Method for manufacturing laminate, and laminate

Abstract

Provided is a method for producing a laminate (transfer film) in which a difference in sensitivity does not readily occur between one end side and the other end side in the longitudinal direction, and the occurrence of foreign matter and scratches between a water-soluble resin layer and a photosensitive resin layer is suppressed. And a pattern having excellent linearity can be formed when the photosensitive resin layer is transferred to an object to be transferred and exposure and development processing are performed. A method for producing a laminate, the method comprising, in this order: a step (Xa) for forming a laminate (A); a step (Xb) for forming a laminate (B); a step Xc for forming a wound body C; a step (Xd) for peeling off the temporary protective layer; a step (Xe) for forming a laminate (D); and a step (Xf) for forming a laminate (E).

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a laminate and the laminate. Background Art

[0002] Since the number of steps for obtaining a predetermined pattern is small, a pattern forming method is widely used in which a photosensitive resin layer is disposed on an arbitrary substrate using a transfer film, and the photosensitive resin is exposed and developed via a mask.

[0003] For example, Patent Document 1 discloses a photosensitive element (transfer film) having a laminated structure in which a predetermined support film having a resin layer containing microparticles, a water-soluble resin layer, and a photosensitive resin layer are laminated in this order. In addition, as a manufacturing method thereof, the following method is disclosed: after forming a water-soluble resin layer on the opposite side of a support film having a resin layer containing microparticles by coating using a water-soluble resin composition, a photosensitive resin layer is formed on the water-soluble resin layer by coating using a photosensitive resin composition.

[0004] Patent Document 1: Japanese Patent Application Publication No. 2013-024913

[0005] The present inventors have studied the method for producing a transfer film described in Patent Document 1 and the obtained transfer film, and have found that a difference in sensitivity may occur between one end side and the other end side in the longitudinal direction of the transfer film.

[0006] Furthermore, regarding the transfer film, in order to prevent poor exposure (optical abnormality) when the photosensitive resin layer is transferred to the transfer body and subjected to exposure treatment, it is also required as a basic performance that the generation of foreign matter or 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 the transfer body and subjected to exposure and development treatment. Summary of the invention

[0007] Therefore, the subject of the present invention is to provide a method for manufacturing a laminate (transfer film), which is not prone to sensitivity difference between one end side and the other end side in the long direction and suppresses the generation of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer, and can form a pattern with excellent linearity when the photosensitive resin layer is transferred to the transfer body and subjected to exposure and development treatment.

[0008] Furthermore, another object of the present invention is to provide a laminated body.

[0009] As a result of intensive studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following configuration.

[0010] [1] A method for producing a laminate, comprising:

[0011] Step Xa, forming a water-soluble resin layer on a support to form a laminate A;

[0012] Step Xb, forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B;

[0013] Step Xc, winding the laminated body B to form a wound body C;

[0014] Step Xd, after unwinding the laminate B from the roll C, peeling the temporary protective layer from between the temporary protective layer and the water-soluble resin layer of the laminate B;

[0015] Step Xe, forming a laminate D by forming a photosensitive resin layer in contact with the exposed water-soluble resin layer; and

[0016] In step Xf, a cover film is formed so as to be in contact with the photosensitive resin layer to form a laminated body E having the support, the water-soluble resin layer, the photosensitive resin layer, and the cover film in this order.

[0017] [2] The method for producing a laminate according to [1], wherein:

[0018] 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.

[0019] [3] The method for producing a laminate according to [1] or [2], wherein:

[0020] The water-soluble resin layer and the photosensitive resin layer substantially do not contain fillers.

[0021] [4] The method for producing a laminate according to any one of [1] to [3], wherein:

[0022] The water-soluble resin layer contains polyvinyl alcohol.

[0023] [5] The method for producing a laminate according to any one of [1] to [4], wherein:

[0024] The photosensitive resin layer includes an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

[0025] [6] The method for producing a laminate according to [5], wherein:

[0026] The polymerizable compound includes a compound represented by formula (B-2) described below.

[0027] [7] The method for producing a laminate according to [5] or [6], wherein:

[0028] The polymerizable compound includes a compound represented by formula (B-3) described later.

[0029] [8] The method for producing a laminate according to any one of [5] to [7], wherein:

[0030] The photopolymerization initiator is one or more selected from acridine-based photopolymerization initiators, benzophenone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, biimidazole-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.

[0031] [9] The method for producing a laminate according to any one of [1] to [8], wherein:

[0032] The photosensitive resin layer includes a polymer D including at least one repeating unit α selected from repeating units represented by formula (A-1) and formula (A-2) described below, and a repeating unit β represented by formula (B) described below.

[0033]

[10] The method for producing a laminate according to any one of [1] to [9], wherein:

[0034] 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.

[0035]

[11] A method for manufacturing a laminate, comprising:

[0036] Step Ya, forming a water-soluble resin layer on a support to form a laminate A;

[0037] Step Yb, forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B;

[0038] Step Yc, winding the laminated body B to form a wound body C; and

[0039] In step Yd, the laminate B is unwound from the winding body C, the temporary protective layer is peeled off from between the temporary protective layer and the water-soluble resin layer of the laminate B, and the photosensitive resin layer of the transfer film including a temporary support and a photosensitive resin layer is adhered to the exposed surface of the laminate B, thereby obtaining a laminate F including the support, the water-soluble resin layer, the photosensitive resin layer and the temporary support.

[0040]

[12] The method for producing a laminate according to

[11] , further comprising:

[0041] In step Ye, the temporary support is peeled off from between the temporary support and the photosensitive resin layer of the stack F, and the covering film is adhered to the exposed surface of the stack F, thereby forming a stack G having the support, the water-soluble resin layer, the photosensitive resin layer and the covering film in sequence.

[0042]

[13] The method for producing a laminate according to

[11] or

[12] , further comprising, before the step Yd:

[0043] Step Yf, forming a photosensitive resin layer on a temporary support to form a laminate H;

[0044] Step Yg, forming a temporary protective layer in contact with the photosensitive resin layer to form a laminated body I;

[0045] Step Yh, winding the laminated body I to form a wound body J; and

[0046] In step Yi, the laminated body I is unwound from the roll body J, and the temporary protective layer is peeled off from between the temporary protective layer and the photosensitive resin layer of the laminated body I, thereby obtaining a transfer film including the temporary support and the photosensitive resin layer.

[0047]

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

[11] to

[13] , wherein:

[0048] 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.

[0049]

[15] The method for producing a laminate according to

[13] , wherein:

[0050] The arithmetic mean roughness of the surface of the temporary protective layer in contact with the photosensitive resin layer is 10 to 50 nm.

[0051]

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

[11] to

[15] , wherein:

[0052] In the above-mentioned laminated body F,

[0053] The water-soluble resin layer has a depression of 1 nm or more and less than 100 nm on the surface of the photosensitive resin layer side, and

[0054] 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.

[0055]

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

[11] to

[16] , wherein:

[0056] The water-soluble resin layer and the photosensitive resin layer substantially do not contain fillers.

[0057]

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

[11] to

[17] , wherein:

[0058] The water-soluble resin layer contains polyvinyl alcohol.

[0059]

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

[11] to

[18] , wherein:

[0060] The photosensitive resin layer includes an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

[0061]

[20] The method for producing a laminate according to

[19] , wherein:

[0062] The polymerizable compound includes a compound represented by formula (B-2) described below.

[0063]

[21] The method for producing a laminate according to

[19] or

[20] , wherein:

[0064] The polymerizable compound includes a compound represented by formula (B-3) described later.

[0065]

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

[19] to

[21] , wherein:

[0066] The photopolymerization initiator is one or more selected from acridine-based photopolymerization initiators, benzophenone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, biimidazole-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.

[0067]

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

[11] to

[22] , wherein:

[0068] The photosensitive resin layer includes a polymer D including at least one repeating unit α selected from repeating units represented by formula (A-1) and formula (A-2) described below, and a repeating unit β represented by formula (B) described below.

[0069]

[24] A laminate comprising, 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,

[0070] 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.

[0071] Effects of the Invention

[0072] According to the present invention, a method for manufacturing a laminate (transfer film) can be provided, which is not prone to a difference in sensitivity between one end side and the other end side in the long direction of the laminate and suppresses the generation of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer, and can form a pattern with excellent linearity when the photosensitive resin layer is transferred to the transfer body and subjected to exposure and development treatment.

[0073] Furthermore, the present invention can provide a laminated body. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 It is a schematic diagram for explaining the step Xa of the first manufacturing method.

[0075] Figure 2 It is a schematic diagram for explaining step Xb of the first manufacturing method.

[0076] Figure 3 It is a schematic diagram for explaining the step Xe of the first manufacturing method.

[0077] Figure 4 It is a schematic diagram for explaining step Xf of the first manufacturing method.

[0078] Figure 5 It is a schematic diagram for explaining step Yd of the second manufacturing method. DETAILED DESCRIPTION

[0079] Hereinafter, the present invention will be described in detail.

[0080] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0081] In this specification, in the numerical ranges recorded in stages, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in this specification, the upper limit or lower limit recorded in a certain numerical range can also be replaced by the value shown in the embodiment.

[0082] In the present specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0083] In this specification, unless otherwise specified, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more.

[0084] 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.

[0085] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​converted using polystyrene of the standard substance measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all product names manufactured by TOSOH Corporation) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance.

[0086] In addition, in this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw).

[0087] In this specification, unless otherwise specified, the content of a metal element is a value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectrometer.

[0088] In this specification, “(meth)acrylic acid” is a concept including both acrylic acid and methacrylic acid, “(meth)acryloyloxy” is a concept including both acryloxy and methacryloyloxy, “(meth)acrylamide” is a concept including both acrylamide and methacrylamide, “(meth)acrylate” is a concept including both acrylate and methacrylate, and (meth)acrylonitrile is a concept including both acrylonitrile and methacrylonitrile.

[0089] In the present specification, "alkali-soluble" means that the solubility in 100 g of a 1 mass % sodium carbonate aqueous 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 solubility condition.

[0090] In this specification, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above solubility condition.

[0091] The "solid content" of a composition refers to 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 refers to all components other than the solvent. Furthermore, if it is a component that forms a composition layer, a liquid component is also regarded as a solid component.

[0092] The thickness of each layer was calculated as an average value of five arbitrary points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0093] [Method for producing the first laminate]

[0094] The first method for producing a laminate of the present invention (hereinafter also referred to as “first production method”) includes the following steps Xa, Xb, Xc, Xd, Xe, and Xf in order.

[0095] Step Xa: Step of forming a water-soluble resin layer on a support to form a laminate A

[0096] Step Xb: a step of forming a laminate B by forming a temporary protective layer in contact with the water-soluble resin layer

[0097] Step Xc: Step of winding the laminated body B to form a wound body C

[0098] Step Xd: After the laminate B is unwound from the roll C, the temporary protective layer is peeled off from between the temporary protective layer and the water-soluble resin layer of the laminate B.

[0099] Step Xe: a step of forming a laminated body D by forming a photosensitive resin layer so as to be in contact with the exposed water-soluble resin layer

[0100] Step Xf: a step of forming a cover film so as to be in contact with the photosensitive resin layer to form a laminated body E having the support, the water-soluble resin layer, the photosensitive resin layer, and the cover film in this order.

[0101] The laminate obtained by the first manufacturing method is less likely to have a difference in sensitivity between one end side and the other end side in the longitudinal direction, and can suppress the generation of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer. In addition, the laminate obtained by the first manufacturing method is transferred to a transfer object and subjected to exposure and development treatments, and the pattern obtained has excellent linearity.

[0102] The mechanism of action by which the above-mentioned effect is obtained by the first production method is not clear, but the present inventors speculate as follows.

[0103] The first manufacturing method includes the following steps: temporarily forming a roll C obtained by winding 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 the temporary protective layer from the laminate B, and then laminating a photosensitive resin layer on the water-soluble resin layer. That is, the first manufacturing method is not a manufacturing method for continuously forming a photosensitive resin layer after forming a water-soluble resin layer, but a manufacturing method temporarily passing through the above-mentioned roll C, thereby making it easy to set the manufacturing conditions of the photosensitive resin layer and the manufacturing conditions of the water-soluble resin layer to different conditions.

