does not progress sufficiently. As a result, a difference in sensitivity may occur between the start and end regions of the winding of the laminate. In contrast, in the first manufacturing method, as described above, the process goes through the roll C once, so that the photosensitive resin layer and the water-soluble resin layer can be manufactured under different manufacturing conditions, and the occurrence of a difference in sensitivity between the start and end regions of the laminate can be suppressed.

[0024] Furthermore, the roll C obtained in step Xc in the first manufacturing method has a temporary protective layer on the water-soluble resin layer to protect the water-soluble resin layer. Therefore, the surface of the water-soluble resin layer on which the photosensitive resin layer is formed can be prevented from generating foreign matter and scratches due to friction with the back side of the support during winding in step Xc. As a result, the laminate obtained by the first manufacturing method is less likely to cause exposure defects (optical abnormalities) when the photosensitive resin layer is transferred to a transfer target and exposed to light. Furthermore, the laminate obtained by the first manufacturing method has a water-soluble resin layer. Therefore, when the photosensitive resin layer is transferred to the transfer target and an exposure and development process is performed, the water-soluble resin layer blocks oxygen, which facilitates the polymerization reaction of the photosensitive resin layer, and the resulting pattern has excellent linearity. In addition, the water-soluble resin layer makes it possible to perform an exposure process (contact exposure) in a state where the temporary support is peeled off, and it is possible to suppress a decrease in linearity of the pattern due to excessive adhesion between the photosensitive resin layer and the photomask.

[0025] Hereinafter, the term "the effect of the present invention is superior" also means that in the laminate obtained by the first manufacturing method, the difference in sensitivity between one end and the other end in the longitudinal direction is more suppressed, that in the laminate obtained by the first manufacturing method, the occurrence of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer is more suppressed, and / or that, when the laminate obtained by the first manufacturing method is transferred to a substrate and subjected to exposure and development treatment, a pattern with superior linearity can be formed.

[0026] The first production method will be described in detail below with reference to the drawings.

[0027] [Process Xa] 1, step Xa is a step of forming a water-soluble resin layer 3 on a support 1 to form a laminate A 5. That is, step Xa is a step of forming a laminate A including a support and a water-soluble resin layer. First, the support and the water-soluble resin layer that constitute the laminate A will be described below.

[0028] <Support> The support is a member (temporary support) that is peeled off before exposure processing or after exposure processing and before development processing when the laminate obtained by the first manufacturing method is transferred to a substrate to form a pattern. The support is preferably in a long shape, and more preferably in a roll state.

[0029] The support may have either a single-layer structure or a multi-layer structure. The support is preferably a film, more preferably a resin film, and is also preferably a film that is flexible and does not significantly deform, shrink or elongate under pressure or under pressure and heat, and is also preferably a film that is free of deformation such as wrinkles and scratches. Examples of the film include a polyethylene terephthalate film (eg, a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film, with a polyethylene terephthalate film being preferred.

[0030] The support is preferably highly transparent in order to allow pattern exposure through the support. Specifically, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. The upper limit is preferably less than 100%. From the viewpoint of pattern formability during pattern exposure through the support and transparency of the support, it is preferable that the haze of the support is small. Specifically, the haze of the support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more.

[0031] From the viewpoint of pattern formability during pattern exposure through the support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects in the support is small. Specifically, the number of fine particles (for example, fine particles with a diameter of 1 μm), foreign matter, and defects in the support is 50 pieces / 10 mm 2 Less than 10 pieces / 10mm is preferable. 2Less than 3 pieces / 10mm is more preferable. 2 Less than 1 piece / 10mm is more preferable. 2 The lower limit is 0 pieces / 10 mm. 2 The above is preferred.

[0032] The thickness of the support is preferably from 5 to 200 μm, and from the viewpoints of ease of handling and versatility, is more preferably from 5 to 150 μm, further preferably from 5 to 50 μm, and particularly preferably from 5 to 25 μm.

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

[0034] The surface of the support which comes into contact with the water-soluble resin layer may be subjected to a surface modification treatment. Examples of surface modification treatments include treatments using UV irradiation, corona discharge, plasma, and the like. The exposure dose for UV irradiation is 10 to 2000 mJ / cm 2 is preferable, and 50 to 1000 mJ / cm 2 is more preferred. As long as the exposure amount is within the above range, the lamp output and illuminance are not particularly limited. 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.

[0035] Examples of the 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 the support 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, and paragraphs

[0029] to

[0040] of WO 2018 / 179370, the contents of which are incorporated herein by reference. Examples of commercially available supports include Lumirror 16KS40 and Lumirror 16FB40 (both manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0036] <Water-soluble resin layer> The water-soluble resin layer contains a water-soluble resin. The water-soluble resin may be used alone or in combination of two or more kinds. Examples of the water-soluble resin include polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyimides, water-soluble celluloses (e.g., hydroxyethyl cellulose, etc.), water-soluble salts of polyvinyl ether-maleic anhydride, water-soluble salts of carboxyalkyl starch, polyacrylamides, polyamides, water-soluble salts of polyacrylic acid, gelatin, and polypropylene glycol, etc. Among them, the water-soluble resin preferably contains polyvinyl alcohol, in that the oxygen barrier properties of the water-soluble resin layer can be further improved and deactivation of radicals generated in the photosensitive resin layer by exposure light during exposure after the laminate is transferred to the transfer target can be suppressed. Polyvinyl alcohol is synthesized, for example, by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. The degree of saponification of polyvinyl alcohol is preferably 50 mol% or more, more preferably 70 mol% or more, and more preferably 80 mol% or more. The upper limit of the degree of saponification is 100 mol%. In this specification, the "degree of saponification" refers to a value measured in accordance with JIS K 6726 (1994) (Test method for polyvinyl alcohol) specified by the Japanese Industrial Standards. The average polymerization degree of polyvinyl alcohol is preferably from 300 to 5,000, more preferably from 300 to 3,500, and even more preferably from 300 to 2,000. Two or more kinds of polyvinyl alcohols having different degrees of saponification, viscosities, degrees of polymerization, modified species, etc. may be used in combination.

[0037] Examples of polyvinyl alcohol include PVA-120, PVA-203, PVA-205, PVA-220, PVA-235, PVA-403, PVA-405, and Kuraray Poval 17-94 (all manufactured by Kuraray Co., Ltd.).

[0038] In the water-soluble resin layer, the content of polyvinyl alcohol (the total amount when multiple types are used in combination) is preferably 50 to 100 mass %, more preferably 70 to 100 mass %, and even more preferably 90 to 100 mass %, from the viewpoints of developability and oxygen barrier property.

[0039] The water-soluble resin layer preferably contains polyvinyl alcohol and polyvinylpyrrolidone as water-soluble resins. When the water-soluble resin layer contains polyvinyl alcohol and polyvinylpyrrolidone, the mass ratio of polyvinyl alcohol to polyvinylpyrrolidone is preferably 40 / 60 to 90 / 10, more preferably 50 / 50 to 90 / 10, and even more preferably 60 / 40 to 90 / 10. The water-soluble resin layer preferably contains, as the water-soluble resin, polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble celluloses.

[0040] The content of the water-soluble resin in the water-soluble resin layer is not particularly limited, but from the viewpoint of further improving the oxygen barrier property, 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. The upper limit is not particularly limited, but for example, it is preferably 100% by mass or less, more preferably 99.9% by mass or less, and even more preferably 99.8% by mass or less.

[0041] The water-soluble resin layer may contain a plasticizer in order to further improve removability, developability, and the like. Examples of the plasticizer include polyvinyl alcohol or polyvinylpyrrolidone copolymerized with 1 to 20 mol % of olefin; glycerins such as glycerin, diglycerin, and triglycerin; trimethylolpropane; polyalkylene oxides and derivatives thereof such as polyalkylene oxide, ester compounds of polyalkylene oxide, and ether compounds of polyalkylene oxide; and phthalate esters such as dibutyl phthalate. In the water-soluble resin layer, the plasticizer may be used alone or in combination of two or more kinds. The content of the plasticizer in the water-soluble resin layer is preferably from 0 to 40% by mass, and more preferably from 0 to 20% by mass, based on the total mass of the water-soluble resin layer.

[0042] The water-soluble resin layer preferably contains a surfactant. The surfactant is not particularly limited, and examples thereof include nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants, with fluorine-based surfactants and silicone-based surfactants being preferred. The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant in the water-soluble resin layer is preferably 0 to 5 mass %, more preferably 0.01 to 1 mass %, further preferably 0.03 to 1 mass %, particularly preferably 0.05 to 1 mass %, based on the total mass of the water-soluble resin layer.

[0043] In addition to the above-mentioned components, the water-soluble resin layer may contain other additives such as a release agent, an adhesion promoter, a filler (for example, oxide particles such as silica), and an ultraviolet absorbing agent. In order to obtain a more excellent effect of the present invention, it is preferable that the water-soluble resin layer does not substantially contain a filler. "Substantially does not contain a filler" means that the content of the filler in the water-soluble resin layer is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.1% by mass or less, based on the total mass of the water-soluble resin layer.

[0044] <Step Xa Procedure> In the step Xa, the water-soluble resin layer is preferably formed by a coating method. As the step Xa, among others, a step of continuously transporting a long support in the longitudinal direction, forming a coating film of a water-soluble resin layer on the support by a coating method, and carrying out a drying treatment to produce a laminate A is preferable. The transport speed of the support is, for example, preferably from 1 to 150 m / min, more preferably from 5 to 100 m / min, and further preferably from 7 to 90 m / min.

[0045] The coating method is not particularly limited, but examples thereof include slit coating and curtain coating. When forming the water-soluble resin layer by coating method, it is preferable to coat the water-soluble resin composition containing the components contained in the water-soluble resin layer and a solvent on the support.The components contained in the water-soluble resin layer are as described above.In addition, 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 is capable of dissolving or dispersing the components contained in the water-soluble resin layer, 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 the water-miscible organic solvent include alcohol, acetone, ethylene glycol, glycerin, and mixed solvents of combinations thereof. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol are more preferred.

[0046] The solvent may be used alone or in combination of two or more kinds. The content of the solvent is preferably from 50 to 2500 parts by mass, more preferably from 50 to 1900 parts by mass, and further preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the water-soluble resin composition.

[0047] The drying method is preferably heat drying. The drying temperature is preferably 50° C. or higher, and more preferably 60° C. or higher. The upper limit is preferably 150° C. or lower, more preferably 130° C. or lower, and even more preferably 120° C. or lower. The drying temperature may have a temperature gradient. For example, a method of providing a temperature gradient in the drying temperature may include a method of using a dryer having a plurality of regions set at different temperatures so as to obtain a predetermined temperature gradient. When a temperature gradient is provided for the drying temperature, the temperature difference between the minimum temperature and the maximum temperature is preferably from 10 to 100°C, more preferably from 10 to 90°C, and even more preferably from 15 to 80°C. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more, and the upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.

