Transfer film, laminate, method for manufacturing laminate having resist pattern, and method for manufacturing laminate having conductor pattern

Abstract

The present invention addresses the problem of providing a transfer film which exhibits excellent adhesion between an object to be bonded and a photosensitive composition layer when bonded to the object to be bonded, and which suppresses the generation of residues in a development step performed when forming a resist pattern. The transfer film according to the present invention has a temporary support and a photosensitive composition layer, and the photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, with respect to the total mass of the photosensitive composition layer, the content of predetermined ions in the photosensitive composition layer is a predetermined amount.

Description

Technical Field

[0001] This invention relates to a transfer film, a laminate, a method for manufacturing a laminate with a resist pattern, and a method for manufacturing a laminate with a conductor pattern. Background Technology

[0002] As a method for obtaining circuit wiring, a common approach is to use an etching process employing a resist pattern formed from a photosensitive composition. Specifically, for example, a method can be described as follows: forming a photosensitive composition layer on a substrate having a conductive layer, exposing the photosensitive composition layer to a pattern, developing it to form a pattern on a conductive layer, and etching the conductive layer where no pattern is formed.

[0003] For example, Patent Document 1 discloses a photosensitive element (transfer film) comprising, in sequence, a support film (temporary support), an intermediate layer, and a photosensitive layer (photosensitive composition layer), wherein the thickness of the support film is 20 μm or more, and the number of particles with a diameter of 5 μm or more contained in the support film is 30 particles / mm. 2 the following.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2017 / 007001 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] When forming a resist pattern using a photosensitive composition layer of a transfer film, the photosensitive composition layer is typically formed on the substrate by bonding the photosensitive composition layer of the transfer film to the etched object (the substrate). From an operational point of view, a high degree of adhesion between the substrate and the photosensitive composition layer is preferred when forming the photosensitive composition layer on the substrate.

[0009] Furthermore, after the photosensitive composition layer is formed on the substrate, it is exposed and developed to form a resist pattern. During the development process, from the viewpoint of obtaining the designed pattern, it is necessary to suppress the generation of residue (development residue) in the photosensitive composition layer.

[0010] Based on our research on the transfer film described in Patent Document 1, we found that it did not meet the standards required in recent years when balancing the adhesion between the substrate and the photosensitive composition layer and the suppression of developing residue. In particular, when the substrate contains silver, further improvement is needed in balancing the above-mentioned properties.

[0011] Therefore, the objective of this invention is to provide a transfer film that exhibits excellent adhesion between the substrate and the photosensitive composition layer when bonded to a substrate, and suppresses the generation of residues during the development process performed when forming a resist pattern.

[0012] Furthermore, the present invention also aims to provide a laminate, a method for manufacturing a laminate having a resist pattern, and a method for manufacturing a laminate having a conductor pattern.

[0013] means for solving technical problems

[0014] The present invention is the result of in-depth research conducted by the inventors to solve the aforementioned problems. Specifically, it was discovered that the above-mentioned problems can be solved according to the following structure.

[0015] [1] A transfer film having a temporary support and a photosensitive composition layer,

[0016] The aforementioned photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having olefinically unsaturated groups, and a photopolymerization initiator.

[0017] The content of phosphate ions in the photosensitive composition layer is less than 10.0 ppm by mass relative to the total mass of the photosensitive composition layer.

[0018] [2] According to the transfer film described in [1], wherein,

[0019] The content of phosphate ions is 0.1 to 7.0 ppm by mass relative to the total mass of the above-mentioned photosensitive composition layer.

[0020] [3] A transfer film having a temporary support and a photosensitive composition layer,

[0021] The aforementioned photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having olefinically unsaturated groups, and a photopolymerization initiator.

[0022] The content of nitrate ions in the photosensitive composition layer is less than 10.0 ppm by mass relative to the total mass of the photosensitive composition layer.

[0023] [4] According to the transfer film described in [3], wherein,

[0024] The content of nitrate ions is 0.1 to 7.0 ppm by mass relative to the total mass of the above-mentioned photosensitive composition layer.

[0025] [5] A transfer film having a temporary support and a photosensitive composition layer,

[0026] The aforementioned photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having olefinically unsaturated groups, and a photopolymerization initiator.

[0027] The content of iodide ions in the photosensitive composition layer is 2.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer.

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

[0029] The content of the iodide ions is 3.0 to 10.0 ppm by mass relative to the total mass of the above-mentioned photosensitive composition layer.

[0030] [7] A transfer film having a temporary support and a photosensitive composition layer,

[0031] The aforementioned photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having olefinically unsaturated groups, and a photopolymerization initiator.

[0032] The bromide ion content in the photosensitive composition layer is 4.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer.

[0033] [8] According to the transfer film described in [7], wherein,

[0034] The content of bromide ions is 6.0 to 10.0 ppm by mass relative to the total mass of the above-mentioned photosensitive composition layer.

[0035] [9] The transfer film according to any one of [1] to [8], wherein,

[0036] The aforementioned temporary support is a biaxially stretched polyethylene terephthalate film.

[0037]

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

[0038] The haze of the aforementioned temporary support structure is 0.1% to 0.5%.

[0039]

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

[10] , wherein,

[0040] The aforementioned photosensitive composition layer also contains a colorless compound.

[0041]

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

[11] , wherein,

[0042] The aforementioned photosensitive composition layer also contains a polymerization inhibitor.

[0043]

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

[12] , wherein,

[0044] The aforementioned photosensitive composition layer also contains a sensitizer.

[0045]

[14] A laminate having, in sequence, a transfer film, a conductive layer and a substrate as described in any one of [1] to

[13] .

[0046]

[15] According to the laminated body described in

[14] , wherein,

[0047] The aforementioned conductive layer contains silver.

[0048]

[16] A method for manufacturing a laminate with a resist pattern, comprising:

[0049] In the bonding process, the transfer film and the substrate are bonded together such that the surface of the photosensitive composition layer of the transfer film described in any one of [1] to

[13] opposite to the temporary support side is in contact with the conductive layer of the substrate having a conductive layer on the surface.

[0050] The exposure process involves patterning the aforementioned photosensitive composition layer; and

[0051] The developing process involves developing the exposed photosensitive composition layer to form a resist pattern.

[0052] The method for manufacturing the above-mentioned laminate with resist pattern further includes a temporary support peeling step between the above-mentioned bonding step and the above-mentioned exposure step, or between the above-mentioned exposure step and the above-mentioned development step, a temporary support peeling step for peeling off the temporary support.

[0053]

[17] A method for manufacturing a laminate having a conductor pattern, comprising:

[0054] In the bonding process, the transfer film and the substrate are bonded together such that the surface of the photosensitive composition layer of the transfer film described in any one of [1] to

[13] opposite to the temporary support side is in contact with the conductive layer of the substrate having a conductive layer on the surface.

[0055] The exposure process involves patterning the aforementioned photosensitive composition layer.

[0056] The developing process involves developing the exposed photosensitive composition layer to form a resist pattern; and

[0057] The etching process involves etching the conductive layer in areas where no resist pattern has been formed.

[0058] The manufacturing method of the above-mentioned laminate with conductor pattern further includes a temporary support peeling step between the above-mentioned bonding step and the above-mentioned exposure step or between the above-mentioned exposure step and the above-mentioned development step.

[0059] Invention Effects

[0060] According to the present invention, a transfer film can be provided which exhibits excellent adhesion between the substrate and the photosensitive composition layer when bonded to a substrate, and suppresses the generation of residues during the developing process performed when forming a resist pattern.

[0061] Furthermore, according to the present invention, it is also possible to provide a laminate, a method for manufacturing a laminate having a resist pattern, and a method for manufacturing a laminate having a conductor pattern. Attached Figure Description

[0062] Figure 1 This is a schematic diagram illustrating an example of the structure of a transfer film used in the manufacturing method of the present invention. Detailed Implementation

[0063] The present invention will now be described in detail.

[0064] The following description of the constituent elements is sometimes used to illustrate representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0065] The following explains the meaning of each statement in this specification.

[0066] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0067] In this specification, within a range of values ​​described in stages, the upper or lower limit of a certain range can be replaced with the upper or lower limit of another range of values ​​described in stages. Furthermore, within the range of values ​​described in this specification, the upper or lower limit of a particular range can also be replaced with the values ​​shown in the embodiments.

[0068] In this specification, the term "process" includes not only independent processes, but also processes that can achieve their intended purpose, even if they cannot be clearly distinguished from other processes.

[0069] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400-700nm is 80% or more, preferably 90% or more.

[0070] In this specification, transmittance is a value measured using a spectrophotometer, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0071] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​converted from polystyrene measured using a gel permeation chromatography (GPC) analyzer, with TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all product names manufactured by TOSOH CORPORATION) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard.

[0072] Unless otherwise specified, the ratio of the structural units of the polymer in this specification is a mass ratio.

[0073] Unless otherwise specified, the molecular weight of compounds with molecular weight distribution in this specification is the weight-average molecular weight (Mw).

[0074] Unless otherwise specified, the content of metal elements in this specification refers to the values ​​determined using an inductively coupled plasma (ICP) spectrophotometer.

[0075] In this specification, ppm is an abbreviation for "parts per million," which refers to 10 -6 ppb is an abbreviation for "parts per billion," meaning 10 parts per billion. -9 .

[0076] In this specification, "(meth)acrylic acid" includes both acrylic acid and methacrylic acid, and "(meth)acryloyloxy" includes both acryloyloxy and methacryloyloxy.

[0077] In addition, in this specification, "alkali solubility" means that the solubility of sodium carbonate in 100g of a 1% by mass aqueous solution at 22°C is 0.1g or more.

[0078] In this specification, "water-soluble" means having a solubility of 0.1g or more in 100g of water at a pH of 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.

[0079] In this specification, "solid components" of a photosensitive composition refer to components that form the photosensitive composition layer formed using the photosensitive composition. When the photosensitive composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. Furthermore, if it is a component that forms the photosensitive composition layer, liquid components are also considered solid components.

[0080] The transfer film of the present invention can be described in four embodiments: the first embodiment, the second embodiment, the third embodiment, and the fourth embodiment. Each embodiment will be described in detail below.

[0081] In addition, the following will also refer to the case where the adhesion between the substrate and the photosensitive composition layer is better when the substrate is attached to the substrate as “superior adhesion”.

[0082] Furthermore, the process of further suppressing the generation of residues during the development process when forming the resist pattern is also referred to as "suppressing the generation of residues".

[0083] <Transfer Film (First Embodiment)>

[0084] The first embodiment of the transfer film of the present invention is a transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having olefinically unsaturated groups, and a photopolymerization initiator, and the content of phosphate ions in the photosensitive composition layer is 10.0 ppm by mass or less relative to the total mass of the photosensitive composition layer. The content of phosphate ions will be described in detail later.

[0085] The first embodiment of the transfer film of the present invention is considered to have excellent adhesion and suppressed residue generation due to the following reasons by having the above-described structure.

[0086] It is believed that in the first embodiment of the transfer film of the present invention, since the content of phosphate ions is below a specified amount, the surface of the substrate is less likely to deteriorate, resulting in excellent adhesion. Furthermore, it is believed that by keeping the content of phosphate ions below a specified amount, ions originating from the substrate are less likely to be generated. It is believed that when the generation of ions originating from the substrate is low, the composition of the photosensitive composition layer is less susceptible to influences such as coordination, and as a result, the generation of residues is suppressed.

[0087] In addition to the temporary support and the photosensitive composition layer, the first embodiment of the transfer film may also have other layers.

[0088] Other layers include, for example, the intermediate layer and the thermoplastic resin layer described later. Furthermore, the first embodiment of the transfer film may include other components described later (e.g., a protective film, etc.).

[0089] As a first embodiment of the transfer film, the following structures (1) to (3) can be cited as examples, with structure (2) being preferred.

[0090] (1) "Temporary support / photosensitive composition layer / protective film"

[0091] (2) "Temporary support / intermediate layer / photosensitive composition layer / protective film"

[0092] (3) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film"

[0093] As the photosensitive composition layer in each of the above-described configurations, the negative photosensitive composition layer or the coloring resin layer described later is preferred.