[0104] Regarding the photosensitive resin layer and the water-soluble resin layer, since the optimal manufacturing conditions (conveying speed or heating and drying temperature, etc.) of each layer are typically different, it is particularly desirable to set at least one of the conveying speed and the heating and drying temperature to different conditions for each layer when forming each layer. In contrast, for example, when manufacturing a long laminate having a support, a water-soluble resin layer and a photosensitive resin layer, after forming the water-soluble resin layer, the photosensitive resin layer is continuously formed under the same manufacturing conditions as the water-soluble resin layer. In the winding start area and the winding end area of ​​the obtained long laminate, the degree of interlayer component penetration of the photosensitive resin layer and the water-soluble resin layer (for example, the amount of penetration of the component of the water-soluble resin layer into the photosensitive resin layer, the amount of penetration of the component of the photosensitive resin layer into the water-soluble resin layer, etc.) is different, and as a result, sometimes a sensitivity difference occurs in the winding start area and the winding end area of ​​the laminate. To give a more specific example, when the optimum drying and heating temperature of the photosensitive resin layer is higher than the optimum drying and heating temperature of the water-soluble resin layer and the water-soluble resin layer and the photosensitive resin layer are continuously formed on a conveyor line, there are many cases where the drying and heating temperature of the photosensitive resin layer has to be made the same as the drying and heating temperature of the water-soluble resin layer due to manufacturing problems. If it is assumed that 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, the volatile solvent is likely to accumulate in the dryer of the photosensitive resin layer and the drying in the dryer may not be fully carried out in the later stage of conveying. As a result, a sensitivity difference sometimes occurs in the winding start area and the winding end area of ​​the laminate.

[0105] In contrast, in the first manufacturing method, as described above, the wound body C is temporarily passed through, so that the photosensitive resin layer and the water-soluble resin layer can be manufactured under different manufacturing conditions, thereby suppressing the sensitivity difference between the winding start region and the winding end region of the stacked body.

[0106] Furthermore, in the first manufacturing method, the wound body C obtained in step XC has a temporary protective layer on the water-soluble resin layer for protecting the water-soluble resin layer. Therefore, the surface of the photosensitive resin layer forming the water-soluble resin layer can suppress the generation of foreign matter and scratches caused by friction with the back side of the support when winding in step XC. As a result, when the photosensitive resin layer is transferred to the transfer body and subjected to exposure treatment, the laminate obtained by the first manufacturing method is less likely to have poor exposure (optical abnormality).

[0107] 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 body and subjected to exposure and development treatment, the polymerization reaction of the photosensitive resin layer is easily carried out by blocking oxygen by the water-soluble resin layer, and the linearity of the obtained pattern is excellent. Furthermore, by having a water-soluble resin layer, it is possible to carry out exposure treatment (contact exposure) in a state where the temporary support body is peeled off, and it is possible to suppress the reduction of the linearity of the pattern caused by excessive adhesion between the photosensitive resin layer and the photomask.

[0108] Hereinafter, further suppressing the difference in sensitivity between one end side and the other end side in the long direction of the laminate obtained by the first manufacturing method, further suppressing the generation of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer in the laminate obtained by the first manufacturing method, and / or being able to form a pattern with better linearity when the laminate obtained by the first manufacturing method is transferred to a transfer body and subjected to exposure and development treatments will also be referred to as “the effect of the present invention is better”.

[0109] Hereinafter, the first manufacturing method will be described in detail with reference to the drawings.

[0110] [Process Xa]

[0111] like Figure 1 As shown in FIG. 1 , step Xa is a step of forming a laminate A5 by forming a water-soluble resin layer 3 on a support 1. That is, step Xa is a step of forming a laminate A including a support and a water-soluble resin layer.

[0112] Hereinafter, first, the support and the water-soluble resin layer constituting the laminate A will be described.

[0113] <Support>

[0114] The support is a member (temporary support) that is peeled off before exposure treatment or after exposure treatment and before development treatment when the laminate obtained by the first manufacturing method is transferred to a transfer target to perform pattern formation.

[0115] The support is preferably in a long strip shape, and more preferably in a roll shape.

[0116] The support may have a single-layer structure or a multi-layer structure.

[0117] The support is preferably a film, more preferably a resin film, and preferably a flexible film that does not significantly deform, shrink or stretch under pressure or under pressure and heating, and preferably a film that does not deform or scratch such as wrinkles.

[0118] Examples of the film include polyethylene terephthalate films (eg, biaxially stretched polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, and polyethylene terephthalate films are preferred.

[0119] From the viewpoint of enabling pattern exposure through the support, the support preferably has high transparency. 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%.

[0120] From the viewpoint of pattern formation when pattern exposure is performed through the support and the transparency of the support, the haze of the support is preferably small. Specifically, the haze of the support is preferably 2% or less, more preferably 0.5% or less, and further preferably 0.1% or less. The lower limit is preferably 0% or more.

[0121] From the viewpoint of pattern formation when pattern exposure is performed through the support and the transparency of the temporary support, it is preferred that the number of particles, foreign matter and defects in the support is small. Specifically, the number of particles (for example, particles with a diameter of 1 μm), foreign matter and defects in the support is preferably 50 / 10 mm 2 Below, more preferably 10 / 10mm 2 Below, more preferably 3 / 10mm 2 Less than 1 / 10 mm 2 The lower limit is preferably 0 / 10mm 2 above.

[0122] The thickness of the support is preferably 5 to 200 μm, more preferably 5 to 150 μm, further preferably 5 to 50 μm, and particularly preferably 5 to 25 μm from the viewpoint of easy handling and versatility.

[0123] From the viewpoint of handleability, the support may have a layer (lubricant layer) containing fine particles on one surface or both surfaces of the support.

[0124] The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

[0125] The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0126] The surface of the support that contacts the water-soluble resin layer may be subjected to surface modification treatment.

[0127] Examples of the surface modification treatment include treatment using UV irradiation, corona discharge, plasma, and the like.

[0128] The exposure amount during UV irradiation is preferably 10 to 2000 mJ / cm 2 , more preferably 50 to 1000 mJ / cm 2 .

[0129] As long as the exposure amount is within the above range, the lamp output and the illuminance are not particularly limited.

[0130] Examples of the light source for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that generate light in a wavelength band of 150 to 450 nm.

[0131] Examples of the support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

[0132] Furthermore, as a support body, for example, paragraphs

[0017] to

[0018] of Japanese Patent Publication No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Publication No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370 can also be cited, and these contents are incorporated into this specification.

[0133] Examples of commercially available products of the support include Lumixr 16KS40 and Lumixr 16FB40 (both manufactured by TORAY INDUSTRIES, INC.); COSMOSHINE A4100, COSMOSHINE A4300, and COSMOSHINE A8300 (both manufactured by TOYOBO CO., LTD.).

[0134] <Water-soluble resin layer>

[0135] The water-soluble resin layer contains a water-soluble resin.

[0136] The water-soluble resin may be used alone or in combination of two or more.

[0137] Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble polyimides, water-soluble celluloses (e.g., hydroxyethyl cellulose, etc.), polyvinyl ether-maleic anhydride water-soluble salts, carboxyalkyl starch water-soluble salts, polyacrylamides, polyamides, polyacrylic acid water-soluble salts, gelatin, and polypropylene glycol, etc. The water-soluble resin preferably includes polyvinyl alcohol from the viewpoint of further improving the oxygen barrier property of the water-soluble resin layer and being able to suppress the deactivation of free radicals generated in the photosensitive resin layer due to exposure light when the laminate is transferred to the transfer body.

[0138] Polyvinyl alcohol is synthesized, for example, by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. The saponification degree of polyvinyl alcohol is preferably 50 mol% or more, more preferably 70 mol% or more, and more preferably 80 mol% or more. In addition, the upper limit of the saponification degree is 100 mol%. The "saponification degree" in this specification refers to the value measured in accordance with JIS K 6726 (1994) (Testing method for polyvinyl alcohol) specified in Japanese Industrial Standards.

[0139] The average degree of polymerization of polyvinyl alcohol is preferably 300 to 5,000, more preferably 300 to 3,500, and even more preferably 300 to 2,000.

[0140] Two or more types of polyvinyl alcohols different in degree of saponification, viscosity, degree of polymerization, type of modification, etc. may be used simultaneously.

[0141] Examples of the 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.).

[0142] From the viewpoint of developability and oxygen barrier properties, the content of polyvinyl alcohol in the water-soluble resin layer (the total amount when using two or more kinds of polyvinyl alcohol) is preferably 50 to 100 mass %, more preferably 70 to 100 mass %, and further preferably 90 to 100 mass %.

[0143] The water-soluble resin layer also preferably contains polyvinyl alcohol and polyvinyl pyrrolidone as the water-soluble resin. When the water-soluble resin layer contains polyvinyl alcohol and polyvinyl pyrrolidone, the mass ratio of polyvinyl alcohol to polyvinyl pyrrolidone is preferably 40 / 60 to 90 / 10, more preferably 50 / 50 to 90 / 10, and further preferably 60 / 40 to 90 / 10.

[0144] Furthermore, the water-soluble resin layer also preferably contains polyvinyl alcohol, polyvinyl pyrrolidone, and water-soluble cellulose as the water-soluble resin.

[0145] 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, more preferably 80% by mass or more, and particularly preferably 90% by mass or more relative to the total mass of the water-soluble resin layer. In addition, there is no particular limitation on the upper limit thereof, 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.

[0146] From the viewpoint of further improving removability and developability, the water-soluble resin layer may contain a plasticizer.

[0147] Examples of the plasticizer include polyvinyl alcohol or polyvinyl pyrrolidone copolymerized with 1 to 20 mol % of an olefin; glycerols such as glycerol, diglycerol and triglycerol; trimethylolpropane; polyalkylene oxides and their derivatives such as polyalkylene oxides, ester compounds of polyalkylene oxides and ether compounds of polyalkylene oxides; and phthalates such as dibutyl phthalate.

[0148] In the water-soluble resin layer, the plasticizer may be used alone or in combination of two or more.

[0149] The content of the plasticizer in the water-soluble resin layer is preferably 0 to 40% by mass, more preferably 0 to 20% by mass, based on the total mass of the water-soluble resin layer.

[0150] The water-soluble resin layer also preferably contains a surfactant.

[0151] The surfactant is not particularly limited, and examples thereof include nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants, and preferably a fluorine-based surfactant or a silicone-based surfactant.

[0152] The surfactant may be used alone or in combination of two or more.

[0153] 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.

[0154] The water-soluble resin layer may contain, in addition to the above-mentioned components, other additives such as a release agent, an adhesion-imparting agent, a filler (for example, oxide particles such as silica), and an ultraviolet absorber.

[0155] In addition, from the viewpoint of achieving a more excellent effect of the present invention, the water-soluble resin layer preferably contains substantially no filler. "Substantially containing no 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 further preferably 0.1% by mass or less relative to the total mass of the water-soluble resin layer.

[0156] <Steps of Process Xa>

[0157] In step Xa, the water-soluble resin layer is preferably formed by a coating method.

[0158] Among them, the step Xa is preferably a step of continuously conveying 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 performing a drying treatment to produce a laminated body A.

[0159] The conveying speed of the support is, for example, preferably 1 to 150 m / min, more preferably 5 to 100 m / min, and further preferably 7 to 90 m / min.

[0160] The coating method is not particularly limited, but examples thereof include slit coating and curtain coating.

[0161] When the water-soluble resin layer is formed by a coating method, it is preferred to coat a water-soluble resin composition containing the components contained in the water-soluble resin layer and a solvent on a support. In addition, 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 above-mentioned water-soluble resin layer.