[0048] [Process Xb] 2, step Xb is a step of providing a temporary protective layer 7 on the surface of the water-soluble resin layer 3 side of the laminate A 5 formed in step Xa to form a laminate B 9. Through step Xb, a laminate B including a support, a water-soluble resin layer, and a temporary protective layer is formed. The step Xb is preferably a step of laminating the laminate A and a resin film for forming a temporary protective layer by roll-to-roll bonding.

[0049] <Temporary protective layer> The materials constituting the temporary protective layer may be the same as those of the support used in the above-mentioned step Xa, and the preferred embodiments are also the same.

[0050] The uneven shape of the temporary protective layer is easily transferred to the water-soluble resin layer, and the unevenness transferred to the water-soluble resin layer may affect the pattern performance when the laminate is transferred to a transfer target and pattern formation is performed. In terms of being able to form a better pattern, it is preferable that the arithmetic mean roughness (Ra) of the surface of the temporary protective layer that contacts the water-soluble resin layer is, for example, 1 to 200 nm. The upper limit of the arithmetic mean roughness of the surface of the temporary protective layer in contact with the water-soluble resin layer is more preferably 100 nm or less, and even more preferably 50 nm or less, in that the occurrence of optical abnormalities during exposure can be further suppressed during pattern formation after the laminate is transferred to the transfer target, and a pattern with excellent linearity can be formed. On the other hand, the lower limit of the arithmetic mean roughness of the surface of the temporary protective layer in contact with the water-soluble resin layer is more preferably 10 nm or more, in that the damage to the water-soluble resin layer during peeling of the temporary protective layer caused by excessive adhesion between the temporary protective layer and the water-soluble resin layer can be suppressed, and a pattern with excellent linearity can be formed during pattern formation after the laminate is transferred to the transfer target.

[0051] The arithmetic mean roughness (Ra) of the temporary protective layer can be measured by the following method. Using a 3D optical profiler (New View7300, manufactured by Zygo), the surface of the temporary protective layer is measured under the following conditions to obtain a surface profile of the temporary protective layer. The Microscope Application of MetroPro ver8.3.2 is used as the measurement and analysis software. Next, the Surface Map screen is displayed in the above analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated to obtain the Ra value of the surface of the temporary protective layer. When the temporary protective layer is attached to a water-soluble resin layer or the like, the temporary protective layer may be peeled off from the water-soluble resin layer or the like, and the Ra value of the surface on the peeled side may be measured.

[0052] The thickness of the temporary protective layer is preferably from 5 to 200 μm, and from the viewpoints of ease of handling and versatility, it is more preferably from 5 to 150 μm, further preferably from 5 to 70 μm, and particularly preferably from 10 to 50 μm.

[0053] The method for laminating the temporary protective layer to the water-soluble resin layer may be, for example, a known method. The device for laminating the temporary protective layer to the water-soluble resin layer may be, for example, a known laminator such as a vacuum laminator or an autocut laminator. The laminator is preferably one equipped with any heatable roller such as a rubber roller and capable of applying pressure and heat.

[0054] [Process Xc] Step Xc is a step of winding the laminate B to form a wound body C. The method for winding the laminate B is not particularly limited, and a known method can be applied.

[0055] [Process Xd] Step Xd is a step of peeling the temporary protective layer of the laminate B between the temporary protective layer and the water-soluble resin layer after unwinding the laminate B from the roll C. The peeling method is not particularly limited, and a known method can be applied.

[0056] [Process Xe] 3, step Xe is a step of forming a photosensitive resin layer 11 so as to be in contact with the water-soluble resin layer 3 exposed by the peeling step of step Xd, thereby forming a laminate D 13. The laminate D obtained by step Xe has a support, a water-soluble resin layer, and a photosensitive resin layer in this order. First, the photosensitive resin layer constituting the laminate D will be described below.

[0057] <Photosensitive resin layer> After the photosensitive resin layer is transferred onto the transfer target, the photosensitive resin layer is exposed to light and developed to form a pattern on the transfer target. The photosensitive resin layer may be either negative or positive, but is preferably negative. The negative photosensitive resin layer is a photosensitive resin layer in which the solubility of the exposed portion in a developer is reduced by exposure. When the photosensitive resin layer is a negative photosensitive resin layer, the pattern formed corresponds to a cured layer. The photosensitive resin layer preferably contains, among others, a binder resin (preferably an alkali-soluble resin), a polymerizable compound, and a photopolymerization initiator.

[0058] (binder resin) The photosensitive resin layer preferably contains a binder polymer, and among these, an alkali-soluble resin is preferable as the binder polymer.

[0059] One preferred embodiment of the binder polymer is a (meth)acrylic resin, which has excellent alkali developability and film formability. In this specification, the (meth)acrylic resin means a resin having a repeating unit derived from a (meth)acrylic compound. The content of the repeating unit derived from the (meth)acrylic compound is, for example, preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more, based on the total repeating units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of repeating units derived from a (meth)acrylic compound, or may have repeating units derived from a polymerizable monomer other than a (meth)acrylic compound. That is, the upper limit of the content of repeating units derived from a (meth)acrylic compound is 100% by mass or less based on the total repeating units of the (meth)acrylic resin.

[0060] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl ester or (meth)acrylic acid benzyl ester is preferred. Examples of (meth)acrylamides include acrylamides such as diacetoneacrylamide.

[0061] Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. As the (meth)acrylic acid ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0062] The (meth)acrylic resin preferably contains a repeating unit derived from an alkyl (meth)acrylate. The content of the alkyl (meth)acrylate in the (meth)acrylic resin is, for example, preferably 10 to 90 mass%, more preferably 15 to 70 mass%, based on the total repeating units of the (meth)acrylic resin.

[0063] The (meth)acrylic resin may have a repeating unit other than the repeating unit derived from the (meth)acrylic compound. The polymerizable monomer that forms the repeating unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that is copolymerizable with a (meth)acrylic compound, and examples thereof include styrene compounds that may have a substituent at the α-position or aromatic ring, such as styrene, vinyl toluene, and α-methyl styrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0064] In order to improve the alkaline developability, the (meth)acrylic resin preferably has a repeating unit having an acid group, such as a carboxy group, a sulfo group, a phosphoric acid group, or a phosphonic acid group. As the repeating unit having an acid group, a repeating unit having a carboxy group is preferable, and a repeating unit derived from (meth)acrylic acid is more preferable.

[0065] When the (meth)acrylic resin contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 10% by mass or more based on the total repeating units of the resin in terms of excellent developability, and although there is no particular upper limit, it is preferably 50% by mass or less, more preferably 40% by mass or less in terms of excellent alkali resistance.

[0066] As the (meth)acrylic resin, a resin having both a repeating unit derived from (meth)acrylic acid and a repeating unit derived from an alkyl (meth)acrylate ester is also preferred.

[0067] A preferred embodiment of the binder polymer is a styrene-acrylic copolymer. In this specification, the styrene-acrylic copolymer refers to a resin having a repeating unit derived from a styrene compound and a repeating unit derived from a (meth)acrylic compound. The total content of the repeating unit derived from a styrene compound and the repeating unit derived from a (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total repeating units of the copolymer. The content of the repeating units derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, based on the total repeating units of the copolymer. The content of the repeating units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, based on all repeating units of the copolymer.

[0068] The binder polymer also preferably has a repeating unit having a reactive group. The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group, and further preferably an allyl group or a (meth)acryloxy group.

[0069] The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably from 10,000 to 100,000, and particularly preferably from 15,000 to 80,000, in terms of achieving better effects of the present invention.

[0070] The acid value of the binder polymer is preferably from 10 to 200 mgKOH / g, more preferably from 60 to 200 mgKOH / g, further preferably from 60 to 150 mgKOH / g, and particularly preferably from 60 to 130 mgKOH / g. The acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992.

[0071] The photosensitive resin layer may contain one type of binder polymer alone, or may contain two or more types of binder polymers. The content of the binder polymer is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and even more preferably from 30 to 70% by mass, based on the total mass of the photosensitive resin layer, in terms of better effects of the present invention.

[0072] (polymerizable compound) The photosensitive resin layer preferably contains a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, and the radical polymerizable group is preferable.

[0073] The polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound"). The ethylenically unsaturated group is preferably a (meth)acryloxy group. The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited as long as it is 1 or more, but 1 to 6 are preferable, 1 to 3 are more preferable, and 2 or 3 are even more preferable. The ethylenically unsaturated compound in this specification is a compound other than the above-mentioned binder polymer, and preferably has a molecular weight of less than 5,000.

[0074] The ethylenically unsaturated compound may have an alkyleneoxy group. The alkylene group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to a polymerizable compound is preferably 2 to 60, more preferably 2 to 30, and even more preferably 2 to 20 per molecule.

[0075] ·Polymerizable compound B1 The photosensitive resin layer also preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in the molecule, among the above polymerizable compounds.

[0076] The aromatic ring of the polymerizable compound B1 may be, for example, an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, or an anthracene ring; an aromatic heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, or a pyridine ring; or a condensed ring thereof, preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent. The polymerizable compound B1 may have one or more aromatic rings.

[0077] The polymerizable compound B1 preferably has a bisphenol structure, since this suppresses swelling of the photosensitive resin layer due to a developer, thereby improving the 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.

[0078] An example of the polymerizable compound B1 having a bisphenol structure is a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure may be directly bonded to the two polymerizable groups, or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, and more preferably ethyleneoxy groups. The number of alkyleneoxy groups (preferably ethyleneoxy groups) added to the bisphenol structure is preferably 2 to 60, more preferably 2 to 30, and even more preferably 2 to 20 per molecule. Examples of the polymerizable compound B1 having a bisphenol structure include those described in paragraphs

[0072] to

[0080] of JP2016-224162A, the contents of which are incorporated herein by reference.

[0079] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include ethoxylated bisphenol A dimethacrylates (BPE series, Shin-Nakamura Chemical Co., Ltd.) such as 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, Shin-Nakamura Chemical Co., Ltd.).

[0080] The polymerizable compound B1 preferably contains a compound represented by the following formula (B-2). Formula (B-2): [ka]

[0081] In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4, and B represents C3H6. n1 and n3 each independently represent an integer of 1 to 39, and n1+n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 represents an integer of 0 to 30. The arrangement of the repeating units -(AO)- and -(BO)- may be either random or block. When the arrangement is block, either -(AO)- or -(BO)- may be on the bisphenyl group side. n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 12. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, still more preferably an integer of 0 to 2, and particularly preferably 0.

