Transfer film, method for manufacturing a laminate, method for manufacturing a circuit wiring, and method for manufacturing an electronic device

Abstract

The first object of the present application is to provide a transfer film capable of forming a resist pattern with excellent resolution. Also, the second object of the present application is to provide a transfer film capable of forming a resin pattern with excellent surface morphology. Furthermore, the third object of the present application is to provide a method for manufacturing a laminate, a method for manufacturing a circuit wiring, and a method for manufacturing an electronic device, each of which uses the above-described transfer film. The transfer film of the present application is a transfer film having a temporary support, a composition layer disposed on the temporary support, the composition layer including a photosensitive resin layer and a water-soluble resin layer, the transfer film being formed by sequentially stacking the temporary support, the water-soluble resin layer, and the photosensitive resin layer, or being formed by sequentially stacking the temporary support, the photosensitive resin layer, and the water-soluble resin layer, the water-soluble resin layer including a compound A having a group represented by the following general formula (1). General formula (1): *-CF2-H; wherein * represents a bonding site.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a transfer film, a laminate, a circuit wiring, and an electronic device. Background Technology

[0002] In recent years, photosensitive transfer materials and other transfer films have been gradually used in many fields.

[0003] Photosensitive transfer materials can help reduce product costs, and therefore have been proposed for use as etching resists and wire protection films.

[0004] On the other hand, the functional requirements for photosensitive transfer materials are becoming increasingly higher, and research is being conducted on structures with multiple functional layers stacked on top of each other.

[0005] For example, Patent Document 1 discloses a transfer film for etching resist and a transfer film for wiring protection film formed by stacking multiple functional layers. Specifically, it discloses a transfer film for etching resist (sections

[0203] to

[0207] , etc.) formed by stacking a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer and a transfer film for wiring protection film (sections

[0197] and

[0208] , etc.) formed by stacking a temporary support / photosensitive resin layer / second transparent resin layer. In addition, the main components of the above-mentioned intermediate layer are polyvinyl alcohol and polyvinylpyrrolidone, and the main components of the above-mentioned second transparent resin layer are metal oxide particles and a copolymer of methacrylic acid / allyl methacrylate. That is, the above-mentioned intermediate layer and the above-mentioned second transparent resin layer contain resins with high water solubility.

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2017 / 057348 Summary of the Invention

[0009] The technical problem to be solved by the invention

[0010] Referring to Patent Document 1, the inventors studied the performance of a transfer film comprising a temporary support, a photosensitive resin layer, and a layer containing a highly water-soluble resin (a water-soluble resin layer), and sequentially stacked the temporary support, the water-soluble resin layer, and the photosensitive resin layer. The results showed that peeling of raised portions and / or residue in recesses occurred (i.e., poor resolution). Furthermore, studies on the performance of a transfer film comprising a temporary support, a photosensitive resin layer, and a water-soluble resin layer, and sequentially stacked the temporary support, the photosensitive resin layer, and the water-soluble resin layer, as a wiring protective film, revealed surface defects caused by optical inhomogeneity in the resin pattern functioning as a protective film (i.e., poor surface morphology).

[0011] Therefore, the first objective of this invention is to provide a transfer film capable of forming resist patterns with excellent resolution.

[0012] Furthermore, the present invention aims to provide a transfer film capable of forming resin patterns with excellent surface morphology as a second objective.

[0013] Furthermore, the present invention provides a third objective: a method for manufacturing a laminate using the aforementioned transfer film, a method for manufacturing circuit wiring, and a method for manufacturing an electronic device.

[0014] means for solving technical problems

[0015] In order to solve the above problems, the inventors conducted in-depth research and discovered that the above problems can be achieved through the following structure.

[0016] A transfer film comprising a temporary support, a composition layer disposed on the temporary support, and the transfer film itself.

[0017] The above-mentioned composition layer comprises a photosensitive resin layer and a water-soluble resin layer.

[0018] The transfer film is formed by sequentially stacking the temporary support, the water-soluble resin layer, and the photosensitive resin layer, or by sequentially stacking the temporary support, the photosensitive resin layer, and the water-soluble resin layer.

[0019] The aforementioned water-soluble resin layer comprises compound A having a group represented by the general formula (1) described below.

[0020] [2] According to the transfer film described in [1], wherein,

[0021] The above compound A is a compound having a group represented by the general formula (2) described below.

[0022] [3] According to the transfer film described in [1] or [2], wherein,

[0023] The above compound A is a compound having a group represented by the general formula (3) described below.

[0024] [4] The transfer film according to any one of [1] to [3], wherein,

[0025] Compound A is a high molecular weight compound with a weight-average molecular weight of 5,000 or more.

[0026] [5] The transfer film according to any one of [1] to [4], wherein,

[0027] Compound A is a polymer compound containing structural units derived from monomers represented by the general formula (4A) described below.

[0028] [6] According to the transfer film described in [5], wherein,

[0029] The aforementioned polymeric compounds further comprise structural units derived from monomers represented by the general formula (5) described below.

[0030] [7] The transfer film according to any one of [1] to [3], wherein,

[0031] The molecular weight of compound A is less than 2,000.

[0032] [8] The transfer film according to any one of [1] to [3] and [7], wherein,

[0033] The compound A described above is represented by the general formula (6A) described later.

[0034] [9] According to the transfer film described in [8], wherein,

[0035] The Z above represents a monovalent organic group containing a poly(oxyolefin) structural site that may have substituents.

[0036]

[10] The transfer film according to any one of [1] to [9], wherein,

[0037] The aforementioned photosensitive resin layer further comprises an alkali-soluble resin and a polymeric compound.

[0038]

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

[10] , wherein,

[0039] The aforementioned water-soluble resin layer further comprises metal oxide particles.

[0040]

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

[11] , wherein,

[0041] The aforementioned water-soluble resin layer contains two or more types of water-soluble resins.

[0042]

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

[12] further has a thermoplastic resin layer.

[0043]

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

[13] is formed by sequentially stacking the temporary support, the water-soluble resin layer and the photosensitive resin layer.

[0044]

[15] The transfer film according to

[14] is formed by sequentially stacking the temporary support, the thermoplastic resin layer, the water-soluble resin layer and the photosensitive resin layer.

[0045]

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

[13] is formed by sequentially stacking the temporary support, the photosensitive resin layer and the water-soluble resin layer.

[0046]

[17] A method for manufacturing a laminate, wherein the laminate uses any one of [1] to

[16] , the method comprising:

[0047] In the bonding process, the substrate is brought into contact with the surface of the outermost layer of the composition layer of the transfer film disposed on the temporary support, and the transfer film and the substrate are bonded together to obtain a substrate with the transfer film.

[0048] The exposure process involves patterning the above-mentioned composite layer.

[0049] The developing process involves developing the exposed composite layer to form a resin pattern; and

[0050] In the peeling process, between the bonding process and the exposure process or between the exposure process and the development process, a temporary support is peeled off from the substrate with the transfer film.

[0051]

[18] A method for manufacturing a circuit wiring, wherein the circuit wiring uses any one of [1] to

[15] transfer film, the method comprising:

[0052] In the bonding process, the surface of the outermost layer of the composition layer of the transfer film disposed on the temporary support is brought into contact with the substrate having a conductive layer, and the transfer film and the substrate having the conductive layer are bonded together to obtain a substrate with a transfer film.

[0053] The exposure process involves patterning the above-mentioned composite layer.

[0054] The developing process involves developing the exposed composite layer to form a resin pattern; and

[0055] The etching process involves etching the conductive layer in areas where the resin pattern is not present; and

[0056] In the peeling process, between the bonding process and the exposure process or between the exposure process and the development process, a temporary support is peeled off from the substrate of the transfer film.

[0057]

[19] A method for manufacturing an electronic device, comprising the method for manufacturing the laminate described in

[17] , wherein,

[0058] The aforementioned electronic device includes the aforementioned resin pattern as a cured film.

[0059] Invention Effects

[0060] According to the present invention, a transfer film capable of forming resist patterns with excellent resolution can be provided.

[0061] Furthermore, according to the present invention, a transfer film with a resin pattern having excellent surface morphology can be provided.

[0062] Furthermore, it is possible to provide a method for manufacturing a laminate using the aforementioned transfer film, a method for manufacturing circuit wiring, and a method for manufacturing an electronic device. Attached Figure Description

[0063] Figure 1 This is a schematic diagram illustrating an example of the structure of the transfer film according to the first embodiment.

[0064] Figure 2 This is a schematic diagram illustrating an example of the structure of the transfer film in the second embodiment. Detailed Implementation

[0065] The present invention will now be described in detail.

[0066] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0067] In addition, in this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0068] Furthermore, in this specification, there are no particular restrictions on the bonding direction of the marked divalent groups (e.g., -CO-O-).

[0069] In this specification, (meth)acrylate means acrylate and methacrylate. (meth)acrylic acid means acrylic acid and methacrylic acid. (meth)acryloyl means methacryloyl or acryloyl.

[0070] Regarding the designation of groups (atomic groups) in this specification, the designations that do not specify substitution and unsubstituent include groups without substituents, and also include groups with substituents. For example, "alkyl" includes not only unsubstituent alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). Furthermore, "organic group" in this specification refers to a group containing at least one carbon atom.

[0071] Furthermore, in this specification, there are no particular limitations on the type, position, or number of substituents when the phrase "may have substituents" is used. The number of substituents can be, for example, one, two, three, or more. Also, they can be unsubstituted.

[0072] Examples of substituents include monovalent nonmetallic groups with hydrogen atoms removed, which can be selected from the following substituent group T.

[0073] (Substituent T)

[0074] Examples of substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methyloxazolyl; alkylthio groups such as methylthio and tert-butylthio; arylthio groups such as phenylthio and p-tolylthio; alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; formyl; sulfonyl; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonylamino; silyl; amino; monoalkylamino; dialkylamino; arylamino; and combinations thereof.

[0075] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​calculated from polystyrene by gel permeation chromatography (GPC).

[0076] Regarding GPC, measurements are performed under the following conditions.

[0077] [Eluent] Tetrahydrofuran (THF)

[0078] [Device Name] EcoSEC HLC-8320GPC (Manufactured by Tosoh Corporation)

[0079] [Tube Columns] TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by TOSOHCORPORATION)

[0080] [Column Temperature] 40℃

[0081] [Flow rate] 0.35 ml / min

[0082] Unless otherwise specified, the molecular weights of the compounds in this specification are weight-average molecular weights (Mw).

[0083] Unless otherwise specified, the room temperature in this instruction manual is 25°C.

[0084] In this specification, "alkali-soluble" means that the solubility of sodium carbonate in 100g of a 1% by mass aqueous solution is 0.1g or more at 22°C. Therefore, for example, an alkali-soluble resin refers to a resin that meets the above solubility condition.

[0085] In this specification, "water-soluble" means having a solubility of 0.1g or more in 100g of water at pH 7.0 and a liquid temperature of 22°C. Therefore, for example, a water-soluble resin refers to a resin that meets the above solubility condition.

[0086] In this specification, "solid component" refers to the component that forms the composition layer formed using the composition. In the case where the composition contains a solvent (organic solvent, water, etc.), it refers to all components except for those containing the solvent. Furthermore, if it is a component that forms the composition layer, liquid components are also considered solid components.

[0087] In this specification, the thickness of each layer in the transfer film, etc., is measured as follows: a cross-section perpendicular to the main surface of the layer (film) is observed using a scanning electron microscope (SEM), and the thickness of each layer is measured at more than 10 points based on the obtained observation image, and the average value is calculated.

[0088] The transfer film of the present invention is a composition layer having a temporary support and disposed on the temporary support.

[0089] The above-mentioned composition layer comprises a photosensitive resin layer and a water-soluble resin layer.

[0090] The transfer film is formed by sequentially stacking the temporary support, the water-soluble resin layer, and the photosensitive resin layer, or by sequentially stacking the temporary support, the photosensitive resin layer, and the water-soluble resin layer.

[0091] Furthermore, the aforementioned water-soluble resin layer contains compound A (hereinafter referred to as "compound A") having a group represented by the following general formula (1).

[0092] General formula (1): *-CF2-H

[0093] In the formula, * represents the bonding position.

[0094] That is, the transfer film of the present invention is a composite layer having a temporary support and disposed on the support.

[0095] The above-mentioned composition layer comprises a photosensitive resin layer and a water-soluble resin layer.

[0096] The transfer film is formed by sequentially stacking the temporary support, the water-soluble resin layer, and the photosensitive resin layer, wherein the water-soluble resin layer has a structure containing compound A (hereinafter also referred to as "the transfer film of the first embodiment").

[0097] or

[0098] The transfer film has a temporary support and a composition layer disposed on the temporary support.

[0099] The above-mentioned composition layer comprises a photosensitive resin layer and a water-soluble resin layer.

[0100] The transfer film is formed by sequentially stacking the temporary support, the photosensitive resin layer, and the water-soluble resin layer, and the water-soluble resin layer has a structure containing compound A (hereinafter also referred to as "the transfer film of the second embodiment").

[0101] The transfer film according to the first embodiment can form a resist pattern with excellent resolution, and the transfer film according to the second embodiment can form a resin pattern with excellent surface morphology.

[0102] Although the mechanism by which this structure solves the problem of the present invention is not yet clear, the inventors speculate as follows.

[0103] The inventors believe that in a transfer film having a temporary support, a photosensitive resin layer, and a water-soluble resin layer containing compound A, compound A functions to suppress uneven film thickness of the water-soluble resin layer. As a result, when forming a resist pattern using the transfer film of the first embodiment, peeling of protrusions and / or residue of pattern recesses that may occur due to uneven film thickness can be suppressed. That is, according to the transfer film of the first embodiment, a resist pattern with excellent resolution can be formed. Furthermore, when forming a resin pattern using the transfer film of the second embodiment, optical non-uniformity (surface defects) that may occur due to uneven film thickness can be suppressed. That is, according to the transfer film of the second embodiment, a film with excellent surface morphology (e.g., a cured film such as a wiring protection film) can be formed.

[0104] In addition, the following will sometimes refer to the ability to form resist patterns with better resolution and / or resin patterns with better surface morphology as "the effect of the present invention is better".

[0105] Furthermore, the effects of the present invention are even more superior when compound A is a low molecular weight compound A represented by general formula (6B) described later, with a molecular weight of 2,000 or less, or a high molecular weight compound A with a weight-average molecular weight of more than 2,000 and less than 15,000, and containing structural units represented by general formula (4) and general formula (5) described later.

[0106] The aforementioned photosensitive resin layer can be a negative photosensitive resin layer or a chemically amplified photosensitive resin layer, preferably a negative photosensitive resin layer.

[0107] Furthermore, the aforementioned composition layer may include layers other than the photosensitive resin layer and the water-soluble resin layer. Examples of such other layers include, for instance, a thermoplastic resin layer.

[0108] Hereinafter, an example of an embodiment of the transfer film of the present invention is shown, but it is not limited thereto. In addition, (1) and (3) below correspond to an example of the transfer film of the first embodiment, and (2) below corresponds to an example of the transfer film of the second embodiment.

[0109] (1) "Temporary support / thermoplastic resin layer / intermediate layer (water-soluble resin layer) / negative photosensitive resin layer / covering film"

[0110] (2) "Temporary support / negative photosensitive resin layer / refractive index adjustment layer (water-soluble resin layer) / covering film"

[0111] (3) "Temporary support / thermoplastic resin layer / intermediate layer (water-soluble resin layer) / negative photosensitive resin layer / covering film"

[0112] Furthermore, in the above structures, the negative photosensitive resin layer is preferably a colored resin layer.

[0113] The transfer film of the first embodiment and the transfer film of the second embodiment described below will be explained below.

[0114] [Transfer film of the first embodiment]

[0115] Hereinafter, an example of an embodiment of the transfer film of the first embodiment will be described.

[0116] Figure 1 The transfer film 10 shown in the figure has, in sequence, a temporary support 1, a thermoplastic resin layer 3, a water-soluble resin layer 5, a photosensitive resin layer 7, and a cover film 9.

[0117] In addition, although Figure 1 The transfer film 10 shown is configured with a cover film 9, but the cover film 9 may not be configured.

[0118] and, Figure 1 The transfer film 10 shown is configured with a thermoplastic resin layer 3, but it is also possible to omit the thermoplastic resin layer 3.

[0119] The following is an explanation of the various elements that make up the transfer film.

[0120] Temporary support

[0121] The transfer film of the first embodiment has a temporary support.

[0122] The temporary support is a support on which multiple composition layers (as composition layers, for example, equivalent to a photosensitive resin layer, a water-soluble resin layer, and a thermoplastic resin layer, etc.) are disposed, and which can be peeled off from these composition layers.

[0123] From the viewpoint that exposure via a temporary support can be performed when patterning the above-described composition layer, it is preferable that the temporary support is light-transmitting. Furthermore, in this specification, "light-transmitting" means that the transmittance of light of the wavelength used in patterning exposure is 50% or more.

[0124] Regarding the temporary support, from the viewpoint of improving exposure sensitivity, the transmittance of light at the wavelength (more preferably 365 nm) used in pattern exposure is preferably 60% or more, and more preferably 70% or more.

[0125] In addition, the transmittance of the transfer film is the ratio of the intensity of the incident light to the intensity of the outgoing light that passes through the layer when light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and it is measured using an MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0126] Materials that constitute a temporary support include, for example, glass substrates, resin films and paper, with resin films being preferred from the viewpoints of strength, flexibility and light transmittance.

[0127] Examples of resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, PET films are preferred, and biaxially stretched PET films are more preferred.

[0128] There are no particular restrictions on the thickness (layer thickness) of the temporary support. From the perspective of the strength of the support, the flexibility required for bonding with the substrate for circuit wiring, and the light transmittance required for the first exposure process, it can be selected according to the material.

[0129] The thickness of the temporary support is preferably 5 to 100 μm, and more preferably 10 to 50 μm from the viewpoint of ease of operation and versatility, even more preferably 10 to 20 μm, and particularly preferably 10 to 16 μm.

[0130] Furthermore, it is preferable that the film used as a temporary support is free from deformations such as wrinkles, scratches, and defects.

[0131] From the viewpoint of pattern formation and transparency of the temporary support during pattern exposure, the number of particles, foreign matter, defects, and precipitates contained in the temporary support is preferably low. The number of particles, foreign matter, and defects with a diameter of 1 μm or more is preferably 50 per 10 mm. 2 The following is more preferably 10 per 10mm 2 The following is a further preferred option: 3 per 10mm 2 The following is particularly preferred: 0 per 10mm 2 .

[0132] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-085643, paragraphs 0019 to 0026 of Japanese Patent Application Publication No. 2016-027363, paragraphs 0041 to 0057 of Japanese Patent Application Publication No. WO2012 / 081680A1, paragraphs 0029 to 0040 of Japanese Patent Application Publication No. WO2018 / 179370A1, and paragraphs 0012 to 0032 of Japanese Patent Application Publication No. 2019-101405, the contents of which are incorporated herein by reference.

[0133] Covering film

[0134] The transfer film preferably has a cover film that contacts the outermost surface of the composition layer furthest from the temporary support among a plurality of composition layers disposed on the temporary support.

[0135] Materials constituting the covering film include resin film and paper, with resin film being preferred from the viewpoint of strength and flexibility.

[0136] Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, polyethylene films, polypropylene films, or polyethylene terephthalate films are preferred.

[0137] There is no particular limitation on the thickness (layer thickness) of the cover film, but it is preferably 5 to 100 μm, more preferably 10 to 50 μm.

[0138] Furthermore, from the viewpoint of superior resolution, the arithmetic mean roughness Ra value of the surface of the cover film in contact with the composition layer (hereinafter also simply referred to as the "cover film surface") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less. This is believed to be because the uniformity of the resin pattern layer thickness formed when the Ra value of the cover film surface is within the above-mentioned range is improved.

[0139] There is no particular limitation on the lower limit of the Ra value of the coating film surface, but it is preferably above 0.001 μm.