[0162] The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the water-soluble resin layer, but is preferably at least one selected from water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0163] Examples of the water-miscible organic solvent include alcohol, acetone, ethylene glycol, glycerin, and mixed solvents of these. An alcohol having 1 to 3 carbon atoms is preferred, and methanol or ethanol is more preferred.

[0164] The solvent may be used alone or in combination of two or more.

[0165] The content of the solvent is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the water-soluble resin composition.

[0166] As a method of drying, heat drying is preferred.

[0167] The drying temperature is preferably 50° C. or higher, more preferably 60° C. or higher. The upper limit is preferably 150° C. or lower, more preferably 130° C. or lower, and further preferably 120° C. or lower.

[0168] The drying temperature may have a temperature gradient. As a method of providing a temperature gradient to the drying temperature, for example, there is a method of using a drying machine having a plurality of zones set to different temperatures so as to form a predetermined temperature gradient.

[0169] When a temperature gradient is provided for the drying temperature, the temperature difference between the lowest temperature and the highest temperature is preferably 10 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C.

[0170] The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer, and the upper limit is preferably 600 seconds or shorter, more preferably 450 seconds or shorter, and even more preferably 300 seconds or shorter.

[0171] [Process Xb]

[0172] like Figure 2 As shown, step Xb is a step of providing a temporary protective layer 7 on the water-soluble resin layer 3 side surface of the laminate A5 formed in step Xa to form a laminate B9. Through step Xb, a laminate B including a support, a water-soluble resin layer and a temporary protective layer is formed.

[0173] The step Xb is preferably a step of bonding the laminate A and the resin film for forming the temporary protective layer in a roll-to-roll manner.

[0174] <Temporary protection layer>

[0175] Examples of the material constituting the temporary protective layer include the same materials as those for the support used in the above-mentioned step Xa, and preferred aspects are also the same.

[0176] The concavoconvex shape of the temporary protective layer is easily transferred to the water-soluble resin layer, and the concavoconvex shape transferred to the water-soluble resin layer may affect the pattern performance z when the laminate is transferred to the transfer body to form a pattern. From the viewpoint of being able to form a more excellent pattern, the arithmetic mean roughness (Ra) of the surface of the temporary protective layer in contact with the water-soluble resin layer is preferably 1 to 200 nm.

[0177] 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 more preferably 50 nm or less, from the viewpoint of further suppressing the occurrence of optical anomalies during exposure and forming a pattern with better linearity when the laminate is transferred to the transfer body. 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, from the viewpoint of suppressing damage to the water-soluble resin layer when the temporary protective layer is peeled off due to excessive adhesion between the temporary protective layer and the water-soluble resin layer and forming a pattern with better linearity when the laminate is transferred to the transfer body.

[0178] The arithmetic mean roughness (Ra) of the temporary protective layer can be measured by the following method.

[0179] The surface of the temporary protective layer was measured under the following conditions using a three-dimensional optical profiler (New View 7300, manufactured by Zygo Corporation) to obtain the surface profile of the temporary protective layer. As the measurement and analysis software, the Microscope Application of MetroProver 8.3.2 was used. Next, the Surface Map screen was displayed using the above analysis software, and histogram data was obtained in the Surface Map screen. The arithmetic mean roughness was calculated based on the obtained histogram data to obtain the Ra value of the surface of the temporary protective layer.

[0180] When the temporary protective layer is bonded to the 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.

[0181] The thickness of the temporary protective layer is preferably 5 to 200 μm, more preferably 5 to 150 μm, further preferably 5 to 70 μm, and particularly preferably 10 to 50 μm from the viewpoint of easy handling and versatility.

[0182] As a method for laminating the temporary protective layer to the water-soluble resin layer, for example, a known method can be mentioned. As an apparatus for laminating the temporary protective layer to the water-soluble resin layer, for example, a known laminator such as a vacuum laminator and an automatic cutting laminator can be mentioned.

[0183] As the laminator, a laminator which is equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat is preferred.

[0184] 〔Process XC〕

[0185] Step XC is a step of winding the laminated body B to form a wound body C. There is no particular limitation on the method for winding the laminated body B, and a known method can be applied.

[0186] [Process Xd]

[0187] 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 the laminate B is unwound from the roll C. The peeling method is not particularly limited, and a known method can be applied.

[0188] 〔Process Xe〕

[0189] like Figure 3 As shown, step Xe is a step of forming a laminate D13 by forming a photosensitive resin layer 11 in contact with the water-soluble resin layer 3 exposed by the peeling step of step Xd. The laminate D obtained through step Xe has a support, a water-soluble resin layer, and a photosensitive resin layer in this order.

[0190] Hereinafter, first, the photosensitive resin layer constituting the laminated body D will be described.

[0191] <Photosensitive Resin Layer>

[0192] After the photosensitive resin layer is transferred to the transfer body, a pattern can be formed on the transfer body by exposure and development. The photosensitive resin layer may be a negative type or a positive type, but is preferably a negative type. In addition, a negative type photosensitive resin layer is a photosensitive resin layer whose solubility in a developer is reduced by exposure. In the case where the photosensitive resin layer is a negative type photosensitive resin layer, the pattern formed is equivalent to a cured layer.

[0193] Among them, the photosensitive resin layer preferably contains a binder resin (preferably an alkali-soluble resin), a polymerizable compound, and a photopolymerization initiator.

[0194] (Binder resin)

[0195] The photosensitive resin layer preferably contains a binder polymer. Among them, an alkali-soluble resin is preferred as the binder polymer.

[0196] As a preferable aspect of the binder polymer, a (meth)acrylic resin is mentioned from a viewpoint of being excellent in alkali developability and film-forming property.

[0197] In addition, in this specification, a (meth)acrylic resin refers to a resin having repeating units derived from a (meth)acrylic compound. The content of the repeating units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more relative to all repeating units of the (meth)acrylic resin.

[0198] The (meth)acrylic resin may be composed of repeating units derived from a (meth)acrylic compound alone, 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 the repeating units derived from the (meth)acrylic compound is 100% by mass or less relative to all the repeating units of the (meth)acrylic resin.

[0199] As a (meth)acrylic acid compound, (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile are mentioned, for example.

[0200] Examples of the (meth)acrylate include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and alkyl (meth)acrylates or benzyl (meth)acrylates are preferred.

[0201] Examples of (meth)acrylamide include acrylamides such as diacetone acrylamide.

[0202] Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates 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.

[0203] As the (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0204] In addition, the (meth)acrylic resin preferably contains repeating units derived from alkyl (meth)acrylate. The content of alkyl (meth)acrylate in the (meth)acrylic resin is, for example, preferably 10 to 90% by mass, more preferably 15 to 70% by mass, relative to all repeating units of the (meth)acrylic resin.

[0205] The (meth)acrylic resin may have a repeating unit other than the repeating unit derived from the (meth)acrylic compound.

[0206] The polymerizable monomer forming the repeating unit is not particularly limited as long as it is a compound other than the (meth)acrylic acid compound that can be copolymerized with the (meth)acrylic acid compound. Examples thereof include styrene compounds that may have a substituent at the α position or on the aromatic ring, such as styrene, vinyltoluene and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid and crotonic acid.

[0207] These polymerizable monomers may be used alone or in combination of two or more.

[0208] Furthermore, from the viewpoint of further improving alkali developability, the (meth)acrylic resin preferably has a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfone group, a phosphoric acid group, and a phosphonic acid group.

[0209] Among them, the repeating unit having an acid group is preferably a repeating unit having a carboxyl group, and more preferably a repeating unit derived from (meth)acrylic acid.

[0210] When the (meth)acrylic resin has a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 10% by mass or more relative to all repeating units of the resin from the viewpoint of better developability. The upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0211] 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 is also preferred.

[0212] Another preferred embodiment of the binder polymer is a styrene-acrylic acid copolymer.

[0213] In addition, in this specification, styrene-acrylic acid copolymer refers to a resin having repeating units derived from styrene compounds and repeating units derived from (meth)acrylic acid compounds. The total content of repeating units derived from styrene compounds and repeating units derived from (meth)acrylic acid compounds is preferably 30% by mass or more, more preferably 50% by mass or more relative to all repeating units of the copolymer.

[0214] The content of the repeating unit 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 all the repeating units of the copolymer.

[0215] The content of the repeating unit derived from the (meth)acrylic acid 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 the repeating units of the copolymer.

[0216] The binder polymer also preferably has a repeating unit having a reactive group.

[0217] The reactive group is preferably a radical polymerizable group, more preferably an ethylenically unsaturated group, and still more preferably an allyl group or a (meth)acryloyloxy group.

[0218] From the viewpoint of achieving more excellent effects of the present invention, the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 100,000, and particularly preferably 15,000 to 80,000.

[0219] The acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 130 mgKOH / g. The acid value of the binder polymer is a value measured by the method described in JIS K0070:1992.

[0220] The photosensitive resin layer may contain one type of binder polymer alone, or may contain two or more types.

[0221] From the viewpoint of achieving more excellent effects of the present invention, the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass based on the total mass of the photosensitive resin layer.

[0222] (Polymerizable compound)

[0223] The photosensitive resin layer preferably contains a polymerizable compound.

[0224] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radical polymerizable groups and cation polymerizable groups, and radical polymerizable groups are preferred.

[0225] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound").

[0226] As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferred.

[0227] The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited as long as it is 1 or more, but is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 to 3.

[0228] In addition, the ethylenically unsaturated compound in this specification is a compound other than the above-mentioned binder polymer, and the molecular weight is preferably less than 5,000.

[0229] The ethylenically unsaturated compound may have an alkyleneoxy group.

[0230] The alkylene group is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of the alkyleneoxy groups added to the polymerizable compound is preferably 2 to 60, more preferably 2 to 30, and even more preferably 2 to 20 per molecule.

[0231] Polymerizable compound B1

[0232] The photosensitive resin layer also preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

[0233] The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in the molecule among the above-mentioned polymerizable compounds.

[0234] Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocyclic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; these condensed rings are preferably aromatic hydrocarbon rings, more preferably benzene rings. The above aromatic rings may have a substituent.

[0235] The polymerizable compound B1 may have one or two or more aromatic rings.

[0236] From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer due to a developer, the polymerizable compound B1 preferably has a bisphenol structure.

[0237] 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), and a bisphenol A structure is preferred.

[0238] Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0239] The two 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 the two 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 per molecule, more preferably 2 to 30, and even more preferably 2 to 20.

[0240] Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs

[0072] to

[0080] of JP-A-2016-224162, and the contents thereof are incorporated herein.

[0241] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0242] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), ethoxylated bisphenol A dimethacrylates such as 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE series, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecylethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ESTER A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0243] As the polymerizable compound B1, it is preferred that a compound represented by the following formula (B-2) is contained.

[0244] Formula (B-2):

[0245] [Chemical formula 1]

[0246]

[0247] 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 of -(A-0)- and -(BO)- can be any of random and block. In the case of a block arrangement, either -(AO)- or -(B-0)- can be a bisphenyl (bisphenol) side.

[0248] n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0249] From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more relative to the total mass of the photosensitive resin layer. From the viewpoint of transferability and edge melting (phenomenon of photosensitive composition seeping out from the end of the transfer member), the upper limit is preferably 90% by mass or less, and more preferably 70% by mass or less.

[0250] From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more relative to the total mass of the polymerizable compound. From the viewpoint of peelability, the upper limit is preferably 100% by mass or less, more preferably 99% by mass or less, and further preferably 95% by mass or less relative to the total mass of the polymerizable compound.

[0251] Other ethylenically unsaturated compounds other than polymerizable compound B1

[0252] There are no particular restrictions on other ethylenically unsaturated compounds other than the polymerizable compound B1, and examples thereof include compounds having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds having no aromatic ring, and trifunctional or higher ethylenically unsaturated compounds.

[0253] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0254] Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0255] Examples of the alkylene glycol di(meth)acrylate 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.

[0256] Examples of the polyalkylene glycol di(meth)acrylate 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.).

[0257] Examples of the urethane di(meth)acrylate include propylene oxide-modified urethane di(meth)acrylate and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylate. Examples of commercially available urethane di(meth)acrylates 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.).