[0094] From the viewpoint of suppressing the generation of air bubbles in the above-mentioned bonding process, the maximum width of the ripples in the first embodiment of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. Furthermore, the lower limit of the maximum ripple width is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.

[0095] The maximum width of the corrugations in the first embodiment of the transfer film is a value determined by the following steps.

[0096] First, the transfer film is cut perpendicular to the main surface to a size of 20cm x 20cm to create a test sample. If the transfer film has a protective film, it is peeled off. Next, the test sample is placed on a smooth, level stage with the surface of the temporary support facing the stage. After standing, a three-dimensional surface image is obtained by scanning the surface of the test sample within a 10cm square area from its center using a laser microscope (e.g., a VK-9700SP manufactured by KEYENCE CORPORATION). The maximum convexity height is subtracted from the minimum concave height observed in the obtained three-dimensional surface image. This process is repeated for 10 test samples, and the arithmetic mean is taken as the "maximum width of the transfer film's ripples".

[0097] In the photosensitive composition layer of the transfer film, when there are other composition layers on the surface of the photosensitive composition layer opposite to the temporary support, the total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, relative to the total thickness of the photosensitive composition layer.

[0098] The transmittance of the photosensitive composition layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.

[0099] An example of an embodiment of the first embodiment of the transfer film will be described.

[0100] Figure 1 The transfer film 10 shown in the figure sequentially includes: a temporary support 11; a composition layer 17 comprising an intermediate layer 13 and a photosensitive composition layer 15; and a protective film 19.

[0101] Figure 1 The transfer film 10 shown has an intermediate layer 13 and a protective film 19, but it may also be without the intermediate layer 13 and the protective film 19. Furthermore, the transfer film 10 may have a thermoplastic resin layer between the temporary support 11 and the intermediate layer 13.

[0102] exist Figure 1 In this context, the layers other than the protective film 19 that can be disposed on the temporary support 11 (e.g., the photosensitive composition layer and the intermediate layer) are also referred to as "composition layers".

[0103] The following describes in detail each component and its composition in the first embodiment of the transfer film.

[0104] [Temporary support]

[0105] The first embodiment of the transfer film has a temporary support.

[0106] The temporary support is a component that supports the composite layer and is eventually removed through a peeling process.

[0107] The temporary support can be a single-layer structure or a multi-layer structure.

[0108] The temporary support is preferably a membrane, more preferably a resin membrane. As a temporary support, a membrane that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat is preferred.

[0109] Examples of such membranes include polyethylene terephthalate membranes (e.g., biaxially stretched polyethylene terephthalate membranes), polymethyl methacrylate membranes, cellulose triacetate membranes, polystyrene membranes, polyimide membranes, and polycarbonate membranes.

[0110] The temporary support is preferably a polyethylene terephthalate film, and more preferably a biaxially stretched polyethylene terephthalate film.

[0111] Furthermore, the membrane used as a temporary support is preferably free from deformations such as wrinkles and scratches.

[0112] From the viewpoint of being able to expose patterns through a temporary support, the temporary support preferably has high transparency, with a transmittance of 60% or more at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm, more preferably 70% or more, further preferably 80% or more, and most preferably 90% or more. Preferred values ​​for transmittance include, for example, 87%, 92%, and 98%.

[0113] From the viewpoint of pattern formation properties during pattern exposure through a temporary support and the transparency of the temporary support, it is preferable that the temporary support has low haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.

[0114] Furthermore, from the viewpoint of transportability during the manufacture of the temporary support, the haze of the temporary support is preferably 0.05% or more, more preferably 0.1% or more.

[0115] In addition, the above haze is the total light haze (%) in accordance with JIS K 7136:2000, which can be measured using a haze meter (device name: HZ-2, manufactured by Suga Test Instruments Co., Ltd.) as the total light haze.

[0116] From the viewpoint of pattern formation properties during pattern exposure through a temporary support and the transparency of the temporary support, it is preferable that the number of particles, foreign matter, and defects contained in the temporary support is low. The number of particles, foreign matter, and defects with a diameter of 1 μm or larger in the temporary support 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 .

[0117] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm. From the viewpoint of ease of operation and versatility, it is more preferably 5 to 150 μm, even more preferably 5 to 50 μm, and especially preferably 5 to 25 μm.

[0118] The thickness of the temporary support was calculated as the average of any five points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0119] To improve the adhesion between the temporary support and the composition layer, the side of the temporary support that is in contact with the composition layer can be surface modified by UV irradiation, corona discharge, plasma, etc.

[0120] When performing surface modification by UV irradiation, the preferred exposure amount is 10 mJ / cm. 2 ~2000mJ / cm 2 More preferably 50–1000 mJ / cm 2Examples of light sources used for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs), which emit light in the 150–450 nm wavelength range. As long as the light intensity is within this range, there are no particular limitations on the lamp output or illuminance.

[0121] Temporary supports can be recycled products. Examples of recycled products include those obtained by cleaning and fragmenting used membranes, and then using them as materials for membrane fabrication. A specific example of a recycled product is the Ecouse series from TORAY INDUSTRIES, INC.

[0122] Examples of temporary supports include biaxially stretched polyethylene terephthalate films with a thickness of 16 μm, 12 μm, and 9 μm.

[0123] Preferred methods for temporary supports include, for example, those described 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 International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370, the contents of which are incorporated herein by reference.

[0124] From the viewpoint of providing operability, a layer containing microparticles (lubricant layer) can also be provided on the surface of the temporary support. The lubricant layer can be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

[0125] Furthermore, the thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40 (manufactured by TORAY INDUSTRIES, INC.), COSMOSHINE A4100, COSMOSHINE A4160, COSMOSHINE A4300, COSMOSHINE A4360, and COSMOSHINE A8300 (manufactured by TOYOBO CO., LTD.).

[0126] [Photosensitive Composition Layer]

[0127] The first embodiment of the transfer film has a photosensitive composition layer.

[0128] After the photosensitive composition layer is transferred onto the substrate, a pattern can be formed on the substrate by exposure and development.

[0129] The photosensitive composition layer is preferably negative. Furthermore, a negative photosensitive composition layer refers to a photosensitive composition layer in which the solubility of the exposed portion in the developer decreases due to exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the resulting pattern is equivalent to a cured layer.

[0130] When the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having olefinic unsaturated groups, and a photopolymerization initiator.

[0131] Based on the total mass of the photosensitive composition layer, this photosensitive composition layer (negative photosensitive composition layer) preferably contains: 10-90% by mass of an alkali-soluble resin; 5-70% by mass of a polymerizable compound having olefinic unsaturated groups; and 0.01-20% by mass of a photopolymerization initiator. Furthermore, the phosphate ion content is 10.0 ppm by mass or less relative to the total mass of the photosensitive composition layer.

[0132] The following details the components that may be included in the photosensitive composition layer.

[0133] (Alkali-soluble resin)

[0134] The photosensitive composition layer contains an alkali-soluble resin (hereinafter also referred to as "Resin A").

[0135] Examples of resin A include (meth)acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenolic resin, ester resin, urethane resin, and acid-modified epoxy acrylate resin obtained by reacting epoxy acrylate resin with acid anhydride, but are not limited thereto.

[0136] As resin A, (meth)acrylic resin is preferred. Furthermore, in this specification, (meth)acrylic resin refers to a resin having structural units derived from (meth)acrylic acid compounds. In the (meth)acrylic resin, the content of structural units derived from (meth)acrylic acid compounds is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, relative to all structural units of the (meth)acrylic resin.

[0137] As resin A, a polymer having structural units derived from (meth)acrylic acid compounds and structural units derived from styrene compounds is also preferred.

[0138] From the viewpoint that the resolution of the photosensitive composition layer is better by suppressing the swelling of the negative photosensitive composition layer caused by the developer, the acid value of resin 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.

[0139] There is no particular limitation on the lower limit of the acid value of resin A, but from the viewpoint of better developability, it is preferred to be 60 mg KOH / g or more, more preferably 100 mg KOH / g or more, further preferably 120 mg KOH / g or more, especially preferably 150 mg KOH / g or more, and most preferably 170 mg KOH / g or more.

[0140] Additionally, the acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1g of the sample. The acid value can be calculated, for example, based on the average content of acid groups in the compound. The acid value of resin A can be adjusted using the types of structural units constituting resin A and the content of acid-containing structural units, as described later.

[0141] In addition, the resolution of the photosensitive composition layer will be referred to as "resolution" below.

[0142] The weight-average molecular weight of resin A is preferably 5,000 to 500,000. When the weight-average molecular weight is 500,000 or less, it is preferred 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 preferred from the viewpoint of controlling the properties of the developed aggregates, and the properties of the unexposed film, such as edge melting and chipping, when used as a negative photosensitive composition 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 composition layer easily overflows from the end face of the roller when wound into a roll as a negative photosensitive composition laminate. Chipping refers to the degree to which chips easily scatter when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the negative photosensitive composition laminate, they will be transferred to the mask in subsequent exposure processes, resulting in defective products. The dispersion of resin 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. In this invention, the dispersion is the ratio of weight-average molecular weight to number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0143] -Structural units derived from monomers containing aromatic hydrocarbon groups-

[0144] Furthermore, from the viewpoint of suppressing the deterioration of linewidth or resolution due to focus position shift during exposure, resin A preferably contains structural units derived from monomers having aromatic hydrocarbon groups. Examples of such aromatic hydrocarbon groups include, for instance, substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.

[0145] Relative to the total mass of resin A, the content of structural units derived from monomers having aromatic hydrocarbon groups in resin A is preferably 20% by mass or more, more preferably 30% by mass or more. There is no particular upper limit, but it is preferably 95% by mass or less, more preferably 85% by mass or less. Furthermore, when multiple types of resin A are included, it is preferable that the average content of structural units derived from monomers having aromatic hydrocarbon groups is within the above-mentioned range.

[0146] Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimers, and styrene trimers). Among these, monomers having an aralkyl group or styrene are preferred.

[0147] When the monomer having an aromatic hydrocarbon group is styrene, the content of structural units derived from styrene relative to the total mass of resin A is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, even more preferably 30 to 60% by mass, and particularly preferably 40 to 60% by mass. Furthermore, when the photosensitive composition layer contains multiple types of resin A, the content of structural units derived from monomers having aromatic hydrocarbon groups is calculated as a weight average.

[0148] Aryl groups include phenylalkyl groups that can have substituents, and preferably benzyl groups that can have substituents.

[0149] Examples of monomers having phenylalkyl groups that can have substituents include phenylethyl (meth)acrylate.

[0150] Examples of monomers having a benzyl group that can have substituents include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinyl benzyl alcohol; preferably (meth)acrylates having a benzyl group, more preferably benzyl (meth)acrylate.

[0151] When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of structural units derived from benzyl (meth)acrylate relative to the total mass of resin A is preferably 50-95% by mass, more preferably 60-90% by mass, further preferably 70-90% by mass, and especially preferably 75-90% by mass.

[0152] Furthermore, resin A, which comprises structural units derived from monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing monomers having aromatic hydrocarbon groups, at least one type of monomer having carboxyl groups (described later), and / or at least one type of non-acidic monomer (described later).

[0153] Resin A, which does not contain structural units derived from monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing at least one of the monomers having carboxyl groups described later, and more preferably by copolymerizing at least one of the monomers having carboxyl groups with at least one of the non-acidic monomers described later.

[0154] -Structural units containing carboxyl groups-

[0155] Resin A preferably contains structural units having carboxyl groups.

[0156] Structural units with carboxyl groups originate from monomers that have carboxyl groups in their molecules.

[0157] Examples of monomers containing a carboxyl group 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.

[0158] The content of carboxyl-containing structural units in resin A is preferably 5 to 50% by mass relative to the total mass of resin A, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass.

[0159] 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 of the resist pattern and edge curling shape, and further from the viewpoint of acid resistance, it is preferable to set the above content to 50% by mass or less.

[0160] -Non-acidic structural unit-

[0161] Resin A may contain non-acidic structural units.

[0162] The non-acidic structural unit is derived from a non-acidic monomer that has at least one polymerizable unsaturated group in the molecule.