[0140] The Ra value of the covering membrane surface can be measured using the following methods.

[0141] The surface profile of the optical thin film is obtained by measuring the surface of the cover film under the following conditions using a three-dimensional optical profilometer (New View7300, manufactured by Zygo Corporation).

[0142] The measurement and analysis software used was the Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen was displayed using the aforementioned analysis software, and histogram data was obtained from the Surface Map screen. The arithmetic mean roughness was calculated based on the obtained histogram data to obtain the Ra value of the cover film surface.

[0143] When the cover film and the transfer film are bonded together, simply peel the cover film off the transfer film and measure the Ra value of the surface of the peeled side.

[0144] Water-soluble resin layer

[0145] In the transfer film 10, the water-soluble resin layer 5 is present between the thermoplastic resin layer 3 and the photosensitive resin layer 7, thereby suppressing the mixing of components that may occur during the coating formation of the thermoplastic resin layer 3 and the photosensitive resin layer 7, and during storage after coating formation. That is, as an embodiment of the transfer film of the first embodiment, the water-soluble resin layer can function as an intermediate layer for suppressing interlayer mixing between layers disposed on one side and layers disposed on the other side of the water-soluble resin layer.

[0146] The water-soluble resin layer 5 comprises compound A and resin. Regarding the aforementioned resin, it may comprise, in part or in whole, a water-soluble resin. As defined above, "water-soluble resin" refers to a resin with a solubility of 0.1g or more in 100g of water at a liquid temperature of 22°C and pH 7.0.

[0147] The following describes the components that a water-soluble resin layer can contain.

[0148] <Compound A>

[0149] The water-soluble resin layer contains compound A.

[0150] Compound A is a compound having a group represented by the following general formula (1).

[0151] General formula (1): *-CF2-H

[0152] In the formula, * represents the bonding position.

[0153] Compound A can be either a high molecular weight compound or a low molecular weight compound. Furthermore, when compound A is a high molecular weight compound, it is sometimes referred to as "high molecular weight compound A." Similarly, when compound A is a low molecular weight compound, it is sometimes referred to as "low molecular weight compound A."

[0154] The lower limit for the weight-average molecular weight of polymer compound A is preferably 1,000 or more, more preferably 1,500 or more, more preferably more than 2,000, and particularly preferably 5,000 or more. Furthermore, the upper limit is preferably 100,000 or less, more preferably 80,000 or less, further preferably 60,000 or less, even more preferably 40,000 or less, particularly preferably 20,000 or less, and most preferably 15,000 or less.

[0155] The number average molecular weight (Mn) of polymer compound A is preferably 500 to 40,000, more preferably 600 to 20,000, and even more preferably 600 to 10,000.

[0156] The dispersion (Mw / Mn) of polymer compound A is preferably 1.00 to 12.00, more preferably 1.00 to 11.00, and even more preferably 1.00 to 10.00.

[0157] The polymer compound A preferably contains structural units having groups represented by the general formula (1).

[0158] The molecular weight of low molecular weight compound A is preferably 100 or more, more preferably 500 or more. The upper limit of the molecular weight of low molecular weight compound A is preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less.

[0159] The number of groups represented by general formula (1) in low molecular weight compound A is not particularly limited as long as there is one or more, but is preferably one to three.

[0160] Specific implementation methods for polymer compound A and low molecular weight compound A will be described in the following section.

[0161] Furthermore, from the viewpoint of achieving better results in this invention, compound A is preferably a compound having a group represented by the general formula (2) described below (hereinafter also referred to as "compound Aa"), and more preferably a compound having a group represented by the general formula (3) described below (hereinafter also referred to as "compound Ab").

[0162] Furthermore, compound Aa is equivalent to a compound that further defines the linkage of the groups represented by general formula (1) in compound A. That is, the -CF2-H at the terminal of the group represented by general formula (2) in compound Aa is equivalent to the group represented by general formula (1) above. And, compound Ab refers to a compound that further defines the linkage of the groups represented by general formula (1) in compound A and the linkage of the groups represented by general formula (2) in compound Aa. That is, the -CF2-H at the terminal of the group represented by general formula (3) in compound Ab is equivalent to the group represented by general formula (1) above, and the -CF2-CF2-H at the terminal of the group represented by general formula (3) in compound Ab is equivalent to the group represented by general formula (2) above.

[0163] General formula (2): *-CF2-CF2-H

[0164] In the formula, * represents the bonding position.

[0165] General formula (3): *-(CH2) m -(CF2-CF2) n -H

[0166] In the formula, m and n independently represent integers from 1 to 6.

[0167] The value of m is preferably 1 to 4, and more preferably 1 or 2.

[0168] The value of n is preferably 1 to 4, and more preferably 2 or 3.

[0169] * indicates the bonding location.

[0170] The following sections will describe both high molecular weight compound A and low molecular weight compound A.

[0171] (Polymer compound A)

[0172] As described above, this is an embodiment where polymer A is a polymer. The preferred embodiments regarding the weight-average molecular weight and dispersity of polymer A are as described above.

[0173] The polymer A preferably comprises a structural unit having a group represented by any one of the general formulas (1) to (3) described above, more preferably a structural unit comprising a monomer derived from the general formula (4) described below, and even more preferably a structural unit comprising a monomer derived from the general formula (4A) described below. Furthermore, the structural unit of the monomer derived from the general formula (4) described below is equivalent to a structural unit having a group represented by the general formula (1) or (2) described above, and the structural unit of the monomer derived from the general formula (4A) described below is equivalent to a structural unit having a group represented by the general formula (3) described above.

[0174] [Chemical Formula 1]

[0175]

[0176] In general formula (4), R 1 Represents a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom, or -N(R) 2 )-, R 2 Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. L 1 Represents a divalent linker group. R T This refers to the group represented by the above general formula (1) or (2).

[0177] As a result of R 2 The alkyl group represented by the carbon atoms (1 to 4) can be any of the following: straight-chain, branched, or cyclic.

[0178] As R 1 Preferably, it contains hydrogen atoms.

[0179] As R 2 Preferably, it is an alkyl group having 1 to 2 carbon atoms or hydrogen atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

[0180] As X, oxygen atom is preferred.

[0181] As a result of L 1 There are no particular limitations on the divalent linking groups represented; for example, -O-, -CO-, -S-, -SO2-, and -NR can be cited. X -(R X (Hydrogen atoms or substituents), alkylene, alkenylene, ynylene, aromatic cyclic, alicyclic, and groups formed by combining these. As a group composed of the above R... X There are no particular limitations on the substituents represented. For example, substituents exemplified in substituent group T can be cited, preferably alkyl groups having 1 or 2 carbon atoms.

[0182] The aforementioned alkylene, alkenylene, ynylene, aromatic cyclic, and alicyclic groups may further have substituents. There are no particular limitations on the substituents; for example, substituents exemplified in substituent group T can be cited. Preferably, a halogen atom is used as a substituent, and more preferably a fluorine atom.

[0183] The aforementioned alkylene group, alkenyl group, and ynylene group can be either linear or branched.

[0184] Furthermore, the number of carbon atoms in the aforementioned alkylene group is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 11, and particularly preferably 1 to 10.

[0185] Furthermore, the number of carbon atoms in the aforementioned alkenyl group and alkyne group is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 11, and particularly preferably 2 to 10.

[0186] The aforementioned aromatic cyclic group can be any of the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group.

[0187] The aromatic ring constituting the above-mentioned aromatic ring group can be a monocyclic or polycyclic ring. Furthermore, the number of ring members in the aromatic ring constituting the above-mentioned aromatic ring group is not particularly limited, for example, it is 5 to 15. Furthermore, the number of heteroatoms contained in the above-mentioned aromatic heterocyclic group is not particularly limited, for example, it is preferably 1 to 3. The type of heteroatom is not particularly limited, for example, nitrogen atoms, oxygen atoms, and sulfur atoms can be included.

[0188] Examples of aromatic rings constituting the aforementioned aromatic ring groups include, for example, aromatic hydrocarbon rings such as benzene rings, naphthalene rings, anthracene rings, and benzyline rings; and aromatic heterocycles such as furan rings, pyrrole rings, thiophene rings, pyridine rings, thiazole rings, and benzothiazole rings.

[0189] The aforementioned alicyclic group can be any of the aliphatic hydrocarbon cyclic group and the aliphatic heterocyclic group.

[0190] The alicyclic group comprising the above-mentioned alicyclic group can be a monocyclic or polycyclic ring. Furthermore, the number of ring members in the alicyclic group is not particularly limited, for example, it can be 5 to 15. Also, the number of heteroatoms contained in the above-mentioned aliphatic heterocyclic group is not particularly limited, for example, it is preferably 1 to 3. The type of heteroatom is not particularly limited, for example, nitrogen atoms, oxygen atoms, and sulfur atoms can be included.

[0191] Examples of alicyclic rings constituting the aforementioned alicyclic groups include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cyclooctane rings, cyclodecane rings, adamantane rings, norcamphene rings, and exo-tetrahydrodicyclopentadiene rings, as well as cycloalkanes and cyclohexene rings.

[0192] As a result of L 1The divalent linking group is represented, wherein preferably it can be * A -Fluorine-substituted alkylene-* B It can be * A -Fluorine-substituted alkenyl-* B Or can be * A -Fluorine-substituted ynyne group-* B More preferably, it can be * A -Fluorine-substituted alkylene-* B .in addition,* A Indicates the connection position with X in general formula (4), * B R in general formula (4) T The link location.

[0193] [Chemical Formula 2]

[0194]

[0195] In general formula (4A), R 1 and X respectively with R in general formula (4) 1 The meaning of X is the same as that of the two, and the preferred implementation methods are also the same.

[0196] m and n each independently represent an integer from 1 to 6. m is preferably 1 to 4, more preferably 1 or 2. n is preferably 1 to 4, more preferably 2 or 3.

[0197] In polymer compound A, the lower limit for the content of structural units having a group represented by any one of the above general formulas (1) to (3) is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total mass of polymer compound A. Furthermore, the upper limit is preferably 100% by mass or less, more preferably 90% by mass, and even more preferably 80% by mass.

[0198] As a structural unit having a group represented by any one of the general formulas (1) to (3), one type can be used alone or more than two types can be used.

[0199] Structural units having a group represented by any one of the general formulas (1) to (3) can be synthesized by known methods.

[0200] Polymer compound A may have structural units other than structural units having a group represented by any one of the general formulas (1) to (3) (hereinafter also referred to as "other structural units").

[0201] There are no particular limitations on other structural units, but from the viewpoint of better performance of the present invention, it is preferable to include structural units having a poly(olefinic) structure.

[0202] As a poly(oxyolefin) structure, the structure represented by the following general formula (PAL) is preferred.

[0203] [Chemical Formula 3]

[0204]

[0205] In the general formula (PAL), nAL represents an integer of 2 or more, more preferably 2 to 100, further preferably 4 to 20, particularly preferably 4 to 15, and most preferably 4 to 12.

[0206] AL represents alkylene. The alkylene can be linear or branched. The number of carbon atoms in the alkylene represented by AL is preferably 1 to 10, more preferably 1 to 6, even more preferably 2 to 4, and particularly preferably 2 or 3.

[0207] There exist nAL values ​​that can be identical or distinct.

[0208] Furthermore, the alkylene group represented by AL can have substituents. There are no particular limitations on the substituents; for example, substituents exemplified in substituent group T can be cited.

[0209] As AL, it is preferably -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2- or -CH(CH2CH3)CH2-, more preferably -CH(CH3)CH2- or -CH2CH2CH2-.

[0210] * indicates the bonding location.

[0211] As a structural unit having a poly(olefinic) structure, it is preferable to have a poly(olefinic) structure in the side chain, and more preferably a structural unit derived from a monomer represented by the general formula (5) described below.

[0212] [Chemical Formula 4]

[0213]

[0214] In the formula, R 3 Y represents a hydrogen atom or a methyl group, and Y represents an oxygen atom, a sulfur atom, or -N(R) 5 )-, AL indicates an alkylene group that can have substituents, nAL indicates an integer greater than 2, R 4 R represents a hydrogen atom or substituent. 5 It represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0215] In general formula (5), AL and nAL have the same meaning as AL and nAL in general formula (PAL), and the preferred implementation is also the same.

[0216] As a result of R 4 There are no particular limitations on the substituents represented, and examples of substituents in substituent group T can be cited, preferably alkyl groups having 1 to 6 carbon atoms.

[0217] As a result of R 5 The alkyl group represented by the carbon atoms (1 to 4) can be any of the following: straight-chain, branched, or cyclic.

[0218] As R 3 and R 4 Preferably, it contains hydrogen atoms.

[0219] As R 5 Preferably, it is an alkyl group having 1 to 2 carbon atoms or hydrogen atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

[0220] As for Y, oxygen atoms are preferred.

[0221] When polymeric compound A contains structural units having a poly(olefinic) structure, its content relative to the total mass of polymeric compound A is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 50% by mass or more. Furthermore, as an upper limit, it is preferably 95% by mass or less, more preferably 90% by mass or less.

[0222] The structural unit with the poly(oxyolefin) structure can be used alone or in more than two types.

[0223] Other structural units that may be included in polymer compound A, in addition to the structural units mentioned above, are preferably structural units derived from (meth)acrylates and structural units derived from (meth)acrylic acid.

[0224] Examples of the aforementioned (meth)acrylates include, for example, alkyl (meth)acrylates with alkyl groups having 1 to 18 carbon atoms. Specifically, examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearate (meth)acrylate.

[0225] When polymeric compound A contains structural units selected from those derived from (meth)acrylates and those derived from (meth)acrylic acid, its content relative to the total mass of polymeric compound A is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. Furthermore, as an upper limit, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0226] When polymer compound A is a copolymer, polymer compound A preferably has a block structure, graft structure, branch structure and / or star structure.

[0227] The various monomers that make up polymer compound A, as well as polymer compound A itself, can be manufactured using known methods.

[0228] (Low molecular weight compound A)

[0229] As described above, this is an embodiment where compound A is a low molecular weight compound. The preferred embodiment regarding the molecular weight of low molecular weight compound A is as described above.

[0230] As the low molecular weight compound A, it is preferably a compound having a group represented by any one of the general formulas (1) to (3) described above, more preferably a compound represented by (6) described later, even more preferably a compound represented by (6A) described later, and particularly preferably a compound represented by (6B) described later. In addition, the compound represented by (6) described later is equivalent to a compound having a group represented by the general formula (1) or (2) described above, and the compound represented by (6A) or (6B) described later is equivalent to a compound having a group represented by the general formula (3) described above.

[0231] [Chemical Formula 5]

[0232] ZL 2 -R T (6)

[0233] In general formula (6), Z represents a monovalent organic group. 2 Represents a single bond or a divalent linker group. R T This refers to the group represented by the above general formula (1) or (2).

[0234] There are no particular limitations on the 1-valent organic group represented by Z; for example, it can contain heteroatoms (in addition, heteroatoms can include, for example, -O-, -CO-, -S-, -SO2-, and -NR). X -(R X (which may be hydrogen atoms or substituents), alkyl, alkenyl, and ynyl groups. As a group composed of the above R... X There are no particular restrictions on the substituents represented; for example, substituents exemplified in substituent group T can be cited.

[0235] The aforementioned alkyl, alkenyl, and alkynyl groups may further have substituents. There are no particular limitations on the substituents; for example, substituents exemplified in substituent group T can be cited.

[0236] The alkyl, alkenyl, and alkynyl groups mentioned above can be any of the straight-chain, branched, and cyclic forms.

[0237] Furthermore, there is no particular limitation on the number of carbon atoms in the alkyl group, for example, it is 1 to 40, preferably 1 to 30, and more preferably 1 to 20.

[0238] Furthermore, there is no particular limitation on the number of carbon atoms in the alkenyl and alkynyl groups described above, for example, 2 to 40, preferably 2 to 30, and more preferably 2 to 20.

[0239] Z is preferably a monovalent organic group having a poly(olefin oxide) structure. The poly(olefin oxide) structure is preferably represented by the above general formula (PAL).

[0240] In addition, Z is the same as L in general formula (6). 2 The atom at the linking position is preferably a carbon atom.

[0241] As a result of L 2 The divalent linking group can be represented, for example, by the L group in the above general formula (4). 1 The divalent linker is the same as the divalent linker.

[0242] As a result of L 2 The divalent linking group is represented, wherein preferably it can be * A -L 21 -Fluorine-substituted alkylene-* B It can be * A -L 21 -Fluorine-substituted alkenyl-* B Or can be * A -L 21 -Fluorine-substituted ynyne group-* B More preferably, it can be * A -L 21 -Fluorine-substituted alkylene-* B .

[0243] L 21 This represents -O-, -CO-, -S-, -SO2-, and -NR. X -(R X (A group consisting of hydrogen atoms or substituents) or combinations thereof. As a group composed of the above R... X The substituents indicated are not particularly limited; for example, substituents exemplified in substituent group T can be cited, preferably alkyl groups having 1 or 2 carbon atoms. As L 21 Preferably, -O-, -S-, or -NR X -, more preferably -O-.

[0244] * A Indicates the connection position with Z in general formula (6), * B R in general formula (6)T The link location.

[0245] [Chemical Formula 6]

[0246]

[0247] In the formula, Z represents a monovalent organic group, and L... 3 Represents oxygen atom, sulfur atom, or -N(R) 6 )-, m and n independently represent integers from 1 to 6, R 6 It represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0248] As the monovalent organic group represented by Z in general formula (6A), examples can be made of the same monovalent organic group as the monovalent organic group represented by Z in general formula (6), and the preferred embodiments are also the same.

[0249] As a result of R 6 The alkyl group represented by the carbon atoms (1 to 4) can be any of the following: straight-chain, branched, or cyclic.

[0250] As L 3 The preferred atom is oxygen.

[0251] The value of m is preferably 1 to 4, and more preferably 1 or 2.

[0252] The value of n is preferably 1 to 4, and more preferably 2 or 3.

[0253] [Chemical Formula 7]

[0254]

[0255] In general formula (6B), AL and nAL have the same meaning as in general formula (PAL), and the preferred implementation is also the same.

[0256] L in general formula (6B) 3 Each of , m, and n corresponds to L in general formula (6A) 3 The meanings of m and n are the same, and the preferred implementation methods are also the same.

[0257] In general formula (6B), R 7 It represents a hydrogen atom or a substituent.

[0258] As a result of R 7 There are no particular limitations on the substituents represented, and examples of substituents in substituent group T can be cited, preferably alkyl groups having 1 to 6 carbon atoms.

[0259] As R 7 Preferably, it contains hydrogen atoms.

[0260] Low molecular weight compound A can be manufactured using known methods.

[0261] The following examples illustrate specific instances of compound A, but compound A in this invention is not limited thereto.

[0262] [Chemical Formula 8]

[0263]

[0264] [Chemical Formula 9]

[0265]

[0266] [Chemical Formula 10]

[0267]

[0268] [Chemical Formula 11]

[0269]

[0270] When compound A includes polymer compound A, polymer compound A can be used alone or in combination with two or more other polymer compounds.

[0271] When compound A contains low molecular weight compound A, one low molecular weight compound A may be used alone, or two or more low molecular weight compounds may be used.

[0272] The water-soluble resin layer, as compound A, can be any one of the following: using only high molecular weight compound A, using only low molecular weight compound A, or using both high molecular weight compound A and low molecular weight compound A.

[0273] The content of compound A (in the case of multiple compounds, its total content) relative to the total mass of the water-soluble resin layer is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, and even more preferably 0.02 to 1% by mass.

[0274] <Resin>

[0275] The water-soluble resin layer contains resin.

[0276] As described above, the resins mentioned above may include water-soluble resins as part or all of them.

[0277] Examples of resins that can be used as water-soluble resins include, for example, polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

[0278] Furthermore, copolymers of (meth)acrylic acid / vinyl ester compounds can also be used as water-soluble resins. Among the copolymers of (meth)acrylic acid / vinyl ester compounds, copolymers of (meth)acrylic acid / (meth)acrylate are preferred, and copolymers of methacrylic acid / methacrylate are more preferred.