[0258] Examples of the trifunctional or higher ethylenically unsaturated compound 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, glycerol tri(meth)acrylate, and alkylene oxide-modified products thereof.

[0259] “(Tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate. Also, “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0260] Examples of the alkylene oxide-modified products of trifunctional or higher ethylenic 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., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glyceryl triacrylate (A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD., etc.), ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.) and SR454 (manufactured by TOAGOSEI CO., LTD.).

[0261] As the above-mentioned trimethylolpropane tri(meth)acrylate and an alkylene oxide-modified product thereof, a compound represented by the following formula (B-3) is also preferred.

[0262] Formula (B-3):

[0263] [Chemical formula 2]

[0264]

[0265] 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. From the viewpoint of further improving the resolution and linearity of the pattern, a+b+c is preferably 0 to 45, more preferably 0 to 39, and even more preferably 0 to 36.

[0266] The polymerizable compound may be an ethylenically unsaturated compound having an acid group (eg, a carboxyl group, etc.). The acid group may form an acid anhydride group.

[0267] Examples of the ethylenically unsaturated compound 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.).

[0268] Examples of the ethylenically unsaturated compound having an acid group include polymerizable compounds described in paragraphs

[0025] to

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

[0269] The polymerizable compound may be used alone or in combination of two or more.

[0270] The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 70% by mass, relative to the total mass of the photosensitive resin layer.

[0271] The content of the ethylenically unsaturated compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 70% by mass, relative to the total mass of the photosensitive resin layer.

[0272] (Photopolymerization Initiator)

[0273] The photosensitive resin layer preferably contains a photopolymerization initiator.

[0274] The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound by active light such as ultraviolet rays, visible rays, and X-rays. As the photopolymerization initiator, known photopolymerization initiators can be cited. As the photopolymerization initiator, among them, a photoradical polymerization initiator and a photocationic polymerization initiator can be cited, preferably a photoradical polymerization initiator, more preferably one or more selected from acridine-based photopolymerization initiators, benzophenone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, biimidazole-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.

[0275] The photopolymerization initiator may be used alone or in combination of two or more.

[0276] The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, relative to the total mass of the photosensitive resin layer.

[0277] (Surfactant)

[0278] The photosensitive resin layer preferably contains a surfactant.

[0279] As the surfactant, nonionic surfactant, fluorine surfactant or silicone surfactant is preferred, and silicone surfactant is more preferred. As the silicone surfactant, for example, linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains and / or the terminals can be cited.

[0280] Among them, the surfactant preferably contains a polymer D containing at least one repeating unit α selected from the repeating unit represented by the following formula (A-1) and the repeating unit represented by the following formula (A-2) and a repeating unit β represented by the following formula (B).

[0281] [Chemical formula 3]

[0282]

[0283] In formula (A-1), R1 represents a hydrogen atom or a methyl group.

[0284] R2 represents an alkylene group having 1 to 10 carbon atoms.

[0285] R3 represents an alkyl group having 1 to 4 carbon atoms. l represents an integer of 5 to 100.

[0286] In formula (A-2), R4 represents a hydrogen atom or a methyl group.

[0287] R5 represents an alkylene group having 1 to 10 carbon atoms.

[0288] L represents a trimethylsilyl group or a tris(trimethylsiloxy)silyl group.

[0289] In formula (B), R6 represents a hydrogen atom or a methyl group.

[0290] R7 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

[0291] m represents an integer from 1 to 100.

[0292] n represents an integer of 1 to 4.

[0293] In polymer D, the content of repeating unit α is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 45% by mass relative to all repeating units of polymer D. Furthermore, the content of repeating unit β is preferably 40 to 99% by mass, more preferably 45 to 95% by mass, and further preferably 50 to 90% by mass relative to all repeating units of polymer D.

[0294] In addition, the polymer D may further include other repeating units in addition to the above-mentioned repeating unit α and repeating unit β.

[0295] The weight average molecular weight (Mw) of the polymer D is preferably 500 or more, more preferably 800 or more, further preferably 1,000 to 30,000, and particularly preferably 2,000 to 20,000.

[0296] The content of the surfactant is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and further preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0297] (Other additives)

[0298] In addition to the above components, the photosensitive resin layer may contain other additives as necessary.

[0299] Examples of other additives include free radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazoles), pyridines (e.g., isonicotinamide), and purine bases (e.g., adenine).

[0300] In addition, other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic anti-precipitation agents, and paragraphs

[0165] to

[0184] of Japanese Patent Application Publication No. 2014-085643, and these contents are incorporated into this specification.

[0301] The other additives may be used alone or in combination of two or more.

[0302] In addition, from the viewpoint of achieving a more excellent effect of the present invention, the photosensitive resin layer preferably contains substantially no filler. "Substantially containing no filler" means that the content of the filler in the photosensitive resin layer is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.1% by mass or less relative to the total mass of the photosensitive resin layer.

[0303] <Steps of Process Xe>

[0304] Process Xe is preferably the following process: peeling off the temporary protective layer from the winding body C obtained in process Xb, continuously conveying the long film with the exposed surface of the water-soluble resin layer in the length direction, forming a coating film of the photosensitive resin layer on the water-soluble resin layer by a coating method and performing a drying treatment to produce a laminate D.

[0305] The conveying speed of the film is, for example, preferably 1 to 150 m / min, more preferably 5 to 100 m / min, and further preferably 7 to 90 m / min.

[0306] The coating method is not particularly limited, but examples thereof include slit coating and curtain coating.

[0307] When the photosensitive resin layer is formed by a coating method, a photosensitive resin composition containing the components contained in the photosensitive resin layer and a solvent is preferably coated on the water-soluble resin layer. In addition, 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 above-mentioned photosensitive resin layer.

[0308] As the solvent, there is no particular limitation as long as it is a solvent capable of dissolving or dispersing the components of the photosensitive resin layer, and a known organic solvent can be used. Specifically, for example, an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (methanol and ethanol, etc.), a ketone solvent (acetone and methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (toluene, etc.), an aprotic polar solvent (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetrahydrofuran, etc.), an ester solvent (n-propyl acetate, etc.), an amide solvent, a lactone solvent, and a mixed solvent containing two or more of these.

[0309] 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 selected from the group consisting 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 further preferred.

[0310] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0311] Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0312] As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of Japanese Patent Application Laid-Open No. 2018-177889 can be used, and these contents are incorporated into this specification.

[0313] The solvent may be used alone or in combination of two or more.

[0314] The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

[0315] The solvent may be used alone or in combination of two or more.

[0316] The content of the solvent is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition.

[0317] As a method of drying, heat drying is preferred.

[0318] The drying temperature is preferably 50° C. or higher, more preferably 60° C. or higher. The upper limit is preferably 150° C. or lower, more preferably 130° C. or lower, and further preferably 120° C. or lower.

[0319] The drying temperature may have a temperature gradient. As a method of providing a temperature gradient to the drying temperature, for example, there is a method of using a drying machine having a plurality of zones set to different temperatures so as to form a predetermined temperature gradient.

[0320] When a temperature gradient is provided for the drying temperature, the temperature difference between the lowest temperature and the highest temperature is preferably 10 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C.

[0321] The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer, and the upper limit is preferably 600 seconds or shorter, more preferably 450 seconds or shorter, and even more preferably 300 seconds or shorter.

[0322] In the formation of the photosensitive resin layer in step Xe, at least one of the conveying speed, drying temperature and drying time of the film is preferably different from the conveying speed, drying temperature and drying time of the support body when forming the water-soluble resin layer in the above step Xa. In the formation of the photosensitive resin layer in step Xe, at least one of the conveying speed and drying temperature of the film is preferably different from the conveying speed and drying temperature of the support body when forming the water-soluble resin layer in the above step Xa.

[0323] In addition, when the drying temperature has a temperature gradient, "different drying temperatures" means that at least one of the lowest temperature and the highest temperature 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., since the highest temperatures are different, it is considered that the drying temperatures are different.

[0324] [Process Xf]

[0325] like Figure 4 As shown, step Xf is a step of forming the cover film 15 so as to be in contact with the photosensitive resin layer 11 to form a laminated body E17 having the support 1, the water-soluble resin layer 3, the photosensitive resin layer 11 and the cover film 15 in this order.

[0326] <Cover film>

[0327] As the cover film, for example, a resin film having heat resistance and solvent resistance can be cited. Specifically, polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films can be cited. In addition, as the cover film, the same cover film as the support body described in step Xa can also be used.

[0328] As the cover film, a polyolefin film is preferred, and a polypropylene film or a polyethylene film is more preferred.

[0329] The thickness of the cover film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.

[0330] The thickness of the cover film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and is preferably 100 μm or less from the viewpoint of being relatively inexpensive.

[0331] The number of fish eyes with a diameter of 80 μm or more contained in the cover film is preferably 5 / m 2 The lower limit is preferably 0 pieces / m 2 above.

[0332] Fisheyes are foreign matter, undissolved matter, oxidative degradation products, etc., which are incorporated into the film when the film is produced by methods such as hot melting, kneading, extrusion, biaxial stretching, and casting.

[0333] The number of particles with a diameter of 3 μm or more contained in the coating is preferably 30 particles / mm. 2 Below, more preferably 10 / mm 2 Below, more preferably 5 / mm 2 The lower limit is preferably 0 pieces / mm 2 When it is within the above range, it is possible to suppress defects caused by the transfer of the irregularities caused by the particles contained in the cover film to the photosensitive resin layer.

[0334] From the viewpoint of giving winding property, the arithmetic mean roughness (Ra) of the surface on the opposite side of the surface in contact with the photosensitive resin layer of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and further preferably 0.30 μm or less. The determination method of the arithmetic mean roughness (Ra) can be cited by the same method as the determination method of the arithmetic mean roughness (Ra) of the temporary protective layer in step Xc.

[0335] 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.

[0336] The above-mentioned depression can be measured by observing an arbitrary 100 μm square range 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). When peeling the photosensitive resin layer, the photosensitive resin layer may be cured by exposure and then peeled off.

[0337] Since the water-soluble resin layer of the laminate E has the above-mentioned depressions on the surface on the photosensitive resin layer side, optical abnormalities during exposure when forming a pattern after transferring the laminate onto a transfer object can be further suppressed, resulting in a more excellent linearity of the obtained pattern.

[0338] As a method of laminating the cover film to the photosensitive resin layer, for example, a known method can be mentioned. As an apparatus for laminating the cover film to the photosensitive resin layer, for example, a known laminator such as a vacuum laminator and an automatic cutting laminator can be mentioned.

[0339] As the laminator, a laminator which is equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat is preferred.

[0340] By rolling up the laminate E, a roll-shaped transfer film can be produced and stored.

[0341] [Method for producing the second laminate]

[0342] The method for producing the second laminate of the present invention (hereinafter also referred to as “the second production method”) includes the following steps Ya, Yb, Yc, and Yd in order.

[0343] Step Ya: Step of forming a water-soluble resin layer on a support to form a laminate A

[0344] Step Yb: a step of forming a laminate B by forming a temporary protective layer in contact with the water-soluble resin layer

[0345] Step Yc: Step of winding the laminated body B to form a wound body C

[0346] Step Yd: unwinding the laminate B from the roll C, peeling off the temporary protective layer from between the temporary protective layer and the water-soluble resin layer of the laminate B, and laminating the photosensitive resin layer of the transfer film including a temporary support and a photosensitive resin layer to the exposed surface of the laminate B, thereby obtaining a laminate F including the support, the water-soluble resin layer, the photosensitive resin layer and the temporary support.

[0347] The laminate obtained by the second manufacturing method is less likely to have a difference in sensitivity between one end side and the other end side in the longitudinal direction, and can suppress the generation of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer. In addition, the laminate obtained by the first manufacturing method is transferred to a transfer object and subjected to exposure and development treatments, and the pattern obtained has excellent linearity.