[0082] The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, based on the total mass of the photosensitive resin layer, from the viewpoint of better resolution. The upper limit is preferably 90% by mass or less, more preferably 70% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which the photosensitive composition seeps out from the edge of the transfer member).

[0083] The content of the polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of superior resolution. The upper limit is preferably 100% by mass or less, more preferably 99% by mass or less, and even more preferably 95% by mass or less, based on the total mass of the polymerizable compound, from the viewpoint of peelability.

[0084] Other ethylenically unsaturated compounds other than polymerizable compound B1 The ethylenically unsaturated compound other than the polymerizable compound B1 is not particularly limited, and examples thereof include a compound having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a difunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0085] 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.

[0086] Examples of difunctional ethylenically unsaturated compounds 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.), 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 (NK Ester 4G, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate (Aronix M-270, etc., manufactured by Toagosei Co., Ltd.). Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Examples of commercially available urethane di(meth)acrylate 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.).

[0087] 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 versions of these. The term "(tri / tetra / penta / hexa)(meth)acrylate" encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. Additionally, the term "(tri / tetra)(meth)acrylate" encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0088] 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., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), 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 Co., Ltd.), 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.), ARONIX M-510 (manufactured by Toagosei Co., Ltd.), and SR454 (manufactured by Tomoe Chemical Co., Ltd.).

[0089] As the above-mentioned trimethylolpropane tri(meth)acrylate and its alkylene oxide modified product, a compound represented by the following formula (B-3) is also preferred.

[0090] Formula (B-3): [ka]

[0091] In formula (B-3), R 1 , R 2 , and R 3each independently represents a hydrogen atom or a methyl group. a, b, and c each independently represent an integer of 0 to 48, and a+b+c represents an integer of 0 to 50. a+b+c is preferably an integer of 0 to 45, more preferably an integer of 0 to 39, and even more preferably an integer of 0 to 36, in that the resolution and linearity of the pattern are further improved.

[0092] The polymerizable compound may be an ethylenically unsaturated compound having an acid group (such as a carboxy group). The acid group may form an acid anhydride group. Examples of ethylenically unsaturated 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.). Examples of the ethylenically unsaturated compound having an acid group include the polymerizable compounds described in paragraphs

[0025] to

[0030] of JP-A-2004-239942.

[0093] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 10 to 70% by mass, more preferably from 15 to 70% by mass, and further preferably from 20 to 70% by mass, based on the total mass of the photosensitive resin layer. The content of the ethylenically unsaturated compound is preferably from 10 to 70% by mass, more preferably from 15 to 70% by mass, and further preferably from 20 to 70% by mass, based on the total mass of the photosensitive resin layer.

[0094] (Photopolymerization initiator) The photosensitive resin layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving active light such as ultraviolet light, visible light, and X-rays. Examples of the photopolymerization initiator include known photopolymerization initiators. Examples of the photopolymerization initiator include photoradical polymerization initiators and photocationic polymerization initiators, and photoradical polymerization initiators are preferred, and one or more selected from the group consisting of acridine-based photopolymerization initiators, benzophenone-based polymerization initiators, oxime ester-based photopolymerization initiators, biimidazole-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators are more preferred.

[0095] The photopolymerization initiator may be used alone or in combination of two or more kinds. The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive resin layer, and the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the photosensitive resin layer.

[0096] (Surfactant) The photosensitive resin layer preferably contains a surfactant. The surfactant is preferably a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant, and more preferably a silicone-based surfactant. Examples of the silicone-based surfactant include a linear polymer consisting of a siloxane bond, and a modified siloxane polymer having an organic group introduced into the side chain and / or the end.

[0097] As the surfactant, it is particularly preferable to use a polymer D containing at least one repeating unit α selected from the group consisting of repeating units represented by the following formula (A-1) and repeating units represented by the following formula (A-2), and a repeating unit β represented by the following formula (B).

[0098] [ka]

[0099] In formula (A-1), R1 represents a hydrogen atom or a methyl group. R2 represents an alkylene group having 1 to 10 carbon atoms. R3 represents an alkyl group having 1 to 4 carbon atoms. 1 represents an integer of 5 to 100.

[0100] In formula (A-2), R4 represents a hydrogen atom or a methyl group. R5 represents an alkylene group having 1 to 10 carbon atoms. L represents a trimethylsilyl group or a tris(trimethylsiloxy)silyl group.

[0101] In formula (B), R6 represents a hydrogen atom or a methyl group. R7 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. m represents an integer of 1 to 100. n represents an integer of 1 to 4.

[0102] In polymer D, the content of repeating unit α is preferably 1 to 50 mass%, more preferably 3 to 40 mass%, and even more preferably 5 to 45 mass%, based on all repeating units in polymer D. Meanwhile, the content of repeating unit β is preferably 40 to 99 mass%, more preferably 45 to 95 mass%, and even more preferably 50 to 90 mass%, based on all repeating units in polymer D. The polymer D may further contain repeating units other than the repeating units α and β.

[0103] The weight average molecular weight (Mw) of polymer D is preferably 500 or more, more preferably 800 or more, further preferably from 1,000 to 30,000, and particularly preferably from 2,000 to 20,000.

[0104] The content of the surfactant is preferably from 0.01 to 5% by mass, more preferably from 0.01 to 3% by mass, and further preferably from 0.05 to 1% by mass, based on the total mass of the photosensitive resin layer.

[0105] (Other additives) The photosensitive resin layer may contain other additives, if necessary, in addition to the above components. Other additives include, for example, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, 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 like, as well as the compounds described in paragraphs

[0165] to

[0184] of JP2014-085643A, the contents of which are incorporated herein by reference. The other additives may be used alone or in combination of two or more. In order to obtain a more excellent effect of the present invention, it is preferable that the photosensitive resin layer does not substantially contain a filler. "Substantially does not contain a filler" means that the content of the filler in the photosensitive resin layer is 1 mass % or less, preferably 0.5 mass % or less, more preferably 0.3 mass % or less, and even more preferably 0.1 mass % or less, based on the total mass of the photosensitive resin layer.

[0106] <Step Xe Procedure> Step Xe is preferably a step in which the temporary protective layer is peeled off from the roll C obtained in step Xb, the long film having the exposed surface of the water-soluble resin layer is continuously transported in the longitudinal direction, a coating of a photosensitive resin layer is formed on the water-soluble resin layer by a coating method, and a drying process is performed to produce a laminate D.

[0107] The film transport speed is, for example, preferably from 1 to 150 m / min, more preferably from 5 to 100 m / min, and further preferably from 7 to 90 m / min.

[0108] The coating method is not particularly limited, but examples thereof include slit coating and curtain coating. When the photosensitive resin layer is formed by a coating method, it is preferable to coat a photosensitive resin composition containing the components contained in the photosensitive resin layer and a solvent on the water-soluble resin layer. The components contained in the photosensitive resin layer are as described above. In addition, in the photosensitive 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 photosensitive resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component of the photosensitive resin layer, and a known organic 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.

[0109] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0110] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of JP-A-2018-177889 may be used, the contents of which are incorporated herein by reference. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1,200 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0111] The solvent may be used alone or in combination of two or more kinds. The content of the solvent is preferably from 50 to 2500 parts by mass, more preferably from 50 to 1900 parts by mass, and further preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive resin composition.

[0112] The drying method is preferably heat drying. The drying temperature is preferably 50° C. or higher, and more preferably 60° C. or higher. The upper limit is preferably 150° C. or lower, more preferably 130° C. or lower, and even more preferably 120° C. or lower. The drying temperature may have a temperature gradient. For example, a method of providing a temperature gradient in the drying temperature may include a method of using a dryer having a plurality of regions set at different temperatures so as to obtain a predetermined temperature gradient. When a temperature gradient is provided for the drying temperature, the temperature difference between the minimum temperature and the maximum temperature is preferably from 10 to 100°C, more preferably from 10 to 90°C, and even more preferably from 15 to 80°C. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more, and the upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.

[0113] In forming the photosensitive resin layer in step Xe, at least one of the film conveying speed, drying temperature, and drying time is preferably different from the support conveying speed, drying temperature, and drying time in forming the water-soluble resin layer in the above-mentioned step Xa. In forming the photosensitive resin layer in step Xe, it is particularly preferable that at least one of the film conveying speed and drying temperature is different from the support conveying speed and drying temperature in forming the water-soluble resin layer in the above-mentioned step Xa. In addition, when there is a temperature gradient in the drying temperature, "drying temperatures are different" means that at least one of the minimum and minimum temperatures is different. For example, when the drying temperature in forming the water-soluble resin layer has a temperature gradient of 50 to 70°C and the drying temperature in forming the photosensitive resin layer has a temperature gradient of 50 to 100°C, the maximum temperatures do not match, so the two drying temperatures are considered to be different.

[0114] [Process Xf] Step Xf is a step of forming a cover film 15 in contact with the photosensitive resin layer 11 to form a laminate E 17 having a support 1, a water-soluble resin layer 3, a photosensitive resin layer 11, and the cover film 15 in this order, as shown in FIG.

[0115] <Cover film> Examples of the cover film include resin films having heat resistance and solvent resistance.Specific examples include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film.In addition, the same support as that described in step Xa can also be used as the cover film. As the cover film, of these, a polyolefin film is preferable, and a polypropylene film or a polyethylene film is more preferable.

[0116] The thickness of the cover film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, further preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. The thickness of the cover film is preferably 1 μm or more because it has excellent mechanical strength, and is preferably 100 μm or less because it is relatively inexpensive.

[0117] The number of fish eyes with a diameter of 80 μm or more contained in the cover film is 5 / m 2 The lower limit is 0 pieces / m 2 The above is preferred. The term "fisheye" refers to foreign matter, unmelted material, oxidized deterioration products, etc., that are trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0118] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The lower limit is 0 pieces / mm 2 When the thickness is within the above range, defects caused by unevenness due to particles contained in the cover film being transferred to the photosensitive resin layer can be suppressed.

[0119] From the viewpoint of providing winding property, the arithmetic mean roughness (Ra) of the surface opposite to the surface contacting the photosensitive resin layer of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. The method for measuring the arithmetic mean roughness (Ra) may be the same as the method for measuring the arithmetic mean roughness (Ra) of the temporary protective layer in the step Xc.

[0120] In the laminate E, the water-soluble resin layer preferably has a depression of 1 nm or more and less than 100 nm on the surface on the photosensitive resin layer side. The above-mentioned depression can be measured by observing an arbitrary 100 μm square area of ​​the surface of the water-soluble resin layer exposed by peeling the photosensitive resin layer from the laminate E using an atomic force microscope (manufactured by Hitachi High-Tech Science Corporation). Note that when peeling the photosensitive resin layer, the photosensitive resin layer may be cured by exposure to light before peeling. By having the water-soluble resin layer of the laminate E have the above-mentioned depression on the surface on the photosensitive resin layer side, optical abnormalities during exposure in pattern formation after transferring the laminate to a substrate can be further suppressed, resulting in a pattern with better linearity.