[0163] Examples of the aforementioned monomers (non-acidic monomers) include, for example, 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, sec-butyl methacrylate, isoamyl methacrylate, tert-amyl methacrylate, sec-amyl methacrylate, 2-octyl methacrylate, 3-octyl methacrylate, tert-octyl methacrylate, and 2-ethylhexyl methacrylate; vinyl acetate and other vinyl alcohol esters; and methacrylonitrile. Among these, methyl methacrylate, 2-ethylhexyl methacrylate, or n-butyl methacrylate are preferred, and methyl methacrylate is more preferred.

[0164] The content of non-acidic structural units in resin A is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 1 to 30% by mass, relative to the total mass of resin A.

[0165] -Other structural units-

[0166] Resin A can have structural units that have any one of the following in their side chains: straight chain structure, branched structure, and alicyclic structure.

[0167] In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to a group of atoms that branch off from the main chain.

[0168] By using monomers containing groups with a straight-chain structure in the side chain, monomers containing groups with a branched structure in the side chain, or monomers containing groups with an alicyclic structure in the side chain, a straight-chain structure, a branched structure, or an alicyclic structure can be introduced into the side chain of resin A. The alicyclic structure can be monocyclic or polycyclic.

[0169] Specific examples of monomers containing branched groups in their side chains include isopropyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, tert-amyl methacrylate, sec-amyl methacrylate, 2-octyl methacrylate, 3-octyl methacrylate, and tert-octyl methacrylate. Among these, isopropyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate are more preferred.

[0170] Specific examples of monomers containing alicyclic groups in their side chains include monomers having monocyclic aliphatic hydrocarbon groups and monomers having polycyclic aliphatic hydrocarbon groups. Furthermore, (meth)acrylates having alicyclic hydrocarbon groups with 5 to 20 carbon atoms can be cited. More specific examples include (meth)acrylate (bicyclo[2.2.1]heptyl-2) ester, (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, and (meth)acrylate-2-ethyl-2-adamantyl ester. 3-hydroxy-1-adamantyl ester of (meth)acrylate, octahydro-4,7-methylindene-5-yl ester of (meth)acrylate, octahydro-4,7-methylindene-1-yl methyl ester of (meth)acrylate, 1-menthyl ester of (meth)acrylate, tricyclodecane of (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester of (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester of (meth)acrylate, (nor)bornyl ester of (meth)acrylate, isobornyl ester of (meth)acrylate, fenofibrate of (meth)acrylate, 2,2,5-trimethylcyclohexyl ester of (meth)acrylate, and cyclohexyl ester of (meth)acrylate, 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.

[0171] Resin A can be used alone or in combination with two or more types.

[0172] When using two or more types, it is preferable to use a mixture of two resins A containing structural units derived from monomers having aromatic hydrocarbon groups, or to use a mixture of resin A containing structural units derived from monomers having aromatic hydrocarbon groups and resin A not containing structural units derived from monomers having aromatic hydrocarbon groups. In the latter case, the proportion of resin A containing structural units derived from monomers having aromatic hydrocarbon groups relative to the total mass of resin A is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0173] The synthesis of resin A can be carried out by polymerizing the above-mentioned single or multiple monomers using free radical polymerization initiators such as peroxide polymerization initiators (e.g., benzoyl peroxide) and azo polymerization initiators (e.g., azobisisobutyronitrile).

[0174] As a polymerization method, it is preferably carried out by dropwise addition of a monomer solution and a free radical polymerization initiator solution to a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and isopropanol) under a nitrogen stream while heating and stirring. Sometimes, further solvent is added after the reaction is complete to adjust it to the desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can be used.

[0175] (Polymerizable compounds with olefinically unsaturated groups)

[0176] The photosensitive composition layer contains a polymeric compound having olefinically unsaturated groups.

[0177] Hereinafter, "polymeric compounds having olefinic unsaturated groups" will also be referred to as polymeric compounds.

[0178] In addition, in this specification, "polymeric compound having olefinic unsaturated groups" refers to a compound that is polymerized under the action of a photopolymerization initiator described later and is different from the resin A mentioned above.

[0179] Examples of olefinic unsaturated groups present in polymerizable compounds include vinyl, acryloyl, methacryloyl, styrene, and maleimide groups, with acryloyl or methacryloyl being preferred.

[0180] From the viewpoint that the negative photosensitive composition layer has better photosensitivity, as a polymerizable compound, it is preferable to be a compound having one or more olefin unsaturated groups (olefin unsaturated compounds), and more preferably a compound having two or more olefin unsaturated groups in one molecule (polyfunctional olefin unsaturated compounds).

[0181] Furthermore, from the viewpoint of superior resolution and peelability, 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.

[0182] From the viewpoint of achieving a better balance between photosensitivity, resolution, and peelability of the negative photosensitive composition layer, 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.

[0183] From the viewpoint of excellent peelability, the content of difunctional olefin unsaturated compounds relative to the total mass of the negative photosensitive composition layer and relative to the total mass of the polymerizable compounds 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.

[0184] Furthermore, as an olefinic unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0185] -Polymerizing compound B1-

[0186] The negative photosensitive composition layer preferably comprises a polymeric compound B1 having an aromatic ring and two olefinic unsaturated groups. The polymeric compound B1 is a difunctional olefinic unsaturated compound having one or more aromatic rings in one molecule of the aforementioned polymeric compound B.

[0187] From the viewpoint of superior resolution, in the negative photosensitive composition layer, the mass ratio of the content of polymeric compound B1 to the total mass of the polymeric compounds is preferably 40% or more, more preferably 50% or more, further preferably 55% or more, and especially 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 especially preferably 85% or less.

[0188] The aromatic rings present in the polymerizable compound B1 can be, 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 their fused rings, preferably aromatic hydrocarbon rings, more preferably benzene rings. Furthermore, the aforementioned aromatic rings may have substituents.

[0189] Polymerizable compound B1 may have only one aromatic ring or more than two aromatic rings.

[0190] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive composition layer caused by the developer, polymeric compound B1 preferably has a bisphenol structure.

[0191] 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.

[0192] 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.

[0193] The two ends of the bisphenol structure can be directly bonded to the 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 are preferred per molecule, more preferably 6 to 14.

[0194] Regarding the polymeric compound B1 having a bisphenol structure, it is described in paragraphs

[0072] to

[0080] of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated herein by reference.

[0195] 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.

[0196] 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-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 2,2-bis(4-(methacryloyloxydecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxydecaethoxy)phenyl)propane (BPE-1300, SHIN-NAKAMURA). CHEMICAL Co., Ltd. manufactures 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.).

[0197] As a polymerizable compound B1, it is also preferred to be a compound represented by the following general formula (B1).

[0198] [Chemical Formula 1]

[0199]

[0200] 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 independent integers from 1 to 39, and n1+n3 is an integer from 2 to 40. n2 and n4 are each independent integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The structural units of -(AO)- and -(BO)- can be arranged randomly or in blocks. Furthermore, when arranged in blocks, both -(AO)- and -(BO)- can be on the diphenyl side.

[0201] 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.

[0202] Polymer compound B1 can be used alone or in combination with two or more compounds.

[0203] From the viewpoint of achieving superior resolution, the content of polymeric compound B1 relative to the total mass of the negative photosensitive composition 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 blending (the phenomenon of the photosensitive composition seeping out from the ends of the transfer component), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0204] The negative photosensitive composition layer may contain polymeric compounds other than the polymeric compound B1 mentioned above.

[0205] 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.

[0206] 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 phenoxyethyl (meth)acrylate.

[0207] 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, urethane di(meth)acrylate and trimethylolpropane diacrylate.

[0208] 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 neopentyl glycol di(meth)acrylate.

[0209] 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.

[0210] Examples of urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available examples 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.).

[0211] From the viewpoint of superior resolution and resist peelability, the content of difunctional olefin unsaturated compounds relative to the total mass of the negative photosensitive composition layer is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. From the viewpoint of transferability and edge melting (the phenomenon of photosensitive composition seeping out from the end of the transfer part), the upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.

[0212] From the viewpoint of superior resolution and resist peelability, the content of difunctional olefin unsaturated compounds is preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, relative to the total mass of the polymeric compounds having olefin unsaturated groups. From the viewpoint of transferability and edge melting (the phenomenon of photosensitive composition seeping out from the end of the transfer part), the upper limit is preferably 100% by mass or less, more preferably 90% by mass or less.

[0213] Examples of olefinic unsaturated compounds with three or more functions include, for example, dipentaerythritol (tris / tetras / penta / hexameth)acrylate, pentaerythritol (tris / tetras)acrylate, trimethylolpropane tri(meth)acrylate, bis-trimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and their epoxide-modified derivatives.

[0214] Here, "(tri / tetra / penta / hexa)meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0215] In one embodiment, the negative photosensitive composition layer preferably includes the aforementioned polymeric compound B1 and a trifunctional or higher olefinic unsaturated compound, more preferably including 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 compound) = 1 : 1 to 5 : 1, more preferably 1.2 : 1 to 4 : 1, and even more preferably 1.5 : 1 to 3 : 1.

[0216] Furthermore, in one embodiment, the negative photosensitive composition layer preferably comprises the aforementioned polymeric compound B1 and two or more trifunctional olefinic unsaturated compounds.

[0217] Examples of epoxide-modified compounds that are trifunctional or higher-functionalized olefinic 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.), and ethoxylated glycerol triacrylates (such as SHIN-NAKAMURA CHEMICAL). A-GLY-9E, etc. manufactured by Co., Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

[0218] 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.).

[0219] As a polymeric compound having an acid radical, for example, a polymeric compound having an acid radical as described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942 can be used.

[0220] Polymers can be used alone or in combination with two or more compounds.

[0221] The content of the polymeric compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass, relative to the total mass of the negative photosensitive composition layer.

[0222] The molecular weight (weight-average molecular weight when having 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.

[0223] (Photopolymerization initiator)

[0224] The photosensitive composition layer contains a photopolymerization initiator.

[0225] Photopolymerization initiators are compounds that initiate the polymerization of polymerizable compounds upon 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.

[0226] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0227] 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.

[0228] Furthermore, from the viewpoint of photosensitivity, visual recognizability, and resolution of the exposed and unexposed portions, the negative photosensitive composition layer preferably includes at least one selected from the group consisting of 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.

[0229] Examples of derivatives of 2,4,5-triarylimidazolium dimers include 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.

[0230] As a photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of Japanese Patent Application Publication No. 2011-95716 and paragraphs

[0064] to

[0081] of Japanese Patent Application Publication No. 2015-14783 can be used.

[0231] Examples of photoradical polymerization initiators include, for example, ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisole (p,p'-dimethoxybenzoin), 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.).

[0232] 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: Omnirad 379EG, 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-morpholinophenyl)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), 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropanoyl-1-one (manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV), 2-hydroxy-1-methyl-1-phenylpropanoyl-1- ...morpholinophenyl ketone (manufactured by IGM Resins BV), 2-method 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.) and 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (manufactured by Tokyo) ChemicalIndustry Co., Ltd.(Manufactured by), 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 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.) ElectronicMaterials Co., Ltd. (manufactured).

[0233] Photocationic polymerization initiators (photoacid generators) are compounds that generate acid upon receiving activation light. Preferably, these initiators are compounds that generate acid when sensitive to activation light with wavelengths of 300 nm or higher (preferably 300–450 nm), but their chemical structure is not limited. Furthermore, for photocationic polymerization initiators that are not directly sensitive to activation light with wavelengths of 300 nm or higher, compounds that generate acid by being used in conjunction with a sensitizer and thus sensitive to activation light with wavelengths of 300 nm or higher are preferred for use in combination with the sensitizer.

[0234] 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 pKa is not particularly specified, but for example, it is preferably -10.0 or higher.

[0235] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0236] Examples of ionic photocationic polymerization initiators include, for example, onium salts such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts.

[0237] 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 can be used.

[0238] 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 Publication No. 2018 / 179640 can be used.

[0239] The negative photosensitive composition layer preferably contains a photoradical polymerization initiator, more preferably containing at least one selected from the group consisting of 2,4,5-triarylimidazolium dimers and their derivatives.