[0348] The mechanism of action by which the above-mentioned effect is obtained by the second production method is not clear, but the present inventors presume it as follows.

[0349] The second manufacturing method includes the following steps: temporarily forming a roll C obtained by winding 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 the temporary protective layer from the laminate B, and then laminating a photosensitive resin layer on the water-soluble resin layer. That is, the second manufacturing method is not a manufacturing method for continuously forming a photosensitive resin layer after forming a water-soluble resin layer, but a manufacturing method temporarily passing through the above-mentioned roll C, thereby making it easy to set the manufacturing conditions of the photosensitive resin layer and the manufacturing conditions of the water-soluble resin layer to different conditions.

[0350] Regarding the photosensitive resin layer and the water-soluble resin layer, since the optimal manufacturing conditions (conveying speed or heating and drying temperature, etc.) of each layer are typically different, it is particularly desirable to set at least one of the conveying speed and the heating and drying temperature to different conditions for each layer when forming each layer. In contrast, for example, when manufacturing a long laminate having a support, a water-soluble resin layer and a photosensitive resin layer, after forming the water-soluble resin layer, the photosensitive resin layer is continuously formed under the same manufacturing conditions as the water-soluble resin layer. In the winding start area and the winding end area of ​​the obtained long laminate, the degree of interlayer component penetration of the photosensitive resin layer and the water-soluble resin layer (for example, the amount of penetration of the component of the water-soluble resin layer into the photosensitive resin layer, the amount of penetration of the component of the photosensitive resin layer into the water-soluble resin layer, etc.) is different, and as a result, sometimes a sensitivity difference occurs in the winding start area and the winding end area of ​​the laminate. To give a more specific example, when the optimum drying and heating temperature of the photosensitive resin layer is higher than the optimum drying and heating temperature of the water-soluble resin layer and the water-soluble resin layer and the photosensitive resin layer are continuously formed on a conveyor line, there are many cases where the drying and heating temperature of the photosensitive resin layer has to be made the same as the drying and heating temperature of the water-soluble resin layer due to manufacturing problems. If it is assumed that 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, the volatile solvent is likely to accumulate in the dryer of the photosensitive resin layer and the drying in the dryer may not be fully carried out in the later stage of conveying. As a result, a sensitivity difference sometimes occurs in the winding start area and the winding end area of ​​the laminate.

[0351] In contrast, in the second manufacturing method, as described above, since the winding body C is temporarily passed, the photosensitive resin layer and the water-soluble resin layer can be manufactured under different manufacturing conditions, thereby being able to suppress the difference in sensitivity between the winding start area and the winding end area of ​​the laminate. Furthermore, since the photosensitive resin layer is laminated on the water-soluble resin layer by lamination, it is possible to more easily suppress the difference in sensitivity between the winding start and the winding end. This is because, when the photosensitive resin layer is coated on the water-soluble resin layer during lamination, sometimes the solvent may easily cause the movement of substances (such as polymerization initiators, etc.) between the layers, but it is presumed that since both the water-soluble resin layer and the photosensitive resin layer have been temporarily dried during lamination, it is not easy for substances to move.

[0352] Furthermore, in the second manufacturing method, the wound body C obtained in step Yc has a temporary protective layer on the water-soluble resin layer for protecting the water-soluble resin layer. Therefore, the surface of the photosensitive resin layer forming the water-soluble resin layer can suppress the generation of foreign matter and scratches caused by friction with the back side of the support when winding in step Yc. As a result, when the laminate obtained by the second manufacturing method is transferred to the transfer body and subjected to exposure treatment, it is not easy to cause exposure failure (optical abnormality).

[0353] 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 body and subjected to exposure and development treatment, the polymerization reaction of the photosensitive resin layer is easily carried out by blocking oxygen by the water-soluble resin layer, and the linearity of the obtained pattern is excellent. Furthermore, by having a water-soluble resin layer, it is possible to implement exposure treatment (contact exposure) in a state where the temporary support body is peeled off, and it is possible to suppress the reduction of the linearity of the pattern caused by excessive adhesion between the photosensitive resin layer and the photomask.

[0354] Hereinafter, further suppressing the difference in sensitivity between one end side and the other end side in the long strip direction in the laminate obtained by the second manufacturing method, further suppressing the generation of foreign matter and scratches between the water-soluble resin layer and the photosensitive resin layer in the laminate obtained by the second manufacturing method, and / or being able to form a pattern with better linearity when the laminate obtained by the second manufacturing method is transferred to a transfer body and subjected to exposure and development treatments will also be referred to as “the effect of the present invention is better”.

[0355] The second manufacturing method is described in detail below. Steps Ya to Yc in the second manufacturing method are respectively the same as steps Xa to Xc in the first manufacturing method, and the preferred methods are also the same. In the second manufacturing method, the winding body C obtained in step Xc is unwound, the temporary protective layer is peeled off from between the temporary protective layer and the water-soluble resin layer of the laminate B, and the photosensitive resin layer of the transfer film including the temporary support and the photosensitive resin layer is attached to the exposed surface of the laminate B, thereby forming a laminate F including a support, a water-soluble resin layer, a photosensitive resin layer and a temporary support. Other than this, it is the same as the first manufacturing method.

[0356] The second manufacturing method preferably further includes the following step Yf, the following step Yg, the following step Yh, and the following step Yi before the above-mentioned step Yd.

[0357] Step Yf: Step of forming a photosensitive resin layer on a temporary support to form a laminate H

[0358] Step Yg: a step of forming a temporary protective layer in contact with the photosensitive resin layer to form a laminated body I

[0359] Step Yh: Step of winding the laminated body I to form a wound body J

[0360] Step Yi: unwinding the roll J, peeling the temporary protective layer from between the temporary protective layer and the photosensitive resin layer of the laminate I, thereby obtaining a transfer film including the temporary support and the photosensitive resin layer

[0361] The second manufacturing method preferably further includes the following step Ye after the above-mentioned step Yd.

[0362] Step Ye: a step of peeling the temporary support from between the temporary support and the photosensitive resin layer of the laminate F, and attaching a cover film to the exposed surface of the laminate F, thereby forming a laminate G having the support, the water-soluble resin layer, the photosensitive resin layer and the cover film in sequence.

[0363] Hereinafter, step Ya, step Yb, step Yc, and step Yd included in the second manufacturing method will be described.

[0364] 〔Process Ya~YC〕

[0365] The steps 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 first production method, and the preferred aspects are also the same.

[0366] 〔Process Yd〕

[0367] Process Yd includes a process of peeling off the temporary protective layer of the stack B between the temporary protective layer and the water-soluble resin layer after the stack B is released from the winding body C, and a process of bonding the photosensitive resin layer of the transfer film including the temporary support body and the photosensitive resin layer to the surface of the exposed water-soluble resin layer after peeling.

[0368] After this process Y, Figure 5 As shown, a laminate F21 including the support 1, the water-soluble resin layer 3, the photosensitive resin layer 11, and the temporary support 19 is obtained.

[0369] The peeling step in step Yd is the same as step Xd in the first manufacturing method, and the preferred aspects are also the same.

[0370] <Transfer film>

[0371] The transfer film used in step Yd is not particularly limited as long as it is a transfer film having a temporary support and a photosensitive resin layer.

[0372] The transfer film used in step Yd is also preferably a transfer film produced through steps Yf to Yi described above.

[0373] The temporary support in step Yd and step Yf to step Yi may be the same temporary support as the support used in step Xa in the first manufacturing method or the same temporary support as the covering film used in step Xf in the first manufacturing method.

[0374] The photosensitive resin layer in step Yd and step Yf to step Yi may be the same photosensitive resin layer as the photosensitive resin layer used in step Xe in the above-mentioned first manufacturing method.

[0375] Hereinafter, the procedure of each step from step Yf to step Yi will be described.

[0376] (Process Yf)

[0377] Step Yf is a step of forming a laminate H by forming a photosensitive resin layer on a temporary support.

[0378] The step of forming the photosensitive resin layer on the temporary support is not particularly limited, and an example thereof may be a coating method. The step of forming the photosensitive resin layer in step Yf is the same as the step of forming the photosensitive resin layer used in step Xe in the first manufacturing method described above.

[0379] In the formation of the photosensitive resin layer in step Yf, at least one of the film conveying speed, drying temperature and drying time is preferably different from the conveying speed, drying temperature and drying time of the support body when forming the water-soluble resin layer in the above step Ya. In the formation of the photosensitive resin layer in step Xf, at least one of the film conveying speed and drying temperature is preferably different from the conveying speed and drying temperature of the support body when forming the water-soluble resin layer in the above step Ya.

[0380] (Process Yg)

[0381] Step Yg is a step of forming a temporary protective layer in contact with the photosensitive resin layer to form the laminated body I. The steps of forming the temporary protective layer and the materials of the temporary protective layer in step Yg are the same as those of forming the temporary protective layer and the materials of the temporary protective layer in step Xb in the first manufacturing method described above.

[0382] The concavoconvex shape of the temporary protective layer is easily transferred to the photosensitive resin layer, and the concavoconvex shape transferred to the photosensitive resin layer may affect the pattern performance when the laminate is transferred to the transfer body to form a pattern. From the viewpoint of being able to form a better pattern, the arithmetic mean roughness (Ra) of the surface of the temporary protective layer in contact with the photosensitive resin layer is preferably 1 to 200 nm.

[0383] The upper limit of the arithmetic mean roughness of the surface of the temporary protective layer in contact with the photosensitive resin layer is more preferably 100 nm or less, and more preferably 50 nm or less, from the viewpoint of further suppressing the occurrence of optical anomalies during exposure and forming a pattern with better linearity when the laminate is transferred to the transfer body. 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, from the viewpoint of suppressing damage to the photosensitive resin layer when the temporary protective layer is peeled off due to excessive adhesion between the temporary protective layer and the photosensitive resin layer and forming a pattern with better linearity when the laminate is transferred to the transfer body.

[0384] The method for measuring the arithmetic mean roughness (Ra) may be the same method as the method for measuring the arithmetic mean roughness (Ra) of the temporary protective layer in step Xc.

[0385] (Process Yh)

[0386] The step Yh is a step of winding the laminated body I to form a wound body J. The method of winding the laminated body I is not particularly limited, and a known method can be applied.

[0387] (Process Yi)

[0388] Step Yi is a step of unwinding the laminate I from the roll J and peeling the temporary protective layer from between the temporary protective layer and the photosensitive resin layer of the laminate I. The peeling method is not particularly limited, and a known method can be applied.

[0389] <Process Yd>

[0390] The process of laminating the photosensitive resin layer of the transfer film including the temporary support and the photosensitive resin layer to the surface of the water-soluble resin layer in step Yd is not particularly limited, and for example, a known method can be cited. As an apparatus for laminating the water-soluble resin layer to the transfer film, for example, a known laminator such as a vacuum laminator and an automatic cutting laminator can be cited.

[0391] As the laminator, a laminator which is equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat is preferred.

[0392] The laminate F obtained through the above step Yd can be wound up to prepare and store a roll-shaped transfer film.

[0393] 〔Process〕

[0394] Step Ye is a step of peeling the temporary support from the laminate F obtained in step Yd and laminating a cover film on 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.

[0395] In the step Ye, the method of peeling the temporary support from the laminated body F is not particularly limited, and a known method can be applied.

[0396] The cover film used in step Ye and the method of laminating the cover films are the same as the cover film used in step Xf and the method of laminating the cover films.

[0397] In laminate F and laminate G, the water-soluble resin layer preferably has a depression of 1 nm or more and less than 100 nm on the surface of the photosensitive resin layer side. Furthermore, in laminate F and laminate G, the photosensitive resin layer preferably has a depression of 1 nm or more and less than 100 nm on the surface of the water-soluble resin layer side. The above-mentioned depression can be measured by observing the surface of the water-soluble resin layer and the surface of the photosensitive resin layer exposed by peeling laminate F and laminate G between the water-soluble resin layer and the photosensitive resin layer using an atomic force microscope (manufactured by Hitachi High-Tech Science Corporation.) in an arbitrary 100 μm square range. In addition, when peeling the photosensitive resin layer and the water-soluble resin layer, the peeling can be performed after the photosensitive resin layer is cured by exposure.