[0279] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the component ratio (mol%) is preferably 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0280] The lower limit for the weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Furthermore, the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0281] The dispersion (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

[0282] Furthermore, from the viewpoint of further improving the suppression performance of interlayer mixing in the water-soluble resin layer, the resin in the water-soluble resin layer is preferably a different resin from the resin contained in the layer disposed on one side and the resin contained in the layer disposed on the other side of the water-soluble resin layer. For example, if the photosensitive resin layer 7 contains polymer A (described later) and the thermoplastic resin layer 3 contains thermoplastic resin (alkali-soluble resin) (described later), the resin in the water-soluble resin layer 5 is preferably a different resin from polymer A and thermoplastic resin (alkali-soluble resin).

[0283] From the viewpoint of further improving oxygen barrier properties and inhibiting interlayer mixing, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0284] Water-soluble resins can be used alone or in combination with two or more.

[0285] The content of water-soluble resin is not particularly limited. However, from the viewpoint of further improving oxygen barrier properties and inhibiting interlayer mixing, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the water-soluble resin layer. Furthermore, there is no particular limitation on its upper limit; for example, it is preferably 99.9% by mass or less, and even more preferably 99.8% by mass or less.

[0286] There is no particular limitation on the thickness of the water-soluble resin layer, but it is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. If the thickness of the water-soluble resin layer is within the above range, the oxygen barrier properties are not reduced and the interlayer mixing suppression performance is excellent. Furthermore, it is also possible to further suppress the increase in the removal time of the water-soluble resin layer during development.

[0287] Photosensitive resin layer

[0288] In display devices with touch panels, such as capacitive input devices (organic electroluminescent (EL) display devices and liquid crystal display devices), conductive layer patterns, including electrode patterns for sensors that function as visual recognition units, peripheral wiring portions, and wiring for take-out wiring portions, are provided inside the touch panel. Typically, to form a patterned layer, the following method is widely used: a negative photosensitive resin layer (photosensitive layer) is deposited on a substrate using a transfer film or the like; the photosensitive layer is exposed to a mask with the desired pattern; and then developed. Therefore, a negative photosensitive resin layer is preferred as the photosensitive resin layer.

[0289] When the photosensitive resin layer is a negative photosensitive resin layer, the negative photosensitive resin layer preferably comprises a resin, a polymerizable compound, and a polymerization initiator. Furthermore, when the photosensitive resin layer is a negative photosensitive resin layer, as described later, it preferably comprises an alkali-soluble resin (such as polymer A) as part or all of the resin. That is, in one embodiment, the photosensitive resin layer preferably contains a resin comprising an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

[0290] Based on the total mass of the photosensitive resin layer, this photosensitive resin layer (negative photosensitive resin layer) preferably contains: resin: 10-90% by mass; polymerizable compound: 5-70% by mass; polymerization initiator: 0.01-20% by mass.

[0291] The following is a description of each component.

[0292] <Polymer A (Resin)>

[0293] When the photosensitive resin layer is a negative photosensitive resin layer, the resin contained in the photosensitive resin layer is specifically referred to as polymer A.

[0294] Polymer A is preferably an alkali-soluble resin.

[0295] From the viewpoint of achieving better resolution by suppressing the swelling of the negative photosensitive resin layer caused by the developer, the acid value of polymer A is preferably less than 220 mg KOH / g, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g.

[0296] There is no particular limitation on the lower limit of the acid value of polymer A, but from the viewpoint of better developability, it is preferably 60 mg KOH / g or more, more preferably 120 mg KOH / g or more, even more preferably 150 mg KOH / g or more, and particularly preferably 170 mg KOH / g or more.

[0297] Furthermore, the acid value, which is the mass of potassium hydroxide [mg] required to neutralize 1g of the sample, is stated in this specification as mgKOH / g. The acid value can be calculated, for example, based on the average content of acid groups in the compound.

[0298] Regarding the acid value of polymer A, it can be adjusted according to the types of structural units that make up polymer A and the content of structural units containing acid groups.

[0299] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. When the weight-average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. More preferably, the weight-average molecular weight is 100,000 or less, and even more preferably 60,000 or less. On the other hand, when the weight-average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the developed aggregate, and the properties of the unexposed film, such as edge melting and wafer cutting properties, when used as a negative photosensitive resin laminate. More preferably, the weight-average molecular weight is 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge melting refers to the degree to which the negative photosensitive resin layer easily overflows from the end face of the roll when wound into a roll as a negative photosensitive resin laminate. Wafer cutting properties refer to the degree to which the wafer easily flies off when the unexposed film is cut with a cutter. If the wafer is attached to the upper surface of a negative photosensitive resin laminate, it will be transferred to a mask in subsequent exposure processes, resulting in a defective product. The dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0300] In the negative photosensitive resin layer, from the viewpoint of suppressing linewidth coarsening and resolution degradation due to focal position shift during exposure, polymer A preferably contains structural units based on monomers having aromatic hydrocarbons. Examples of such aromatic hydrocarbons include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of structural units based on monomers having aromatic hydrocarbons in polymer A relative to the total mass of polymer A is preferably 20% by mass or more, more preferably 30% by mass or more. While not particularly limited to an upper limit, it is preferably 95% by mass or less, more preferably 85% by mass or less. Furthermore, when multiple polymers A are included, the average content of structural units based on monomers having aromatic hydrocarbons is preferably within the above-mentioned range.

[0301] Examples of monomers containing aromatic hydrocarbons include, for example, monomers containing aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Among these, monomers containing aralkyl groups or styrene are preferred. In one embodiment, when the aromatic hydrocarbon monomer component in polymer A is styrene, the content of styrene-based structural units relative to the total mass of polymer A is preferably 20–70% by mass, more preferably 25–65% by mass, further preferably 30–60% by mass, and particularly preferably 30–55% by mass.

[0302] Examples of aryl alkyl groups include substituted or unsubstituted phenylalkyl groups (with benzyl removed) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0303] Examples of monomers containing phenyl alkyl groups include phenylethyl (meth)acrylate.

[0304] Examples of monomers containing a benzyl group include (meth)acrylates, such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; and vinyl monomers, such as vinyl benzyl chloride and benzyl alcohol. Benzyl (meth)acrylate is preferred. In one embodiment, when the aromatic hydrocarbon monomer component in polymer A is benzyl (meth)acrylate, the content of the (meth)acrylate-based structural unit relative to the total mass of polymer A is preferably 50-95% by mass, more preferably 60-90% by mass, further preferably 70-90% by mass, and particularly preferably 75-90% by mass.

[0305] The polymer A comprising structural units based on monomers having aromatic hydrocarbons is preferably obtained by polymerizing the monomers having aromatic hydrocarbons with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0306] Polymer A, which does not contain structural units based on monomers having aromatic hydrocarbons, is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0307] The first monomer is a monomer having a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half ester. Among these, (meth)acrylic acid is preferred.

[0308] The content of structural units based on the first monomer in polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, relative to the total mass of polymer A.

[0309] From the viewpoints of good developability and control of edge melting, it is preferable to set the above content to 5% by mass or more. From the viewpoints of high resolution and edge shape of the resist pattern, and further from the viewpoints of chemical resistance of the resist pattern, it is preferable to set the above content to 50% by mass or less.

[0310] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate; esters of vinyl alcohol such as vinyl acetate; and methacrylonitrile. Among these, methyl methacrylate, 2-ethylhexyl methacrylate, or n-butyl methacrylate are preferred, and methyl methacrylate is more preferred.

[0311] The content of the second monomer-based structural unit in polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 17 to 45% by mass, relative to the total mass of polymer A.

[0312] When polymer A contains structural units based on monomers having aralkyl groups and / or structural units based on monomers having styrene, it is preferable from the viewpoint of suppressing linewidth thickening and resolution degradation due to focus position shift during exposure. For example, copolymers containing structural units based on methacrylic acid, structural units based on benzyl methacrylate, and structural units based on styrene, copolymers containing structural units based on methacrylic acid, structural units based on methyl methacrylate, structural units based on benzyl methacrylate, and structural units based on styrene are preferred.

[0313] In one embodiment, polymer A is preferably a polymer comprising 25-55% by mass of structural units based on a monomer having an aromatic hydrocarbon, 20-35% by mass of structural units based on a first monomer, and 15-45% by mass of structural units based on a second monomer. Furthermore, in another embodiment, it is preferably a polymer comprising 70-90% by mass of structural units based on a monomer having an aromatic hydrocarbon and 10-25% by mass of structural units based on a first monomer.

[0314] Polymer A may have branched and / or alicyclic structures in its side chains. It may also have straight-chain structures in its side chains. Branched or alicyclic structures can be introduced into the side chains of polymer A by using monomers containing groups with branched side chains or monomers containing groups with alicyclic side chains. The groups with alicyclic structures can be monocyclic or polycyclic.

[0315] Specific examples of monomers containing groups having a branched structure in their side chains include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl (meth)acrylate are preferred, and isopropyl (meth)acrylate or tert-butyl (meth)acrylate are more preferred.

[0316] Specific examples of monomers containing a group having an alicyclic structure in the side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (meth)acrylate (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate-2-methyl-2-adamantyl ester, (meth)acrylate-2-ethyl-2-adamantyl ester, 3-Hydroxy-1-adamantyl methacrylate, octahydro-4,7-mentanoindene-5-yl methacrylate, octahydro-4,7-mentanoindene-1-yl methyl methacrylate, 1-menthyl methacrylate, tricyclodecane methacrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl methacrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl methacrylate, camphene methacrylate, isocamphene methacrylate, fumarate methacrylate, 2,2,5-trimethylcyclohexyl methacrylate, and cyclohexyl methacrylate, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, norcamphene (meth)acrylate, isocamphene (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fumarate (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and more preferably cyclohexyl (meth)acrylate, norcamphene (meth)acrylate, isocamphene (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.

[0317] Polymer A can be used alone or in combination with two or more polymers.

[0318] When using two or more polymers, it is preferable to use a mixture of two polymers A containing structural units based on monomers having aromatic hydrocarbons, or to use a mixture of polymer A containing structural units based on monomers having aromatic hydrocarbons and polymer A not containing structural units based on monomers having aromatic hydrocarbons. In the latter case, the proportion of polymer A containing structural units based on monomers having aromatic hydrocarbons relative to the total mass of polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

[0319] Regarding the synthesis of polymer A, it is preferably carried out by adding appropriate amounts of free radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile to a solution of one or more monomers diluted with solvents such as acetone, methyl ethyl ketone, and isopropanol, and then heating and stirring. Sometimes, a portion of the mixture is added dropwise to the reaction solution while the synthesis is proceeding. Sometimes, after the reaction is complete, further solvent is added to adjust to the desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

[0320] The glass transition temperature (Tg) of polymer A is preferably 30–135°C. By using polymer A with a Tg of 135°C or lower, it is possible to suppress linewidth thickening and resolution degradation due to focus position shift during exposure. From this viewpoint, the Tg of polymer A is preferably 130°C or lower, more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, from the viewpoint of improving edge melt resistance, it is preferable to use polymer A with a Tg of 30°C or higher. From this viewpoint, the Tg of polymer A is more preferably 40°C or higher, more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0321] The negative photosensitive resin layer, as polymer A, contains other resins besides those mentioned above.

[0322] Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyethylene formaldehyde, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, silicone resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0323] As polymer A, an alkali-soluble resin described in the following description of the thermoplastic resin layer can be used.

[0324] The content of polymer A relative to the total mass of the negative photosensitive resin layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the content of polymer A to 90% by mass or less. On the other hand, from the viewpoint of improving resistance to edge melting, it is preferable to set the content of polymer A to 10% by mass or more.

[0325] <Polymerizing compounds>

[0326] When the photosensitive resin layer is a negative photosensitive resin layer, the negative photosensitive resin layer preferably contains a polymeric compound having polymeric groups. Furthermore, in this specification, "polymeric compound" refers to a compound polymerized by the polymerization initiator described later, and specifically refers to a compound different from polymer A described above.

[0327] As for the polymerizable groups in a polymerizable compound, there are no particular restrictions as long as they are groups related to the polymerization reaction. For example, groups with olefinic unsaturated groups such as vinyl, acryloyl, methacryloyl, styrene, and maleimide can be cited; as well as groups with cationic polymerizable groups such as epoxy and oxybutyl.

[0328] As a polymerizable group, it is preferably a group having an olefinic unsaturated group, and more preferably an acryloyl or methacryloyl group.

[0329] From the viewpoint of superior photosensitivity of negative photosensitive resin layers, compounds having one or more olefin unsaturated groups (olefin unsaturated compounds) are preferred as polymerizable compounds, and compounds having two or more olefin unsaturated groups in one molecule (polyfunctional olefin unsaturated compounds) are more preferred.

[0330] Furthermore, from the viewpoint of superior resolution and exfoliability, the number of olefinic unsaturated groups in one molecule of the olefinic unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0331] From the viewpoint of achieving a better balance between photosensitivity, resolution, and peelability of negative photosensitive resin layers, it is preferable to include a difunctional or trifunctional olefin unsaturated compound having two or three olefin unsaturated groups in one molecule, and more preferably a difunctional olefin unsaturated compound having two olefin unsaturated groups in one molecule.

[0332] From the viewpoint of excellent peelability, the content of difunctional olefin unsaturated compounds relative to the total solid content of the composition and relative to the total mass of the negative photosensitive resin layer is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more. There is no particular upper limit, and it can be 100% by mass. That is, all polymerizable compounds can be difunctional olefin unsaturated compounds.

[0333] Furthermore, as an olefinic unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0334] (Polymerizing compound B1)

[0335] The negative photosensitive resin layer preferably comprises a polymeric compound B1 having an aromatic ring and two olefinic unsaturated groups. Polymeric compound B1 is a difunctional olefinic unsaturated compound having one or more aromatic rings in one molecule of the aforementioned polymeric compound B.

[0336] From the viewpoint of superior resolution, the mass ratio of polymeric compound B1 in the negative photosensitive resin layer relative to the total mass of the polymeric compound is preferably 40% or more, more preferably 50% or more, further preferably 55% or more, and particularly preferably 60% or more. There is no particular upper limit, but from the viewpoint of peelability, it is, for example, 100% or less, preferably 99% or less, more preferably 95% or less, further preferably 90% or less, and particularly preferably 85% or less.

[0337] The aromatic rings present in the polymerizable compound B1 include, for example, aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings, as well as fused rings of these, preferably aromatic hydrocarbon rings, more preferably benzene rings. Furthermore, the aforementioned aromatic rings may have substituents.

[0338] Polymerizable compound B1 may have only one aromatic ring or more than two aromatic rings.

[0339] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, it is preferable that the polymeric compound B1 has a bisphenol structure.

[0340] Examples of bisphenol structures include, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0341] As a polymeric compound B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymeric groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0342] The two ends of the bisphenol structure can be directly bonded to two polymerizable groups, or they can be bonded via one or more alkene oxygen groups. The alkene oxygen groups added to the two ends of the bisphenol structure are preferably ethoxylides or propoxylides, more preferably ethoxylides. There is no particular limitation on the number of alkene oxygen groups added to the bisphenol structure, but 4 to 16 per molecule are preferred, more preferably 6 to 14.

[0343] Regarding polymeric compound B1 having a bisphenol structure, it is described in Japanese Patent Application Publication No. 2016-224162, paragraphs 0072 to 0080, the contents of which are incorporated herein by reference.

[0344] As the polymerizable compound B1, it is preferably a difunctional olefinic unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane.

[0345] Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include, for instance, 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentathoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.). 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0346] As a polymerizable compound B1, it is also preferred to be a compound represented by the following general formula (B1).

[0347] [Chemical Formula 12]

[0348]

[0349] In general formula B1, R1 and R2 independently represent a hydrogen atom or a methyl group, respectively. A represents C2H4. B represents C3H6. n1 and n3 are each independently integers from 1 to 39, and n1+n3 is an integer from 2 to 40. n2 and n4 are each independently integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The arrangement of the structural units -(AO)- and -(BO)- can be random or block. Furthermore, in the case of blocks, both -(AO)- and -(BO)- can be on the diphenyl side.

[0350] In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0351] Polymer compound B1 can be used alone or in combination with two or more compounds.

[0352] From the viewpoint of achieving better resolution, the content of polymeric compound B1 relative to the total mass of the negative photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but from the viewpoint of transferability and edge melting (the phenomenon of photosensitive resin seeping out from the end of the transfer part), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0353] The negative photosensitive resin layer may contain polymeric compounds other than the polymeric compound B1 mentioned above.

[0354] There are no particular restrictions on polymerizable compounds other than polymerizable compound B1, and appropriate selections can be made from known compounds. For example, compounds having one olefinic unsaturated group in one molecule (monofunctional olefinic unsaturated compounds), difunctional olefinic unsaturated compounds without an aromatic ring, and olefinic unsaturated compounds with three or more functions can be cited.

[0355] Examples of monofunctional alkenyl unsaturated compounds include, for example, ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxy(meth)acrylate.

[0356] Examples of difunctional olefinic unsaturated compounds that do not have an aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, amine ester di(meth)acrylate and trimethylolpropane diacrylate.

[0357] Examples of alkylene glycol di(meth)acrylates include, for example, tricyclodecanediethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and pentaerythritol di(meth)acrylate.

[0358] Examples of polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di(meth)acrylate.

[0359] Examples of amine di(meth)acrylates include, for example, propylene oxide-modified amine di(meth)acrylates and ethylene oxide and propylene oxide-modified amine di(meth)acrylates. Examples of commercially available products include, for example, 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.).

[0360] Examples of olefinic unsaturated compounds with three or more functions include, for example, dipentaerythritol (tris / tetras / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and epoxide-modified versions of these.

[0361] Here, "(tri / tetra / penta / hexa)meth)acrylate" refers to the concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" refers to the concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0362] In one embodiment, the negative photosensitive resin layer preferably comprises the aforementioned polymeric compound B1 and a trifunctional or higher olefinic unsaturated compound, more preferably comprising the aforementioned polymeric compound B1 and two or more trifunctional or higher olefinic unsaturated compounds. In this case, the mass ratio of polymeric compound B1 to the trifunctional or higher olefinic unsaturated compound is preferably (total mass of polymeric compound B1) : (total mass of trifunctional or higher olefinic unsaturated compounds) = 1 : 1 to 5 : 1, more preferably 1.2 : 1 to 4 : 1, and even more preferably 1.5 : 1 to 3 : 1.

[0363] Furthermore, in one embodiment, the negative photosensitive resin layer preferably comprises the aforementioned polymeric compound B1 and two or more trifunctional olefinic unsaturated compounds.

[0364] Examples of epoxide-modified compounds that are trifunctional or higher olefin unsaturated compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL 135 manufactured by DAI-CELL-ALLNEX LTD.), ethoxylated glycerol triacrylate (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and ARONIX TO-2349 (TOAGOSEI). (Manufactured by TOAGOSEI CO., LTD.) ARONIX M-520 (Manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (Manufactured by TOAGOSEI CO., LTD.).

[0365] Furthermore, polymerizable compounds containing acid groups (such as carboxyl groups) can be used. These acid groups can form anhydride groups. Examples of polymerizable compounds containing acid groups 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.).

[0366] As a polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 can be used.

[0367] Polymers can be used alone or in combination with two or more compounds.

[0368] The content of the polymeric compound relative to the total mass of the negative photosensitive resin layer is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass.

[0369] The molecular weight (weight-average molecular weight in the case of a molecular weight distribution) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0370] <Polymerization initiator>

[0371] When the photosensitive resin layer is a negative photosensitive resin layer, the negative photosensitive resin layer preferably contains a polymerization initiator.

[0372] Polymerization initiators can be selected based on the form of the polymerization reaction; for example, thermal polymerization initiators and photopolymerization initiators can be cited.