[0240] Photopolymerization initiators can be used alone or in combination with two or more.

[0241] The content of the 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 composition 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 composition layer.

[0242] (Phosphate ion content)

[0243] The content of phosphate ions in the photosensitive composition layer is 10.0 ppm by mass or less relative to the total mass of the photosensitive composition layer. There is no particular limitation on the lower limit; 0.0 ppm by mass is an example. From the viewpoint of better adhesion and further suppression of residue formation, the content of phosphate ions relative to the total mass of the photosensitive composition layer is preferably 0.1 to 7.0 ppm by mass.

[0244] Furthermore, the phosphate ion content of the photosensitive composition layer refers to the phosphate ion content when the photosensitive composition layer is analyzed by ion chromatography. Chromatographic analysis will be discussed in detail later.

[0245] The phosphate ion content mentioned above refers to the total content of phosphate ions derived from salts containing phosphate ions and the content of ionized phosphate ions. Furthermore, when the phosphate ion content in the photosensitive composition layer exceeds 0.0 ppm by mass relative to the total mass of the photosensitive composition layer, it means that the photosensitive composition layer contains phosphate ions or salts containing phosphate ions.

[0246] Phosphate ions are anions formed by removing one or more hydrogen atoms from phosphate (H3PO4).

[0247] A salt containing phosphate ions is a compound composed of phosphate ions and a counter cation. There are no particular limitations on the counter cation; any known cation can be cited. The cation can be either organic or inorganic. Examples of organic cations include quaternary ammonium cations and quaternary phosphorus cations. Examples of inorganic cations include alkali metal ions such as lithium ions and potassium ions.

[0248] In this specification, the content of phosphate ions is determined by ion chromatography according to the following steps.

[0249] First, 100 mg of sample was collected from the photosensitive composition layer of the transfer film, and the 100 mg sample was dissolved in 1 g of ethyl acetate. 2.00 g of 0.0200 mol / L potassium hydroxide aqueous solution was added to the ethyl acetate solution and stirred thoroughly to prepare a mixture. The mixture was then allowed to stand for 1 hour.

[0250] The aqueous phase was extracted from the above mixture and subjected to cation exchange treatment to remove potassium ions. Next, the potassium-removed aqueous phase was concentrated using an anion exchange column. Using the anion-concentrated aqueous phase, the phosphate ion content was determined by ion chromatography under the following conditions.

[0251] Measurement equipment: DIONEX INTEGRION HPIC (Thermo Fisher Scientific KK)

[0252] Column: Dionex IonPac AS22 (anion analysis column, size: 4×250mm)

[0253] Flow rate: 1 mL / min

[0254] Temperature: 35℃

[0255] The phosphate ion content relative to the sample was determined based on the above measurement results, and this content was used as the phosphate ion content relative to the total mass of the photosensitive composition layer.

[0256] (Content of other ions)

[0257] The photosensitive composition layer may contain ions other than phosphate ions or salts containing ions other than salts containing phosphate ions.

[0258] Examples of other ions include nitrate ions, iodide ions, and bromide ions. Additionally, examples of salts containing other ions include compounds composed of any one of nitrate ions, iodide ions, and bromide ions combined with a counter cation. Examples of counter cations include, for instance, cations exemplified as counter cations contained in the aforementioned salts containing phosphate ions.

[0259] From the viewpoint of better adhesion and further suppression of residue formation, the content of nitrate ions in the photosensitive composition layer is preferably 10.0 ppm by mass or less, more preferably 0.1 to 7.0 ppm by mass, relative to the total mass of the photosensitive composition layer.

[0260] In addition, the nitrate ion content can be 0.0 ppm by mass.

[0261] In the first embodiment of the transfer film, the ratio of nitrate ion content to phosphate ion content is preferably 0.3 to 2.0, more preferably 0.5 to 1.5.

[0262] From the viewpoint of better adhesion and further suppression of residue formation, the content of iodide ions in the photosensitive composition layer is preferably 2.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer, more preferably 3.0 to 10.0 ppm by mass.

[0263] In the first embodiment of the transfer film, the ratio of iodide ion content to phosphate ion content is preferably 1.0 to 50.0, more preferably 1.4 to 30.0.

[0264] From the viewpoint of achieving better adhesion and further suppressing the generation of residues, the bromide ion content in the photosensitive composition layer is preferably 4.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer, more preferably 6.0 to 10.0 ppm by mass.

[0265] In the first embodiment of the transfer film, the ratio of bromide ion content to phosphate ion content is preferably 1.0 to 100.0, more preferably 1.4 to 60.0.

[0266] The contents of each of the aforementioned other ions refer to the total contents of other ions derived from salts containing other ions and the total contents of ionized other ions. For example, the contents of nitrate ions refer to the total contents of nitrate ions derived from salts containing nitrate ions and the total contents of ionized nitrate ions.

[0267] The contents of the other ions mentioned above were determined using the same method as those of phosphate ions.

[0268] (pigment)

[0269] From the viewpoints of visual recognizability of the exposed and unexposed areas, visual recognizability of the developed pattern, and resolution, the photosensitive composition layer preferably contains a pigment (also called "pigment N") with a maximum absorption wavelength of 450 nm or more in the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength varies with acids, bases, or free radicals. While the detailed mechanism of including pigment N is unclear, improved adhesion to adjacent layers (e.g., water-soluble resin layers) results in superior resolution.

[0270] In this specification, the phrase "the maximum absorption wavelength of the pigment changes due to acid, alkali or free radical" can refer to any of the following: a pigment in a chromogenic state is decolorized by acid, alkali or free radical; a pigment in a decolorized state is chromogenic by acid, alkali or free radical; or a pigment in a chromogenic state changes to another hue.

[0271] Specifically, pigment N can be a compound that changes color from a decolorized state upon exposure, or a compound that changes color from a color-developing state upon exposure. In this case, it can be a pigment whose color-developing or decolorizing state changes due to the generation and action of acids, bases, or free radicals within the photosensitive composition layer upon exposure, or a pigment whose color-developing or decolorizing state changes due to changes in the state (e.g., pH) within the photosensitive composition layer caused by acids, bases, or free radicals. Furthermore, it can also be a pigment whose color-developing or decolorizing state changes directly upon stimulation by acids, bases, or free radicals without exposure.

[0272] From the viewpoint of visual recognizability and resolution of the exposed and unexposed portions, pigment N is preferably a pigment whose maximum absorption wavelength is changed by acid or free radicals, and more preferably a pigment whose maximum absorption wavelength is changed by free radicals.

[0273] From the viewpoint of visual recognizability and resolution of the exposed and unexposed areas, when the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a pigment whose maximum absorption wavelength changes through free radicals and a photoradical polymerization initiator as pigment N.

[0274] Furthermore, from the viewpoint of visual recognizability of the exposed and unexposed parts, pigment N is preferably a pigment that develops color through acid, alkali or free radicals.

[0275] An example of the color-developing mechanism of pigment N can be given as follows: a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator is added to a photosensitive composition layer, and after exposure, the free radical reactive pigment, acid reactive pigment, or alkali reactive pigment (e.g., colorless pigment) develops color through free radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator.

[0276] Regarding pigment N, from the viewpoint of visual recognition of the exposed and unexposed parts, the maximum absorption wavelength within the wavelength range of 400 to 780 nm during color development is preferably 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm.

[0277] Furthermore, pigment N can have only one maximum absorption wavelength within the wavelength range of 400–780 nm during color development, or it can have two or more maximum absorption wavelengths. When pigment N has two or more maximum absorption wavelengths within the wavelength range of 400–780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0278] 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 environment 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).

[0279] As pigments that develop or fade color through exposure, colorless compounds can be cited as an example.

[0280] Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane pigments, oxazine pigments, xanthones, iminonaphthoquinone pigments, azomethyl alkaloid pigments, and anthraquinone pigments.

[0281] From the viewpoint of visual distinguishability of the exposed and unexposed parts, colorless compound is preferred as pigment N.

[0282] Examples of colorless compounds include, for example, colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropyran skeleton (spiropyran pigments), colorless compounds having a fluorane skeleton (fluorane 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 colorless auramine skeleton (colorless auramine pigments).

[0283] Preferably, the pigment is a triarylmethane pigment or a fluorane pigment, and more preferably, it is a colorless compound (triarylmethane pigment) or a fluorane pigment having a triphenylmethane skeleton.

[0284] From the viewpoint of visual distinguishability of the exposed and unexposed portions, colorless compounds preferably 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, thereby decolorizing the colorless compound by changing it to a closed-ring state, or by changing it to an open-ring state, thereby giving it color. Preferably, the colorless compound is a compound having a lactone ring, sultine ring, or sulfonyl lactone ring that develops color by opening the lactone ring, sultine ring, or sulfonyl lactone ring through a free radical or acid; more preferably, it is a compound having a lactone ring that develops color by opening the lactone ring through a free radical or acid.

[0285] As pigment N, examples include the following dyes and colorless compounds.

[0286] Specific examples of dyes in pigment N include: brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzene red violet 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, 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.), and 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.), Oil Green #502 (manufactured by Orient Chemical Co., Ltd.), SPIRON Red BEHSPECIAL (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.

[0287] 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, 2-phenylamino-3-methyl-6-(N-ethyl-p-toluidine)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-phenyl Aminofluorane, 3-(N,N-diethylamino)-6-methyl-7-phenylaminofluorane, 3-(N,N-diethylamino)-6-methyl-7-aminofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chlorophenylamino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-methoxy-7-aminofluorane 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-butylamino) -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]xanthon-3-one.

[0288] From the viewpoint of visual recognizability of the exposed and unexposed areas, visual recognizability of the developed pattern, and resolution, pigment N is preferably a pigment that changes the maximum absorption wavelength through free radicals, and more preferably a pigment that develops color through free radicals.

[0289] As pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate are preferred.

[0290] Pigment N can be used alone or in combination with two or more pigments.

[0291] From the viewpoint of visual recognizability of the exposed and unexposed areas, visual recognizability of the developed pattern, and resolution, the content of pigment N 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, relative to the total mass of the photosensitive composition layer.

[0292] The content of pigment N refers to the amount of pigment in which all of the pigment N contained in the total mass of the photosensitive composition layer is in a chromogenic 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.

[0293] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigment 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, thereby generating free radicals and activating the pigments in their chromogenic state. Subsequently, the absorbance of each solution at 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) under atmospheric conditions, and calibration curves were constructed.

[0294] Next, instead of pigments, 3g of the photosensitive composition layer was dissolved in methyl ethyl ketone. Otherwise, the absorbance of the solution that caused all pigments to develop color was measured using the same method as described above. Based on the calibration curve, the pigment content in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer.

[0295] In addition, the 3g of photosensitive composition layer is the same as the 3g of solid component of the photosensitive composition layer.

[0296] (Thermocrosslinkable compounds)

[0297] When the photosensitive composition layer is a negative photosensitive composition 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, the thermally crosslinking compound having olefinic unsaturated groups described later is treated as a thermally crosslinking compound, not as a polymerizable compound.

[0298] 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.

[0299] End-capped isocyanate compounds react with hydroxyl and carboxyl groups, and therefore, for example, when resins and / or polymeric compounds have at least one of hydroxyl and carboxyl groups, the hydrophilicity of the formed film decreases, and the film obtained by curing a negative photosensitive composition layer tends to have enhanced functionality when used as a protective film.

[0300] In addition, capped isocyanate compounds are defined as "compounds having a structure in which the isocyanate group of the isocyanate is protected (so-called masking) by a capping agent".

[0301] There is no particular limitation on the dissociation temperature of the capped isocyanate compound, but it is preferably 100 to 160°C, and more preferably 130 to 150°C.

[0302] The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates when measured using a differential scanning calorimeter and analyzed by DSC (Differential Scanning Calorimetry)".

[0303] As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. is preferred. However, the differential scanning calorimeter is not limited to this.

[0304] 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, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, etc., which have an intramolecular structure represented by -C (=N-OH)-).

[0305] 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 preserving stability.

[0306] For example, from the viewpoint of improving the brittleness of the film and further enhancing the adhesion to the substrate, the end-capped isocyanate compound preferably has an isocyanurate structure.