[0398] By having the above-mentioned depressions on the surface of the photosensitive resin layer side of the water-soluble resin layer in stack F and stack G and / or the surface of the water-soluble resin layer side of the photosensitive resin layer in stack F and stack G, optical abnormalities during exposure when forming a pattern after transferring the stack to the transfer body can be further suppressed, resulting in better linearity of the obtained pattern.

[0399] [Method for forming resin pattern]

[0400] By using the laminated body (transfer film, hereinafter also referred to as “laminated body of the present invention”) obtained by the above-mentioned first production method and second production method, a resin pattern can be formed on a transfer target body.

[0401] The laminate of the present invention is preferably used for a protective film pattern for protecting a conductive layer in a touch panel.

[0402] The method for forming the resin pattern includes:

[0403] A laminating step of bringing a surface of the laminate of the present invention opposite to the support body into contact with and laminating the substrate having the conductive portion, thereby obtaining a substrate with a composition layer having a substrate, a conductive layer, a composition layer, and a support body in this order;

[0404] An exposure step of performing pattern exposure on the composition layer; and

[0405] a developing step of developing the exposed composition layer to form a protective film pattern for protecting the conductive layer,

[0406] The method for forming a resin pattern preferably further includes a peeling step of peeling the support from the substrate having the composition layer between the laminating step and the exposure step or between the exposure step and the development step.

[0407] Furthermore, when forming the resin pattern, it is preferred that the laminate of the present invention is used in a roll-shaped manner and is implemented by a roll-to-roll process. That is, the laminating step is a step of laminating the laminate of the present invention and the substrate having a conductive layer described later in a roll-to-roll manner, and it is preferred that at least the exposure step and the development step are performed on the long-strip laminate formed by the laminating step.

[0408] Hereinafter, the steps of the above process will be described in detail.

[0409] 〔Lamination process〕

[0410] The laminating step is a step of laminating the surface of the laminate of the present invention on the side opposite to the support body to a substrate having a conductive portion so as to obtain a substrate having a substrate, a conductive layer, a composition layer (photosensitive resin layer and water-soluble resin layer) and a support body with a composition layer in sequence. In addition, when the laminate of the present invention has a cover film, the laminating step is performed after the cover film is peeled off.

[0411] In the bonding, pressure bonding is performed so that the conductive layer is in contact with the surface of the composition layer.

[0412] The pressure-bonding method is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferred to overlap the surface of the composition layer on a substrate having a conductive portion and apply pressure and heat with a roller or the like.

[0413] For lamination, a known laminator such as a vacuum laminator and an automatic cutting laminator can be used.

[0414] The lamination temperature is not particularly limited, but is preferably 70 to 130°C, for example.

[0415] The substrate having a conductive layer has a conductive layer on a substrate, and any layer can be formed as needed. That is, the substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0416] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

[0417] As a preferred embodiment of the substrate, for example, it is described in paragraph

[0140] of International Publication No. 2018 / 155193, and the content is incorporated into this specification. As the material of the resin substrate, cycloolefin polymer and polyimide are preferred. The thickness of the resin substrate is preferably 5 μm to 200 μm, and more preferably 10 to 100 μm.

[0418] 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 from the viewpoint of conductivity and thin line formability.

[0419] 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, the conductive layers are preferably made of different materials.

[0420] A preferred embodiment of the conductive layer is described in, for example, paragraph

[0141] of International Publication No. 2018 / 155193, and the content is incorporated into this specification.

[0421] As the substrate having a conductive layer, a substrate having at least one of a transparent electrode and a routing wiring is preferred. Such a substrate can be preferably used as a substrate for a touch panel.

[0422] The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide) and a metal fine wire such as a metal mesh and a metal nanowire.

[0423] Examples of the metal thin wires include thin wires of silver, copper, and the like, of which silver conductive materials such as silver mesh and silver nanowires are preferred.

[0424] As a material of the bypass wiring, metal is preferable.

[0425] The metal used as the material of the bypass wiring includes gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, and alloys composed of two or more of these metal elements. The material of the bypass wiring is preferably copper, molybdenum, aluminum or titanium, and particularly preferably copper.

[0426] For the purpose of protecting electrodes and / or wirings, the protective film for a touch panel formed by the laminate of the present invention can be provided in a manner that covers the electrodes and / or wirings directly or via other layers, or can also be provided as a protective film for insulating between electrodes (specifically, a protective film for insulating between electrodes such as bridge wiring).

[0427] [Exposure process]

[0428] The exposure step is a step of pattern-exposing the composition layer.

[0429] In addition, here, "pattern exposure" means a method of exposing in a pattern, that is, exposure in a method in which there are exposed parts and non-exposed parts.

[0430] The positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited and can be adjusted appropriately.

[0431] The exposure may be performed from the side opposite to the substrate of the composition layer, or from the substrate side of the composition layer.

[0432] As the light source for pattern exposure, any light having a wavelength region that can at least cure the photosensitive resin layer (e.g., 365 nm or 405 nm) can be appropriately selected for use. The dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. In addition, the dominant wavelength is the wavelength with the highest intensity.

[0433] Examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0434] The exposure dose is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 200 mJ / cm 2 .

[0435] Preferred aspects of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and these contents are incorporated into this specification.

[0436] By performing the exposure step and the development step described later, a protective film pattern that protects at least a portion of the conductive layer can be formed on the conductive layer on the substrate.

[0437] [Peeling process]

[0438] 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 later.

[0439] The peeling method is not particularly limited, and the same cover film peeling mechanism as that described in paragraphs

[0161] to

[0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

[0440] 〔Development process〕

[0441] The development step is a step of developing the exposed composition layer to form a pattern.

[0442] The development of the composition layer can be performed using a developer.

[0443] As the developer, an alkaline aqueous solution is preferred. Examples of alkaline compounds that may be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0444] Examples of the method of development include flooding development, shower development, spin development, and dip development, and shower development is preferred.

[0445] As one of the preferable aspects of the developer used in the development step, for example, there can be mentioned the developer described in paragraph

[0194] of International Publication No. 2015 / 093271.

[0446] Furthermore, as one of the suitable methods of the development method for carrying out the development step, for example, the development method described in paragraph

[0195] of International Publication No. 2015 / 093271 can be cited.

[0447] Furthermore, the developing step is preferably a step of repeatedly using the developing solution by circulating the developing solution, and preferably a step of repeatedly using the developing solution by circulating the developing solution by shower development. As a specific method for implementing the above-mentioned developing step, for example, the developing method described in Japanese Patent Application Laid-Open No. 2012-137574 can be cited.

[0448] [Post-exposure process and post-baking process]

[0449] The method for producing the laminated body may include a step of exposing the pattern obtained in the development step (post-exposure step) and / or a step of heating (post-baking step).

[0450] When both the post-exposure step and the post-bake step are included, it is preferred to perform the post-bake after the post-exposure. The exposure dose of the post-exposure is preferably 100 to 5000 mJ / cm 2 , more preferably 200 to 3000 mJ / cm 2The post-baking temperature is preferably 80 to 250° C., more preferably 90 to 160° C. The post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[0451] [Method for forming a conductor pattern]

[0452] By using the laminated body (laminated body of the present invention) obtained by the above-mentioned first production method and second production method, a conductor pattern (circuit wiring) can be formed on a transfer target body.

[0453] One embodiment of a method for forming a conductor pattern of the present invention includes:

[0454] A laminating step of bringing the surface of the laminate of the present invention opposite to the support into contact with a substrate having a metal layer, thereby obtaining a substrate having a composition layer which sequentially comprises a substrate, a metal layer, a composition layer (a photosensitive resin layer and a water-soluble resin layer), and a support;

[0455] An exposure step of exposing the composition layer in a pattern;

[0456] A developing step of developing the exposed composition layer to form a resin pattern;

[0457] an etching process step of etching the metal layer in the region where the resin pattern is not arranged; or a plating process step of performing plating; and

[0458] a resist stripping step of stripping the resin pattern;

[0459] In the case where the plating treatment step is included, a removal step of removing the metal layer exposed by the resist stripping step and forming a conductor pattern on the substrate is also included.

[0460] The method for forming a conductive pattern preferably further includes a support peeling step of peeling the support between the laminating step and the exposure step or between the exposure step and the development step.

[0461] Hereinafter, specific steps of the method for forming the conductor pattern will be described.

[0462] The laminating step, exposure step, developing step, and peeling step in the method for forming a conductor pattern are the same as those in the method for forming the resin pattern, and the preferred aspects are also the same.

[0463] 〔Etching process〕

[0464] The manufacturing method of circuit wiring includes a process (etching process) of etching the metal layer located in an area where a resin pattern is not arranged on a stacked body in which a substrate, a metal layer (a metal layer possessed by a substrate) and a resin pattern (more preferably a resin pattern manufactured by a manufacturing method including the above-mentioned bonding process, the above-mentioned exposure process and the above-mentioned development process) are stacked in sequence.

[0465] In the etching step, the metal layer is etched using the resin pattern obtained from the photosensitive resin layer in the developing step as an etching resist.

[0466] As the etching treatment method, a known method can be applied, for example, the method described in paragraphs

[0209] to

[0210] of Japanese Patent Gazette No. 2017-120435, the method described in paragraphs

[0048] to

[0054] of Japanese Patent Gazette No. 2010-152155, and a wet etching method based on immersion in an etching solution and a dry etching method such as plasma etching.

[0467] 〔Plating process〕

[0468] The plating step is a step of forming a plated layer by plating treatment on the metal layer located in a region where the resin pattern is not arranged (the metal layer exposed to the surface by the development step).

[0469] Examples of the plating method include electrolytic plating and electroless plating. From the viewpoint of productivity, electrolytic plating is preferred.

[0470] When the plating step is performed, a plated layer having the same pattern shape as that of a region (opening of the resist pattern) where the resist pattern is not arranged is obtained on the substrate with the metal layer.

[0471] Examples of the metal contained in the plating layer include well-known metals.

[0472] Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals.

[0473] Among them, from the viewpoint of further improving the conductivity of the conductive pattern, the plating layer preferably contains copper or its alloy. Also, from the viewpoint of further improving the conductivity of the conductive pattern, the plating layer preferably contains copper as a main component.

[0474] 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.

[0475] Furthermore, it is also preferable to include a protective layer forming step between the plating step and the resist stripping step described later.

[0476] The protective layer forming step is a step of forming a protective layer on the plated layer.

[0477] The material of the protective layer is preferably a material having resistance to the stripping solution and / or etching solution in the resist stripping process and / or removal process. For example, metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, their alloys, and resins can be cited. Among them, the material of the protective layer is preferably nickel or chromium.

[0478] Examples of a method for forming the protective layer include electroless plating and electroplating, and electroplating is preferred.

[0479] 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. The upper limit is not particularly limited, but is preferably 3.0 μm or less, more preferably 2.0 μm or less.

[0480] [Resist stripping process]

[0481] The resist stripping step is a step of removing the remaining resist pattern after the etching step and the plating step.

[0482] As a method of removing the remaining resin pattern, for example, a method of removing by chemical treatment is mentioned, and a method of removing using a stripping liquid is preferred.

[0483] Examples of a method for removing the remaining resist pattern include a method of removing by a known method such as a spray method, a shower method, or a spin immersion method using a stripping liquid.

[0484] It is also preferable to perform a rinsing process to remove the stripping liquid remaining on the substrate after the resin pattern is stripped with the stripping liquid. Water or the like can be used for the rinsing process.

[0485] After the stripping and / or rinsing process of the resin pattern using the stripping liquid, a drying process may be performed to remove excess liquid from the substrate.

[0486] 〔Removal process〕

[0487] 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.

[0488] In the removal step, the plated layer formed in the plating step is used as an etching resist to perform etching treatment on the metal layer located in the non-pattern formation region (in other words, the region not protected by the plated layer).