[0373] The polymerization initiator can be a free radical polymerization initiator or a cationic polymerization initiator.

[0374] The negative photosensitive resin layer preferably contains a photopolymerization initiator.

[0375] Photopolymerization initiators are compounds that initiate the polymerization of polymerizable compounds by receiving activating light such as ultraviolet light, visible light, and X-rays. There are no particular limitations on photopolymerization initiators, and known photopolymerization initiators can be used.

[0376] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0377] Examples of photoradical polymerization initiators include, for example, photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0378] Furthermore, from the viewpoints of photosensitivity, visibility of the exposed portion, and resolution of the unexposed portion, it is preferable that the negative photosensitive resin layer contains at least one selected from 2,4,5-triarylimidazolium dimers and their derivatives as a photoradical polymerization initiator. Additionally, the two 2,4,5-triarylimidazolium structures in the 2,4,5-triarylimidazolium dimer and its derivatives may be identical or different.

[0379] Examples of derivatives of 2,4,5-triarylimidazolium dimers include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0380] As a photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-095716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-014783 can be used.

[0381] Examples of photoradical polymerization initiators include, for example, ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, methoxyphenyl (p,p'-dimethoxybenzyl ester), TAZ-110 (manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0382] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(o-benzoyl oxime) (product name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(o-acetyl oxime) (product name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad379EG, IGM Resins). Omnirad 907 (manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-2-dimethylamino-1-(4-methylpropanoyl)butanone-1 (manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenyl ...1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV), 2-hydroxy-1-dimethylamino-1-(4-methylpropanoyl)butanone-1 (manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-1-methylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-1-methylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-1-methylpropanoyl-1-one (manufactured by IGM Resins BV), 2-hydroxy-1-methylpropanoyl-1-one (manufactured Omnirad 651 (manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethyl-1-one (manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by IGM Resins BV), oxime ester-based photopolymerization initiators (manufactured by DKSH Management Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (manufactured by Hampford Research Inc.).(Manufactured) and 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (product name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(o-acetyl oxime) (product name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials (Manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(o-benzoyl oxime) (Product name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.).

[0383] Photocationic polymerization initiators (photoacid generators) are compounds that generate acid upon receiving activation light. As photocationic polymerization initiators, compounds that generate acid upon sensing activation light with wavelengths of 300 nm or higher, preferably 300–450 nm, are preferred, but their chemical structure is not particularly limited. Furthermore, regarding photocationic polymerization initiators that do not directly sense activation light with wavelengths of 300 nm or higher, compounds that generate acid upon sensing activation light with wavelengths of 300 nm or higher by means of a sensitizer can also be used preferably in combination with a sensitizer.

[0384] As a photocationic polymerization initiator, a photocationic polymerization initiator that produces acids with a pKa of 4 or less is preferred, a photocationic polymerization initiator that produces acids with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that produces acids with a pKa of 2 or less is particularly preferred. The lower limit of the pKa is not particularly limited, but for example, -10.0 or more is preferred.

[0385] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0386] Examples of ionic photocationic polymerization initiators include, for example, onium salts such as diaryl sulfonium salts and triaryl sulfonium salts, as well as quaternary ammonium salts.

[0387] As an ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-085643 may be used.

[0388] Examples of nonionic photocationic polymerization initiators include trichloromethyltriazine derivatives, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among the trichloromethyltriazine derivatives, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494 can be used. Furthermore, among the oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Patent Publication No. 2018 / 179640 can be used.

[0389] The negative photosensitive resin layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from 2,4,5-triarylimidazolium dimers and their derivatives.

[0390] Polymerization initiators can be used alone or in combination with two or more.

[0391] The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the negative photosensitive resin layer. There is no particular upper limit, but it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the negative photosensitive resin layer.

[0392] Pigment

[0393] From the viewpoints of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, it is preferable that the photosensitive resin layer contains a pigment (also called "pigment N") with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength changes due to acids, alkalis, or free radicals. While the detailed mechanism of including pigment N is not yet clear, the adhesion to adjacent layers (e.g., water-soluble resin layers) is improved, resulting in superior resolution.

[0394] In this specification, the phrase "the pigment's absorption wavelength changes dramatically due to acid, alkali, or free radicals" can refer to any of the following embodiments: an embodiment in which a pigment in a color-developing state is decolorized by acid, alkali, or free radicals; an embodiment in which a pigment in a decolorized state is color-developed by acid, alkali, or free radicals; and an embodiment in which a pigment in a color-developing state changes to a different hue.

[0395] Specifically, pigment N can be a compound that changes from an achromatic state to a chromatic state through exposure, or a compound that changes from a chromatic state to an achromatic state through exposure. In this case, it can be a pigment that changes its chromatic or achromatic state by generating acids, bases, or free radicals within the photosensitive resin layer through exposure, or a pigment that changes its chromatic or achromatic state by changing the state (e.g., pH) within the photosensitive resin layer due to acids, bases, or free radicals. Furthermore, it can also be a pigment that changes its chromatic or achromatic state directly by accepting acids, bases, or free radicals as stimuli without exposure.

[0396] From the viewpoint of visibility and resolution of the exposed and unexposed portions, pigment N is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes due to free radicals.

[0397] When the photosensitive resin layer is a negative photosensitive resin layer, from the viewpoint of visibility and resolution of the exposed and unexposed areas, it is preferable that the negative photosensitive resin layer contains both a pigment N, which has a maximum absorption wavelength that changes due to free radicals, and a photoradical polymerization initiator.

[0398] Furthermore, from the viewpoint of visibility of both the exposed and unexposed areas, pigment N is preferably a pigment that develops color through acid, alkali, or free radicals.

[0399] An example of a color-developing mechanism for pigment N can be described as follows: a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator is added to a photosensitive resin layer. After exposure, the free radical reactive pigment, acid reactive pigment, or alkali reactive pigment (e.g., colorless pigment) develops color due to the free radicals, acids, or alkalis generated by the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator.

[0400] Regarding pigment N, from the viewpoint of visibility of the exposed and unexposed portions, the maximum absorption wavelength in the wavelength range of 400–780 nm during color development is preferably 550 nm or more, more preferably 550–700 nm, and even more preferably 550–650 nm.

[0401] Furthermore, pigment N can have only one maximum absorption wavelength in the wavelength range of 400–780 nm during color development, or it can have two or more. If pigment N has two or more maximum absorption wavelengths in the wavelength range of 400–780 nm during color development, it is acceptable as long as the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is above 450 nm.

[0402] The maximum absorption wavelength of pigment N was obtained by measuring the transmission spectrum of a solution containing pigment N (at a liquid temperature of 25°C) in an atmospheric atmosphere using a UV3100 spectrophotometer (manufactured by SHIMADZU CORPORATION) in the range of 400–780 nm, and detecting the wavelength at which the light intensity reaches its minimum (maximum absorption wavelength).

[0403] As pigments that develop or decolorize upon exposure, colorless compounds can be cited as an example.

[0404] Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane pigments, oxazine pigments, xanthones, iminonaphthoquinone pigments, azomethine pigments, and anthraquinone pigments.

[0405] From the viewpoint of visibility of both the exposed and unexposed areas, colorless compounds are preferred as pigment N.

[0406] Examples of colorless compounds include, for example, colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropipran skeleton (spiropipran pigments), colorless compounds having a fluorane parent skeleton (fluorane parent system pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam pigments), colorless compounds having an indolephthalide skeleton (indolephthalide pigments), and colorless compounds having a white goldamine skeleton (white goldamine pigments).

[0407] Preferably, the pigment is a triarylmethane-based pigment or a fluorane parent system pigment, and more preferably, it is a colorless compound (triphenylmethane-based pigment) with a triphenylmethane skeleton or a fluorane parent system pigment.

[0408] From the viewpoint of visibility of both the exposed and unexposed areas, it is preferable for the colorless compound to have a lactone ring, a sultine ring, or a sulfonyl lactone ring. This allows the lactone ring, sultine ring, or sulfonyl lactone ring of the colorless compound to react with free radicals generated by a photoradical polymerization initiator or acids generated by a photocationic polymerization initiator, causing the colorless compound to either change to a closed-ring state and become colorless, or to change to an open-ring state and become colorless. Preferably, the colorless compound is one that has a lactone ring, sultine ring, or sulfonyl lactone ring, and becomes colorless due to the opening of the lactone ring, sultine ring, or sulfonyl lactone ring caused by a free radical or acid; more preferably, it is a compound that has a lactone ring and becomes colorless due to the opening of the lactone ring caused by a free radical or acid.

[0409] As pigment N, examples include the following dyes and colorless compounds.

[0410] Specific examples of dyes in pigment N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsin, Methyl Violet 2B, Methylquinoline Red, Bengal Rose Red, m-amine Yellow, Bromophenol Blue, Xylenol Blue, Methyl Orange, p-Methyl Red, Congo Red, Benzoin Violet 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Para-Fuchsin, Victoria Blue - Naphthalene Sulfonate, Victoria Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Powder #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Co., Ltd.), and Oil Green #502 (manufactured by Orient Chemical Co., Ltd.). (Manufactured by Chemical Co., Ltd.), SPIRON Red BEH SPECIAL (Manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonyl rhodamine B, goldamine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyphenylamino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0411] Specific examples of colorless compounds in pigment N include p,p',p”-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane parent compound, 2-phenylamino-3-methyl-6-(N-ethyl-p-toluidine)fluorane parent compound, 3,6-dimethoxyfluorane parent compound, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane parent compound, and 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-phenyl Aminofluorane parent compound, 3-(N,N-diethylamino)-6-methyl-7-phenylaminofluorane parent compound, 3-(N,N-diethylamino)-6-methyl-7-aminofluorane parent compound, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane parent compound, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane parent compound, 3-(N,N-diethylamino)-7-(4-chlorophenylamino)fluorane parent compound, 3-(N The parent compounds are 3-(N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-phenylaminofluorane, 3-(N,N-dibutylamino)-6-methyl-7-phenylaminofluorane, 3-piperidinyl-6-methyl-7-phenylaminofluorane, 3-pyrrolidinyl-6-methyl-7-phenylaminofluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalolactone, 3, 3-Bis(1-n-butyl-2-methylindole-3-yl)phthalolide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalolide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalolide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalolide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xepide-3-one.

[0412] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the pattern after development, and resolution, pigment N is preferably a pigment whose maximum absorption wavelength changes due to free radicals, and more preferably a pigment that develops color through free radicals.

[0413] As pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate are preferred.

[0414] Pigment N can be used alone or in combination with two or more pigments.

[0415] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the content of pigment N relative to the total mass of the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass.

[0416] The content of pigment N refers to the amount of pigment required for all of the pigment N contained in the total mass of the photosensitive resin layer to be in a colored state. The following explanation uses pigments that develop color via free radicals as an example to illustrate the quantitative method for determining the content of pigment N.

[0417] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigments in 100 mL of methyl ethyl ketone. Irgacure OXE01 (product name, BASF Japan Ltd.) as a photoradical polymerization initiator was added to each solution, and the solutions were irradiated with 365 nm light to generate free radicals, thus setting all pigments to a colored state. Then, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) to create calibration curves.

[0418] Next, 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigment. The absorbance of the solution in which the pigment was fully developed was then measured using the same method as described above. Based on the absorbance of the resulting solution containing the photosensitive resin layer, the pigment content in the photosensitive resin layer was calculated according to the calibration curve.

[0419] In addition, the 3g of photosensitive resin layer is the same as the 3g of total solids in the photosensitive resin composition.

[0420] <Thermocrosslinking compounds>

[0421] When the photosensitive resin layer is a negative photosensitive resin layer, from the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film, it is preferable to include a thermally crosslinking compound. Furthermore, in this specification, thermally crosslinking compounds having olefinically unsaturated groups (described later) are not considered polymerizable compounds, but rather thermally crosslinking compounds.

[0422] Examples of thermally crosslinking compounds include hydroxymethyl compounds and end-capped isocyanate compounds. Among these, end-capped isocyanate compounds are preferred from the viewpoint of the strength of the cured film and the adhesion of the uncured film.

[0423] The capped isocyanate compound reacts with hydroxyl and carboxyl groups, thus, for example, in the case of resins and / or polymeric compounds having at least one of hydroxyl and carboxyl groups, the hydrophilicity of the formed film decreases, and the film tends to enhance its function as a protective film when the film formed by curing a negative photosensitive resin layer is used.

[0424] In addition, capped isocyanate compounds are defined as "compounds having a structure in which isocyanate groups of isocyanate are protected (so-called masking) with capping agents".

[0425] There is no particular limitation on the dissociation temperature of the capped isocyanate compound, but it is preferably 100 to 160°C, more preferably 130 to 150°C.

[0426] The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates, as measured by differential scanning calorimetry (DSC) using a differential scanning calorimeter".

[0427] As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be appropriately used. However, the differential scanning calorimeter is not limited to this.

[0428] Examples of end-capping agents with dissociation temperatures of 100–160°C include active methylene compounds (malonate esters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)) and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, etc., which have a structure represented by -C (=N-OH)- in the molecule).

[0429] Among these, at least one type of oxime compound is preferred as a capping agent with a dissociation temperature of 100 to 160°C, for example, from the viewpoint of storage stability.

[0430] For example, from the viewpoint of improving the brittleness of the film and enhancing the adhesion to the substrate, it is preferable that the end-capped isocyanate compound has an isocyanurate structure.

[0431] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuration of hexamethylene diisocyanate.

[0432] Among the isocyanurate compounds with a capped isocyanate structure, compounds with an oxime structure having an oxime compound as a capping agent are preferred from the viewpoint that it is easier to set the dissociation temperature within a preferred range compared to compounds without an oxime structure, and it is easier to reduce development residue.

[0433] End-capped isocyanate compounds can have polymerizable groups.

[0434] There are no particular restrictions on the polymerizable group; any known polymerizable group can be used, with free radical polymerizable groups being preferred.

[0435] Examples of polymerizable groups include olefinic unsaturated groups such as (meth)acryloyloxy, (meth)acryloylamino, and styryl, as well as groups with epoxy groups such as glycidyl.

[0436] Among them, the polymerizable group is preferably an olefinic unsaturated group, more preferably (meth)acryloyloxy, and even more preferably acryloyloxy.

[0437] As a capped isocyanate compound, it can be used in commercially available products.

[0438] Examples of commercially available terminal isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and the block DURANATE series (e.g., DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0439] Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0440] [Chemical Formula 13]

[0441]

[0442] One type of thermally crosslinking compound can be used alone, or two or more types can be used.

[0443] When the photosensitive resin layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound relative to the total mass of the photosensitive resin layer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.

[0444] <Other Additives>

[0445] In addition to the above-mentioned components, the photosensitive resin layer may also contain known additives as needed.

[0446] Examples of additives include free radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (triazoles, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamides, etc.), purine bases (adenine, etc.), and surfactants.

[0447] Each additive can be used alone or in combination with two or more.

[0448] The photosensitive resin layer may contain a free radical polymerization inhibitor.

[0449] Examples of free radical polymerization inhibitors include the thermal polymerization inhibitor described in Japanese Patent No. 4502784, paragraph 0018. Among these, phenoxazine, phenoxazine, or 4-methoxyphenol are preferred. Other free radical polymerization inhibitors include naphthylamine, cuprous chloride, aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive resin layer, aluminum nitrosophenylhydroxylamine is preferably used as the free radical polymerization inhibitor.

[0450] Examples of benzotriazoles include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0451] Examples of carboxylated benzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxylated benzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxylated benzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylene carboxylated benzotriazole. Commercially available products such as CBT-1 (JOHOKU CHEMICAL CO., LTD, product name) can also be used as carboxylated benzotriazoles.

[0452] The total content of free radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles relative to the total mass of the photosensitive resin layer is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. When the content is 0.01% by mass or more, the storage stability of the photosensitive resin layer is better. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and the suppression of dye decolorization are better.

[0453] The photosensitive resin layer may contain a sensitizer.

[0454] There are no particular restrictions on the sensitizer; known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthonone compounds, thiazolinone compounds, acridinone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), piracene compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds, and aminoacridine compounds.

[0455] A single sensitizer can be used alone, or two or more sensitizers can be used.

[0456] When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. However, from the viewpoint of improving the sensitivity to the light source and improving the curing speed based on the balance between polymerization rate and chain transfer, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0457] The photosensitive resin layer may contain at least one selected from plasticizers and heterocyclic compounds.

[0458] As plasticizers and heterocyclic compounds, examples include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0459] Furthermore, the photosensitive resin layer may also contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferation agents, development promoters, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.

[0460] Regarding the additives contained in the photosensitive resin layer, the contents of Japanese Patent Application Publication No. 2014-085643 are described in paragraphs 0165 to 0184, and are incorporated herein by reference.

[0461] From the viewpoint of improving reliability and lamination, the water content in the photosensitive resin layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0462] The thickness (film thickness) of the photosensitive resin layer is typically 0.1–300 μm, preferably 0.2–100 μm, more preferably 0.5–50 μm, even more preferably 0.5–15 μm, particularly preferably 0.5–10 μm, and most preferably 0.5–8 μm. This improves the developability of the photosensitive resin layer, thereby increasing resolution.

[0463] Furthermore, in one embodiment, the preferred size is 0.5–5 μm, more preferably 0.5–4 μm, and even more preferably 0.5–3 μm.

[0464] Furthermore, from the viewpoint of superior adhesion, the transmittance of the photosensitive resin layer for light with a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular upper limit, but it is preferably 99.9% or less.

[0465] <Impurities, etc.>

[0466] The photosensitive resin layer may contain a certain amount of impurities.

[0467] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are more likely to be introduced as impurities, and therefore the following concentrations are preferred.

[0468] The impurity content in the photosensitive resin layer is preferably 80 ppm or less by mass, more preferably 10 ppm or less, and even more preferably 2 ppm or less by mass. Regarding the impurity content, it can be set to 1 ppb or more by mass, or 0.1 ppm or more.

[0469] As a method for keeping impurities within the aforementioned range, examples include: selecting raw materials with low impurity content as raw materials for the composition; preventing impurities from being introduced during the fabrication of the photosensitive resin layer; and removing them by washing. By using this method, the amount of impurities can be kept within the aforementioned range.

[0470] Regarding impurities, they can be quantified using known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0471] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive resin layer is preferably low. The content of these compounds relative to the total mass of the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, on a mass basis.

[0472] Based on mass standards, the lower limit relative to the total mass of the photosensitive resin layer can be set to 10 ppb or more, and can be set to 100 ppb or more. The content of these compounds can be suppressed using the same method as for the aforementioned metal impurities. Furthermore, quantification can be performed using known measurement methods.

[0473] From the viewpoint of improving reliability and lamination, the water content in the photosensitive resin layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0474] Pigments

[0475] The photosensitive resin layer can be a colored resin layer containing pigments.

[0476] In recent years, liquid crystal display windows in electronic devices have sometimes been fitted with cover glass, on which a black frame-like light-shielding layer is formed on the periphery of the back side of a transparent glass substrate, etc., to protect the liquid crystal display window. A colored resin layer can be used to form this light-shielding layer.

[0477] As for pigments, they can be selected appropriately based on the desired hue, and can be chosen from black pigments, white pigments, and colored pigments other than black and white. Among these, black pigment can be appropriately selected when creating a black-based pattern.

[0478] As the black pigment, any known black pigment (organic or inorganic pigment, etc.) can be appropriately selected, provided it does not impair the effects of the present invention. From the viewpoint of optical concentration, suitable examples of black pigments include carbon black, titanium dioxide, titanium carbide, iron oxide, titanium dioxide, and lead black, with carbon black being particularly preferred. From the viewpoint of surface resistivity, carbon black in which at least a portion of the surface is coated with resin is preferred.

[0479] Regarding the particle size of the black pigment, from the viewpoint of dispersion stability, it is preferably 0.001 to 0.1 μm in terms of number average particle size, and more preferably 0.01 to 0.08 μm.