[0307] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuration of hexamethylene diisocyanate.

[0308] Among isocyanate compounds with an isocyanurate structure, compounds with an oxime structure that use an oxime compound as a capping agent are preferred from the viewpoint that it is easier to keep the dissociation temperature within a preferred range and easier to reduce development residue compared to compounds without an oxime structure.

[0309] End-capped isocyanate compounds can have polymerizable groups.

[0310] There are no particular restrictions on the polymerizable group; any known polymerizable group can be used, with free radical polymerizable groups being preferred.

[0311] Examples of polymerizable groups include olefinic unsaturated groups such as (meth)acryloyloxy, (meth)acrylamido, and styryl, as well as groups with epoxy groups such as glycidyl.

[0312] Among them, the polymerizable group is preferably an olefinic unsaturated group, more preferably (meth)acryloyloxy, and even more preferably acryloyloxy.

[0313] As a capped isocyanate compound, it can be used in commercially available products.

[0314] Examples of commercially available 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 end-capped DURANATE series (e.g., DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0315] Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0316] [Chemical Formula 2]

[0317]

[0318] One type of thermally crosslinking compound can be used alone, or two or more types can be used.

[0319] When the photosensitive composition layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the total mass of the photosensitive composition layer.

[0320] (Other additives)

[0321] In addition to the above-mentioned components, the photosensitive composition layer may also contain known additives as needed.

[0322] Examples of additives include free radical polymerization inhibitors, antioxidants (e.g., phenidones), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles), sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazoles), pyridines (e.g., isonicotinamide), and purine bases (e.g., adenine).

[0323] Furthermore, other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid proliferators, development promoters, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic suspending agents, and paragraphs

[0165] to

[0184] of Japanese Patent Application Publication No. 2014-085643, and these contents are incorporated herein by reference.

[0324] Each additive can be used alone or in combination with two or more.

[0325] The photosensitive composition layer may contain a polymerization inhibitor. Examples of polymerization inhibitors include free radical polymerization inhibitors.

[0326] Examples of free radical polymerization inhibitors include the thermal polymerization inhibitor described in Japanese Patent No. 4502784, paragraph

[0018] . Phenothiazine, phenoxazine, 1-phenyl-3-pyrazolone, 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 composition layer, aluminum nitrosophenylhydroxylamine is preferably used as the free radical polymerization inhibitor.

[0327] The content of the free radical polymerization inhibitor relative to the total mass of the polymerizable compound is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.01 to 1.0% by mass.

[0328] 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.

[0329] 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.

[0330] The total content of benzotriazoles and carboxybenzotriazoles relative to the total mass of the photosensitive composition 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 composition 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.

[0331] The photosensitive composition layer may contain a sensitizer.

[0332] There are no particular limitations on the sensitizer; known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridinone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), piracetam compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds, and aminoacridine compounds.

[0333] One type of sensitizer can be used alone, or two or more types can be used.

[0334] When the photosensitive composition 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 through the balance between polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer.

[0335] The photosensitive composition layer may contain a surfactant.

[0336] As surfactants, examples include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Unexamined Patent Publication No. 2009-237362.

[0337] Examples of surfactants include hydrocarbon-based surfactants, fluorinated surfactants, and silicone surfactants. From the viewpoint of improving environmental adaptability, surfactants that do not contain fluorine atoms are preferred. Hydrocarbon-based surfactants or silicone surfactants are preferred. Furthermore, nonionic surfactants are preferred.

[0338] Commercially available fluorinated surfactants include, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, and EXP. MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-6 31. EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above is DIC (Manufactured by Corporation), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC INC.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions). (manufactured by NEOS COMPANY LIMITED), FTERGENT 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS COMPANY LIMITED), U-120E (UNICHEM CO., LTD.), etc.

[0339] Furthermore, acrylic compounds are preferred as fluorinated surfactants. These compounds have a molecular structure containing functional groups with fluorine atoms, and when heated, the functional groups containing fluorine atoms are partially cleaved, causing the fluorine atoms to volatilize. Examples of such fluorinated surfactants include the MEGAFACE DS series manufactured by DIC Corporation (Hydrogen Kagaku Nihon (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as MEGAFACE DS-21.

[0340] Furthermore, as a fluorinated surfactant, a polymer of a fluorinated vinyl ether compound having fluorinated alkyl or fluorinated alkylene ether groups and a hydrophilic vinyl ether compound is preferred.

[0341] Furthermore, as a fluorinated surfactant, it can also be used with end-capped polymers.

[0342] Furthermore, as a fluorinated surfactant, it is preferable to use a fluorinated polymer compound containing structural units derived from (meth)acrylate compounds having fluorine atoms and structural units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propylene oxide).

[0343] Furthermore, as a fluorinated surfactant, it can also be used on fluorinated polymers with olefinically unsaturated groups on their side chains. Examples include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DICCorporation).

[0344] From the viewpoint of improving environmental adaptability, surfactants derived from alternative materials of compounds having a straight-chain perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are preferred as fluorinated surfactants.

[0345] Examples of hydrocarbon-based surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitol fatty acid esters. Specific examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (all manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM WakoPure Chemical Corporation), PIONIN D-1105, D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical). Co., Ltd. (manufacturing), etc.

[0346] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers obtained by introducing organic groups into the side chains or ends.

[0347] Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray... SiliconeSH8400 (all manufactured by BYK-Chemie GmbH) and models X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, KF-6002, KP-101, KP-103, KP- 104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (the above are Shin-Etsu (Manufactured by Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (all manufactured by BYK JAPAN KK.), etc.

[0348] Surfactants can be used alone or in combination with two or more.

[0349] When the photosensitive composition layer contains a surfactant, the surfactant content is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.80% by mass, relative to the total mass of the photosensitive composition layer.

[0350] Furthermore, the photosensitive composition layer may also contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development promoters, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents.

[0351] Regarding the additives contained in the photosensitive composition layer, they are described in paragraphs

[0165] to

[0184] of Japanese Patent Application Publication No. 2014-085643, and the contents of that publication are incorporated herein by reference.

[0352] From the viewpoint of improving reliability and lamination, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0353] The thickness (film thickness) of the photosensitive composition 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 composition layer and enhances resolution.

[0354] 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.

[0355] Furthermore, the transmittance of the photosensitive composition layer at 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.

[0356] (Impurities, etc.)

[0357] The photosensitive composition layer may contain a specified amount of impurities.

[0358] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions. Among these, sodium and potassium ions are easily introduced as impurities, and therefore are preferably set to the following concentrations.

[0359] The impurity content in the photosensitive composition layer, on a mass basis, is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content in the photosensitive composition layer, on a mass basis, can be set to 1 ppb or more or 0.1 ppm or more. As a specific example of the impurity content in the photosensitive composition layer, all the above-mentioned impurities can be set to 0.6 ppm on a mass basis.

[0360] Methods for keeping impurities within the aforementioned range include: selecting raw materials with low impurity content as raw materials for the photosensitive composition layer; preventing impurities from being introduced during the formation of the photosensitive composition layer; and removing impurities by washing. These methods enable the impurity content to be kept within the aforementioned range.

[0361] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) luminescence spectrophotometry, atomic absorption spectrometry, and ion chromatography.

[0362] The preferred photosensitive composition layer contains low levels of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these compounds in the photosensitive composition layer, on a mass basis, is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less. The lower limit, on a mass basis, can be set to 10 ppb or more, or 100 ppb or more. The content of these compounds can be suppressed using the same methods as for impurities of the aforementioned metals. Furthermore, they can be quantified using known methods.

[0363] From the viewpoint of improving reliability and lamination, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0364] (pigment)

[0365] The photosensitive composition layer can be a coloring resin layer containing pigments.

[0366] In recent years, electronic devices have sometimes installed cover glass on their liquid crystal display windows to protect the display windows. This cover glass has a black, frame-like light-shielding layer formed on the back periphery of a transparent glass substrate or similar material. A colored resin layer can be used to form this light-shielding layer.

[0367] As for pigments, they can be selected appropriately according to the desired hue, and can be chosen from black pigments, white pigments, and colored pigments other than black and white. Among them, when forming a black-based pattern, black pigment is preferred.

[0368] As for 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, examples of preferred 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 its surface is coated with resin is preferred.

[0369] From the viewpoint of dispersion stability, the particle size of the black pigment, measured by number-average particle size, is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm.

[0370] Particle size refers to the diameter of a circle whose area is calculated from a photograph of pigment particles taken with an electron microscope and whose area is the same as that of the pigment particles. 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.

[0371] 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, among the white pigments, titanium dioxide, zinc oxide, zinc barium white, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, 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.

[0372] Furthermore, the surface of titanium oxide can be treated with silica, alumina, titanium dioxide, zirconium dioxide, or organic substances, or even two or more of these treatments. This inhibits the catalytic activity of titanium oxide and improves its heat resistance and fading properties.

[0373] From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, at least one of aluminum oxide treatment and zirconium oxide treatment is preferred as a surface treatment for the titanium oxide surface, and both aluminum oxide treatment and zirconium oxide treatment are particularly preferred.

[0374] Furthermore, when the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, the photosensitive composition layer preferably 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.

[0375] As colored pigments, examples include Victoria Blue BO (Color Index 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hostaperm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Supura (CI Pigment Red 81), and Monastella Fast Blue. The pigments include CI Pigment Blue 15 (blue), Monolight 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.

[0376] When the photosensitive composition layer contains pigment, the pigment content relative to the total mass of the photosensitive composition 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 especially preferably more than 10% by mass and less than 35% by mass.

[0377] When the photosensitive composition layer contains pigments other than black pigment (white pigments and colored pigments), the content of pigments other than black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass, relative to black pigment.

[0378] Furthermore, when the photosensitive composition layer contains a black pigment and the photosensitive composition layer is formed from the photosensitive composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion.

[0379] A dispersion can be prepared by adding a pre-mixed mixture of black pigment and pigment dispersant to an organic solvent (or vehicle) and dispersing it using a disperser. The pigment dispersant can be selected based on the pigment and solvent; for example, commercially available dispersants can be used. The vehicle refers to the medium through which the pigment is dispersed during the preparation of the dispersion. It is liquid and includes 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.

[0380] Examples of dispersants include, for example, urethane-based dispersants such as polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, their modifications, oily dispersants such as amides and their salts formed by the reaction of poly(lower alkylene imides) with polyesters having free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, and other water-soluble resins or water-soluble polymers, polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, and phosphate esters. The dispersant can be selected from the contents described in paragraphs

[0021] to

[0065] of Japanese Patent Application Publication No. 2021-012355.

[0381] As a preferred dispersant, for example, an alkaline polymeric dispersant can be cited. As an example of an alkaline polymeric dispersant, a polymer containing nitrogen atoms can be cited. The nitrogen atoms can be contained in the polymer backbone, in the polymer side chains, or in both the backbone and side chains. Among these, the alkaline polymeric dispersant is preferably a polymer containing nitrogen atoms in its side chains. Since the surface of carbon black is generally acidic, when using carbon black as a pigment, an alkaline polymeric dispersant is particularly preferred as a dispersant.

[0382] As a polymer containing nitrogen atoms (preferably a polymer containing nitrogen atoms in its side chain), examples include polymers containing at least one atomic group selected from the group consisting of primary amine, secondary amine, tertiary amine, quaternary ammonium salt, and nitrogen-containing heterocyclic groups. For example, polymers containing quaternary ammonium salt groups are preferred. The atomic group is preferably incorporated into the side chain of the polymer. For example, polymers containing at least one atomic group selected from the group consisting of primary amine, secondary amine, tertiary amine, quaternary ammonium salt, and nitrogen-containing heterocyclic groups in their side chains are preferred, and polymers containing quaternary ammonium salt groups in their side chains are more preferred. As a counterion to the quaternary ammonium cation in the quaternary ammonium salt group, for example, a carboxylate ions can be mentioned. As carboxylate ions, for example, aliphatic carboxylate ions and aromatic carboxylate ions can be mentioned.

[0383] The polymer containing nitrogen atoms (preferably a polymer containing nitrogen atoms in the side chain) is preferably a polymer containing structural units derived from styrene and structural units derived from maleimide derivatives, more preferably a copolymer of styrene and maleimide derivatives.