[0489] The method for removing a part of the metal layer is not particularly limited, but a known etching solution is preferably used.

[0490] 〔Other processes〕

[0491] The method for forming a conductive pattern may include any steps (other steps) other than the above-mentioned steps.

[0492] For example, the process of reducing the visible light reflectance described in paragraph

[0172] of International Publication No. 2019 / 022089, the process of forming a new conductive layer on the insulating film described in paragraph

[0172] of International Publication No. 2019 / 022089, etc. can be cited, but it is not limited to these processes.

[0493] [Laminated body]

[0494] The laminate of the present invention comprises a support, a water-soluble resin layer, a photosensitive resin layer arranged in contact with the water-soluble resin layer, and a cover film in this order, wherein:

[0495] 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.

[0496] The laminated body of the present invention can be formed by the first production method and the second production method described above.

[0497] As the support body, water-soluble resin layer, photosensitive resin layer and covering film in the laminate of the present invention, there can be cited the same support body, water-soluble resin layer, photosensitive resin layer and covering film as those described in the first manufacturing method, and the preferred embodiments are also the same.

[0498] Furthermore, in the above-mentioned laminate, 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.

[0499] The above-mentioned depression can be measured by observing an arbitrary 100 μm square range 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 Corporation.) Alternatively, the photosensitive resin layer may be peeled off after being cured by exposure.

[0500] The water-soluble resin layer of the laminate having the above-mentioned depressions on the surface of the photosensitive resin layer side can further suppress optical abnormalities during exposure when forming a pattern after transferring the laminate to a transfer object, resulting in more excellent linearity of the obtained pattern.

[0501] Example

[0502] Below, the present invention is further described in detail based on embodiment.The material, usage, ratio, processing content and processing step etc. shown in the following embodiment can be appropriately changed as long as they do not depart from the gist of the present invention.Thereby, the scope of the present invention should not be interpreted restrictively by the embodiment shown below.

[0503] In addition, unless otherwise specified, "part" and "%" are based on mass.

[0504] [Preparation of water-soluble resin composition]

[0505] Water-soluble resin compositions (compositions 1-1 to 1-6) having the components and formulations shown in Table 1 described below were prepared.

[0506] In Table 1, the numerical values ​​described in the columns of each component represent the content (parts by mass) of each component.

[0507] [Table 1]

[0508]

[0509] The details of the various components described in Table 1 are shown below.

[0510] A-1: KURARAY POVAL PVA-205 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.)

[0511] A-2: KURARAY POVAL 17-94 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.)

[0512] A-3: Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.)

[0513] A-4: METOLOSE 60SH (modified cellulose, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0514] D-1: MA-ST-M (silica sol, manufactured by Nissan Chemical Industries, Ltd.)

[0515] E-1: MEGAFACE F-444 (fluorinated surfactant, manufactured by DIC Corporation)

[0516] E-2: BYK-348 (silicone-based surfactant, manufactured by BYK JAPAN KK.)

[0517] E-3: KF-6115 (silicone-based surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0518] F-1: Ion exchange water

[0519] F-2: Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

[0520] [Preparation of photosensitive resin composition]

[0521] Photosensitive resin compositions (compositions 2-1 to 2-14) having the components and formulations shown in Table 2 described later were prepared.

[0522] In Table 2, the numerical values ​​described in the columns of each component represent the content (parts by mass) of each component.

[0523] [Table 2]

[0524]

[0525] The details of the various components described in Table 2 are shown below.

[0526] A-5: Propylene glycol monomethyl ether acetate solution of a copolymer of styrene / methacrylic acid / methyl methacrylate (equivalent to an alkali-soluble resin) (solid content concentration: 30.0 mass%, ratio of each monomer: 52 mass% / 29 mass% / 19 mass%, Mw: 20,000)

[0527] A-6: Propylene glycol monomethyl ether acetate solution of a copolymer of styrene / methacrylic acid / benzyl methacrylate (equivalent to an alkali-soluble resin) (solid content concentration: 30.0% by mass, ratio of each monomer: 25% by mass / 25% by mass / 50% by mass, Mw: 50,000)

[0528] A-7: Propylene glycol monomethyl ether acetate solution of a copolymer of ethyl acrylate / methacrylic acid / methyl methacrylate (equivalent to an alkali-soluble resin) (solid content concentration: 30.0 mass%, ratio of each monomer: 30 mass% / 12 mass% / 58 mass%, Mw: 60,000)

[0529] B-1: NK ester BPE-100 (ethoxylated bisphenol A dimethacrylate (equivalent to the compound represented by the above formula (B-2)), manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.)

[0530] B-2: ARONIX M-270 (polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.)

[0531] B-3: A compound represented by the above formula (B-2), wherein n1=n3=average 2, n2=n4=average 3, R1=R2=methyl monomer (synthetic product)

[0532] B-4: A-DPH (dipentaerythritol polyacrylate, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.)

[0533] B-5: A-TMPT-9EO (ethoxylated trimethylolpropane triacrylate (equivalent to the compound represented by the above formula (B-3)), manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.)

[0534] B-6: A-9300 (tris(2-acryloyloxyethyl)isocyanurate, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.)

[0535] B-7: UA-160TM (urethane acrylate, manufactured by SHIN-NAKAMURA CHEMICALCO, LTD.)

[0536] C-1: B-CIM (biimidazole photopolymerization initiator, manufactured by KUROGANE KASEI Co., Ltd.)

[0537] C-2: SB-PI 701 (benzophenone-based photopolymerization initiator, obtained from SANYO TRADING CO., LTD.)

[0538] C-3: Irgacure OXE02 (oxime ester-based photopolymerization initiator, manufactured by BASF Japan LLd.)

[0539] C-4: 9-phenylacridine (acridine-based photopolymerization initiator, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0540] C-5: 0mnirad 379EG (alkyl phenone-based photopolymerization initiator, manufactured by IGM Resins BV)

[0541] D-2: CHO-ST-M (silica sol, manufactured by Nissan Chemical Industries, Ltd.)

[0542] D-3: TDP-G (phenothiazine (polymerization inhibitor), manufactured by Kawaguchi Chemical Industry Co., Ltd.)

[0543] D-4: 1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0544] D-5: Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0545] D-6: N-phenylcarbamoylmethyl-N-carbonylmethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0546] D-7: CBT-1 (carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.)

[0547] E-4: MEGAFACE F-552 (fluorinated surfactant, manufactured by DIC Corporation, solid)

[0548] E-5: polymer E-5 produced by the method described below (30% by mass butyl acetate solution)

[0549] <Synthesis of Polymer E-5>

[0550] 150 parts of butyl acetate were added to a 1000 ml reaction container equipped with a stirring device, a reflux cooler, a dropping funnel, a thermometer and a nitrogen inlet, and reflux was performed while introducing nitrogen. Under the reflux condition of butyl acetate, 300 parts of the dropwise solution shown below were dropped at a constant rate over 2 hours through the dropping funnel.

[0551] One hour after the addition of the dropwise solution was completed, 1.5 parts of tert-amyl peroxide-2-ethylhexanoate was added, and the reaction was allowed to proceed 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 mass %).

[0552] The polystyrene-equivalent number average molecular weight of the synthesized polymer E-5 determined by gel permeation chromatography was 7,500.

[0553] - Composition of the dropwise solution -

[0554] Monomer represented by the following formula (a-1-1): 57 parts by mass

[0555] Monomer represented by the following formula (b-1): 243 parts by mass

[0556] [Chemical formula 4]

[0557]

[0558] E-6: KP-326 (silicone-based surfactant, manufactured by Shin-Etsu Chemical Co., Ltd., 50 mass% toluene solution)

[0559] F-3: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0560] F-4: Propylene glycol monomethyl ether acetate (manufactured by SHINKO ORGANIC CHEMICAL INDUSTRY LTD.)

[0561] [Manufacturing of Laminated Body]

[0562] Laminated bodies 1 to 19 (Examples 1 to 24 and Comparative Examples 1 to 3) having the layer structures shown in Table 3 described below were produced by various production methods shown in Table 4 described below.

[0563] [Layer Structure of Laminated Bodies 1 to 19]

[0564] Table 3 is shown below.

[0565] [Table 3]

[0566]

[0567] [Types of temporary protective layers]

[0568] The temporary protective layer shown in Table 4 described below is as follows. The arithmetic mean roughness (Ra) of the temporary protective layer shown in Table 4 is a value measured by the method described above as the arithmetic mean roughness (Ra) of the temporary protective layer in the step Xc.

[0569] P1: ALFAN FG-201 (polypropylene film, thickness 25 μm, manufactured by Oji F-Tex Co., Ltd.)

[0570] P2: ALFAN EM-501 (polypropylene film, thickness 15 μm, manufactured by Oji F-Tex Co., Ltd.)

[0571] P3: Lumirror 16FB50 (polyethylene terephthalate film, thickness 16 μm, manufactured by TORAY INDUSTRIES, INC.)

[0572] [Example 1]

[0573] <Preparation of Water-Soluble Resin Layer>

[0574] The water-soluble resin composition shown in Table 4 was applied to a roll of polyethylene terephthalate film (support, Lumirror16KS40, TORAY INDUSTRIES, INC., thickness: 16 μm, length: 200 m) conveyed at the conveying speed described in Table 4 so that the thickness after drying became 1.0 μm, and the obtained coating was dried to remove the solvent using a hot air convection dryer having a temperature gradient of 50° C. to 70° C. (refer to the heating conditions in Table 4), thereby forming a water-soluble resin layer. In addition, a temporary protective layer shown in Table 4 was pressed onto the water-soluble resin layer using a roller 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 steps was wound to produce a roll.

[0575] <Preparation of Photosensitive Resin Layer>

[0576] Next, the laminate was unwound from the obtained roll, and the temporary protective layer was peeled off from the laminate while being conveyed at the conveying speed described in Table 4 to expose the water-soluble resin layer, and then the photosensitive resin composition shown in Table 4 was applied to the exposed surface so that the thickness after drying was 3.0 μm. After coating, the solvent was dried and removed using a hot air convection dryer with a temperature gradient of 50° C. to 100° C. (refer to the heating conditions in Table 4), thereby forming a photosensitive resin layer on the water-soluble resin layer.

[0577] Furthermore, a rolled 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.

[0578] [Examples 2 to 18, 21 to 24]

[0579] A laminate (200 m long roll) consisting of support / water-soluble resin layer / photosensitive resin layer / covering film was prepared by the same method as in Example 1, except that the water-soluble resin composition, photosensitive resin composition and / or various manufacturing conditions were changed as described in Table 4.

[0580] [Example 19]

[0581] <Preparation of Water-Soluble Resin Layer>

[0582] The water-soluble resin composition shown in Table 4 was applied to a roll of polyethylene terephthalate film (support, Lumirror16KS40, TORAY INDUSTRIES, INC., thickness: 16 μm, length: 200 m) conveyed at the conveying speed described in Table 4 so that the thickness after drying became 1.0 μm, and the obtained coating was dried to remove the solvent using a hot air convection dryer having a temperature gradient of 50° C. to 70° C. (refer to the heating conditions in Table 4), thereby forming a water-soluble resin layer. In addition, a temporary protective layer shown in Table 4 was pressed onto the water-soluble resin layer using a roller 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 steps was wound to produce a roll A.

[0583] <Preparation of Photosensitive Resin Layer>

[0584] The photosensitive resin composition shown in Table 4 was applied to a roll of polyethylene terephthalate film (temporary support, Lumirror 16KS40, TORAY INDUSTRIES, INC., thickness: 16 μm, length: 200 m) conveyed at the conveying speed described in Table 4 so that the thickness after drying became 3.0 μm, and the obtained coating was dried to remove the solvent using a hot air convection dryer having a temperature gradient of 50° C. to 100° C. (refer to the heating conditions in Table 4), thereby forming a photosensitive resin layer. In addition, a temporary protective layer shown in Table 4 was pressed onto the photosensitive resin layer using a roller 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 steps was wound to produce a roll B.