[0121] The method for laminating the cover film to the photosensitive resin layer may be, for example, a known method. The device for laminating the cover film to the photosensitive resin layer may be, for example, a known laminator such as a vacuum laminator or an autocut laminator. The laminator is preferably one equipped with any heatable roller such as a rubber roller and capable of applying pressure and heat.

[0122] The laminate E may be wound up to produce and store a transfer film in roll form.

[0123] [Method for producing the second laminate] The second laminate manufacturing method of the present invention (hereinafter also referred to as the "second manufacturing method") includes the following steps Ya, Yb, Yc, and Yd in this order. Step Ya: A step of forming a water-soluble resin layer on a support to form a laminate A Step Yb: A step of forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B. Step Yc: A ​​step of winding the laminate B to form a wound body C. Step Yd: unwinding the laminate B from the roll C, peeling the temporary protective layer from the laminate B between the temporary protective layer and the water-soluble resin layer, and laminating the photosensitive resin layer of a transfer film including a temporary support and a photosensitive resin layer to the exposed surface of the laminate B to obtain a laminate F including the support, the water-soluble resin layer, the photosensitive resin layer, and the temporary support.

[0124] The laminate obtained by the second manufacturing method is unlikely to have a difference in sensitivity between one end side and the other end side in the longitudinal direction, and the occurrence of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer can be suppressed. Moreover, the pattern obtained by transferring the laminate obtained by the first manufacturing method to a transfer target and carrying out an exposure process and a development process has excellent linearity.

[0125] The mechanism by which the second production method provides the above-mentioned effects is not clear, but the present inventors speculate as follows. The second production method involves first forming a roll C by winding up a laminate B including a support, a water-soluble resin layer, and a temporary protective layer, then unwinding the laminate B from the roll C, peeling off the temporary protective layer from the laminate B, and then laminating a photosensitive resin layer on the water-soluble resin layer. In other words, the second production method is a production method that first goes through the above-mentioned roll C, rather than forming the photosensitive resin layer continuously after forming the water-soluble resin layer, and this makes it easy to set different production conditions for the photosensitive resin layer and the water-soluble resin layer.

[0126] Since the photosensitive resin layer and the water-soluble resin layer typically have different optimal manufacturing conditions (conveying speed, heat drying temperature, etc.) for each layer, it is desirable that at least one of the conveying speed and heat drying temperature can be set to different conditions for each layer when forming each layer. On the other hand, for example, when preparing a long laminate having a support, a water-soluble resin layer, and a photosensitive resin layer, if the photosensitive resin layer is continuously formed under the same manufacturing conditions as the water-soluble resin layer after the formation of the water-soluble resin layer, the degree of component penetration between the photosensitive resin layer and the water-soluble resin layer (for example, the amount of component of the water-soluble resin layer permeated into the photosensitive resin layer, the amount of component of the photosensitive resin layer permeated into the water-soluble resin layer, etc.) will be different between the start and end regions of the winding of the obtained long laminate, and as a result, a sensitivity difference may occur between the start and end regions of the winding of the laminate. To give a more specific example, for example, when the optimal drying and heating temperature of the photosensitive resin layer is higher than the optimal drying and heating temperature of the water-soluble resin layer, and when the water-soluble resin layer and the photosensitive resin layer are continuously formed on one conveying line, it is often necessary to make the drying and heating temperature of the photosensitive resin layer the same as the drying and heating temperature of the water-soluble resin layer due to manufacturing issues. If the drying and heating temperature of the photosensitive resin layer is made the same as the drying and heating temperature of the water-soluble resin layer, volatile solvent is likely to accumulate in the dryer for the photosensitive resin layer, and in the later stages of conveying, a situation is likely to occur in which drying in the dryer does not progress sufficiently. As a result, a difference in sensitivity may occur between the start and end regions of the winding of the laminate. In contrast, in the second manufacturing method, since the photosensitive resin layer and the water-soluble resin layer go through the roll C once as described above, it is possible to manufacture the photosensitive resin layer and the water-soluble resin layer under different manufacturing conditions, and it is possible to suppress the occurrence of a difference in sensitivity between the start and end regions of the laminate. Furthermore, since the photosensitive resin layer is laminated on the water-soluble resin layer by lamination, it is possible that the difference in sensitivity between the start and end of the roll may be more easily suppressed. This is because, when the photosensitive resin layer is applied on the water-soluble resin layer during lamination, the solvent may easily cause the transfer of substances (e.g., polymerization initiator, etc.) between the layers, but in the case of lamination, both the water-soluble resin layer and the photosensitive resin layer have already been dried once, so it is presumed that the transfer of substances is unlikely to occur.

[0127] Furthermore, the roll C obtained in step Yc in the second manufacturing method has a temporary protective layer on the water-soluble resin layer to protect the water-soluble resin layer. Therefore, the surface of the water-soluble resin layer on which the photosensitive resin layer is formed can be prevented from generating foreign matter and scratches due to friction with the back side of the support during winding in step Yc. As a result, the laminate obtained by the second manufacturing method is less likely to cause exposure defects (optical abnormalities) when the photosensitive resin layer is transferred to the transfer target and exposed to light. Furthermore, the laminate obtained by the second manufacturing method has a water-soluble resin layer. Therefore, when the photosensitive resin layer is transferred to the transfer target and an exposure and development process is performed, the water-soluble resin layer blocks oxygen, which facilitates the polymerization reaction of the photosensitive resin layer to proceed, and the resulting pattern has excellent linearity. In addition, the water-soluble resin layer makes it possible to perform an exposure process (contact exposure) in a state where the temporary support is peeled off, and it is possible to suppress a decrease in linearity of the pattern due to excessive adhesion between the photosensitive resin layer and the photomask.

[0128] Hereinafter, the term "the effect of the present invention is superior" also means that in the laminate obtained by the second production method, the difference in sensitivity between one end and the other end in the longitudinal direction is more suppressed, that in the laminate obtained by the second production method, the occurrence of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer is more suppressed, and / or that, when the laminate obtained by the second production method is transferred to a substrate and subjected to exposure and development treatment, a pattern with superior linearity can be formed.

[0129] The second manufacturing method will be described in detail below. Steps Ya to Yc in the second manufacturing method are the same as steps Xa to Xc in the first manufacturing method, respectively, and the preferred embodiments are also the same. The second manufacturing method is the same as the first manufacturing method except that the roll C obtained in step Xc is unwound, the temporary protective layer is peeled off from the laminate B between the temporary protective layer and the water-soluble resin layer, and the photosensitive resin layer of the transfer film including the temporary support and the photosensitive resin layer is laminated on the exposed surface of the laminate B to form a laminate F including a support, a water-soluble resin layer, a photosensitive resin layer, and a temporary support.

[0130] The second production method preferably further includes the following step Yf, the following step Yg, the following step Yh, and the following step Yi, before the above step Yd. Step Yf: A step of forming a photosensitive resin layer on a temporary support to form a laminate H Step Yg: A step of forming a temporary protective layer in contact with the photosensitive resin layer to form a laminate I. Step Yh: A step of winding the laminate I to form a wound body J. Step Yi: a step of unwinding the roll J and peeling the temporary protective layer from the laminate I between the temporary protective layer and the photosensitive resin layer to obtain a transfer film including the temporary support and the photosensitive resin layer.

[0131] The second production method preferably further includes the following step Ye after the above step Yd. Step Ye: A step of peeling the temporary support from the laminate F between the temporary support and the photosensitive resin layer, and laminating a cover film to the exposed surface of the laminate F to form a laminate G having the support, the water-soluble resin layer, the photosensitive resin layer, and the cover film in this order.

[0132] Hereinafter, steps Ya, Yb, Yc, and Yd of the second production method will be described.

[0133] [Process Ya~Yc] The procedures and materials used in steps Ya to Yc in the second production method are the same as those in steps Xa to Xc in the above-mentioned first production method, and the preferred embodiments are also the same.

[0134] [Process Yd] Process Yd includes a process of unwinding the laminate B from the roll C, peeling off the temporary protective layer of the laminate B between the temporary protective layer and the water-soluble resin layer, and a process of laminating a photosensitive resin layer of a transfer film including a temporary support and a photosensitive resin layer to the surface of the water-soluble resin layer exposed after peeling. Through this step Yd, a laminate F 21 including the support 1, the water-soluble resin layer 3, the photosensitive resin layer 11, and the temporary support 19 is obtained, as shown in FIG. The peeling step in step Yd is the same as step Xd in the above-mentioned first production method, and the preferred embodiment is also the same.

[0135] <Transfer film> The transfer film used in the process Yd is not particularly limited as long as it is a transfer film having a temporary support and a photosensitive resin layer. The transfer film used in the step Yd is preferably a transfer film produced through the above-mentioned steps Yf to Yi. The temporary support in steps Yd and Yf ​​to Yi may be the same as the support used in step Xa in the first manufacturing method described above, or may be the same as the cover film used in step Xf in the first manufacturing method described above. The photosensitive resin layer in step Yd, and steps Yf to Yi may be the same as the photosensitive resin layer used in step Xe in the above-mentioned first manufacturing method.

[0136] The procedure of each of the steps Yf to Yi will be described below. (Process Yf) The step Yf is a step of forming a photosensitive resin layer on a temporary support to form a laminate H. The procedure for forming the photosensitive resin layer on the temporary support is not particularly limited, and may be, for example, a coating method. The photosensitive resin layer forming process in the step Yf is the same as the photosensitive resin layer forming process used in the step Xe in the first manufacturing method described above. In the formation of the photosensitive resin layer in the step Yf, at least one of the film conveying speed, drying temperature, and drying time is preferably different from the support conveying speed, drying temperature, and drying time in the formation of the water-soluble resin layer in the above-mentioned step Ya. In the formation of the photosensitive resin layer in the step Xf, it is particularly preferable that at least one of the film conveying speed and drying temperature is different from the support conveying speed and drying temperature in the formation of the water-soluble resin layer in the above-mentioned step Ya.

[0137] (Process Yg) Step Yg is a step of forming a temporary protective layer so as to be in contact with the photosensitive resin layer to form a laminate I. The procedure for forming the temporary protective layer and the material of the temporary protective layer in step Yg are similar to the procedure for forming the temporary protective layer and the material of the temporary protective layer in step Xb in the first manufacturing method described above.