[0384] Maleimide derivatives have a structure in which at least one hydrogen atom of the maleimide is substituted with a substituent. Examples of maleimide derivatives include those comprising at least one group selected from the group consisting of primary amino, secondary amino, tertiary amino, quaternary ammonium salt, and nitrogen-containing heterocyclic groups. Maleimide derivatives comprising a quaternary ammonium salt are preferred.

[0385] The dispersant can be a commercially available dispersant, for example, BYK-2012 (BYK JAPAN KK.).

[0386] In addition to pigments, dispersions may also contain dispersing aids (also known as pigment dispersing aids). Dispersing aids may be selected from known dispersing aids.

[0387] As dispersing agents, for example, compounds having organic pigment residues can be cited. Examples of organic pigments include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, violet ketone pigments, perylene pigments, thiamethoxam-indigo pigments, triazine pigments, benzimidazolone pigments, benziisoindole and other indole pigments, isoindoline pigments, isoindolineone pigments, quinophthalone pigments, naphthol pigments, vat pigments, metal complex pigments, azo, diazo, polyazo and other azo pigments, etc. Compounds having organic pigment residues can have acidic substituents, basic substituents, or neutral substituents. Examples of acidic substituents include sulfonyl, carboxyl, and phosphate groups. Examples of basic substituents include sulfonamide and amino groups. Examples of neutral substituents include phenyl and phthalimide alkyl groups. The method of using the dispersing agent can be selected from the contents described in paragraphs

[0067] to

[0084] of Japanese Patent Application Publication No. 2021-012355.

[0388] Preferred dispersing agents include, for example, compounds having phthalocyanine residues. Specifically, the dispersing agent is preferably a phthalocyanine pigment derivative or a salt thereof having an acidic substituent, more preferably a phthalocyanine pigment derivative or a salt thereof having at least one acidic substituent selected from the group consisting of sulfonyl, carboxyl, and phosphate groups, and even more preferably a phthalocyanine pigment derivative or a salt thereof having a sulfonyl group. Phthalocyanine pigment derivatives are described, for example, in Japanese Patent Application Publication No. 2007-226161, International Publication No. 2016 / 163351, Japanese Patent Application Publication No. 2017-165820, and Japanese Patent No. 5753266. These publications are incorporated herein by reference.

[0389] There are no particular limitations on the type of dispersing machine; for example, well-known dispersing machines such as kneaders, roller mills, attritors, super mills, dissolvers, homogenizers, and sandmills can be cited. Alternatively, mechanical grinding and micronization can be achieved using friction. For information on dispersing machines and micronization, please refer to the "Dictionary of Pigments" (Kunozou Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0390] [Protective film]

[0391] The first embodiment of the transfer film may have a protective film.

[0392] As a protective film, resin films with heat resistance and solvent resistance can be used. Examples include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

[0393] Furthermore, a resin film made of the same material as the temporary support described above can be used as a protective film.

[0394] The protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0395] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and especially preferably 15 to 30 μm.

[0396] From the viewpoint of excellent mechanical strength, the thickness of the protective film is preferably 1 μm or more, and from the viewpoint of relatively low cost, it is preferably 100 μm or less.

[0397] Furthermore, the protective film preferably contains 5 fisheyes with a diameter of 80 μm or larger per meter. 2 the following.

[0398] In addition, "fisheye" refers to substances that are formed when foreign matter, undissolved matter, and oxidized deterioration products of the material enter the membrane during the manufacturing process of the membrane by methods such as hot melting, kneading, extrusion, biaxial stretching, and casting.

[0399] The number of particles with a diameter of 3 μm or larger contained in the protective film is preferably 30 particles / mm. 2 The following is more preferably 10 pieces / mm 2 The following is a further preferred option: 5 per mm 2 the following.

[0400] Therefore, it is possible to suppress defects caused by unevenness due to particles contained in the protective film being transferred onto the photosensitive composition layer or conductive layer.

[0401] From the viewpoint of imparting rollability, the arithmetic mean roughness Ra of the surface of the protective film and the side opposite to the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0402] From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface of the protective film in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0403] (Relationship between temporary support, photosensitive composition layer, and protective film)

[0404] The first embodiment of the transfer film is preferably as follows: the cured film obtained by curing the photosensitive composition layer has an elongation at break of 15% or more at 120°C, the arithmetic mean roughness Ra of the surface of the photosensitive composition layer side of the temporary support is 50 nm or less, and the arithmetic mean roughness Ra of the surface of the photosensitive composition layer side of the protective film is 150 nm or less.

[0405] Furthermore, the transfer film preferably satisfies the following formula (1).

[0406] X×Y<1500 Equation (1)

[0407] Here, in formula (1), X represents the elongation at break (%) of the cured film obtained by curing the photosensitive composition layer at 120°C, and Y represents the arithmetic mean roughness Ra (nm) of the surface of the photosensitive composition layer side of the temporary support. More preferably, X×Y is 750 or less. Specific values ​​for X include 18%, 25%, 30%, and 35%. Specific values ​​for X×Y include 4nm, 8nm, 15nm, and 30nm. Specific values ​​for X×Y include 150, 200, 300, 360, and 900.

[0408] Preferably, the elongation at break at 120°C is more than twice that of the cured film obtained by curing the photosensitive composition layer at 23°C.

[0409] Regarding the elongation at break, the following cured films were measured by tensile testing: using an ultra-high pressure mercury lamp at 120 mJ / cm². 2 After exposing and curing a 20 μm thick photosensitive composite layer, a high-pressure mercury lamp at 400 mJ / cm² was used. 2 Further exposure was performed, followed by curing at 145°C for 30 minutes.

[0410] Furthermore, the transfer film preferably satisfies the following formula (2).

[0411] Y≤Z Equation (2)

[0412] Here, in equation (2), Y represents the arithmetic mean roughness Ra (nm) of the surface of the photosensitive composition layer side of the temporary support, and Z represents the arithmetic mean roughness Ra (nm) of the surface of the photosensitive composition layer side of the protective film.

[0413] [Thermoplastic resin layer]

[0414] The first embodiment of the transfer film may have a thermoplastic resin layer.

[0415] When the first embodiment of the transfer film includes a thermoplastic resin layer, the thermoplastic resin layer is typically disposed between the temporary support and the photosensitive composition layer. The presence of the thermoplastic resin layer in the transfer film improves the substrate-to-substrate tracking during the bonding process, thereby suppressing air bubbles from entering 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.

[0416] The thermoplastic resin layer comprises resin. The resin may comprise thermoplastic resin as a part or all thereof. That is, in one embodiment, the resin of the thermoplastic resin layer is also preferably a thermoplastic resin.

[0417] (Alkali-soluble resins (thermoplastic resins))

[0418] As a thermoplastic resin, an alkali-soluble resin is preferred.

[0419] Examples of alkali-soluble resins include, for example, acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0420] From the viewpoint of developability and adhesion to adjacent layers, acrylic resin is preferred as an alkali-soluble resin.

[0421] Here, acrylic resin means a resin having at least one structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide.

[0422] 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, relative to the total mass of the acrylic resin, is preferably 50% by mass or more.

[0423] Of which, relative to the total mass of the acrylic resin, the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

[0424] Furthermore, the alkali-soluble resin is preferably a polymer with acid groups.

[0425] Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl being the most preferred.

[0426] From the viewpoint of developability, alkali-soluble resin is more preferably an alkali-soluble resin with an acid value of 60 mg KOH / g or higher, and even more preferably an acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher.

[0427] There is no particular limitation on 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 especially preferably below 150 mg KOH / g.

[0428] There are no particular restrictions on the use of carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher, and they can be appropriately selected from known resins.

[0429] For example, examples include the alkali-soluble acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher 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 higher 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 higher described in paragraphs

[0053] to

[0068] of Japanese Patent Application Publication No. 2016-224162.

[0430] 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.

[0431] 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.

[0432] 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 addition polymerization reactive groups such as epoxy and (block) isocyanate groups.

[0433] 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.

[0434] Alkali-soluble resins can be used alone or in combination with two or more types.

[0435] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin relative to the total mass of the thermoplastic resin layer is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass.

[0436] (Compounds that produce acids, bases, or free radicals through light)

[0437] 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").

[0438] As compound C, it is preferably a compound that generates an acid, base or free radical when activated by ultraviolet light or visible light.

[0439] As compound C, known photoacid generators, photoalkali generators, and photoradical polymerization initiators (photoradical generators) can be used.

[0440] (Photo-acid generator)

[0441] From a resolution perspective, the thermoplastic resin layer can contain a photoacid generator.

[0442] As photoacid generators, examples of photocationic polymerization initiators that can be included in the aforementioned negative photosensitive composition layer are as follows, except for the points described later.

[0443] From the viewpoint of sensitivity and resolution, the photoacid generator preferably includes at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, it is more preferably to include oxime sulfonate compounds.

[0444] Furthermore, as a photoacid generator, a photoacid generator having the following structure is preferred.

[0445] [Chemical Formula 3]

[0446]

[0447] (Photoradical polymerization initiator)

[0448] The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0449] As photoradical polymerization initiators, examples of photoradical polymerization initiators that can be included in the aforementioned negative photosensitive composition layer are given, and the preferred method is also the same.

[0450] (Photo-induced alkali production agent)

[0451] Thermoplastic resin compositions may contain photoalkali-generating agents.

[0452] As a photo-alkali-generating agent, there are no particular limitations as long as it is a well-known photo-alkali-generating agent. Examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl}cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) (2-Nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethyl borate), 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.

[0453] Compound C can be used alone or in more than two forms.

[0454] From the viewpoint of visual recognizability 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.

[0455] (pigment)

[0456] The thermoplastic resin layer preferably contains a pigment (also referred to as "pigment B") with a maximum absorption wavelength of 450 nm or higher within the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength can be changed by acids, alkalis or free radicals.

[0457] Except for the points described later, the preferred method for pigment B is the same as the preferred method for pigment N described above.

[0458] From the viewpoint of visual recognizability and resolution of the exposed and unexposed portions, pigment B is preferably a pigment whose maximum absorption wavelength changes through acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes through acid.

[0459] From the viewpoint of visual recognizability and resolution of the exposed and unexposed portions, the thermoplastic resin layer preferably includes both a pigment (as pigment B) whose maximum absorption wavelength changes due to acid transmission, and a compound that generates acid upon light transmission (described later).

[0460] Pigment B can be used alone or in combination with two or more pigments.

[0461] From the viewpoint of visual distinguishability of the exposed and unexposed portions, the content of pigment B relative to the total mass of the thermoplastic resin layer 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.

[0462] The content of pigment B refers to the total amount of pigment B contained in the thermoplastic resin layer that is in its color-developing 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 B.

[0463] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigment 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, thereby generating free radicals and activating the pigments in their chromogenic state. Subsequently, the absorbance of each solution at 25 °C was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) under atmospheric conditions, and calibration curves were constructed.

[0464] Next, 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. Otherwise, the absorbance of the solution that caused all the pigments to develop color was measured using the same method as described above. Based on the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of pigment contained in the thermoplastic resin layer was calculated using a calibration curve.

[0465] In addition, the 3g of thermoplastic resin layer is the same as the 3g of solid component of the thermoplastic resin layer.

[0466] (Plasticizer)

[0467] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0468] The molecular weight (weight-average molecular weight when it is an oligomer or polymer with a molecular weight distribution) of the plasticizer is preferably less than that of the alkali-soluble resin. The molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000.

[0469] There are no particular limitations on plasticizers as long as they are compounds that are compatible with alkali-soluble resins and exhibit plasticity. However, from the viewpoint of imparting plasticity, plasticizers preferably have alkene groups in their molecules, and more preferably are polyalkylene glycol compounds. The alkene groups contained in the plasticizer are more preferably polyoxyethylene or polyoxypropylene structures.

[0470] Furthermore, from the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, an alkali-soluble resin is more preferably an acrylic resin, and the plasticizer contains a (meth)acrylate compound.

[0471] Examples of (meth)acrylate compounds used as plasticizers include polymeric compounds described in the above-mentioned negative photosensitive composition layer.