[0585] <Lamination of Water-Soluble Resin Layer and Photosensitive Resin Layer>

[0586] Next, the laminate was unwound from the roll A and the roll B, respectively, and 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 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 support / water-soluble resin layer / photosensitive resin layer / cover film.

[0587] (Example 20)

[0588] Except that the water-soluble resin composition, photosensitive resin composition and / or various manufacturing conditions were changed as described in Table 4, a laminate (200 m long roll) consisting of a support / water-soluble resin layer / photosensitive resin layer / covering film was prepared by the same method as Example 19.

[0589] [Comparative Example 1]

[0590] A laminate (200 m long roll) consisting of support / water-soluble resin layer / photosensitive resin layer / cover film was prepared by the same procedure as in Example 1, except that the temporary protective layer was not pressed onto the surface of the water-soluble resin layer after the water-soluble resin layer was prepared.

[0591] [Comparative Example 2]

[0592] A laminate (200 m long roll) consisting of support / photosensitive resin layer / cover film was produced by the same procedure as in Example 1 except that the water-soluble resin layer was not provided.

[0593] [Comparative Example 3]

[0594] On a roll of polyethylene terephthalate film (support, Lumirror 16KS40, TORAY INDUSTRIES, INC., thickness: 16 μm, length: 200 m) conveyed at the conveying speed described 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 then the solvent was dried and removed using a hot air convection dryer having a temperature gradient of 50° C. to 70° C. (refer to the heating conditions in Table 4), and the photosensitive resin composition shown in Table 4 was continuously applied in the same coater so as to have a thickness of 3.0 μm after drying without winding up the roll, and then the solvent was dried and removed using a hot air convection dryer having the same temperature gradient as that of the water-soluble resin layer, thereby forming a photosensitive resin layer on the water-soluble resin layer. Furthermore, a rolled 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.

[0595] [Measurement and evaluation]

[0596] The following measurements and evaluations were performed using each of the produced laminated bodies (transfer films) of Examples and Comparative Examples.

[0597] [Measurement of surface depression depth]

[0598] The winding end portion of the laminated body produced in the upper stage was subjected to a high pressure mercury lamp at 200 mJ / cm 2 (i-ray reference) exposure to solidify the photosensitive resin layer. Afterwards, 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, an atomic force microscope (manufactured by Hitachi High-Tech Science Corporation.) was used to measure the depth of depressions on each surface of the water-soluble resin layer and the photosensitive resin layer exposed by peeling off the tape within a range of 100 μm square. However, when measuring the depth of the depression, erroneous causes of irregular shapes such as scratches and dust were excluded, and only the recesses judged to be caused by the temporary protective layer were taken as the measurement objects. The results are shown in Table 4.

[0599] 〔Surface abnormality evaluation〕

[0600] The winding end portion of the laminated body produced in the upper stage was subjected to a high pressure mercury lamp at 200 mJ / cm 2 The photosensitive resin layer was cured by exposure to (i-ray reference). Thereafter, the photosensitive resin layer was slowly peeled off from the water-soluble resin layer using an adhesive tape to expose the interface between the water-soluble resin layer and the photosensitive resin layer. Next, foreign matter / abnormal parts on each surface of the water-soluble resin layer and the photosensitive resin layer exposed by peeling off the adhesive tape were observed within a 100 μm square range using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation).

[0601] Based on the observation results, surface abnormalities were evaluated according to the following criteria. The results are shown in Table 5.

[0602] “A”: No scratches or dust of irregular shapes not judged to be caused by the unevenness of the temporary protective layer were observed in either the water-soluble resin layer or the photosensitive resin layer.

[0603] “B”: In at least one of the water-soluble resin layer and the photosensitive resin layer, scratches or dust of irregular shapes not judged to be caused by the unevenness of the temporary protective layer are observed in a range of more than 0% and less than 30% of the evaluation area.

[0604] “C”: In at least one of the water-soluble resin layer and the photosensitive resin layer, scratches or dust of an irregular shape not judged to be caused by the unevenness of the temporary protective layer were observed in 30% or more of the evaluation area.

[0605] 〔Pattern linearity evaluation〕

[0606] After peeling off the cover film from the winding end portion 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 sputtered with 100 nm thick copper 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.

[0607] Next, after peeling the support from the obtained laminate with a glass substrate, a glass mask having a line and space wiring pattern with a line width of 10 μm was brought into close contact with the surface of the water-soluble resin layer exposed by peeling 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.

[0608] After leaving the film for 1 hour after exposure, a developing solution (28° C., 1.0 mass % potassium carbonate aqueous solution) was sprayed by shower to remove the uncured portion, thereby producing a resin pattern.

[0609] The produced resin pattern was observed in a 500 μm square range using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation), and the pattern width (line width) was measured at any 30 locations within the observation field of view. The standard deviation σ was calculated based on the obtained line width data, and the value obtained by multiplying it by 3 (3σ) was defined as LWR (Line Width Roughness) as an indicator of pattern linearity, and the evaluation was implemented according to the following evaluation criteria. In addition, the smaller the LWR value, the more preferred, more preferably B evaluation or above, and particularly preferably A evaluation. The results are shown in Table 5.

[0610] "A": LWR ≤ 0.6

[0611] "B": 0.6 <LWR≤2.0

[0612] "C": 2.0 <LWR

[0613] "D": A large-scale defect abnormality occurred in the patterned wiring, and linearity evaluation could not be performed.

[0614] 〔Sensitivity evaluation〕

[0615] Samples were taken from two locations, namely, the beginning and end of the winding of the laminate (200 m long roll) produced in the upper section, and after peeling off the covering films respectively, the exposed surface of the laminate after peeling off the covering film was bonded to a glass substrate sputtered with 100 nm thick copper under lamination conditions of a roller temperature of 100°C, a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min.

[0616] Next, after the support was peeled off from each of the obtained samples, 300 mJ / cm 2 Next, a developer (28° C., 1.0 mass % potassium carbonate aqueous solution) was sprayed on the exposed sample by shower to remove the uncured portion, thereby determining the minimum exposure amount at which the resin film remained.

[0617] Evaluation was performed with B being the case where the minimum exposure amount at the start and end of winding changed by 10% or more, and A being the case where the minimum exposure amount at the start and end of winding did not change or changed by less than 10%. The results are shown in Table 5.

[0618] Table 4 and Table 5 are shown below.

[0619]

[0620]

[0621] [Table 6]

[0622]

[0623] As shown in the above table, it can be seen that the laminate (transfer film) produced by the manufacturing method of the laminate of the embodiment is not easy to produce a difference in sensitivity between one end side and the other end side in the long direction, and the generation 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 the transfer body and exposed and developed.

[0624] From the comparison of the examples, it was confirmed that when the water-soluble resin layer substantially contains no filler, a pattern with better linearity can be formed when the photosensitive resin layer is transferred to a transfer object and subjected to exposure and development treatment (especially, refer to the results of Example 18).

[0625] 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 anomalies during exposure caused by the concavity and convexity of the temporary protective layer are not likely to occur, and a pattern with better linearity can be formed (especially, refer to the results of Example 21). On the other hand, it was confirmed that 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 adhesion 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 when peeling off the temporary protective layer is not likely to occur (especially, partial peeling of the water-soluble resin layer caused by reverse printing of the water-soluble resin layer to the temporary protective layer), and a pattern with better linearity can be formed (especially, refer to the results of Example 22). And, for the same reason, it was confirmed that surface anomalies were also further suppressed (especially, refer to the results of Example 22).

[0626] On the other hand, in the method for producing a laminated body of the comparative example, the expected effect was not obtained.

[0627] Explanation of symbols

[0628] 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 method for manufacturing a laminate, comprising: Step Xa, forming a water-soluble resin layer on a support to form a laminate A; Step Xb, forming a temporary protective layer in contact with the water-soluble resin layer to form a laminate B; Step Xc, winding the laminate B to form a wound body C; Step Xd, after unwinding the laminate B from the roll C, peeling the temporary protective layer from between the temporary protective layer and the water-soluble resin layer of the laminate B; Step Xe, forming a laminate D by forming a photosensitive resin layer in contact with the exposed water-soluble resin layer; and In step Xf, a cover film is formed 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.

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 nm to 50 nm.

3. The method for producing a laminate according to claim 1 or 2, wherein: The water-soluble resin layer and the photosensitive resin layer substantially do not contain fillers.

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

5. The method for producing a laminate according to claim 1 or 2, wherein: The photosensitive resin layer includes 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 includes a compound represented by the following formula (B-2), Formula (B-2): In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, A represents C2H4, B represents C3H6, n1 and n3 each independently represent an integer of 1 to 39, and n1+n3 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, and the arrangement of the repeating units of -(A-0)- and -(BO)- is either random or block. When the arrangement is block, either -(A-0)- or -(B-0)- is a biphenyl side.

7. The method for producing a laminate according to claim 5, wherein: The polymerizable compound includes a compound represented by the following formula (B-3), Formula (B-3): 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. The method for producing a laminate according to claim 5, wherein: The photopolymerization initiator is one or more selected from acridine-based photopolymerization initiators, benzophenone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, biimidazole-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.

9. The method for producing a laminate according to claim 1 or 2, wherein: The photosensitive resin layer includes a polymer D, wherein the polymer D includes at least one repeating unit α selected from the repeating unit represented by the following formula (A-1) and the repeating unit represented by the following formula (A-2) and a repeating unit β represented by the following formula (B). 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, and l represents an integer of 5 to 100. 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, 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, and 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 the surface on the photosensitive resin layer side.

11. A method for manufacturing a laminate, comprising: Step Ya, forming a water-soluble resin layer on a support to form a laminate A; Step Yb, forming a temporary protective layer in contact with the water-soluble resin layer to form a laminated body B; Step Yc, winding the laminate B to form a roll C; and In step Yd, the laminate B is unwound from the winding body C, the temporary protective layer is peeled off from between the temporary protective layer and the water-soluble resin layer of the laminate B, and the photosensitive resin layer of the transfer film including a temporary support body and a photosensitive resin layer is adhered to the exposed surface of the laminate B, thereby obtaining a laminate F including the support body, the water-soluble resin layer, the photosensitive resin layer and the temporary support body.

12. The method for manufacturing a laminate according to claim 11, further comprising: In step Ye, the temporary support is peeled off from between the temporary support and the photosensitive resin layer of the stack F, and the covering film is adhered to the exposed surface of the stack F, thereby forming a stack G having the support, the water-soluble resin layer, the photosensitive resin layer and the covering film in sequence.

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

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 nm 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 nm to 50 nm.

16. The method for producing a laminate according to claim 11, wherein: 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 of the photosensitive resin layer side, and 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 claim 11 or 12, wherein: The water-soluble resin layer and the photosensitive resin layer substantially do not contain fillers.

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

19. The method for producing a laminate according to claim 11 or 12, wherein: The photosensitive resin layer includes 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 includes a compound represented by the following formula (B-2), Formula (B-2): In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, A represents C2H4, B represents C3H6, n1 and n3 each independently represent an integer of 1 to 39, and n1+n3 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, and the arrangement of the repeating units of -(A-0)- and -(BO)- is either random or block. When the arrangement is block, either -(AO)- or -(BO)- is a biphenyl side.

21. The method for producing a laminate according to claim 19, wherein: The polymerizable compound includes a compound represented by the following formula (B-3), Formula (B-3): 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. The method for producing a laminate according to claim 19, wherein: The photopolymerization initiator is one or more selected from acridine-based photopolymerization initiators, benzophenone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, biimidazole-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators.

23. The method for producing a laminate according to claim 11 or 12, wherein: The photosensitive resin layer includes a polymer D, wherein the polymer D includes at least one repeating unit α selected from the repeating unit represented by the following formula (A-1) and the repeating unit represented by the following formula (A-2) and a repeating unit β represented by the following formula (B). 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, and l represents an integer of 5 to 100. 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, 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, and n represents an integer of 1 to 4.

24. A laminate comprising, in 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 the surface on the photosensitive resin layer side.

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