[0138] The uneven shape of the temporary protective layer is easily transferred to the photosensitive resin layer, and the unevenness transferred to the photosensitive resin layer may affect the pattern performance when the laminate is transferred to a transfer target and pattern formation is performed. In terms of being able to form a better pattern, the arithmetic mean roughness (Ra) of the surface of the temporary protective layer that contacts the photosensitive resin layer is preferably, for example, 1 to 200 nm. The upper limit of the arithmetic mean roughness of the surface of the temporary protective layer in contact with the photosensitive resin layer is preferably 100 nm or less, and more preferably 50 nm or less, in order to suppress the occurrence of optical abnormalities during exposure during pattern formation after the laminate is transferred to the transfer target, and to form a pattern with excellent linearity. On the other hand, the lower limit of the arithmetic mean roughness of the surface of the temporary protective layer in contact with the photosensitive resin layer is more preferably 10 nm or more, in order to suppress damage to the photosensitive resin layer during peeling of the temporary protective layer caused by excessive adhesion between the temporary protective layer and the photosensitive resin layer, and to form a pattern with excellent linearity during pattern formation after the laminate is transferred to the transfer target. The method for measuring the arithmetic mean roughness (Ra) may be the same as the method for measuring the arithmetic mean roughness (Ra) of the temporary protective layer in the step Xc.

[0139] (Process Yh) The step Yh is a step of winding the laminate I to form a wound body J. The method for winding the laminate I is not particularly limited, and a known method can be applied.

[0140] (Process Yi) Step Yi is a step of unwinding the laminate I from the roll J and peeling the temporary protective layer between the temporary protective layer and the photosensitive resin layer from the laminate I. The peeling method is not particularly limited, and a known method can be applied.

[0141] <Process Yd> In the step Yd, the step of laminating the photosensitive resin layer of the transfer film including the temporary support and the photosensitive resin layer on the surface of the water-soluble resin layer is not particularly limited, and may be, for example, a known method. As the device for laminating the water-soluble resin layer and the transfer film, for example, known laminators such as a vacuum laminator and an autocut laminator may be mentioned. The laminator is preferably one equipped with any heatable roller such as a rubber roller and capable of applying pressure and heat. The laminate F obtained by the above-mentioned step Yd may be wound up, and then a transfer film in a roll form may be produced and stored.

[0142] [Process Ye] Step Ye is a step of peeling off the temporary support from the laminate F obtained in step Yd and laminating a cover film onto the exposed surface of the laminate F. Through step Ye, a laminate G having a support, a water-soluble resin layer, a photosensitive resin layer, and a cover film in this order is obtained. In the step Ye, the method for peeling off the temporary support from the laminate F is not particularly limited, and any known method can be applied. The cover film and the method for laminating the cover film used in the process Ye are similar to the cover film and the method for laminating the cover film used in the process Xf.

[0143] In the laminates F and G, the water-soluble resin layer preferably has a recess of 1 nm or more and less than 100 nm on the surface facing the photosensitive resin layer. In the laminates F and G, the photosensitive resin layer preferably has a recess of 1 nm or more and less than 100 nm on the surface facing the water-soluble resin layer. The above-mentioned depressions can be measured by observing an arbitrary 100 μm square area of ​​the surface of the water-soluble resin layer and the surface of the photosensitive resin layer exposed by peeling the water-soluble resin layer and the photosensitive resin layer of the laminate F and the laminate G with an atomic force microscope (manufactured by Hitachi High-Tech Science Corp.) Note that when peeling the photosensitive resin layer and the water-soluble resin layer, the photosensitive resin layer may be cured by exposure to light before peeling. By having the above-mentioned depression on the surface of the water-soluble resin layer on the photosensitive resin layer side in laminates F and G, and / or on the surface of the photosensitive resin layer on the water-soluble resin layer side in laminates F and G, optical abnormalities during exposure in pattern formation after transferring the laminate to a substrate can be further suppressed, and the linearity of the resulting pattern can be more excellent.

[0144] [Method of forming resin pattern] By using the laminate (transfer film; hereinafter, also referred to as "the laminate of the present invention") obtained by the above-mentioned first and second production methods, a resin pattern can be formed on a transfer-receiving body.

[0145] The laminate of the present invention is preferably used for a protective film pattern that protects a conductive layer in a touch panel. The method for forming a resin pattern includes a lamination step of contacting a surface of the laminate of the present invention opposite to the support with a substrate having a conductive portion, thereby obtaining a substrate with a composition layer having a substrate, a conductive layer, a composition layer, and a support in this order; an exposure step of pattern-exposing the composition layer; A development step of developing the exposed composition layer to form a protective film pattern that protects the conductive layer, Furthermore, it is preferable to have a peeling step of peeling the support from the substrate with the composition layer between the laminating step and the exposure step, or between the exposure step and the development step.

[0146] In addition, when forming a resin pattern, it is preferable to use the laminate of the present invention in a rolled form and carry out the process by a roll-to-roll process. That is, the lamination step is a step of laminating the laminate of the present invention and a substrate having a conductive layer described later by a roll-to-roll method, and it is preferable to carry out at least the exposure step and the development step on the long laminate formed by the lamination step. The steps of the above process will be described in detail below.

[0147] [Lamination process] The lamination step is a step of contacting the surface of the laminate of the present invention opposite to the support with a substrate having a conductive part and laminating them to obtain a substrate with a composition layer having a substrate, a conductive layer, a composition layer (a photosensitive resin layer and a water-soluble resin layer), and a support in this order. When the laminate of the present invention has a cover film, the cover film is peeled off before the lamination step.

[0148] In the lamination, the conductive layer and the composition layer are pressed together so that their surfaces come into contact with each other. The method of pressure bonding 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 composition layer on a substrate having a conductive portion, and apply pressure and heat with a roll or the like. For lamination, a known laminator such as a vacuum laminator or an autocut laminator can be used. The lamination temperature is not particularly limited, but is preferably from 70 to 130°C, for example.

[0149] The substrate having a conductive layer has a conductive layer on a substrate, and may have an optional layer formed thereon, i.e., the substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0150] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the substrate is described in, for example, paragraph

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

[0151] From the viewpoints of electrical conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Furthermore, only one conductive layer may be disposed on the substrate, or two or more conductive layers may be disposed on the substrate. When two or more conductive layers are disposed, it is preferable that the conductive layers are made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph

[0141] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0152] The substrate having a conductive layer is preferably a substrate having at least one of a transparent electrode and a routed wiring. Such a substrate can be suitably used as a substrate for a touch panel. The transparent electrode can function suitably as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a metal mesh or a metal thin wire such as a metal nanowire. Examples of the thin metal wires include thin wires of silver, copper, etc. Among them, conductive silver materials such as silver mesh and silver nanowires are preferred.

[0153] The material of the lead wiring is preferably a metal. Examples of the metal material for the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys of two or more of these metal elements. The material for the wiring is preferably copper, molybdenum, aluminum, or titanium, and particularly preferably copper.

[0154] The protective film for a touch panel formed by the laminate of the present invention may be provided so as to cover the electrodes and / or wiring directly or via another layer for the purpose of protecting the electrodes and / or wiring, or may be provided as a protective film for insulating between electrodes (specifically, a protective film for insulating between electrodes such as bridge wiring).

[0155] [Exposure process] The exposure step is a step of pattern-exposing the composition layer. Here, the term "pattern exposure" refers to a form of exposure in a pattern, that is, exposure in a form in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and may be appropriately adjusted. The composition layer may be exposed from the side opposite to the substrate, or from the substrate side of the composition layer.

[0156] The light source for the 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 resin layer. Among them, the dominant wavelength of the exposure light for the pattern exposure is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity.

[0157] 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 preferable, and 10 to 200 mJ / cm 2 is more preferred.

[0158] 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.

[0159] By carrying out an exposure step and a development step described later, a protective film pattern that protects at least a part of the conductive layer is formed on the conductive layer on the substrate.

[0160] [Peeling process] The peeling step is a step of peeling the support from the substrate with the composition layer between the laminating step and the exposure step, or between the exposure step and the development step described below. The peeling method is not particularly limited, and is described in paragraph 2 of JP 2010-072589 A.

[0161] ~

[0162] It is possible to use a mechanism similar to the cover film peeling mechanism described in .

[0161] [Development process] The development step is a step of developing the exposed composition layer to form a pattern. The 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).

[0162] Examples of the development method include paddle development, shower development, spin development, and dip development, with shower development being preferred.

[0163] A preferred embodiment of the developer used in the development step is, for example, the developer described in paragraph

[0194] of WO 2015 / 093271. A suitable embodiment of the development method for carrying out the development step is, for example, the development method described in paragraph

[0195] of WO 2015 / 093271.

[0164] In addition, the developing step is preferably a step of repeatedly using the developing solution by circulating the developing solution, and the developing method is preferably shower development, and the developing solution is preferably repeatedly used by circulating the developing solution. Specific examples of the developing step include the developing method described in JP-A-2012-137574 and the like.

[0165] [Post-exposure process and post-bake process] The method for producing the laminate may include a step of exposing the pattern obtained by the development step (a post-exposure step) and / or a step of heating the pattern (a 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 preferable, and 200 to 3000 mJ / cm 2 The post-baking temperature is preferably from 80 to 250° C., more preferably from 90 to 160° C. The post-baking time is preferably from 1 to 180 minutes, more preferably from 10 to 60 minutes.

[0166] [Conductor pattern formation method] By using the laminate (the laminate of the present invention) obtained by the above-mentioned first and second production methods, a conductor pattern (circuit wiring) can be formed on a transfer recipient. As one embodiment of the method for forming a conductor pattern of the present invention, a lamination step of bringing a surface of the laminate of the present invention opposite to the support into contact with a substrate having a metal layer to obtain a substrate with a composition layer having a substrate, a metal layer, a composition layer (a photosensitive resin layer and a water-soluble resin layer), and a support in this order; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed composition layer to form a resin pattern; an etching process for performing an etching process on the metal layer in an area where the resin pattern is not disposed, or a plating process for performing a plating process on the metal layer in an area where the resin pattern is not disposed; a resist stripping step of stripping the resin pattern; When the plating process is further performed, the method for forming a conductive pattern further comprises a removing process of removing the metal layer exposed by the resist stripping process and forming a conductive pattern on the substrate, It is preferable that the method further includes a support peeling step of peeling off the support between the laminating step and the exposure step, or between the exposure step and the development step.

[0167] A specific procedure for forming the conductor pattern will be described below. The laminating step, exposing step, developing step, and peeling step in the method for forming a conductor pattern are the same as the laminating step, exposing step, developing step, and peeling step in the method for forming a resin pattern described above, and the preferred embodiments are also the same.