[0472] In a transfer film, when a thermoplastic resin layer and a negative photosensitive composition layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound. This is because by having both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound, interlayer diffusion is suppressed, thereby improving storage stability.

[0473] 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.

[0474] Furthermore, from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred as the (meth)acrylate compound used as a plasticizer.

[0475] Furthermore, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

[0476] Plasticizers can be used alone or in combination with two or more.

[0477] From the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the content of plasticizer relative to the total mass of the thermoplastic resin layer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass.

[0478] (Sensitizer)

[0479] The thermoplastic resin layer may contain sensitizers.

[0480] There are no particular limitations on the sensitizers used, and examples of sensitizers that can be included in the aforementioned negative photosensitive composition layer can be cited.

[0481] One type of sensitizer can be used alone, or two or more types can be used.

[0482] 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 visual distinguishability 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.

[0483] (Additives, etc.)

[0484] In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives such as surfactants, as needed.

[0485] 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.

[0486] There is no particular limitation on the thickness of the thermoplastic resin layer, 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.

[0487] [Middle Layer]

[0488] The first embodiment of the transfer film may have an intermediate layer.

[0489] In the transfer film 10, by disposing the intermediate layer 13 between the thermoplastic resin layer and the photosensitive composition layer 15, it is possible to suppress the mixing of components that may occur during the coating formation of the thermoplastic resin layer and the photosensitive composition layer 15 and during storage after coating formation.

[0490] As an intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used.

[0491] Furthermore, as the intermediate layer, an oxygen barrier layer with oxygen barrier function, as described in Japanese Patent Application Publication No. 5-072724 (JP5-072724), can also be used. If the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and thus the productivity is improved, which is therefore preferred.

[0492] The oxygen barrier layer used as the intermediate layer can be appropriately selected from the known layers described in the aforementioned publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0493] The following describes the components that may be included in a water-soluble resin layer (intermediate layer).

[0494] The water-soluble resin layer (intermediate layer) contains resin.

[0495] The aforementioned resins include water-soluble resins as part or all of them.

[0496] 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.

[0497] Furthermore, copolymers of (meth)acrylic acid / vinyl compounds can also be used as water-soluble resins. Among the copolymers of (meth)acrylic acid / vinyl compounds, copolymers of (meth)acrylic acid / allyl (meth)acrylate are preferred, and copolymers of methacrylic acid / allyl methacrylate are more preferred.

[0498] 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.

[0499] 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.

[0500] The dispersion (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

[0501] Furthermore, from the viewpoint of further improving the interlayer mixing suppression ability of the water-soluble resin layer (intermediate layer), the resin in the water-soluble resin layer (intermediate layer) is preferably a different resin from the resin contained in the layer disposed on one side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other side. For example, when the photosensitive composition layer 15 contains polymer A and the thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer, the resin in the water-soluble resin layer (intermediate layer) is preferably a different resin from polymer A and thermoplastic resin (alkali-soluble resin).

[0502] From the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0503] Water-soluble resins can be used alone or in combination with two or more.

[0504] The content of water-soluble resin is not particularly limited, but from the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability, it is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more, relative to the total mass of the water-soluble resin layer (intermediate layer). Furthermore, there is no particular limitation on its upper limit, but for example, it is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.

[0505] Depending on the requirements, the intermediate layer may contain known additives such as surfactants.

[0506] The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. If the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier properties are not reduced, and the interlayer mixing inhibition ability is excellent. Furthermore, it can further suppress the increase in the removal time of the water-soluble resin layer (intermediate layer) during development.

[0507] <Transfer Film (Second Embodiment)>

[0508] A second embodiment of the transfer film of the present invention is a transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having olefinically unsaturated groups, and a photopolymerization initiator, and the content of nitrate ions in the photosensitive composition layer is 10.0 ppm by mass or less relative to the total mass of the photosensitive composition layer. The content of nitrate ions will be described in detail later.

[0509] The second embodiment of the transfer film of the present invention is considered to have excellent adhesion and suppressed residue generation due to the following reasons by having the above-described structure.

[0510] It is believed that in the second embodiment of the transfer film of the present invention, since the content of nitrate ions is below a specified amount, the surface of the substrate is less likely to deteriorate, resulting in excellent adhesion. Furthermore, it is believed that by keeping the content of nitrate ions below a specified amount, ions originating from the substrate are less likely to be generated. It is believed that when the generation of ions originating from the substrate is low, the composition of the photosensitive composition layer is less susceptible to influences such as coordination, and as a result, the generation of residues is suppressed.

[0511] The second embodiment of the transfer film of the present invention differs from the first embodiment in that the content of nitrate ions is specified instead of the content of phosphate ions in the photosensitive composition layer. Regarding the second embodiment of the transfer film, all other aspects are the same as the first embodiment, and the preferred embodiments are also the same; therefore, only the differences from the first embodiment will be described, and the same aspects will be omitted.

[0512] [Photosensitive Composition Layer]

[0513] Regarding the photosensitive composition layer of the second embodiment of the transfer film, the content of nitrate ions is 10.0 ppm by mass or less relative to the total mass of the photosensitive composition layer.

[0514] (Nitrate ion content)

[0515] The content of nitrate ions in the photosensitive composition layer is 10.0 ppm by mass or less relative to the total mass of the photosensitive composition layer. There is no particular limitation on the lower limit; 0.0 ppm by mass is an example. From the viewpoint of better adhesion and further suppression of residue formation, the content of nitrate ions relative to the total mass of the photosensitive composition layer is preferably 0.1 to 7.0 ppm by mass.

[0516] Furthermore, the nitrate ion content in the photosensitive composition layer refers to the nitrate ion content when analyzed by ion chromatography. Chromatographic analysis will be discussed in detail later.

[0517] The nitrate ion content mentioned above refers to the total content of nitrate ions derived from salts containing nitrate ions and the content of ionized nitrate ions. Furthermore, when the nitrate ion content in the photosensitive composition layer exceeds 0.0 ppm by mass relative to the total mass of the photosensitive composition layer, it means that the photosensitive composition layer contains nitrate ions or salts containing nitrate ions.

[0518] Nitrate ions refer to the ions formed by NO3- - The anion is represented.

[0519] A salt containing nitrate ions is a compound composed of nitrate ions and a counter cation. Examples of counter cations include those contained in the aforementioned salts containing phosphate ions.

[0520] In this specification, the nitrate ion content is determined by ion chromatography. The details of the ion chromatography-based determination method are the same as those for the determination of phosphate ion content.

[0521] (Content of other ions)

[0522] The photosensitive composition layer may contain ions other than nitrate ions or salts containing ions other than salts containing nitrate ions.

[0523] Examples of other ions include phosphate ions, iodide ions, and bromide ions. Additionally, examples of salts containing other ions include compounds composed of any one of phosphate ions, iodide ions, and bromide ions combined with a counter cation. Examples of counter cations include, for instance, cations exemplified as counter cations contained in the aforementioned salts containing phosphate ions.

[0524] From the viewpoint of better adhesion and further suppression of residue formation, the content of phosphate ions in the photosensitive composition layer is preferably 10.0 ppm by mass or less, more preferably 0.1 to 7.0 ppm by mass, relative to the total mass of the photosensitive composition layer.

[0525] In addition, the phosphate ion content can be 0.0 ppm by mass.

[0526] In the second embodiment of the transfer film, the ratio of phosphate ion content to nitrate ion content is preferably 0.5 to 3.3, more preferably 0.7 to 2.0.

[0527] From the viewpoint of better adhesion and further suppression of residue formation, the content of iodide ions in the photosensitive composition layer is preferably 2.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer, more preferably 3.0 to 10.0 ppm by mass.

[0528] In the second embodiment of the transfer film, the ratio of iodide ion content to nitrate ion content is preferably 1.0 to 120.0, more preferably 1.4 to 30.0.

[0529] From the viewpoint of achieving better adhesion and further suppressing the generation of residues, the bromide ion content in the photosensitive composition layer is preferably 4.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer, more preferably 6.0 to 10.0 ppm by mass.

[0530] In the second embodiment of the transfer film, the ratio of bromide ion content to nitrate ion content is preferably 1.0 to 230.0, more preferably 1.4 to 55.0.

[0531] The contents of each of the other ions mentioned above refer to the total contents of other ions derived from salts containing other ions and the contents of other ions ionized.

[0532] The contents of the other ions mentioned above were determined using the same method as those of nitrate ions.

[0533] <Transfer Film (Third Embodiment)>

[0534] A third embodiment of the transfer film of the present invention is a transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having olefinically unsaturated groups, and a photopolymerization initiator, and the content of iodide ions in the photosensitive composition layer is 2.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer. The content of iodide ions will be described in detail later.

[0535] It is believed that the third embodiment of the transfer film of the present invention, by having the above-described structure, has excellent adhesion and suppresses the generation of residue for the following reasons.

[0536] It is believed that in the third embodiment of the transfer film of the present invention, since the iodide ion content is at or above a predetermined amount, the iodide ions interact with the surface of the substrate, resulting in excellent adhesion. Furthermore, it is believed that by keeping the iodide ion content below the predetermined amount, ions originating from the substrate are less likely to be generated. It is believed that when the generation of ions originating from the substrate is low, the composition of the photosensitive composition layer is less susceptible to influences such as coordination, and as a result, residue generation is suppressed.

[0537] The third embodiment of the transfer film of the present invention differs from the first embodiment in that the content of iodide ions is specified instead of the content of phosphate ions in the photosensitive composition layer. Regarding the third embodiment of the transfer film, all other aspects are the same as the first embodiment, and the preferred embodiments are also the same; therefore, only the differences from the first embodiment will be described, and the same aspects will be omitted.

[0538] [Photosensitive Composition Layer]

[0539] Regarding the photosensitive composition layer of the third embodiment of the transfer film, the iodide ion content is 2.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer.

[0540] (Content of iodide ions)

[0541] The content of iodide ions in the photosensitive composition layer is 2.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer. From the viewpoint of better adhesion and further suppression of residue formation, the content of iodide ions is preferably 3.0 to 10.0 ppm by mass relative to the total mass of the photosensitive composition layer.

[0542] Furthermore, the iodide ion content in the photosensitive composition layer refers to the iodide ion content when analyzed by ion chromatography. Chromatographic analysis will be discussed in detail later.

[0543] The iodide ion content mentioned above refers to the total content of iodide ions derived from salts containing iodide ions and the content of ionized iodide ions. Furthermore, when the iodide ion content in the photosensitive composition layer exceeds 0.0 ppm by mass relative to the total mass of the photosensitive composition layer, it means that the photosensitive composition layer contains iodide ions or salts containing iodide ions.

[0544] Iodide ions refer to ions composed of I - The anion is represented.

[0545] A salt containing iodide ions is a compound composed of iodide ions and a counter cation. Examples of counter cations include those contained in the aforementioned salts containing phosphate ions.

[0546] In this specification, the iodide ion content is determined by ion chromatography. The details of the ion chromatography-based determination method are the same as those for the determination of phosphate ion content.

[0547] (Content of other ions)

[0548] The photosensitive composition layer may contain ions other than iodide ions or salts containing ions other than salts containing iodide ions.

[0549] Examples of other ions include phosphate ions, nitrate ions, and bromide ions. Additionally, examples of salts containing other ions include compounds composed of any one of phosphate ions, nitrate ions, and bromide ions combined with a counter cation. Examples of counter cations include, for instance, cations exemplified as counter cations contained in the aforementioned salts containing phosphate ions.

[0550] From the viewpoint of better adhesion and further suppression of residue formation, the content of phosphate ions in the photosensitive composition layer is preferably 10.0 ppm by mass or less, more preferably 0.1 to 7.0 ppm by mass, relative to the total mass of the photosensitive composition layer.

[0551] In addition, the phosphate ion content can be 0.0 ppm by mass.

[0552] In the third embodiment of the transfer film, the ratio of phosphate ion content to iodide ion content is preferably 0.0 to 1.0, more preferably 0.03 to 0.7.