[0480] Here, particle size refers to the diameter of a circle whose area is calculated from an electron microscope image of the pigment particle and which is considered to be the same as the area of ​​the pigment particle. The number-average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 particle sizes.

[0481] Regarding white pigments other than black pigments, the white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Publication No. 2005-007765 can be used. Specifically, as an inorganic pigment, the preferred white pigments are titanium dioxide, zinc oxide, zinc barium white, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium dioxide or zinc oxide, and even more preferably titanium dioxide. As an inorganic pigment, rutile or anatase titanium dioxide is even more preferred, and rutile titanium dioxide is particularly preferred.

[0482] Furthermore, the surface of titanium oxide can be treated with silica, alumina, titanium dioxide, zirconium dioxide, or organic substances, or two or more of these treatments can be applied. This suppresses the catalytic activity of titanium oxide and improves its heat resistance and fading properties.

[0483] From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, the surface treatment of titanium oxide is preferably at least one of alumina treatment and zirconium dioxide treatment, and particularly preferably both alumina treatment and zirconium dioxide treatment.

[0484] Furthermore, when the photosensitive resin layer is a colored resin layer, from the viewpoint of transferability, it is preferable that the photosensitive resin layer further includes colored pigments other than black and white pigments. When colored pigments are included, from the viewpoint of better dispersibility, the particle size of the colored pigments is preferably 0.1 μm or less, more preferably 0.08 μm or less.

[0485] Examples of colored pigments include Victoria Blue BO (Color Index: CI 42595), Golden Amine (CI 41000), Lipid Black HB (CI 26150), Monoright Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Magenta FBB (CI Pigment Red 146), Prime Yeast Red ESB (CI Pigment Violet 19), Permanent Gem FBH (CI Pigment Red 11), and Faster Pink B Super (CI Pigment Red 81). The pigments include Mona Strahl Blue (CI Pigment Blue 15), Monoright Black B (CI Pigment Black 1), carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Among these, CI Pigment Red 177 is preferred.

[0486] When the photosensitive resin layer contains pigments, the pigment content relative to the total mass of the photosensitive resin layer is preferably more than 3% by mass and less than 40% by mass, more preferably more than 3% by mass and less than 35% by mass, even more preferably more than 5% by mass and less than 35% by mass, and particularly preferably more than 10% by mass and less than 35% by mass.

[0487] When the photosensitive resin layer contains pigments other than black pigments (white pigments and colored pigments), the content of pigments other than black pigments relative to black pigments is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass.

[0488] In addition, when the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed from a photosensitive resin composition, it is preferable that the black pigment (preferably carbon black) is introduced into the photosensitive resin composition in the form of a pigment dispersion.

[0489] A dispersion can be prepared by adding a pre-mixed mixture of black pigment and pigment dispersant to an organic solvent (or medium) and dispersing it using a disperser. Regarding the pigment dispersant, it can be selected based on the pigment and solvent; for example, a commercially available dispersant can be used. Furthermore, the medium refers to the portion of the medium in which the pigment is dispersed when it is a pigment dispersion; it is liquid and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0490] There are no particular limitations on the type of dispersant; for example, known dispersants include kneaders, roller mills, grinders, supermills, dissolvers, homogenizers, and sand mixers. Furthermore, fine grinding can be achieved through mechanical grinding using friction. For information on dispersants and fine grinding, please refer to the "Encyclopedia of Pigments" (Kunozou Asakura, 1st edition, Asakura Publishing Co., Ltd., 2000, pp. 438, 310).

[0491] Thermoplastic resin layer

[0492] A thermoplastic resin layer is typically disposed between a temporary support and a photosensitive resin layer. The transfer film includes a thermoplastic resin layer, thereby improving the substrate's tracking ability during the bonding process and suppressing air bubble ingress between the substrate and the transfer film. As a result, the adhesion of layers adjacent to the thermoplastic resin layer (e.g., the temporary support) can be ensured.

[0493] The thermoplastic resin layer comprises resin. Regarding the aforementioned resin, some or all of it comprises thermoplastic resin. That is, in one embodiment, the resin in the thermoplastic resin layer is preferably a thermoplastic resin.

[0494] Alkali-soluble resins (thermoplastic resins)

[0495] As a thermoplastic resin, an alkali-soluble resin is preferred.

[0496] Examples of alkali-soluble resins include, for example, acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyethylene formaldehyde, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, silicone resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0497] From the viewpoint of developability and adhesion to adjacent layers, acrylic resin is preferred as an alkali-soluble resin.

[0498] Here, acrylic resin refers to a resin having at least one structural unit selected from structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide.

[0499] As an acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide is preferably 50% or more by mass relative to the total mass of the acrylic resin.

[0500] The total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate, relative to the total mass of the acrylic resin, is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

[0501] Furthermore, the alkali-soluble resin is preferably a polymer with acid groups.

[0502] Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl being the most preferred.

[0503] From the viewpoint of developability, alkali-soluble resins are more preferably alkali-soluble resins with an acid value of 60 mg KOH / g or higher, and even more preferably acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher.

[0504] There is no particular limit to the upper limit of the acid value of the alkali-soluble resin, but it is preferably below 300 mg KOH / g, more preferably below 250 mg KOH / g, even more preferably below 200 mg KOH / g, and particularly preferably below 150 mg KOH / g.

[0505] There are no particular restrictions on the use of acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher, and they can be appropriately selected from known resins.

[0506] For example, examples include the alkali-soluble acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or more described in paragraph 0025 of Japanese Patent Application Publication No. 2011-095716; the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or more described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589; and the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or more described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0507] The copolymerization ratio of carboxyl-containing structural units in the above-mentioned carboxyl-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, relative to the total mass of the acrylic resin.

[0508] From the viewpoint of developability and adhesion to adjacent layers, acrylic resins having structural units derived from (meth)acrylic acid are particularly preferred as alkali-soluble resins.

[0509] Alkali-soluble resins can possess reactive groups. Any group capable of addition polymerization can be considered a reactive group; examples include olefinic unsaturated groups; condensation groups such as hydroxyl and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (block) isocyanate groups.

[0510] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0511] Alkali-soluble resins can be used alone or in combination with two or more types.

[0512] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, further preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0513] Pigment

[0514] The preferred thermoplastic resin layer contains a pigment (also referred to as "pigment B") whose maximum absorption wavelength is above 450 nm in the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength is altered by acids, alkalis, or free radicals.

[0515] The preferred embodiment of pigment B is the same as the preferred embodiment of pigment N described above, except for the points described later.

[0516] From the viewpoint of visibility and resolution of the exposed and unexposed areas, pigment B is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes due to acid.

[0517] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a pigment (as pigment B) whose absorption wavelength changes maximally with acid and a compound that generates acid with light (described later).

[0518] Pigment B can be used alone or in combination with two or more pigments.

[0519] From the viewpoint of visibility of both the exposed and non-exposed areas, the content of pigment B relative to the total mass of the thermoplastic resin is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, even more preferably 0.2 to 5% by mass, and particularly preferably 0.25 to 3.0% by mass.

[0520] Here, the content of pigment B refers to the content of pigment when all pigment B contained in the thermoplastic resin layer is set to a colored state. The following explanation uses a pigment that develops color via free radicals as an example to illustrate the quantitative method for determining the content of pigment B.

[0521] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigments in 100 mL of methyl ethyl ketone. Irgacure OXE01 (product name, BASF Japan Ltd.) as a photoradical polymerization initiator was added to each solution, and the solutions were irradiated with 365 nm light to generate free radicals, thus setting all pigments to a colored state. Then, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) to create calibration curves.

[0522] Next, 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. The absorbance of the solution in which the pigment was fully developed was then measured using the same method as described above. Based on the absorbance of the resulting solution containing the thermoplastic resin layer, the amount of pigment contained in the thermoplastic resin layer was calculated according to the calibration curve.

[0523] In addition, the 3g thermoplastic resin layer is the same as the 3g solid component of the composition.

[0524] <Compounds that produce acids, bases, or free radicals through light>

[0525] The thermoplastic resin layer may contain compounds that generate acids, bases, or free radicals upon exposure to light (also referred to simply as "Compound C").

[0526] As compound C, it is preferably a compound that generates an acid, base or free radical by receiving activating light such as ultraviolet light and visible light.

[0527] Compound C can be any known photoacid generator, photoalkali generator, or photoradical polymerization initiator (photoradical generator). Among these, a photoacid generator is preferred.

[0528] (Photo-acid generator)

[0529] From a resolution perspective, it is preferable that the thermoplastic resin layer contains a photoacid-generating agent.

[0530] As a photoacid generator, the photocationic polymerization initiator that can be included in the above-mentioned negative photosensitive resin layer can be cited as an example. Except for the points described later, the preferred embodiments are also the same.

[0531] As a photoacid generator, from the viewpoint of sensitivity and resolution, it is preferable to include at least one compound selected from onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, it is more preferable to include oxime sulfonate compounds.

[0532] Furthermore, as a photoacid generator, a photoacid generator having the following structure is preferred.

[0533] [Chemical Formula 14]

[0534]

[0535] (Photoradical polymerization initiator)

[0536] The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0537] As photoradical polymerization initiators, examples of photoradical polymerization initiators that can be included in the aforementioned negative photosensitive resin layer are given, and the preferred embodiments are also the same.

[0538] (Photoalkali generator)

[0539] Thermoplastic resin compositions may contain photoalkali generating agents.

[0540] As a photoalkali generating agent, there are no particular limitations as long as it is a known photoalkali generating agent. Examples include 2-nitrobenzylcyclohexylaminocarbamate, triphenylmethanol, o-aminoformylhydroxylamide, o-aminoformyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- 1-Benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0541] Compound C can be used alone or in more than two forms.

[0542] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the content of compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0543] <Plasticizer>

[0544] From the viewpoints of resolution, adhesion to adjacent layers, and developability, it is preferable that the thermoplastic resin layer contains a plasticizer.

[0545] Preferably, the plasticizer has a lower molecular weight (weight-average molecular weight if it is an oligomer or polymer with a molecular weight distribution) than the alkali-soluble resin. The preferred molecular weight (weight-average molecular weight) of the plasticizer is 200 to 2,000.

[0546] Regarding plasticizers, there are no limitations as long as they are compounds that are compatible with alkali-soluble resins and exhibit plasticizing properties. From the viewpoint of imparting plasticizing properties, it is preferable that the plasticizer has an alkene group in its molecule, and more preferably a polyalkylene glycol compound. More preferably, the alkene group contained in the plasticizer has a polyethylene oxygen structure or a polypropylene oxygen structure.

[0547] Furthermore, from the viewpoint of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin, and the plasticizer contains a (meth)acrylate compound.

[0548] Examples of (meth)acrylate compounds that can be used as plasticizers include polymeric compounds described in the above-mentioned negative photosensitive resin layer.

[0549] In transfer films, where a thermoplastic resin layer and a negative photosensitive resin layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. This is because: by having the thermoplastic resin layer and the negative photosensitive resin layer each contain the same (meth)acrylate compound, interlayer diffusion is suppressed, and storage stability is improved.

[0550] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of the adhesion between the thermoplastic resin layer and the adjacent layer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed portion after exposure.

[0551] Furthermore, from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in one molecule are preferred as (meth)acrylate compounds that can be used as plasticizers.

[0552] Furthermore, (meth)acrylate compounds that can be used as plasticizers are preferably (meth)acrylate compounds having acid groups or amine (meth)acrylate compounds.

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

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

[0555] Sensitizer

[0556] The thermoplastic resin layer may contain a sensitizer.

[0557] There are no particular limitations on the sensitizers used, and examples of sensitizers that can be included in the aforementioned negative photosensitive resin layer can be cited.

[0558] A single sensitizer can be used alone, or two or more sensitizers can be used.

[0559] The content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and unexposed parts, it is preferably 0.01 to 5% by mass relative to the total mass of the thermoplastic resin layer, and more preferably 0.05 to 1% by mass.

[0560] <Additives, etc.>

[0561] In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives as needed.

[0562] Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-085643, and the contents described in that publication are incorporated into this specification.

[0563] The thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of good adhesion to adjacent layers, it is preferably 1 μm or more, more preferably 2 μm or more. There is no particular upper limit, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

[0564] Furthermore, as the transfer film of the first embodiment, although... Figure 1 The transfer film 10 is described as an example, but the present invention is not limited thereto. For example, it may have a structure in which other layers besides the thermoplastic resin layer 3, the water-soluble resin layer 5, and the photosensitive resin layer 7 are further provided between the temporary support 1 and the cover film 9, or it may have a structure without the thermoplastic resin layer 3. Furthermore, it may have a structure in which the thermoplastic resin layer 3, the water-soluble resin layer 5, the photosensitive resin layer 7, and the cover film 9 are provided not only on one side of the temporary support 1, but also on both sides.

[0565] Method for manufacturing transfer film according to the first embodiment

[0566] The method for manufacturing the transfer film in the first embodiment is not particularly limited, and known manufacturing methods, such as known methods for forming each layer, can be used.

[0567] The following is for reference. Figure 1 The manufacturing method of the transfer film according to the first embodiment will be described. However, the transfer film of the first embodiment is not limited to having... Figure 1 The transfer film with the structure shown in the figure.

[0568] As a method for manufacturing the transfer film 10 described above, for example, a method including the following steps: coating a thermoplastic resin composition onto the surface of a temporary support 1 to form a coating film, and further drying the coating film to form a thermoplastic resin layer 3; coating a water-soluble resin composition onto the surface of the thermoplastic resin layer 3 to form a coating film, and further drying the coating film to form a water-soluble resin layer 5; coating a photosensitive resin composition (negative photosensitive resin composition) onto the surface of the water-soluble resin layer 5 to form a coating film, and further drying the coating film to form a photosensitive resin layer 7 (negative photosensitive resin layer).

[0569] Furthermore, the methods for forming thermoplastic resin compositions and thermoplastic resin layers, water-soluble resin compositions and water-soluble resin layers, and photosensitive resin compositions (negative photosensitive resin compositions) and photosensitive resin layers (negative photosensitive resin layers) will be described later.

[0570] The transfer film 10 is manufactured by pressing the cover film 9 onto the photosensitive resin layer 7 of the laminate manufactured by the above manufacturing method.

[0571] As a method for manufacturing the transfer film according to the first embodiment, it is preferable to manufacture a transfer film 10 having a temporary support 1, a thermoplastic resin layer 3, a water-soluble resin layer 5, a photosensitive resin layer 7 and a cover film 9 by a step including setting a cover film 9 to contact the surface of the photosensitive resin layer 7 opposite to the side having the temporary support 1.

[0572] After the transfer film 10 is manufactured using the above manufacturing method, the transfer film 10 is wound up, thereby enabling the production and storage of a roller-type transfer film. The roller-type transfer film can be provided in its original form during the roll-to-roll bonding process with the substrate, as described later.

[0573] Furthermore, as a method for manufacturing the aforementioned transfer film 10, it can be a method of forming a thermoplastic resin layer 3 on the surface of the water-soluble resin layer 5 after forming a photosensitive resin layer 7 and a water-soluble resin layer 5 on the cover film 9.

[0574] <Thermoplastic Resin Composition and Method for Forming Thermoplastic Resin Layer>

[0575] The thermoplastic resin composition preferably includes various components and solvents that form the aforementioned thermoplastic resin layer. Furthermore, in the thermoplastic 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 aforementioned thermoplastic resin layer.

[0576] As a solvent, there are no particular restrictions as long as it can dissolve or disperse all components other than the solvent itself, and known solvents can be used. Specifically, examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents (such as n-propyl acetate), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0577] As a solvent, it is preferred to include at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, it is a mixed solvent including at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from ketone solvents and cyclic ether solvents. More preferably, it is a mixed solvent including at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0578] Examples of alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0579] Examples of solvents for alkylene glycol ether acetates include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0580] As solvents, solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated in this specification.

[0581] The solvent content is preferably 50 to 1,900 parts by mass relative to 100 parts by mass of the total solids in the composition, more preferably 100 to 900 parts by mass.

[0582] The method of forming thermoplastic resin is not particularly limited as long as it is a method that can form a layer containing the above-mentioned components, for example, well-known coating methods (slot coating, spin coating, curtain coating and inkjet coating, etc.) can be cited.

[0583] <Water-soluble resin composition and method for forming water-soluble resin layer>

[0584] The water-soluble resin composition preferably includes various components and solvents that form the water-soluble resin layer described above. Furthermore, in the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the water-soluble resin layer described above.

[0585] As a solvent, there are no particular limitations as long as it can dissolve or disperse water-soluble resins. Preferably, it is selected from at least one of water and water-mixed organic solvents, more preferably water or a mixture of water and water-mixed organic solvents.

[0586] Examples of water-mixable organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols with 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0587] You can use one solvent alone, or you can use two or more solvents.

[0588] The solvent content is preferably 50 to 2,500 parts by mass relative to 100 parts by mass of the total solids in the composition, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0589] The method for forming the water-soluble resin is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, for example, well-known coating methods (slot coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0590] <Method for forming photosensitive resin composition (negative photosensitive resin composition) and photosensitive resin layer (negative photosensitive resin layer)>>

[0591] As a photosensitive resin composition (negative photosensitive resin composition), it is preferable to include various components and solvents that form the aforementioned photosensitive resin layer (negative photosensitive resin layer). Furthermore, in the photosensitive resin composition (negative 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 aforementioned photosensitive resin layer (negative photosensitive resin layer).

[0592] There are no particular limitations on the solvent, as long as it can dissolve or disperse all components other than the solvent (compound A and polymer A, etc.), and known solvents can be used. Examples of solvents that are the same as those described in the above-described thermoplastic resin composition are preferred.

[0593] You can use one solvent alone, or you can use two or more solvents.

[0594] The solvent content is preferably 50 to 1,900 parts by mass relative to 100 parts by mass of the total solids in the composition, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass.

[0595] The method for forming the photosensitive resin layer (negative photosensitive resin layer) is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, for example, known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0596] [Transfer film of the second embodiment]

[0597] Hereinafter, an example of an embodiment of the transfer film of the second embodiment will be described.

[0598] Figure 2 The transfer film 20 shown in the figure has a temporary support 11, a photosensitive resin layer 13, a water-soluble resin layer 15 and a cover film 17 in sequence.

[0599] In addition, although Figure 2 The transfer film 20 shown is configured with a cover film 17, but the cover film 17 may not be configured.

[0600] The elements constituting the transfer film of the second embodiment will be described below.

[0601] In the transfer film of the second embodiment, the temporary support 11, the photosensitive resin layer 13, and the cover film 17 can be the same as those in the first embodiment described above, and the preferred embodiment is also the same.

[0602] Water-soluble resin layer

[0603] In the transfer film 20, the water-soluble resin layer 15 functions as a refractive index adjustment layer for adjusting the refractive index. That is, as one embodiment of the transfer film in the second embodiment, the water-soluble resin layer can function as a refractive index adjustment layer for adjusting the refractive index.

[0604] The water-soluble resin layer 15 comprises materials for adjusting compound A, the resin, and the refractive index (refractive index adjusting material: for example, at least one material selected from metal oxides, compounds having a triazine ring, and compounds having a cyclohexane skeleton). The resin described above comprises, in part or in whole, a water-soluble resin. As defined above, "water-soluble resin" refers to a resin with a solubility of 0.1 g or more in 100 g of water at a liquid temperature of 22°C and pH 7.0.

[0605] The following describes the components that a water-soluble resin layer can contain.

[0606] <Compound A>

[0607] The water-soluble resin layer contains compound A.

[0608] Examples of compound A include the same compound A contained in the water-soluble resin layer of the transfer film of the first embodiment, and its preferred embodiments are also the same.

[0609] Compound A can be used alone or in more than two forms.

[0610] The content of compound A relative to the total mass of the water-soluble resin layer is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, and even more preferably 0.02 to 1% by mass.