[0168] [Etching process] The method for manufacturing circuit wiring includes a step of etching the metal layer in an area where the resin pattern is not arranged in a laminate in which a substrate, a metal layer (a metal layer possessed by the substrate), and a resin pattern (more preferably, a resin pattern manufactured by a manufacturing method including the lamination step, the exposure step, and the development step) are laminated in this order (etching step). In the etching step, the resin pattern obtained from the photosensitive resin layer in the developing step is used as an etching resist to etch the metal layer. As the etching method, a known method can be applied, and examples of the method include the method described in paragraphs

[0209] to

[0210] of JP2017-120435A, the method described in paragraphs

[0048] to

[0054] of JP2010-152155A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.

[0169] [Plating process] The plating step is a step of forming a plating layer by plating on the metal layer in the area where the resin pattern is not arranged (the metal layer exposed on the surface by the development step). Examples of the plating method include electrolytic plating and electroless plating, with electrolytic plating being preferred from the viewpoint of productivity. When the plating step is carried out, a plating layer having a pattern shape 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.

[0170] 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 the conductive pattern has better electrical conductivity. Also, the plating layer preferably contains copper as a main component, since the conductive pattern has better electrical conductivity.

[0171] The thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm, and the upper limit is preferably 20 μm or less.

[0172] It is also preferable to have a protective layer forming step between the plating step and the resist stripping step described below. The protective layer lamination step is a step of forming a protective layer on the plating layer. The material of the protective layer is preferably a material that is resistant to the stripping solution and / or etching solution in the resist stripping step and / or removal step. Examples of the material include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, alloys thereof, and resins. Among them, the material of the protective layer is preferably nickel or chromium.

[0173] Examples of methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0174] The lower limit of the thickness of the protective layer is not particularly limited, but is preferably 0.3 μm or more, more preferably 0.5 μm or more, and the upper limit is not particularly limited, but is preferably 3.0 μm or less, more preferably 2.0 μm or less.

[0175] [Resist Stripping Process] The resist stripping step is a step of removing the remaining resist pattern after the etching step and the plating step. The remaining resin pattern can be removed, for example, by chemical treatment, and is preferably removed using a stripping solution. The remaining resist pattern can be removed by a known method such as a spray method, a shower method, or a paddle method using a stripping solution.

[0176] After the resin pattern is peeled off with the peeling solution, it is also preferable to carry out a rinsing treatment to remove the peeling solution remaining on the substrate. Water or the like can be used for the rinsing treatment. After the peeling and / or rinsing process of the resin pattern with the peeling liquid, a drying process may be carried out to remove excess liquid from the substrate.

[0177] [Removal process] The removal step is a step of removing the metal layer exposed by the resist stripping step to obtain a conductor 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.

[0178] The method for removing the part of the metal layer is not particularly limited, but it is preferable to use a known etching solution.

[0179] [Other steps] The method for forming a conductive pattern may include any steps (other steps) other than the steps described above. For example, there may be mentioned a process for reducing visible light reflectance described in paragraph

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

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

[0180] [Laminate] The laminate of the present invention is a laminate having, in this order, a support, a water-soluble resin layer, a photosensitive resin layer arranged in contact with the water-soluble resin layer, and a cover film, The water-soluble resin layer has a depression having a size of 1 nm or more and less than 100 nm on the surface facing the photosensitive resin layer. The laminate of the present invention can be formed by the first and second production methods described above. The support, water-soluble resin layer, photosensitive resin layer, and cover film in the laminate of the present invention may be the same as the support, water-soluble resin layer, photosensitive resin layer, and cover film described in the first manufacturing method, and the preferred embodiments are also the same.

[0181] In the laminate, the water-soluble resin layer has a depression having a size of 1 nm or more and less than 100 nm on the surface on the photosensitive resin layer side. The above-mentioned depressions can be measured by observing an arbitrary 100 μm square area of ​​the surface of the water-soluble resin layer exposed by peeling the photosensitive resin layer from the laminate using an atomic force microscope (manufactured by Hitachi High-Tech Science Corp.) Note that when peeling the photosensitive resin layer, the photosensitive resin layer may be cured by exposure to light before peeling. By having the above-mentioned depression on the surface of the water-soluble resin layer of the laminate facing the photosensitive resin layer, optical abnormalities during exposure in pattern formation after transferring the laminate to a substrate can be further suppressed, resulting in a pattern with better linearity. EXAMPLES

[0182] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. In the following, unless otherwise specified, "parts" and "%" are by mass.

[0183] [Preparation of Water-Soluble Resin Composition] Water-soluble resin compositions (compositions 1-1 to 1-6) having the components and proportions shown in Table 1 below were prepared. In Table 1, the numerical values ​​shown in each component column indicate the content (parts by mass) of each component.

[0184] [Table 1]

[0185] Details of the various components listed in Table 1 are shown below. A-1: Kuraray Poval PVA-205 (Polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) A-2: Kuraray Poval 17-94 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) A-3: Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.) A-4: Metolose 60SH (modified cellulose, manufactured by Shin-Etsu Chemical Co., Ltd.) D-1: MA-ST-M (silica sol, manufactured by Nissan Chemical Co., Ltd.) E-1: Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation) E-2: BYK-348 (silicone surfactant, manufactured by BYK Japan Co., Ltd.) E-3: KF-6115 (silicone surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.) F-1: Ion-exchanged water F-2: Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0186] [Preparation of photosensitive resin composition] Photosensitive resin compositions (compositions 2-1 to 2-14) having the components and compositions shown in Table 2 below were prepared. In Table 2, the numerical values ​​shown in each component column indicate the content (parts by mass) of each component.

[0187] [Table 2]

[0188] Details of the various components listed in Table 2 are shown below. A-5: Propylene glycol monomethyl ether acetate solution of styrene / methacrylic acid / methyl methacrylate copolymer (corresponding to alkali-soluble resin) (solid concentration: 30.0% by mass, ratio of each monomer: 52% by mass / 29% by mass / 19% by mass, Mw: 20,000) A-6: Propylene glycol monomethyl ether acetate solution of styrene / methacrylic acid / benzyl methacrylate copolymer (corresponding to alkali-soluble resin) (solid concentration: 30.0% by mass, ratio of each monomer: 25% by mass / 25% by mass / 50% by mass, Mw: 50,000) A-7: Propylene glycol monomethyl ether acetate solution of ethyl acrylate / methacrylic acid / methyl methacrylate copolymer (corresponding to alkali-soluble resin) (solid concentration: 30.0% by mass, ratio of each monomer: 30% by mass / 12% by mass / 58% by mass, Mw: 60,000)

[0189] B-1: NK Ester BPE-100 (ethoxylated bisphenol A dimethacrylate (corresponding to the compound represented by the above formula (B-2)), manufactured by Shin-Nakamura Chemical Co., Ltd.) B-2: Aronix M-270 (polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.) B-3: A monomer (synthetic product) represented by the above formula (B-2), in which n1 = n3 = 2 on average, n2 = n4 = 3 on average, and R1 = R2 = methyl group. B-4: A-DPH (dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B-5: A-TMPT-9EO (ethoxylated trimethylolpropane triacrylate (corresponding to the compound represented by the above formula (B-3)), manufactured by Shin-Nakamura Chemical Co., Ltd.) B-6: A-9300 (tris-(2-acryloxyethyl) isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd.) B-7: UA-160TM (urethane acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0190] C-1: B-CIM (biimidazole-based photopolymerization initiator, manufactured by Kurogane Kasei Co., Ltd.) C-2: SB-PI 701 (benzophenone-based photopolymerization initiator, obtained from Sanyo Trading Co., Ltd.) C-3: Irgacure OXE02 (oxime ester photoinitiator, manufactured by BASF Japan Ltd.) C-4: 9-phenylacridine (acridine-based photopolymerization initiator, manufactured by Tokyo Chemical Industry Co., Ltd.) C-5: Omnirad 379EG (alkylphenone photopolymerization initiator, manufactured by IGM Resins BV)

[0191] D-2: CHO-ST-M (silica sol, manufactured by Nissan Chemical Co., Ltd.) D-3: TDP-G (phenothiazine (polymerization inhibitor), manufactured by Kawaguchi Chemical Industry Co., Ltd.) D-4: 1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) D-5: Leuco Crystal Violet (Tokyo Chemical Industry Co., Ltd.) D-6: N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) D-7: CBT-1 (carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.)

[0192] E-4: Megafac F-552 (fluorosurfactant, manufactured by DIC Corporation, solid)

[0193] E-5: Polymer E-5 (30% by mass butyl acetate solution) produced by the method described below <Synthesis of Polymer E-5> In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, 150 parts of butyl acetate was charged and refluxed while introducing nitrogen gas. Under the condition that butyl acetate was refluxed, 300 parts of the dropping solution shown below was dropped at a constant rate from the dropping funnel over 2 hours. One hour after the dropwise addition of the solution was completed, 1.5 parts of t-amylperoxy-2-ethylhexanoate was added, and the mixture was further reacted for 2 hours while maintaining the reflux temperature to synthesize polymer E-5. After the reaction was completed, the concentration of polymer X-1-1 was adjusted with butyl acetate to obtain a solution containing polymer E-5 (the mass of polymer E-5 relative to the mass of the entire solution was 30% by mass). The synthesized polymer E-5 had a number average molecular weight of 7,500 in terms of polystyrene as determined by gel permeation chromatography.

[0194] - Composition of the dripping solution - Monomer represented by the following formula (a-1-1): 57 parts by mass Monomer represented by the following formula (b-1): 243 parts by mass

[0195] [ka]

[0196] E-6: KP-326 (silicone surfactant, manufactured by Shin-Etsu Chemical Co., Ltd., 50% by mass in toluene solution) F-3: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) F-4: Propylene glycol monomethyl ether acetate (Shinko Organic Chemical Industry Co., Ltd.)

[0197] [Laminate manufacturing] Laminates 1 to 19 having layer structures shown in Table 3 below were produced by various production methods shown in Table 4 below (Examples 1 to 24, Comparative Examples 1 to 3).

[0198] [Layer configurations of laminates 1 to 19] Table 3 is shown below.

[0199] [Table 3]

[0200] [Types of temporary protective layers] The temporary protective layers shown in Table 4 below are as follows. The arithmetic mean roughness (Ra) of the temporary protective layers shown in Table 4 is the value measured by the method already described as the arithmetic mean roughness (Ra) of the temporary protective layer in step Xc. P1: Alphan FG-201 (polypropylene film, thickness 25 μm, manufactured by Oji F-Tex Co., Ltd.) P2: Alphan EM-501 (polypropylene film, thickness 15 μm, manufactured by Oji F-Tex Co., Ltd.) P3: Lumirror 16FB50 (polyethylene terephthalate film, thickness 16 μm, manufactured by Toray Industries, Inc.)

[0201] Example 1 <Preparation of Water-Soluble Resin Layer> On a rolled polyethylene terephthalate film (support, Lumirror 16KS40, Toray Industries, Inc., thickness: 16 μm, length: 200 m) conveyed at a conveying speed shown in Table 4, the water-soluble resin composition shown in Table 4 was applied so as to have a thickness of 1.0 μm after drying, and the obtained coating film was dried and removed using a hot air convection dryer having a temperature gradient of 50 ° C. to 70 ° C. (see heating conditions in Table 4) to form a water-soluble resin layer. Furthermore, a temporary protective layer shown in Table 4 was pressed onto the water-soluble resin layer using a roll to protect the surface of the water-soluble resin layer. The laminate consisting of the support, the water-soluble resin layer, and the temporary protective layer obtained by the above procedure was wound up to prepare a roll.

[0202] <Preparation of Photosensitive Resin Layer> Next, the laminate was unwound from the obtained roll and transported at the transport speed shown in Table 4, the temporary protective layer was peeled off from the laminate to expose the water-soluble resin layer, and then the photosensitive resin composition shown in Table 4 was applied to the exposed surface to a thickness of 3.0 μm after drying. After coating, the solvent was dried and removed using a hot air convection dryer having a temperature gradient of 50° C. to 100° C. (see heating conditions in Table 4), and a photosensitive resin layer was formed on the water-soluble resin layer. Furthermore, a roll-shaped polypropylene film (cover film, Alphan FG-201, manufactured by Oji F-Tex Co., Ltd., thickness: 30 μm) was laminated onto the photosensitive resin layer to produce a laminate (200 m long roll) consisting of support / water-soluble resin layer / photosensitive resin layer / cover film.

[0203] [Examples 2 to 18, 21 to 24] A laminate (200 m long roll) consisting of a support / water-soluble resin layer / photosensitive resin layer / cover film was prepared in the same manner as in Example 1, except that the water-soluble resin composition, the photosensitive resin composition, and / or the various manufacturing conditions were changed as shown in Table 4.

[0204] Example 19 <Preparation of Water-Soluble Resin Layer> On a rolled polyethylene terephthalate film (support, Lumirror 16KS40, Toray Industries, Inc., thickness: 16 μm, length: 200 m) conveyed at a conveying speed shown in Table 4, the water-soluble resin composition shown in Table 4 was applied so as to have a thickness of 1.0 μm after drying, and the obtained coating film was dried and removed using a hot air convection dryer having a temperature gradient of 50 ° C. to 70 ° C. (see heating conditions in Table 4) to form a water-soluble resin layer. Furthermore, a temporary protective layer shown in Table 4 was pressed onto the water-soluble resin layer using a roll to protect the surface of the water-soluble resin layer. The laminate consisting of the support, the water-soluble resin layer, and the temporary protective layer obtained by the above procedure was wound up to prepare a roll A.

[0205] <Preparation of Photosensitive Resin Layer> On a roll-shaped polyethylene terephthalate film (temporary support, Lumirror 16KS40, Toray Industries, Inc., thickness: 16 μm, length: 200 m) conveyed at a conveying speed shown in Table 4, the photosensitive resin composition shown in Table 4 was applied so as to have a thickness of 3.0 μm after drying, and the obtained coating film was dried and removed using a hot air convection dryer having a temperature gradient of 50 ° C. to 100 ° C. (see heating conditions in Table 4) to form a photosensitive resin layer. Furthermore, a temporary protective layer shown in Table 4 was pressed onto the photosensitive resin layer using a roll to protect the surface of the photosensitive resin layer. The laminate consisting of the temporary support, the photosensitive resin layer, and the temporary protective layer obtained by the above procedure was wound up to produce a roll B.

[0206] <Lamination of water-soluble resin layer and photosensitive resin layer> Next, while unwinding the laminate from each of the rolls A and B, the temporary protective layer of the laminate unwound from the roll A and the temporary protective layer of the laminate unwound from the roll B were peeled off, and the exposed water-soluble resin layer of the laminate unwound from the roll A and the exposed photosensitive resin layer of the laminate unwound from the roll B were pressure-bonded. Thereafter, the temporary support on the photosensitive resin layer side of the obtained laminate was peeled off, and a roll-shaped polypropylene film (cover film, Alphan FG-201, manufactured by Oji F-Tex Co., Ltd., thickness: 30 μm) was attached to obtain a laminate (200 m long roll) consisting of a support / water-soluble resin layer / photosensitive resin layer / cover film.

[0207] Example 20 A laminate (200 m long roll) consisting of a support / water-soluble resin layer / photosensitive resin layer / cover film was prepared in the same manner as in Example 19, except that the water-soluble resin composition, the photosensitive resin composition, and / or the various manufacturing conditions were changed as shown in Table 4.

[0208] Comparative Example 1 A laminate (200 m long roll) consisting of a support / water-soluble resin layer / photosensitive resin layer / cover film was prepared using the same procedure as in Example 1, except that a temporary protective layer was not laminated to the surface of the water-soluble resin layer after preparation of the water-soluble resin layer.

[0209] Comparative Example 2 A laminate (200 m long roll) consisting of a support / photosensitive resin layer / cover film was produced in the same manner as in Example 1, except that the water-soluble resin layer was not provided.

[0210] Comparative Example 3 On a rolled polyethylene terephthalate film (support, Lumirror 16KS40, Toray Industries, Inc., thickness: 16 μm, length: 200 m) conveyed at a conveying speed shown in Table 4, the water-soluble resin composition shown in Table 4 was applied so that the thickness after drying was 1.0 μm, and then the solvent was dried and removed using a hot air convection dryer having a temperature gradient of 50 ° C. to 70 ° C. (see heating conditions in Table 4). Furthermore, the photosensitive resin composition shown in Table 4 was continuously applied in the same coater without winding the roll so that the thickness after drying was 3.0 μm, and then the solvent was dried and removed using a hot air convection dryer having the same temperature gradient as the water-soluble resin layer, forming a photosensitive resin layer on the water-soluble resin layer. Furthermore, a rolled polypropylene film (cover film, Alphan FG-201, Oji F-Tex Co., Ltd., thickness: 30 μm) was laminated on the photosensitive resin layer to prepare a laminate (200 m long roll) consisting of a support / water-soluble resin layer / photosensitive resin layer / cover film.

[0211] [Measurement and Evaluation] The following measurements and evaluations were carried out using each of the laminates (transfer films) produced in the Examples and Comparative Examples.

[0212] [Measurement of surface concavity depth] A high-pressure mercury lamp was used to irradiate the end of the laminated body at 200 mJ / cm 2 The photosensitive resin layer was exposed to light of 1000 nm (based on i-line) to harden the photosensitive resin layer. The photosensitive resin layer was then slowly peeled off from the water-soluble resin layer using tape to expose the interface between the water-soluble resin layer and the photosensitive resin layer. Next, the concave depths of the surfaces of the water-soluble resin layer and the photosensitive resin layer exposed by peeling off the tape were measured in an area of ​​100 μm square using an atomic force microscope (manufactured by Hitachi High-Tech Science Corporation). However, when measuring the concave depths, indefinite error factors such as scratches and dust were excluded, and only concaves determined to be caused by the temporary protective layer were measured. The results are shown in Table 4.

[0213] [Surface abnormality evaluation] A high-pressure mercury lamp was used to irradiate the end of the laminated body at 200 mJ / cm 2The photosensitive resin layer was exposed to light (based on i-line) to harden the photosensitive resin layer. After that, the photosensitive resin layer was slowly peeled off from the water-soluble resin layer using tape to expose the interface between the water-soluble resin layer and the photosensitive resin layer. Next, the surfaces of the water-soluble resin layer and the photosensitive resin layer exposed by peeling off the tape were examined for foreign matter / abnormalities in a 100 μm square area using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation). Based on the observation results, surface abnormalities were evaluated according to the following criteria, and the results are shown in Table 5. "A": No irregular scratches or dust particles that are not considered to be due to the unevenness of the temporary protective layer are observed in either the water-soluble resin layer or the photosensitive resin layer. "B": In at least one of the water-soluble resin layer and the photosensitive resin layer, irregular scratches or dust particles that are not determined to be caused by the unevenness of the temporary protective layer are observed in more than 0% and less than 30% of the evaluation area. "C": In at least one of the water-soluble resin layer and the photosensitive resin layer, irregular scratches or dust particles that are not determined to be caused by the unevenness of the temporary protective layer are observed in 30% or more of the evaluation area.

[0214] [Evaluation of Pattern Linearity] After peeling off the cover film from the end of the laminate produced in the upper section, the exposed surface of the laminate after peeling off the cover film was bonded to a glass substrate on which copper had been sputtered to a thickness of 100 nm under lamination conditions of a roll temperature of 100°C, a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min. Next, the support was peeled off from the obtained laminate with the glass substrate, and then a glass mask having a line-and-space wiring pattern with a line width of 10 μm was adhered to the surface of the water-soluble resin layer exposed by peeling off the support, and the photosensitive resin layer was exposed using an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.). The exposure amount was adjusted so that the average line width of the resin pattern remaining after development was 9.5 to 10.5 μm. After leaving the film for 1 hour after exposure, the uncured portions were removed by spraying a developer (28° C., 1.0% by mass aqueous potassium carbonate solution) onto the film with a shower to produce a resin pattern.

[0215] The prepared resin pattern was observed in a 500 μm square area using a scanning electron microscope (Hitachi High-Technologies Corporation), and the pattern width (line width) was measured at any 30 points within the observation field. The standard deviation σ was calculated from the obtained line width data, and the value obtained by multiplying this by three (3σ) was defined as LWR (Line Width Roughness) and used as an index of pattern linearity. Evaluation was performed based on the following evaluation criteria. The smaller the LWR value, the better, with a grade of B or higher being more preferable, and a grade of A being particularly preferable. The results are shown in Table 5. "A": LWR≦0.6 "B": 0.6 <LWR≦2.0 "C": 2.0 <LWR "D": Large-scale defects have occurred in the patterned wiring, making linearity evaluation impossible.

[0216] [Sensitivity evaluation] Samples were taken from two locations, the beginning and end of the laminate (200 m long roll) produced in the upper section, and the cover film was removed from each sample. The exposed surface of the laminate was then bonded to a glass substrate that had been sputtered with copper to a thickness of 100 nm under lamination conditions of a roll temperature of 100°C, a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min. Next, the support was peeled off from each of the obtained samples, and then the samples were irradiated with 300 mJ / cm 2 via a step wedge sheet (T4105, Stouffer). 2 Next, the uncured portions were removed by spraying a developer (28°C, 1.0% by mass aqueous potassium carbonate solution) onto the exposed sample using a shower, and the minimum exposure dose at which the resin film remained was determined. The evaluation was carried out by assigning a grade of B to cases where the minimum exposure amount at each of the start and end parts of the winding changed by 10% or more, and a grade of A to cases where the minimum exposure amount at each of the start and end parts of the winding did not change or changed by less than 10%. The results are shown in Table 5.