[0611] <Resin>

[0612] The water-soluble resin layer contains resin.

[0613] As described above, the resins mentioned above may include water-soluble resins as part or all of them.

[0614] As the resin included in the water-soluble resin layer, examples include the same water-soluble resin included in the water-soluble resin layer of the transfer film of the first embodiment.

[0615] Water-soluble resins can be used alone or in combination with two or more.

[0616] The content of water-soluble resin relative to the total mass of the water-soluble resin layer is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 5 to 30% by mass, and particularly preferably 5 to 20% by mass.

[0617] Furthermore, the water-soluble resin layer may contain an alkali-soluble resin.

[0618] As the aforementioned alkali-soluble resin, the alkali-soluble resin contained in the thermoplastic resin layer and the photosensitive resin layer in the transfer film of the first embodiment can also be used.

[0619] Furthermore, the alkali-soluble resin is preferably a copolymer of (meth)acrylic acid / vinyl ester compound, more preferably a copolymer of (meth)acrylic acid / (meth)acrylate allyl ester, and even more preferably a copolymer of methacrylic acid / methacrylate allyl ester.

[0620] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the component ratio (mol%) is preferably 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0621] Alkali-soluble resins can be used alone or in combination with two or more types.

[0622] The content of alkali-soluble resin relative to the total mass of the water-soluble resin layer is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 5 to 30% by mass, and particularly preferably 5 to 20% by mass.

[0623] Furthermore, the water-soluble resin mentioned above is preferably an alkali-soluble resin.

[0624] <Refractive index adjusting materials>

[0625] Furthermore, the water-soluble resin layer contains at least one material selected from metal oxides, compounds having triazine rings, and compounds having a fusiform skeleton (refractive index adjusting material).

[0626] (metal oxides)

[0627] There are no particular restrictions on the types of metal oxides; well-known metal oxides can be cited. Metals in metal oxides also include half-metals such as B, Si, Ge, As, Sb, and Te.

[0628] Examples of metal oxides include zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide.

[0629] Among these, as a metal oxide, for example, from the viewpoint of easy adjustment of the refractive index, at least one selected from zirconium oxide and titanium oxide is preferred.

[0630] Metal oxides are preferably in particulate form.

[0631] For example, from the viewpoint of the transparency of the cured film, the average primary particle size of the metal oxide particles is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0632] The average first-order particle size was calculated by measuring the particle size of any 200 particles using an electron microscope and then arithmetically averaging the results. Additionally, in cases where the particle shape is not spherical, the longest side was used as the particle size.

[0633] Commercially available metal oxide particles include sintered zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), sintered zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), sintered zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), sintered zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (Nanouse OZ-S30M, manufactured by NISSANCHEMICAL INDUSTRIES, LTD.), and zirconia particles (Nanouse OZ-S30K, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.).

[0634] (Compounds containing a triazine ring)

[0635] As compounds having a triazine ring, examples include polymers having a triazine ring in their structural units, and compounds having structural units represented by the following general formula (X).

[0636] Preferably, the polymer having a triazine ring in the above-mentioned structural unit is different from the resin that can be contained in the water-soluble resin.

[0637] [Chemical Formula 15]

[0638]

[0639] In the formula, Ar represents a divalent group comprising at least one of an aromatic ring (e.g., 6 to 20 carbon atoms) and a heterocycle (e.g., 5 to 20 atoms).

[0640] X is independently NR 1 R 1 Each of the following can be independently represented: hydrogen atom, alkyl group (e.g., 1 to 20 carbon atoms), alkoxy group (e.g., 1 to 20 carbon atoms), aryl group (e.g., 6 to 20 carbon atoms), and aralkyl group (e.g., 7 to 20 carbon atoms). Multiple X's can be the same or different.

[0641] Specifically, hyperbranched polymers with triazine rings are preferred, for example, those available commercially as part of the HYPERTECH series (manufactured by NISSANCHEMICAL INDUSTRIES, LTD., product name).

[0642] (Compounds with a fusiform skeleton)

[0643] As compounds with a cyclohexane backbone, compounds having a 9,9-bis[4-2-(meth)acryloyloxyethoxyphenyl]cyclohexane backbone are preferred. These compounds can be modified with (poly)oxyethylene or (poly)oxypropylene. For example, these are commercially available as EA-0200 (manufactured by Osaka Gas Chemicals Co., Ltd., product name). Furthermore, epoxy modification can be performed using epoxy acrylates. For example, these are commercially available as GA5000 and EG200 (manufactured by Osaka Gas Chemicals Co., Ltd., product name).

[0644] One type of refractive index adjusting material can be used alone, or two or more types can be used.

[0645] The content of the refractive index adjusting material in the water-soluble resin layer is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to the total mass of the water-soluble resin layer. There is no particular upper limit, but it is preferably 95% by mass or less, more preferably 90% by mass or less.

[0646] <Metal Oxidation Inhibitors>

[0647] Furthermore, the water-soluble resin layer preferably contains a metal oxidation inhibitor.

[0648] When the water-soluble resin layer contains a metal oxidation inhibitor, the acidification of the metal in the water-soluble resin layer can be suppressed.

[0649] As a metal oxidation inhibitor, for example, a compound having an aromatic ring containing a nitrogen atom within the molecule is preferred. Examples of metal oxidation inhibitors include imidazoles, benzimidazoles, tetrazolazoles, mercaptothiadiazoles, benzotriazoles, pyridines (such as isoniazidamides), and purine bases (such as adenine).

[0650] As for the aforementioned benzotriazoles, for example, the benzotriazoles described in the description of the photosensitive resin layer in the transfer film of the first embodiment can also be used.

[0651] The content of the metal oxidation inhibitor relative to the total mass of the water-soluble resin layer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.

[0652] <Polymerizing compounds>

[0653] The water-soluble resin layer may contain polymeric compounds.

[0654] The content of the polymeric compound is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the total mass of the water-soluble resin layer.

[0655] As a polymeric compound, examples include polymeric compounds that are the same polymeric compounds that can be contained in the photosensitive resin layer of the transfer film of the first embodiment, wherein polymeric compounds having acid groups are preferred.

[0656] <Other Ingredients>

[0657] The water-soluble resin layer may contain other components besides those mentioned above.

[0658] Other components may include amino alcohols (such as N-methyldiethanolamine and monoisopropanolamine). Preferably, the amino alcohol is a compound having one or more (e.g., one to five) primary alcohol groups and one or more (e.g., one to five) primary to tertiary amino groups. The content of the amino alcohol is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the total mass of the water-soluble resin layer.

[0659] The refractive index of the water-soluble resin layer is preferably 1.60 or higher, more preferably 1.63 or higher. The upper limit of the refractive index is preferably 2.10 or lower, more preferably 1.85 or lower.

[0660] The thickness of the water-soluble resin layer is preferably 500 nm or less, more preferably 110 nm or less, and even more preferably 100 nm or less. The lower limit of the above thickness is, for example, 20 nm or more.

[0661] Method for manufacturing transfer film according to the second embodiment

[0662] The method for manufacturing the transfer film in the second embodiment is not particularly limited, and known manufacturing methods, such as known methods for forming each layer, can be used.

[0663] The following is for reference. Figure 2 The manufacturing method of the transfer film according to the second embodiment will be described. However, the transfer film of the second embodiment is not limited to having... Figure 2 The transfer film with the structure shown in the figure.

[0664] As a method for manufacturing the transfer film 20, for example, a method including the following steps can be described: a step of coating a photosensitive resin composition (negative photosensitive resin composition) onto the surface of a temporary support 11 to form a coating film, and further drying the coating film to form a photosensitive resin layer 13 (negative photosensitive resin layer); a step of coating a water-soluble resin composition onto the surface of the photosensitive resin layer 13 (negative photosensitive resin layer) to form a coating film, and further drying the coating film to form a water-soluble resin layer 15.

[0665] Furthermore, the water-soluble resin composition and the method for forming the water-soluble resin layer will be described later. The method for forming the photosensitive resin composition (negative photosensitive resin composition) and the photosensitive resin layer (negative photosensitive resin layer) is the same as described in the method for manufacturing the transfer film in the first embodiment described above, and the preferred embodiment is also the same.

[0666] The transfer film 20 is manufactured by pressing the cover film 17 onto the water-soluble resin layer 15 of the laminate manufactured by the above manufacturing method.

[0667] As a method for manufacturing the transfer film according to the second embodiment, it is preferable to manufacture a transfer film 20 having a temporary support 11, a photosensitive resin layer 13, a water-soluble resin layer 15 and a cover film 17 by a step including setting a cover layer 17 to contact the surface of the water-soluble resin layer 15 opposite to the side having the temporary support 11.

[0668] After the transfer film 20 is manufactured using the above manufacturing method, it is wound up, thereby enabling the production and storage of a roller-type transfer film. The roller-type transfer film can be provided in its original form during the roll-to-roll bonding process with the substrate, as described later.

[0669] Furthermore, as a method for manufacturing the transfer film 20, a photosensitive resin layer 13 can be formed on the surface of the water-soluble resin layer 15 after forming a water-soluble resin layer 15 on the cover film 17.

[0670] <Water-soluble resin composition and method for forming water-soluble resin layer>

[0671] The water-soluble resin composition preferably includes various components and solvents that form the water-soluble resin layer described above. Furthermore, in the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the water-soluble resin layer described above.

[0672] As a solvent, there are no particular limitations as long as it can dissolve or disperse compound A and water-soluble resin. Preferably, it is selected from at least one of water and water-mixed organic solvents, more preferably water or a mixture of water and water-mixed organic solvents.

[0673] Examples of water-mixable organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols with 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0674] You can use one solvent alone, or you can use two or more solvents.

[0675] The solvent content is preferably 50 to 2,500 parts by mass relative to 100 parts by mass of the total solids in the composition, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0676] The method for forming the water-soluble resin is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, for example, well-known coating methods (slot coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0677] [Manufacturing methods for laminated structures and circuit wiring]

[0678] The present invention also relates to a method for manufacturing a laminate.

[0679] There are no particular limitations on the manufacturing method of the laminate, as long as it is a manufacturing method of the laminate using the transfer film of the first embodiment and the second embodiment described above.

[0680] The preferred manufacturing method for the laminate is as follows: It includes a bonding step (hereinafter also referred to as the "bonding step"), in which a substrate (preferably a conductive substrate) is brought into contact with the surface of the outermost layer of the composition layer disposed on a temporary support in the transfer film, and the transfer film and the substrate (preferably a conductive substrate) are bonded together to obtain a substrate with the transfer film; an exposure step (hereinafter also referred to as the "exposure step"), in which the composition layer is patterned and exposed; a developing step (hereinafter also referred to as the "developing step"), in which the exposed composition layer is developed to form a resin pattern; and a peeling step (hereinafter also referred to as the "peeling step"), in which the temporary support is peeled from the substrate with the transfer film between the bonding step and the exposure step or between the exposure step and the developing step.

[0681] There are no particular limitations on the method of manufacturing circuit wiring, as long as it is a method of manufacturing circuit wiring using the transfer film of the first and second embodiments described above.

[0682] As a method for manufacturing circuit wiring, the preferred method includes the following steps (hereinafter also referred to as "etching steps"): etching the conductive layer located in the region where the resin pattern is not disposed in a laminate in which a substrate, a conductive layer (a conductive layer having the substrate) and a resin pattern manufactured using the above-mentioned transfer film are sequentially stacked.

[0683] That is, the preferred method for manufacturing circuit wiring is as follows: a bonding process (hereinafter also referred to as "bonding process"), in which a substrate having a conductive layer is brought into contact with the surface of the outermost layer of a composite layer disposed on a temporary support in a transfer film, thereby bonding the transfer film and the substrate having a conductive layer to obtain a substrate with a transfer film; an exposure process (hereinafter also referred to as "exposure process"), in which the composite layer is patterned and exposed; a developing process (hereinafter also referred to as "developing process"), in which the exposed composite layer is developed to form a resin pattern; an etching process (hereinafter also referred to as "etching process") of the conductive layer located in areas where no resin pattern is disposed; and a peeling process (hereinafter also referred to as "peeling process"), in which the temporary support is peeled from the substrate with the transfer film between the bonding process and the exposure process or between the exposure process and the developing process.

[0684] The following describes the process included in the manufacturing method of the laminate and the manufacturing method of the circuit wiring. However, unless otherwise specified, the description of the process included in the manufacturing method of the laminate also applies to the process included in the manufacturing method of the circuit wiring.

[0685] [Lamination process]

[0686] The preferred method for manufacturing laminates includes a bonding process.

[0687] In the bonding process, it is preferable to bring the substrate (or conductive layer if a conductive layer is provided on the surface of the substrate) into contact with the surface of the outermost layer of the composition layer disposed on the temporary support in the transfer film, and to press the transfer film and the substrate together. With the above embodiment, the adhesion between the composition layer and the substrate is improved, and therefore it is particularly suitable as an etch resist when etching a conductive layer using a resin pattern formed after exposure and development.

[0688] Alternatively, if the transfer film has a cover film, you can simply remove the cover film from the surface of the transfer film and then apply it.

[0689] There are no particular limitations on the method of bonding the substrate and the transfer film; known transfer and lamination methods can be used.

[0690] For bonding the transfer film to the substrate, it is preferable to stack the substrate on the side of the transfer film opposite to the temporary support, and apply pressure and heat using methods such as rollers. Known laminators such as laminators, vacuum laminators, and automatic cutting laminators that can further improve productivity can be used in the bonding process.

[0691] Preferably, the manufacturing method of the laminate, including the bonding process, and the manufacturing method of the circuit wiring are carried out by a roller-to-roll method.

[0692] Roll-to-roll refers to a method comprising: using a substrate capable of being wound and unwound as a substrate; an unwinding process (also called an "unwinding process") of the substrate or a structure including the substrate before any step in the manufacturing method of the laminate or the manufacturing method of the circuit wiring; and a winding process (also called a "winding process") of the substrate or a structure including the substrate after any step, wherein at least one step (preferably all steps or all steps except the heating step) is performed while the substrate or the structure including the substrate is being transported.

[0693] There are no particular restrictions on the unwinding method in the unwinding process and the winding method in the winding process, as long as a known method is used in the manufacturing method using the roll-to-roll method.

[0694] <Substrate>

[0695] As a substrate for forming the resin pattern using the transfer film of the first embodiment and the second embodiment, any known substrate can be used, but a substrate having a conductive layer is preferred, and a substrate having a conductive layer on the surface of the substrate is more preferred.

[0696] Depending on the requirements, the substrate can have any layer other than the conductive layer.

[0697] Examples of substrates that form a substrate include glass, silicon, and thin films.

[0698] The substrate constituting the substrate is preferably transparent. In this specification, "transparent" means that the transmittance of light with a wavelength of 400 to 700 nm is 80% or more.

[0699] Furthermore, the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

[0700] Examples of transparent glass substrates include tempered glass, such as Corning Incorporated Gorilla Glass. Furthermore, materials used in Japanese Patent Application Publication Nos. 2010-086684, 2010-152809, and 2010-257492 can also be used as transparent glass substrates.

[0701] When using a thin film substrate as a base material, it is preferable to use a thin film substrate with low optical distortion and / or high transparency. Examples of such thin film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cyclic olefin polymers.

[0702] When the substrate is manufactured by a roll-to-roll process, a thin film substrate is preferred. Furthermore, when manufacturing circuit wiring for a touch panel by a roll-to-roll process, a sheet-like resin composition is preferred as the substrate.

[0703] Examples of conductive layers in a substrate include those used in general circuit wiring and touch panel wiring.

[0704] From the viewpoint of conductivity and fine line formation, the conductive layer is preferably selected from at least one layer selected from metal layers, conductive metal oxide layers, graphene layers, carbon nanotube layers and conductive polymer layers, more preferably metal layers, and even more preferably copper or silver layers.

[0705] The substrate may have a single conductive layer or two or more conductive layers. When there are two or more conductive layers, it is preferable that the conductive layers are made of different materials.

[0706] Materials that can be used as conductive layers include metals and conductive metal oxides.

[0707] Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0708] Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2.

[0709] In addition, in this specification, "conductivity" refers to a volume resistivity of less than 1×10⁻⁶. 6 Ωcm. Preferably, the volume resistivity of the conductive metal oxide is less than 1×10⁻⁶. 4 Ωcm.

[0710] When using a substrate having multiple conductive layers to manufacture resin patterns, it is preferable that at least one of the multiple conductive layers comprises a conductive metal oxide.

[0711] As a conductive layer, it is preferably the electrode pattern of the sensor that corresponds to the visual recognition part or the wiring of the peripheral extraction part used in the electrostatic capacitive touch panel.

[0712] [Exposure process]

[0713] The manufacturing method of the laminate preferably includes a step of patterning the composition layer after the above-mentioned bonding step (exposure step).

[0714] There are no particular limitations on the detailed configuration and specific size of the pattern in the pattern exposure. At least a portion of the pattern (preferably the electrode pattern of the touch panel and / or the portion of the take-out wiring) preferably includes fine lines with a width of 20 μm or less to improve the display quality of the display device (e.g., touch panel) having an input device with circuit wiring manufactured by a circuit wiring manufacturing method, and to reduce the area occupied by the take-out wiring, more preferably including fine lines with a width of 10 μm or less.

[0715] Regarding the light source used in the exposure, any light source that illuminates the photosensitive resin layer at a wavelength capable of exposing the light (e.g., 365nm or 405nm) can be appropriately selected. Specifically, examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

[0716] The preferred exposure level is 5–200 mJ / cm². 2 More preferably 10–100 mJ / cm 2 .

[0717] [Stripping process]

[0718] The peeling process is the process of peeling a temporary support from a substrate with a photosensitive composition layer between the bonding process and the exposure process, or between the exposure process and the development process described later.

[0719] There are no particular limitations on the peeling method, and the same mechanism as the covering film peeling mechanism described in paragraphs

[0161] to

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

[0720] Therefore, in the exposure process, pattern exposure can be performed after the temporary support is peeled off from the composition layer, or pattern exposure can be performed via the temporary support before peeling off the temporary support, and then the temporary support is peeled off. Regarding the mask, if the temporary support is peeled off before exposure, exposure can be performed in contact with the composition layer, or it can be performed close to it without contact. If exposure is performed without peeling off the temporary support, the mask can be exposed in contact with the temporary support, or it can be performed close to it without contact. To prevent mask contamination caused by contact between the composition layer and the mask, and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. Furthermore, regarding the exposure method, in the case of contact exposure, a contact exposure method can be appropriately selected; in the case of non-contact exposure, a proximity exposure method, a lens system and mirror system projection exposure method, or a direct exposure method using an exposure laser can be appropriately selected. In the case of lens system and mirror system projection exposure, an exposure machine with an appropriate number of lens apertures (NA) can be used according to the required resolution and depth of focus. In the direct exposure method, the image can be drawn directly onto the photosensitive layer, or it can be projected onto the photosensitive layer through a lens to reduce its size. Furthermore, exposure can be performed not only in the atmosphere, but also under reduced pressure or vacuum, and even by placing a liquid such as water between the light source and the photosensitive layer for exposure.

[0721] [Developing process]

[0722] The preferred method for manufacturing the laminate includes a step (development step) after the above-mentioned exposure step, in which the exposed composition layer is developed to form a resin pattern.

[0723] When the composition layer includes a negative photosensitive resin layer, the composition layer undergoes a curing reaction according to the exposed pattern to become a cured film (patterned cured film), and only the non-exposed parts of the composition layer can be removed using a developer (alkaline developer, etc.).

[0724] When the transfer film has a negative photosensitive resin layer and thus a different composition layer, the different composition layer may remove only the portion that is the same as the portion removed in the negative photosensitive resin layer, or it may remove all portions except the portion removed in the negative photosensitive resin layer.

[0725] For example, when the transfer film has a negative photosensitive resin layer, a thermoplastic resin layer, and a water-soluble resin layer, in the developing process, only the thermoplastic resin layer and water-soluble resin layer of the non-exposed area need to be removed together with the negative photosensitive resin layer of the non-exposed area. Furthermore, in the developing process, the thermoplastic resin layer and water-soluble resin layer in both the exposed and non-exposed areas can be removed by dissolving or dispersing them in the developing solution.

[0726] The development of the exposed composite layer in the development process can be performed using a developing solution.

[0727] The developer can be appropriately selected according to the properties of the composite layer of the transfer film and the form of development. For example, alkaline developers and organic developers can be cited.

[0728] As an alkaline developer, for example, known developers such as the one described in Japanese Patent Application Publication No. 5-072724 can be used.

[0729] As an alkaline developer, an aqueous alkaline developer containing a compound with pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferred. The alkaline developer may contain a water-soluble organic solvent and / or a surfactant. The developer described in paragraph 0194 of International Publication No. 2015 / 093271 is also preferred. The content of organic solvent in the alkaline developer is preferably 0% by mass or more and less than 90% by mass relative to the total mass of the developer.

[0730] As an organic-based developer, one or more developers can be used, including polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents. The content of organic solvent in the organic-based developer is preferably 90-100% by mass relative to the total mass of the developer, and more preferably 95-100% by mass.

[0731] There are no particular restrictions on the development method; it can be any of the following: spin-dip development, spray development, spray and spin development, or immersion development. Spray development refers to the development process that removes unexposed areas by spraying developing solution onto the exposed photosensitive resin layer.

[0732] Preferably, after the developing process, the developing residue is removed by spraying cleaning agent and wiping with a brush.

[0733] There are no particular restrictions on the temperature of the developer, but it is preferably 20–40°C.

[0734] [Etching process]

[0735] The preferred method for manufacturing circuit wiring includes the following step (etching step): in a laminate in which a substrate, a conductive layer (the conductive layer on the substrate) and a resin pattern (more preferably a resin pattern manufactured by a manufacturing method including the above-described bonding step, the above-described exposure step and the above-described development step) are sequentially stacked, the conductive layer located in the region where the resin pattern is not disposed is etched.

[0736] In the etching process, the resin pattern formed by the photosensitive resin layer is used as an etching resist to etch the conductive layer.

[0737] As a method for etching, known methods can be applied, such as the methods described in paragraphs 0209 to 0210 of Japanese Patent Application Publication No. 2017-120435, the methods described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, wet etching methods immersed in etching solution, and dry etching methods based on plasma etching, etc.

[0738] Regarding the etching solution used in wet etching, simply select an acidic or alkaline etching solution according to the object being etched.

[0739] Examples of acidic etching solutions include, for example, aqueous solutions containing only acidic components selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as mixed aqueous solutions containing the acidic component and salts selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component can be a combination of multiple acidic components.

[0740] Examples of alkaline etching solutions include aqueous solutions containing only alkaline components selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), as well as mixed aqueous solutions containing alkaline components and salts (such as potassium permanganate). The alkaline component can be a combination of multiple alkaline components.

[0741] [Removal process]

[0742] Preferably, in the manufacturing method of the circuit wiring, a process for removing residual resin patterns (removal process) is performed.

[0743] There are no particular restrictions on the removal process, and it can be performed as needed, but it is preferred to perform it after the etching process.

[0744] There are no particular limitations on the method for removing residual resin patterns, but methods that remove them by chemical treatment are exemplified, and methods that remove them by using a removal solution are preferred.

[0745] As a method for removing the photosensitive resin layer, one example is to immerse a substrate with residual resin patterns in a stirring removal solution at a temperature preferably 30-80°C, more preferably 50-80°C, for 1-30 minutes.

[0746] Examples of removal solutions include those obtained by dissolving an inorganic or organic basic component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic basic components include sodium hydroxide and potassium hydroxide. Examples of organic basic components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0747] Furthermore, it can be removed using a removal liquid and by known methods such as spraying, rinsing, and immersion.

[0748] [Other processes]

[0749] The manufacturing method of circuit wiring may include any steps other than those described above (other steps). For example, the following steps can be cited, but are not limited to these steps.

[0750] Furthermore, the exposure process, development process, and other processes that can be applied in the manufacturing method of circuit wiring can be exemplified by the processes described in paragraphs 0035 to 0051 of Japanese Patent Application Publication No. 2006-023696.

[0751] Cover film peeling process

[0752] When the transfer film has a cover film, the manufacturing method of the laminate preferably includes a step of peeling off the cover film from the transfer film. There are no restrictions on the method of peeling off the cover film, and known methods can be used.

[0753] Processes that reduce the reflectivity of visible light

[0754] The manufacturing method of circuit wiring may include a process of performing a treatment to reduce the visible light reflectivity of some or all of the multiple conductive layers of a substrate.

[0755] Oxidation is an example of a process to reduce visible light reflectivity. When the substrate has a conductive layer containing copper, oxidizing the copper to produce copper oxide and blackening the conductive layer reduces the visible light reflectivity of the conductive layer.

[0756] The treatment for reducing visible light reflectance is described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, and the contents described in these publications are incorporated herein by reference.

[0757] The process of forming an insulating film and the process of forming a new conductive layer on the surface of the insulating film.

[0758] The manufacturing method of the circuit wiring also preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.

[0759] Through the above process, a second electrode pattern that is insulated from the first electrode pattern can be formed.

[0760] There are no particular limitations on the process of forming the insulating film, and methods for forming known permanent films can be cited. Furthermore, an insulating film with a desired pattern can be formed by photolithography using a photosensitive material with insulating properties.

[0761] There are no particular limitations on the process of forming a new conductive layer on an insulating film. For example, a new conductive layer with a desired pattern can be formed by using a photosensitive material with conductive properties through photolithography.

[0762] In a preferred method for manufacturing circuit wiring, a substrate having multiple conductive layers on each of its two surfaces is used, and circuits are formed sequentially or simultaneously on the conductive layers formed on the two surfaces of the substrate. This structure allows for the formation of touch panel circuit wiring with a first conductive pattern on one surface of the substrate and a second conductive pattern on the other surface. Furthermore, it is also preferable to form this type of touch panel circuit wiring from both sides of the substrate using a roller-to-roll method.

[0763] [Applications of circuit wiring]

[0764] Circuit wiring manufactured using the aforementioned method can be applied to various devices. Examples of devices equipped with circuit wiring manufactured using this method include input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, these input devices can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[0765] Manufacturing methods for electronic devices

[0766] The present invention also relates to a method for manufacturing an electronic device.

[0767] As a method for manufacturing the above-mentioned electronic device, a method for manufacturing an electronic device using the transfer film of the first embodiment and the second embodiment described above is preferred.

[0768] The manufacturing method of the electronic device preferably includes the manufacturing method of the above-mentioned laminate.

[0769] Examples of such electronic devices include input devices, with touch panels being a preferred choice. Furthermore, these input devices can be applied to display devices such as organic light-emitting diode (OLED) displays and liquid crystal displays (LCDs).

[0770] As a method for manufacturing a touch panel, a method including the following steps is preferred: in a laminate in which a substrate, a conductive layer (the conductive layer having the substrate) and a resin pattern manufactured using the transfer film of the first embodiment and the second embodiment are sequentially stacked, the conductive layer located in the area where the resin pattern is not disposed is etched, thereby forming wiring for a touch panel, and more preferably, a method using a resin pattern manufactured by a manufacturing method including the above-described bonding step, the above-described exposure step and the above-described development step.

[0771] Regarding the specific implementation methods of each step in the method for manufacturing a touch panel, including the step of forming wiring for the touch panel, and the order in which each step is performed, the preferred implementation method is the same as described in the above-mentioned "Method for Manufacturing Circuit Wiring".

[0772] Furthermore, the manufacturing method of the touch panel, including the process of forming wiring for the touch panel, may include any other process (other processes) besides those described above.

[0773] As a method for forming wiring for a touch panel, reference can also be made to International Publication No. 2016 / 190405. Figure 1 The methods recorded in the text.

[0774] The above-described method for manufacturing a touch panel allows for the production of a touch panel with at least wiring for the touch panel. The touch panel preferably includes a transparent substrate, electrodes, and an insulating or protective layer.

[0775] Commonly known detection methods in touch panels include resistive film detection, capacitive detection, ultrasonic detection, electromagnetic induction, and optical detection. Among these, capacitive detection is preferred.

[0776] Examples of touch panels include embedded types (e.g., the touch panels described in Figures 5, 6, 7, and 8 of Japanese Patent Application Publication No. 2012-517051) and embedded types (e.g., the touch panels described in Figure 19 of Japanese Patent Application Publication No. 2013-168125 and Japanese Patent Application Publication No. 2012-89102). Figure 1and the touch panel shown in Figure 5), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, Japanese Patent Application Publication No. 2013-54727). Figure 2 The touch panel described in the document), various plug-in types (such as GG, G1·G2, GFF, GF2, GF1 and G1F, etc.) and other structures (for example, the touch panel described in Figure 6 of Japanese Patent Application Publication No. 2013-164871).

[0777] As a touch panel, for example, the touch panel described in paragraph 0229 of Japanese Patent Application Publication No. 2017-120345 can be cited.

[0778] Preferably, in the method for manufacturing an electronic device using the transfer film of the first embodiment and the second embodiment (especially in the case where the transfer film includes a negative photosensitive composition layer), the manufactured electronic device includes a resin pattern as a cured film.

[0779] This type of resin-patterned cured film can be used as a protective film (permanent film) to cover part or all of the electrodes of electronic devices (such as touch panels). By applying the above-mentioned resin-patterned cured film as a protective film (permanent film) to the electrodes, it is possible to prevent defects such as metal corrosion, increased resistance between the electrodes and the driving circuit, and wire breaks.

[0780] Example

[0781] The present invention will now be described in further detail based on embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0782] In the following embodiments, unless otherwise specified, “parts” and “%” refer to “parts by mass” and “% by mass”, respectively.

[0783] [Synthesis of Compound A]

[0784] [Synthetic Examples 1-4: Synthesis of Polymer Compound A]

[0785] <Synthesis example 1>

[0786] 25.0 g of cyclohexanone (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to a 300 mL three-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet, and the mixture was heated to 80 °C. Next, 10.40 g (36.6 mmol) of 1H,1H,5H-octafluoropentyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 60.5 g (111.8 mmol) of polyethylene glycol monoacrylate (BLEMMER AE-400 (n≈10, manufactured by NOF CORPORATION.), 25.0 g of cyclohexanone, and initiator "V-601" (FUJIFILM Wako Pure Chemical Corporation) were added. A 0.342 g mixed solution (manufactured by Chemical Corporation) was added dropwise at a constant rate to complete the addition within 180 minutes. After the addition was complete, stirring was continued for another hour, followed by the addition of a solution containing 0.342 g of "V-601" and 1.00 g of cyclohexanone. Immediately after the addition, the temperature was raised to 93°C, and stirring was continued for another 2 hours to obtain 121.5 g of a cyclohexanone solution of polymer A-1 as shown in the following section. The weight-average molecular weight (Mw) of this polymer was calculated from polystyrene using gel permeation chromatography (EcoSECHLC-8320GPC (manufactured by TOSOH CORPORATION)) with THF eluent, a flow rate of 0.35 ml / min, and a temperature of 40°C, using TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by TOSOH CORPORATION) columns.

[0787] <Synthesis Example 2 to Synthesis Example 4>

[0788] Except for changing the monomers and composition ratios used in Synthesis Example 1 as shown in Table 1, polymers A-5, A-6 and A-9 were synthesized by the same method.

[0789] The structures of polymers A-1, A-5, A-6, and A-9 are shown below. Additionally, the numerical values ​​of the structural units added to the polymers represent their content (mass %) relative to the total mass of the polymer.

[0790] [Chemical Formula 16]

[0791]

[0792] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersity (Mw / Mn) of each polymer are shown below.

[0793] [Table 1]

[0794] Synthesis example Types of polymers Mw Mn Mw / Mn 1 A-1 11000 5000 2.2 2 A-5 12000 6030 1.99 3 A-6 18000 7400 2.43 4 A-9 9000 3900 2.29

[0795] [Synthetic Example 5: Synthesis of Low Molecular Weight Compound A]

[0796] References (“Ritsumatsu et al., Oil Chemistry, 1980, Vol.29(1), p23” and “Ritsumatsu et al., Pharmaceutical Science, 1976, Vol.25(5), p287”) were used to synthesize the low molecular weight compound B-1 shown below using known methods.

[0797] [Chemical Formula 17]

[0798]

[0799] [Examples 1-8 and Comparative Examples 1 and 2]

[0800] [Preparation of photosensitive resin composition]

[0801] <Resin Manufacturing>

[0802] In the following synthetic examples, the following abbreviations refer to the following compounds.

[0803] St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0804] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0805] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0806] BzMA: Benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0807] AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0808] PGMEA: Propylene Glycol Monomethyl Ether Acetate (manufactured by SHOWA DENKO KK)

[0809] MEK: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0810] V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0811] Synthesis of Resin P-1

[0812] 116.5 parts of PGMEA were placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. After 2 hours, a solution containing 52.0 parts of St, 19.0 parts of MMA, 29.0 parts of MAA, 4.0 parts of V-601, and 116.5 parts of PGMEA was added dropwise to the solution in the flask, which was maintained at 90°C ± 2°C. After the addition was complete, the solution in the flask was stirred at 90°C ± 2°C for 2 hours to obtain resin P-1 (solid content concentration of 30.0% by mass).

[0813] (Synthesis of resins P-2 and P-3)

[0814] As shown in Table 1 below, the types of monomers used were changed. Regarding other conditions, solutions containing resin P-2 and resin P-3 were obtained using the same method as for resin P-1. The solid content concentration of the solutions containing resin P-2 and resin P-3 was set to 30% by mass.

[0815] The following shows the types of monomers used to synthesize each resin, the mass percentage (mass%) of the structural units derived from each monomer, and the weight-average molecular weight of each resin.

[0816] In addition, resins P-1 to P-3 are all equivalent to alkali-soluble resins.

[0817] [Table 2]

[0818] P-1 P-2 P-3 St 52 32 BzMA 81 MAA 29 19 28 MMA 19 40 Weight-average molecular weight (Mw) 60,000 4,0000 40,000

[0819] <Preparation of photosensitive resin compositions 1-4>

[0820] According to the formulations described in Table 3 shown later, these components were mixed by stirring to prepare photosensitive resin compositions 1 to 4. Furthermore, the amount of each component is expressed in parts by mass.

[0821] The following shows the blending of each photosensitive resin composition 1 to 4.

[0822] In the table, the numerical values ​​for each component in each photosensitive resin composition represent the amount (parts by mass) of each component added.

[0823] In addition, the resin is added to each photosensitive resin composition in the form of a resin-containing solution. The values ​​in the table indicating the amount of resin added are the mass of the added "resin-containing solution".

[0824] Unless otherwise specified, the following applies to components added to the composition in a manner that includes them in a mixed solution.

[0825] [Table 3]

[0826]

[0827] The details of each component are shown in Table 3.

[0828] BPE-500: 2,2-bis(4-((meth)acryloyloxypentethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0829] BPE-200: 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0830] M-270: Polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO., LTD.

[0831] • A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0832] SR-454: Ethoxylated (3)trimethylolpropane triacrylate, manufactured by Arkema

[0833] SR-502: Ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema

[0834] • A-9300-CL1: Caprolactone-modified (meth)acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0835] • B-CIM: 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-Tetraphenylbisimidazole, Hampford

[0836] SB-PI 701: 4,4'-bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO., LTD.

[0837] • Colorless crystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0838] Bright Green: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0839] N-Phenylglycine: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0840] • CBT-1: Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD

[0841] • TDP-G: Phenylephrine, manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0842] Irganox 245: A hindered phenolic antioxidant manufactured by BASF.

[0843] • N-Nitrophenylhydroxylamine aluminum salt: Manufactured by FUJIFILM Wako Pure Chemical Corporation

[0844] • Phenylidene: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0845] Megaface F552, manufactured by DIC CORPORATION

[0846] [Preparation of thermoplastic resin compositions]

[0847] Synthesis of Resin P-4

[0848] As shown in Table 4 below, the types of monomers used were changed, and other conditions were handled using the same method as for resin P-1 to obtain a solution containing resin P-4. The solid content concentration of the solution containing resin P-4 was set to 30% by mass.

[0849] In addition, resin P-4 is equivalent to an alkali-soluble resin.

[0850] The following shows the types of monomers used to synthesize the resin, the mass percentage (mass%) of the structural units derived from each monomer, and the weight-average molecular weight of the resin.

[0851] [Table 4]

[0852] P-4 BzMA 75 MAA 10 MMA 15 Weight-average molecular weight (Mw) 30,000

[0853] <Preparation of thermoplastic resin compositions 1 and 2>

[0854] Thermoplastic resin compositions 1 to 2 were prepared by mixing the following components in the parts by mass shown in Table 5 below.

[0855] [Table 5]

[0856]

[0857] In Table 5, the abbreviations represent the following compounds.

[0858] • P-4: A resin comprising, relative to the total mass of the resin, 75% by mass, 10% by mass, and 15% by mass of benzyl methacrylate-based structural units, methyl methacrylate-based structural units, and acrylic acid-based structural units, respectively, and having a weight-average molecular weight of 30,000. Furthermore, P-4 is equivalent to an alkali-soluble resin as a thermoplastic resin. P-4 is added to the thermoplastic resin composition as a solution containing P-4 (solids concentration of 30.0% by mass, solvent: PGMEA).

[0859] • Acrybase FF187: A solution containing a resin as an alkali-soluble thermoplastic resin (solids concentration 40% by mass, solvent: PGMEA, manufactured by FUJIKURAKASEI CO., LTD.)

[0860] BB-1: Compounds with the structure shown below (pigments that develop color via acid).

[0861] [Chemical Formula 18]

[0862]

[0863] • C-1: A compound with the structure shown below (a photoacid generator, the compound described in paragraph 0227 of Japanese Patent Application Publication No. 2013-047765, synthesized according to the method described in paragraph 0227).

[0864] [Chemical Formula 19]

[0865]

[0866] [Adjustment of the water-soluble resin composition]

[0867] <Preparation of water-soluble resin compositions 1-7>

[0868] Water-soluble resin compositions 1 to 7 were prepared by mixing the following components in the parts by mass shown in Table 6 below.

[0869] In addition, water-soluble resin compositions 1 to 7 are preferred compositions for forming an intermediate layer.

[0870] Furthermore, the URARAY POVAL4-88LA, KURARAYPOVAL205, and polyvinylpyrrolidone used in the preparation of water-soluble resin compositions 1 to 7 have a solubility of more than 10g in 100g of water at a liquid temperature of 22°C and pH 7.0.

[0871] [Table 6]

[0872]

[0873] [Preparation of transfer film]

[0874] <Example 1>

[0875] Using a slit nozzle, the adjusted thermoplastic resin composition 1 was applied to a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) with a width of 1.0 m, so that the average film thickness of the dried composition layer was the specified film thickness (film thickness recorded in Table 5: 2.0 μm). After 60 seconds, the film was dried in a 3 m drying zone set to 80°C and with the air intake and exhaust rates adjusted, and the film surface wind speed set to 0.2 m / sec, thereby obtaining a laminate A of a temporary support and a thermoplastic resin layer.

[0876] Subsequently, using a slit nozzle, the coating amount was adjusted on the thermoplastic resin layer of the prepared laminate A so that the average film thickness of the dried composition layer was the specified film thickness (film thickness recorded in Table 6: 1.0 μm), and the water-soluble resin composition 1 was coated with a width of 1.0 m. Then, the laminate A was passed through a 3 m drying zone at a temperature of 100°C with the air intake and exhaust volumes adjusted and the film surface wind speed set to 3 m / sec for 60 seconds, thus obtaining a laminate B with a water-soluble resin layer formed on the thermoplastic resin layer.