[0217] Tables 4 and 5 are shown below.

[0218] [Table 4]

[0219] [Table 5]

[0220] [Table 6]

[0221] As shown in the table above, it is clear that the laminate (transfer film) produced by the laminate manufacturing method of the embodiment is less likely to have a difference in sensitivity between one end and the other end in the longitudinal direction, the occurrence of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer is suppressed, and a pattern with excellent linearity can be formed when the photosensitive resin layer is transferred to a transfer target and subjected to exposure and development processing.

[0222] Comparing the examples, it was confirmed that when the water-soluble resin layer does not substantially contain a filler, a pattern with superior linearity can be formed when the photosensitive resin layer is transferred to an object to be transferred and then exposed and developed (see in particular the results of Example 18).

[0223] From the comparison of the examples, it was confirmed that in the temporary protective layer protecting the surface of the water-soluble resin layer, when the upper limit of the arithmetic mean roughness of the surface on the water-soluble resin layer side is 50 nm or less, optical abnormalities due to the unevenness of the temporary protective layer are unlikely to occur during exposure, and a pattern with better linearity can be formed (particularly, see the results of Example 21). On the other hand, when the lower limit of the arithmetic mean roughness of the surface on the water-soluble resin layer side is 10 nm or more, the adhesive strength between the temporary protective layer and the water-soluble resin layer is not too high, and as a result, damage to the water-soluble resin layer during peeling of the temporary protective layer (particularly, partial peeling of the water-soluble resin layer due to reverse transfer of the water-soluble resin layer to the temporary protective layer) is unlikely to occur, and a pattern with better linearity can be formed (particularly, see the results of Example 22). In addition, for the same reason, it was confirmed that surface abnormalities were also more suppressed (particularly, see the results of Example 22).

[0224] On the other hand, the laminate manufacturing method of the comparative example did not produce the expected effects. [Explanation of symbols]

[0225] 1 Support 3 Water-soluble resin layer 5. Laminate A 7 Temporary protective layer 9 Laminate B 11 Photosensitive resin layer 13 Laminate D 15 Cover film 17 Laminate E 19 Temporary Support 21 Laminate F

Claims

1. A step Xa of forming a water-soluble resin layer on a support to form a laminate A; A step Xb of forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B; A step Xc of winding the laminate B to form a wound body C; A process Xd of unwinding the laminate B from the roll C and then peeling the temporary protective layer from the laminate B between the temporary protective layer and the water-soluble resin layer; a step Xe of forming a photosensitive resin layer so as to be in contact with the exposed water-soluble resin layer to form a laminate D; and a step Xf of forming a cover film in contact with the photosensitive resin layer to form a laminate E having, in this order, the support, the water-soluble resin layer, the photosensitive resin layer, and the cover film.

2. The method for producing a laminate according to claim 1, wherein the arithmetic mean roughness of the surface of the temporary protective layer in contact with the water-soluble resin layer is 10 to 50 nm.

3. The method for producing a laminate according to claim 1 , wherein neither the water-soluble resin layer nor the photosensitive resin layer contains substantially any filler.

4. The method for producing a laminate according to claim 1 or 2, wherein the water-soluble resin layer contains polyvinyl alcohol.

5. The method for producing a laminate according to claim 1 or 2, wherein the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

6. The method for producing a laminate according to claim 5 , wherein the polymerizable compound contains a compound represented by the following formula (B-2): Formula (B-2): 【Chemistry 1】 In the formula, R １ and R ２ Each of A and C independently represents a hydrogen atom or a methyl group. ２ H ４ B represents C ３ H ６ Represents n １ and n ３ Each independently represents an integer from 1 to 39, and １ +n ３ represents an integer from 2 to 40. ２ and n ４ Each independently represents an integer of 0 to 29, and ２ +n ４ represents an integer of 0 to 30. The arrangement of the repeating units -(A-O)- and -(B-O)- may be either random or block. When the arrangement is block, either -(A-O)- or -(B-O)- may be on the bisphenyl group side.

7. The method for producing a laminate according to claim 5, wherein the polymerizable compound contains a compound represented by the following formula (B-3): Formula (B-3): 【Chemistry 2】 In formula (B-3), R １ , R ２ , and R ３ each independently represents a hydrogen atom or a methyl group. a, b, and c each independently represent an integer of 0 to 48, and a+b+c represents an integer of 0 to 50.

8. 6. The method for producing a laminate according to claim 5, wherein the photopolymerization initiator is at least one selected from the group consisting of an acridine-based photopolymerization initiator, a benzophenone-based polymerization initiator, an oxime ester-based photopolymerization initiator, a biimidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator.

9. The method for producing a laminate according to claim 1 or 2, wherein the photosensitive resin layer contains a polymer D containing at least one repeating unit α selected from the group consisting of a repeating unit represented by the following formula (A-1) and a repeating unit represented by the following formula (A-2), and a repeating unit β represented by the following formula (B). 【Chemistry 3】 In formula (A-1), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms. ３ represents an alkyl group having 1 to 4 carbon atoms. 1 represents an integer of 5 to 100. In formula (A-2), R ４ represents a hydrogen atom or a methyl group. ５ represents an alkylene group having 1 to 10 carbon atoms. L represents a trimethylsilyl group or a tris(trimethylsiloxy)silyl group. In formula (B), R ６ represents a hydrogen atom or a methyl group. ７ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. m represents an integer of 1 to 100. n represents an integer of 1 to 4.

10. The method for producing a laminate according to claim 1 or 2, wherein the water-soluble resin layer in the laminate E has a depression of 1 nm or more and less than 100 nm on a surface on the photosensitive resin layer side.

11. A process Ya of forming a water-soluble resin layer on a support to form a laminate A; A process Yb of forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B; a step Yc of winding the laminate B to form a wound body C; A method for manufacturing a laminate, comprising: unwinding the laminate B from the roll C; peeling the temporary protective layer from the laminate B between the temporary protective layer and the water-soluble resin layer; laminating the photosensitive resin layer of a transfer film comprising a temporary support and a photosensitive resin layer to the exposed surface of the laminate B; and obtaining a laminate F comprising the support, the water-soluble resin layer, the photosensitive resin layer, and the temporary support.

12. The method for producing a laminate according to claim 11 further comprises a process Ye of peeling the temporary support from the laminate F between the temporary support and the photosensitive resin layer, and laminating a cover film to the exposed surface of the laminate F to form a laminate G having the support, the water-soluble resin layer, the photosensitive resin layer, and the cover film in this order.

13. Furthermore, before the step Yd, A process Yf of forming a photosensitive resin layer on a temporary support to form a laminate H; a step Yg of forming a temporary protective layer in contact with the photosensitive resin layer to form a laminate I; A process Yh of winding the laminate I to form a wound body J; The laminate I is unwound from the roll J, and the temporary protective layer is peeled off from the laminate I between the temporary protective layer and the photosensitive resin layer to obtain a transfer film including the temporary support and the photosensitive resin layer. A method for producing a laminate according to claim 11 or 12, comprising the steps of:

14. The method for producing a laminate according to claim 11 or 12, wherein the arithmetic mean roughness of the surface of the temporary protective layer in contact with the water-soluble resin layer is 10 to 50 nm.

15. The method for producing a laminate according to claim 13, wherein the arithmetic mean roughness of the surface of the temporary protective layer in contact with the photosensitive resin layer is 10 to 50 nm.

16. In the laminate F, the water-soluble resin layer has a depression of 1 nm or more and less than 100 nm on a surface facing the photosensitive resin layer, and The method for producing a laminate according to claim 11 , wherein the photosensitive resin layer has a depression having a size of 1 nm or more and less than 100 nm on a surface on the water-soluble resin layer side.

17. The method for producing a laminate according to claim 11 or 12, wherein neither the water-soluble resin layer nor the photosensitive resin layer substantially contains a filler.

18. The method for producing a laminate according to claim 11 or 12, wherein the water-soluble resin layer contains polyvinyl alcohol.

19. The method for producing a laminate according to claim 11 or 12, wherein the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

20. The method for producing a laminate according to claim 19, wherein the polymerizable compound contains a compound represented by the following formula (B-2): Formula (B-2): 【Chemistry 4】 In the formula, R １ and R ２ Each of A and C independently represents a hydrogen atom or a methyl group. ２ H ４ B represents C ３ H ６ Represents n １ and n ３ Each independently represents an integer from 1 to 39, and １ +n ３ represents an integer from 2 to 40. ２ and n ４ Each independently represents an integer of 0 to 29, and ２ +n ４ represents an integer of 0 to 30. The arrangement of the repeating units -(A-O)- and -(B-O)- may be either random or block. When the arrangement is block, either -(A-O)- or -(B-O)- may be on the bisphenyl group side.

21. The method for producing a laminate according to claim 19, wherein the polymerizable compound contains a compound represented by the following formula (B-3): Formula (B-3): 【Chemistry 5】 In formula (B-3), R １ , R ２ , and R ３ each independently represents a hydrogen atom or a methyl group. a, b, and c each independently represent an integer of 0 to 48, and a+b+c represents an integer of 0 to 50.

22. 20. The method for producing a laminate according to claim 19, wherein the photopolymerization initiator is at least one selected from the group consisting of an acridine-based photopolymerization initiator, a benzophenone-based polymerization initiator, an oxime ester-based photopolymerization initiator, a biimidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator.

23. The method for producing a laminate according to claim 11 or 12, wherein the photosensitive resin layer contains a polymer D containing at least one repeating unit α selected from the group consisting of a repeating unit represented by the following formula (A-1) and a repeating unit represented by the following formula (A-2), and a repeating unit β represented by the following formula (B): 【Chemistry 6】 In formula (A-1), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms. ３ represents an alkyl group having 1 to 4 carbon atoms. 1 represents an integer of 5 to 100. In formula (A-2), R ４ represents a hydrogen atom or a methyl group. ５ represents an alkylene group having 1 to 10 carbon atoms. L represents a trimethylsilyl group or a tris(trimethylsiloxy)silyl group. In formula (B), R ６ represents a hydrogen atom or a methyl group. ７ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. m represents an integer of 1 to 100. n represents an integer of 1 to 4.

24. A laminate having, in this order, a support, a water-soluble resin layer, a photosensitive resin layer arranged in contact with the water-soluble resin layer, and a cover film, The water-soluble resin layer has a depression of 1 nm or more and less than 100 nm on a surface facing the photosensitive resin layer.

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