[0877] Subsequently, using a slit nozzle, the coating amount was adjusted on the water-soluble resin layer of the prepared laminate B to achieve a specified average film thickness (film thickness recorded in Table 3: 2.0 μm), and the photosensitive resin composition 1 was coated with a width of 1.0 m. Then, the laminate B was passed through a 3 m drying zone at a temperature of 80°C with the air intake and exhaust rates adjusted and the film surface wind speed set to 0.2 m / sec for 60 seconds, thus obtaining the transfer film of Example 1 in which a photosensitive resin layer was formed on the water-soluble resin layer.

[0878] <Examples 2-8 and Comparative Examples 1 and 2>

[0879] As shown in Table 7, the transfer film was prepared in the same manner as in Example 1, except that the types of thermoplastic resin composition, water-soluble resin composition and photosensitive resin composition were changed.

[0880] However, for Examples 2-8 and Comparative Examples 1 and 2, the film thickness of the composition layer formed by each composition was varied according to the type of thermoplastic resin composition, water-soluble resin composition, and photosensitive resin composition. The film thickness of the formed composition layer refers to the average film thickness (μm) shown together with the composition in Tables 3, 5, and 6.

[0881] In addition, the transfer films of Examples 1 to 8 are equivalent to the transfer film of the first embodiment.

[0882] [Resolution Evaluation]

[0883] A PET substrate with a copper layer was prepared by sputtering a 200 nm thick copper layer onto a 100 μm thick polyethylene terephthalate (PET) film.

[0884] After unwinding the prepared transfer films (Examples 1-8 and Comparative Examples 1 and 2), the outermost layer (photosensitive resin layer) of the composite layer disposed on the temporary support was bonded to a PET substrate with the aforementioned copper layer under lamination conditions of 100°C roller temperature, 1.0 MPa linear pressure, and 4.0 m / min linear speed, thereby laminating a PET substrate with a copper layer onto the transfer film. Next, without peeling off the temporary support, the film was exposed under an ultra-high pressure mercury lamp through a line and space pattern (Duty ratio 1:1, linewidth 20 μm), and then the temporary support was peeled off for development. Development was performed using a 1.0% sodium carbonate aqueous solution at 25°C, by spray development for 30 seconds. When a line and space pattern was formed by the above method, an exposure amount with a resist linewidth of 20 μm was set as the optimal exposure amount.

[0885] Observation of any 1 cm of the line and spatial pattern formed under optimal exposure using scanning electron microscopy (SEM). 2 The resolution was evaluated based on the minimum linewidth obtained in the absence of resist pattern stripping and residue formation, according to the following evaluation criteria. Grades A, B, and C represent the acceptable ranges for practical applications. The results are shown in Table 7.

[0886] (Evaluation Criteria)

[0887] A: Resolution less than 5μm

[0888] B: Resolution of 5μm or higher but less than 7μm

[0889] C: Resolution of 7μm or higher and less than 9μm

[0890] D: Resolution of 9μm or higher and less than 11μm

[0891] E: Resolution of 11μm or higher

[0892] [Table 7]

[0893]

[0894] The results in Table 7 confirm that the transfer film according to the embodiment can form resist patterns with excellent resolution.

[0895] Furthermore, a comparison of the examples revealed the following: when compound A is a low molecular weight compound A represented by the above general formula (6B) with a molecular weight of 2,000 or less (equivalent to Examples 5, 6, and 8), or a high molecular weight compound A containing both the structural units represented by the above general formula (4) and the structural units represented by the above general formula (5) (equivalent to Examples 1 to 3 and 6), the resolution is even better. Specifically, when compound A is a low molecular weight compound A represented by the above general formula (6B) with a molecular weight of 2,000 or less (equivalent to Examples 5, 6, and 8), or a high molecular weight compound A with a weight-average molecular weight of 15,000 or less and containing both the structural units represented by the above general formula (4) and the structural units represented by the above general formula (5) (equivalent to Examples 1, 2, and 6), the resolution is even better.

[0896] [Examples 9-16 and Comparative Examples 3 and 4]

[0897] [Preparation of photosensitive resin composition]

[0898] <Resin Manufacturing>

[0899] (Synthesis of polymer P-5)

[0900] Propylene glycol monomethyl ether acetate (60 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) and propylene glycol monomethyl ether (240 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) were introduced into a 2000 mL flask. The resulting liquid was stirred at 250 rpm (round per minute; the same applies below) while the temperature was raised to 90 °C.

[0901] As a preparation of the dropping solution (1), methacrylic acid (107.1 g, manufactured by MITSUBISHI RAYON CO., LTD., product name Acryester M), methyl methacrylate (5.46 g, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name MMA) and cyclohexyl methacrylate (231.42 g, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name CHMA) were mixed and diluted with propylene glycol monomethyl ether acetate (60.0 g) to obtain the dropping solution (1).

[0902] As a preparation of the droplet (2), dimethyl 2,2'-azobis(2-methylpropionate) (9.637g, manufactured by FUJIFILM Wako Pure Chemical Corporation, product name V-601) was dissolved in propylene glycol monomethyl ether acetate (136.56g) to obtain the droplet (2).

[0903] After 3 hours, dropwise solutions (1) and (2) were simultaneously added dropwise to the aforementioned 2000 mL flask (specifically, a flask containing liquid heated to 90°C with a capacity of 2000 mL). After the addition was complete, V-601 (2.401 g) was added to the flask 3 times every 1 hour. Then, the mixture was stirred further at 90°C for 3 hours.

[0904] The solution (reaction solution) obtained in the flask above was then diluted with propylene glycol monomethyl ether acetate (178.66 g). Next, tetraethylammonium bromide (1.8 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) and hydroquinone monomethyl ether (0.8 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added to the reaction solution. The temperature of the reaction solution was then raised to 100°C.

[0905] Next, glycidyl methacrylate (76.03 g, manufactured by NOF CORPORATION, product name BLEMMER G) was added dropwise to the reaction solution over a period of 1 hour. The reaction solution was then allowed to react at 100°C for 6 hours, yielding 1158 g of resin P-5 solution (solid content concentration of 36.3% by mass). The obtained resin P-5 had a weight-average molecular weight of 27,000, a number-average molecular weight of 15,000, and an acid value of 95 mg KOH / g. The amount of residual monomer, measured by gas chromatography, was less than 0.1% by mass relative to the polymer solid content.

[0906] Synthesis of Resin P-6

[0907] Resin P-6 was obtained by referring to the synthesis method of resin P-5.

[0908] Specifically, in the dropwise solution (1) used in the synthesis of resin P-5, the structure of the monomers methacrylic acid (107.1 g), methyl methacrylate (5.46 g), and cyclohexyl methacrylate (231.42 g) used as monomers was changed to the structure of monomers in the mass ratios shown in Table 8 below. Furthermore, the amount of glycidyl methacrylate (76.03 g) added was also changed to achieve the composition of MAA-GMA in Table 8 below.

[0909] The obtained resin P-6 solution had a solid content concentration of 36.3% by mass and a weight-average molecular weight of 17,000.

[0910] Table 8 shows the types of monomers used in the synthesis of the resin, the mass percentage (mass%) of the structural units derived from each monomer, and the weight-average molecular weight of the resin. Furthermore, in Table 8, MAA-GMA indicates structural units derived from methacrylic acid that have been converted to glycidyl methacrylate.

[0911] [Table 8]

[0912] P-6 St 47.7 MAA-GMA 32 MAA-GMA 19 MMA 1.3 Weight-average molecular weight (Mw) 17,000

[0913] Furthermore, resins P-5 and P-6 are equivalent to any alkali-soluble resin. Resins P-5 and P-6 are added to the photosensitive resin composition in the form of solutions containing the resins.

[0914] Synthesis of the capped isocyanate compound Q-1

[0915] Under a nitrogen stream, 453 g of butanone oxime (manufactured by Idemitsu Kosan Co., Ltd.) was dissolved in 700 g of methyl ethyl ketone. Under ice-cold conditions, 500 g of 1,3-bis(methyl isocyanate)cyclohexane (a mixture of cis and trans isomers, manufactured by Mitsui Chemicals, Inc., Takenate 600) was added dropwise to the resulting solution over 1 hour, followed by a further 1 hour of reaction. The solution was then heated to 40°C and reacted for another 1 hour. 1H-NMR (Nuclear Magnetic Resonance) and HPLC (High Performance Liquid Chromatography) confirmed that the reaction had ended, and a methyl ethyl ketone solution (solid content concentration of 57.7% by mass) of the capped isocyanate compound Q-1 (refer to the formula below) was obtained.

[0916] In addition, the capped isocyanate compound Q-1 is added to the photosensitive resin composition in the form of a solution containing the capped isocyanate compound Q-1.

[0917] [Chemical Formula 20]

[0918]

[0919] Synthesis of the capped isocyanate compound Q-8

[0920] Following the synthetic method of the terminal isocyanate compound Q-1, a methyl ethyl ketone solution (solid content concentration of 75.0% by mass) of the terminal isocyanate compound Q-8 (refer to the formula below) was obtained.

[0921] In addition, the capped isocyanate compound Q-8 is added to the photosensitive resin composition in the form of a solution containing the capped isocyanate compound Q-8.

[0922] [Chemical Formula 21]

[0923]

[0924] [Preparation of photosensitive resin compositions 5-6]

[0925] According to the formulations described in Table 9 below, these components were mixed by stirring to prepare photosensitive resin compositions 5-6. The amounts of each component are expressed in parts by mass.

[0926] [Table 9]

[0927]

[0928] [Preparation of water-soluble resin compositions]

[0929] Synthesis of Polymer P-7

[0930] Propylene glycol monomethyl ether (270.0 g) was introduced into three round-bottomed flasks and heated to 70 °C under nitrogen flow while stirring.

[0931] On the other hand, a dropping solution was prepared by dissolving allyl methacrylate (45.6 g, FUJIFILM Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) in propylene glycol monomethyl ether (270.0 g), and further dissolving V-65 (3.94 g, FUJIFILM Wako Pure Chemical Corporation). This solution was added dropwise to the aforementioned flask over 2.5 hours. The mixture was stirred and reacted for 2.0 hours. Then, the contents of the flask were allowed to return to room temperature, and the contents were added dropwise to 2.7 L of deionized water under stirring to induce redeposition and obtain a suspension. The suspension was filtered using a suction filter (Buchner funnel) with filter paper, and the filtrate was further washed with deionized water to obtain a wet powder. After drying at 45°C with forced air and confirming constant yield, resin P-7 was obtained as a powder in 70% yield. The amount of residual monomer, measured by gas chromatography, is less than 0.1% by mass relative to the polymer solids content.

[0932] <Preparation of water-soluble resin compositions 8-14>

[0933] According to the formulations described in Table 10 below, these components were mixed by stirring to prepare water-soluble resin compositions 8 to 14. The amounts of each component are expressed in parts by mass.

[0934] In addition, water-soluble resin compositions 8 to 14 can be used to form a refractive index adjustment layer.

[0935] Furthermore, resins P-7 and ARUFON UC-3920 used in the preparation of water-soluble resin compositions 8-14 are alkali-soluble resins. Moreover, resins P-7 and ARUFON UC-3920 have a solubility of 0.1g or more in 100g of water at a liquid temperature of 22°C and pH 7.0. That is, these resins are also equivalent to water-soluble resins.

[0936] [Table 10]

[0937]

[0938] [Preparation of transfer film]

[0939] <Example 9>

[0940] On a temporary support of a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAYINDUSTRIES, INC.)), using a slit nozzle, the coating amount of the photosensitive resin composition was adjusted to achieve a 1.0 m wide photosensitive composition layer with a specified film thickness (film thickness listed in Table 9: 8.0). The resulting laminate was then passed through a 3 m drying zone at 80°C with the air intake and exhaust rates adjusted and the film surface velocity set to 0.2 m / sec for 60 seconds, thus obtaining a laminate C of the temporary support and the photosensitive resin layer.

[0941] Subsequently, using a slit nozzle, the coating amount was adjusted on the photosensitive resin layer of the prepared laminate C to achieve a specified average film thickness (film thickness recorded in Table 10: 80 nm), and the water-soluble resin composition 8 was coated with a width of 1.0 m. Then, the laminate C was passed through a 3 m drying zone at a temperature of 80°C with the air intake and exhaust rates adjusted to a film surface wind speed of 3 m / sec for 60 seconds, thus obtaining the transfer film of Example 9 in which a water-soluble resin layer was formed on the photosensitive resin layer.

[0942] <Examples 10-16 and Comparative Examples 3 and 4>

[0943] As shown in Table 11, the transfer film was prepared in the same manner as in Example 9, except that the types of photosensitive resin composition and water-soluble resin composition were changed.

[0944] However, for Examples 10-16 and Comparative Examples 3 and 4, the film thickness of the composition layer formed by each composition was varied according to the type of water-soluble resin composition and photosensitive resin composition. The film thickness of the formed composition layer refers to the average film thickness shown together with the composition in Tables 9 and 10.

[0945] In addition, the transfer films of Examples 9 to 16 are equivalent to the transfer films of Embodiment 2.

[0946] [Surface Morphology Evaluation]

[0947] A polyethylene terephthalate (PET) film with a thickness of 100 μm was prepared.

[0948] After unwinding the prepared transfer film, the outermost layer (water-soluble resin layer) of the composite layer disposed on the temporary support was laminated to the PET substrate under lamination conditions of roller temperature 100°C, linear pressure 1.0 MPa, and linear speed 4.0 m / min, thereby laminating the PET substrate onto the transfer film. Next, without peeling off the temporary support, the film was exposed to an ultra-high pressure mercury lamp, and then the temporary support was peeled off for development. Development was performed using a 1.0% sodium carbonate aqueous solution at 25°C, by spray development for 30 seconds. When forming a pattern using the above method and via a line and space pattern mask (duty ratio 1:1, linewidth 20 μm), an exposure amount with a resist linewidth of 20 μm was set as the optimal exposure amount.

[0949] The surface of the cured film formed with the optimal exposure was visually observed from the PET film side over a length of 10 m × total width (1.0 m), and the surface morphology was evaluated according to the following evaluation criteria. Grades A, B, and C represent the acceptable ranges for practical applications. The results are shown in Table 11.

[0950] (Evaluation Criteria)

[0951] A: Surface defects less than 1 per m 2 .

[0952] B: Surface defects are 1 per m 2 More than or less than 3 per m 2 .

[0953] C: Surface defects are 3 per m 2 More than or less than 5 per m 2 .

[0954] D: Surface defects are 5 per m 2 More than or less than 10 per m 2 .

[0955] E: Surface defects are 10 per m 2 above.

[0956] [Table 11]

[0957]

[0958] The results in Table 11 confirm that the transfer film of the embodiment has few surface defects.

[0959] Furthermore, the comparison of the examples revealed the following: when compound A is a low molecular weight compound A with a molecular weight of 2,000 or less and represented by the above general formula (6B) (equivalent to Examples 15 and 16), or when it is a high molecular weight compound A containing structural units represented by the above general formula (4) and the above general formula (5) (equivalent to Examples 9 to 11, 13), surface defects are further suppressed. Specifically, when compound A is a low molecular weight compound A with a molecular weight of 2,000 or less and represented by the above general formula (6B) (equivalent to Examples 15 and 16), or when it is a high molecular weight compound A with a weight-average molecular weight of 15,000 or less and containing structural units represented by the above general formula (4) and the above general formula (5) (equivalent to Examples 9 and 10), surface defects are further suppressed.

[0960] Symbol Explanation

[0961] 1, 11 - Temporary support; 3 - Thermoplastic resin layer; 5, 15 - Water-soluble resin layer; 7, 13 - Negative photosensitive resin layer; 9, 17 - Cover film; 10, 20 - Transfer film.

Claims

1. A transfer film having a temporary support and a composition layer disposed on the temporary support, The composition layer comprises a photosensitive resin layer and a water-soluble resin layer. The transfer film is formed by sequentially stacking the temporary support, the water-soluble resin layer, and the photosensitive resin layer, or by sequentially stacking the temporary support, the photosensitive resin layer, and the water-soluble resin layer. The water-soluble resin layer contains one or more resins selected from polyvinyl alcohol resins, polyvinylpyrrolidone resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. The water-soluble resin layer comprises compound A having a group represented by the following general formula (1), General formula (1): *-CF2-H In the formula, * indicates the bonding position. Compound A is a high molecular weight compound with a weight average molecular weight exceeding 2000, or a low molecular weight compound with a molecular weight below 2000. In the case where compound A is a polymer, the polymer comprises structural units derived from monomers represented by the following general formula (4A) and structural units derived from monomers represented by the following general formula (5). In general formula (4A), R 1 X represents a hydrogen atom or a methyl group, and X represents an oxygen atom, a sulfur atom, or -N(R) 2 )-, m and n independently represent integers from 1 to 6, R 2 Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. In general formula (5), R 3 Y represents a hydrogen atom or a methyl group, and Y represents an oxygen atom, a sulfur atom, or -N(R) 5 )-, AL represents an alkylene group optionally having substituents, nAL represents an integer greater than 2, R 4 R represents a hydrogen atom or substituent. 5 Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. When compound A is a low-molecular-weight compound, compound A is a compound represented by the following general formula (6B). In general formula (6B), R 7 Represents a hydrogen atom or substituent; AL represents an alkylene group; nAL represents an integer greater than 2; L 3 Represents oxygen atom, sulfur atom, or -N (R 6 )-, m and n independently represent integers from 1 to 6, R 6 It represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

2. The transfer film according to claim 1, wherein, Compound A is a high molecular weight compound with a weight-average molecular weight of 5000 or more.

3. The transfer film according to claim 1 or 2, wherein, The photosensitive resin layer further comprises an alkali-soluble resin and a polymeric compound.

4. The transfer film according to claim 1 or 2, wherein, The water-soluble resin layer further comprises metal oxide particles.

5. The transfer film according to claim 1 or 2, wherein, The water-soluble resin layer contains two or more types of water-soluble resins.

6. The transfer film according to claim 1 or 2, further comprising a thermoplastic resin layer.

7. The transfer film according to claim 1 or 2, wherein the temporary support, the water-soluble resin layer and the photosensitive resin layer are sequentially stacked.

8. The transfer film according to claim 6, wherein the temporary support, the thermoplastic resin layer, the water-soluble resin layer and the photosensitive resin layer are sequentially stacked.

9. The transfer film according to claim 1 or 2, wherein the temporary support, the photosensitive resin layer and the water-soluble resin layer are sequentially stacked.

10. A method for manufacturing a laminate, wherein the laminate uses the transfer film according to any one of claims 1 to 9, the method for manufacturing the laminate comprising: In the bonding process, the substrate is brought into contact with the surface of the outermost layer of the composition layer disposed on the temporary support in the transfer film, and the transfer film and the substrate are bonded together to obtain a substrate with the transfer film. The exposure process involves patterning the composite layer. The developing process involves developing the exposed composition layer to form a resin pattern; and In the peeling process, between the bonding process and the exposure process or between the exposure process and the developing process, a temporary support is peeled off from the substrate with the transfer film.

11. A method for manufacturing a circuit wiring, wherein the circuit wiring uses the transfer film according to any one of claims 1 to 8, the method for manufacturing the circuit wiring comprising: In the bonding process, the surface of the outermost layer of the composition layer of the transfer film disposed on the temporary support is brought into contact with the substrate having a conductive layer, and the transfer film and the substrate having the conductive layer are bonded together to obtain a substrate with the transfer film. The exposure process involves patterning the composite layer. The developing process involves developing the exposed composition layer to form a resin pattern; and The etching process involves etching the conductive layer in areas where the resin pattern is not configured. and In the peeling process, between the bonding process and the exposure process or between the exposure process and the developing process, a temporary support is peeled off from the substrate with the transfer film.

12. A method for manufacturing an electronic device, comprising the method for manufacturing a laminate as described in claim 10, wherein, The electronic device includes the resin pattern as a cured film.

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