[0553] From the viewpoint of better adhesion and further suppression of residue formation, the content of nitrate ions in the photosensitive composition layer is preferably 10.0 ppm by mass or less, more preferably 0.1 to 7.0 ppm by mass, relative to the total mass of the photosensitive composition layer.

[0554] In addition, the nitrate ion content can be 0.0 ppm by mass.

[0555] In the third embodiment of the transfer film, the ratio of nitrate ion content to iodide ion content is preferably 0.0 to 1.0, more preferably 0.03 to 0.7.

[0556] From the viewpoint of achieving better adhesion and further suppressing the generation of residues, the bromide ion content in the photosensitive composition layer is preferably 4.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer, more preferably 6.0 to 10.0 ppm by mass.

[0557] In the third embodiment of the transfer film, the ratio of bromide ion content to iodide ion content is preferably 0.8 to 2.5, more preferably 0.9 to 2.1.

[0558] The contents of each of the other ions mentioned above refer to the total contents of other ions derived from salts containing other ions and the contents of other ions ionized.

[0559] The contents of the other ions mentioned above were determined using the same method as those for iodide ions.

[0560] <Transfer Film (Fourth Embodiment)>

[0561] The fourth embodiment of the transfer film of the present invention is a transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer comprises an alkali-soluble resin, a polymerizable compound having olefinically unsaturated groups, and a photopolymerization initiator, and the bromide ion content in the photosensitive composition layer is 4.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer. The iodide ion content will be described in detail later.

[0562] The fourth embodiment of the transfer film of the present invention is considered to have excellent adhesion and suppressed residue generation due to the following reasons by having the above-described structure.

[0563] In the fourth embodiment of the transfer film of the present invention, since the bromide ion content is at or above a predetermined amount, the bromide ions interact with the surface of the substrate, resulting in excellent adhesion. Furthermore, it is believed that by keeping the bromide ion content below the predetermined amount, ions originating from the substrate are less likely to be generated. It is also believed that when the generation of ions originating from the substrate is low, the composition of the photosensitive composition layer is less susceptible to influences such as coordination, and as a result, residue generation is suppressed.

[0564] The fourth embodiment of the transfer film of the present invention differs from the first embodiment in that the content of bromide ions is specified instead of the content of phosphate ions in the photosensitive composition layer. Regarding the fourth embodiment of the transfer film, all other aspects are the same as the first embodiment, and the preferred embodiments are also the same; therefore, only the differences from the first embodiment will be described, and the same aspects will be omitted.

[0565] [Photosensitive Composition Layer]

[0566] Regarding the photosensitive composition layer of the fourth embodiment of the transfer film, the bromide ion content is 4.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer.

[0567] (Content of bromide ions)

[0568] The bromide ion content in the photosensitive composition layer is 4.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer. From the viewpoint of better adhesion and further suppression of residue formation, the bromide ion content is preferably 6.0 to 10.0 ppm by mass relative to the total mass of the photosensitive composition layer.

[0569] Furthermore, the bromide ion content in the photosensitive composition layer refers to the bromide ion content when the photosensitive composition layer is analyzed by ion chromatography. Chromatographic analysis will be discussed in detail later.

[0570] The bromide ion content mentioned above refers to the total content of bromide ions derived from salts containing bromide ions and the content of ionized bromide ions. Furthermore, when the bromide ion content in the photosensitive composition layer exceeds 0.0 ppm by mass relative to the total mass of the photosensitive composition layer, it means that the photosensitive composition layer contains bromide ions or salts containing bromide ions.

[0571] Bromide ions refer to those formed by Br₂ - The anion is represented.

[0572] A salt containing bromide ions is a compound composed of bromide ions and a counter cation. Examples of counter cations include those contained in the aforementioned salts containing phosphate ions.

[0573] In this specification, the bromide ion content is determined by ion chromatography. The details of the ion chromatography-based determination method are the same as those for the determination of phosphate ion content.

[0574] (Content of other ions)

[0575] The photosensitive composition layer may contain ions other than bromide ions or salts containing ions other than salts containing bromide ions.

[0576] Examples of other ions include phosphate ions, nitrate ions, and iodide ions. Additionally, examples of salts containing other ions include compounds composed of any one of phosphate ions, nitrate ions, and iodide ions combined with a counter cation. Examples of counter cations include, for instance, cations exemplified as counter cations contained in the aforementioned salts containing phosphate ions.

[0577] From the viewpoint of better adhesion and further suppression of residue formation, the content of phosphate ions in the photosensitive composition layer is preferably 10.0 ppm by mass or less, more preferably 0.1 to 7.0 ppm by mass, relative to the total mass of the photosensitive composition layer.

[0578] In addition, the phosphate ion content can be 0.0 ppm by mass.

[0579] In the fourth embodiment of the transfer film, the ratio of phosphate ion content to bromide ion content is preferably 0.0 to 1.0, more preferably 0.015 to 0.7.

[0580] From the viewpoint of better adhesion and further suppression of residue formation, the content of nitrate ions in the photosensitive composition layer is preferably 10.0 ppm by mass or less, more preferably 0.1 to 7.0 ppm by mass, relative to the total mass of the photosensitive composition layer.

[0581] In addition, the nitrate ion content can be 0.0 ppm by mass.

[0582] In the fourth embodiment of the transfer film, the ratio of nitrate ion content to bromide ion content is preferably 0.0 to 1.0, more preferably 0.018 to 0.7.

[0583] From the viewpoint of better adhesion and further suppression of residue formation, the content of iodide ions in the photosensitive composition layer is preferably 4.0 to 20.0 ppm by mass relative to the total mass of the photosensitive composition layer, more preferably 6.0 to 10.0 ppm by mass.

[0584] In the fourth embodiment of the transfer film, the ratio of iodide ion content to bromide ion content is preferably 0.4 to 1.25, more preferably 0.47 to 1.1.

[0585] The contents of each of the other ions mentioned above refer to the total contents of other ions derived from salts containing other ions and the contents of other ions ionized.

[0586] The contents of the other ions mentioned above were determined using the same method as those of the bromide ions.

[0587] <Method for manufacturing transfer film>

[0588] There are no particular limitations on the manufacturing method of the transfer film (Embodiments 1 to 4), and known methods can be cited.

[0589] Examples of manufacturing methods for the transfer film 10 include: a method comprising the steps of coating a coating film by applying an intermediate layer forming composition to the surface of a temporary support 11, and then drying the coating film to form an intermediate layer 13; a method comprising the steps of coating a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and then drying the coating film to form a photosensitive composition layer 15; and a method comprising the steps of coating a photosensitive composition to the surface of a temporary support 11 to form a coating film, and then drying the coating film to form a photosensitive composition layer 15.

[0590] When the transfer film has a thermoplastic resin layer between the temporary support and the intermediate layer, the intermediate layer 13 can be formed by coating the surface of the temporary support 11 with a thermoplastic resin composition to form a coating film, drying the coating film to form a thermoplastic resin layer, and then forming the intermediate layer 13 by the same method as described above.

[0591] When the transfer film 10 has a protective film 19, the protective film 19 can be pressed onto the composition layer 17 of the transfer film 10 manufactured by the above manufacturing method.

[0592] As a method for manufacturing the transfer film 10, it is preferable to manufacture the transfer film 10 having a temporary support 11, an intermediate layer 13, a photosensitive composition layer 15 and a protective film 19 by a process including setting a protective film 19 in contact with the side of the composition layer 17 opposite to the side opposite to the temporary support 11.

[0593] After the transfer film 10 is manufactured by the above manufacturing method, the transfer film 10 is wound up, thereby producing and storing a roll of transfer film. The roll of transfer film 10 can be provided in its original form to the subsequent roll-to-roll bonding process with the substrate.

[0594] Furthermore, the method for manufacturing the transfer film 10 can be a method of forming a composition layer 17 on a protective film 19. Alternatively, it can be a method of further forming an intermediate layer 13 after forming the composition layer 17 on the protective film 19.

[0595] [Composition for forming thermoplastic resin layers and method for forming thermoplastic resin layers]

[0596] There are no particular limitations on the method for forming a thermoplastic resin layer on a temporary support, and known methods can be used. For example, it can be formed by coating a thermoplastic resin layer forming composition onto a temporary support and then drying it as needed.

[0597] The composition for forming a thermoplastic resin layer preferably includes various components and solvents for forming the aforementioned thermoplastic resin layer. Furthermore, in the composition for forming a thermoplastic resin layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the thermoplastic resin layer described above.

[0598] There are no particular limitations on the solvent, as long as it can dissolve or disperse all components other than the solvent itself; any known solvent can be used. Examples of solvents that are the same as those contained in the photosensitive composition described later are also preferred.

[0599] 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.

[0600] There are no particular limitations on the method of forming the thermoplastic resin layer, 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.

[0601] [Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)]

[0602] As a water-soluble resin composition, it is preferable to include various components and solvents that form the aforementioned intermediate layer (water-soluble resin layer). 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.

[0603] 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 the group consisting of water and water-mixed organic solvents, and more preferably, it is water or a mixture of water and water-mixed organic solvents.

[0604] 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.

[0605] You can use one solvent alone, or you can use two or more solvents.

[0606] 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.

[0607] There are no particular limitations on the method of forming the water-soluble resin layer, 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.

[0608] [Photosensitive composition and method for forming photosensitive composition layer]

[0609] From the viewpoint of high productivity and ease of forming the aforementioned photosensitive composition layer, it is preferable to use a photosensitive composition comprising the components constituting the aforementioned photosensitive composition layer (e.g., adhesive polymers, polymeric compounds, and polymerization initiators) and a solvent, and form it by a coating method.

[0610] As a method for manufacturing transfer film, a preferred method is to coat a photosensitive composition onto an intermediate layer to form a coating film and then dry the coating film at a specified temperature to form a photosensitive composition layer.

[0611] The photosensitive composition preferably includes various components and solvents that form the photosensitive composition layer described above. Furthermore, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive composition layer described above.

[0612] 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.

[0613] As a solvent, it is preferred to include at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, it is a mixed solvent including at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from the group consisting of ketone solvents and cyclic ether solvents. More preferably, it is a mixed solvent including at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0614] Examples of alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0615] 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.

[0616] As solvents, the solvents described in paragraphs

[0092] to

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

[0014] of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated in this specification.

[0617] You can use one solvent alone, or you can use two or more solvents.

[0618] 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.

[0619] The content of each ion in the photosensitive composition layer of the transfer film in the first to fourth embodiments can be adjusted, for example, by the following methods.

[0620] For example, one method could be to add a compound containing each ion after reducing the content of each ion in the composition that forms the photosensitive composition layer.

[0621] More specifically, examples include: methods that separately perform ion removal treatment on the components and solvent constituting the photosensitive composition layer, mix them to form a composition, and add a specified salt to adjust the ion content; methods that mix the components and solvent constituting the photosensitive composition layer to form a composition, perform ion removal treatment on the composition, and add a specified salt to adjust the ion content; methods that separately perform ion removal treatment on the components and solvent constituting the photosensitive composition layer, mix them to form a composition, perform ion removal treatment on the composition, and add a specified salt to adjust the ion content; and methods that mix the components and solvent constituting the photosensitive composition layer to form a composition, and perform ion removal treatment in a manner that ensures the ion content in the composition is within a specified range.

[0622] Examples of salts specified above include salts of various ions and cations (e.g., hydrogen ions, alkali metal ions).

[0623] Examples of methods for ion removal treatment include contacting the treated material with ion-exchange water, contacting the treated material with anion exchange resin, and contacting the treated material with anion adsorbent material. As a method for contacting the treated material with ion-exchange water, examples include mixing the treated material with the ion-exchange water and then separating the treated material from the ion-exchange water (e.g., liquid-liquid separation, contact with a desiccant, and distillation). As methods for contacting the treated material with anion exchange resin and with anion adsorbent material, examples include mixing a solid anion exchange resin or anion adsorbent material with the treated material and separating it from the treated material, and passing the treated material through a filter containing a solid anion exchange resin or anion adsorbent material.

[0624] In addition to the above-mentioned ion removal treatment, cation exchange resins and cation adsorption materials can also be used to remove cations.

[0625] Examples of coating methods for photosensitive compositions include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0626] As a drying method for the coating film of the photosensitive composition, heating drying and vacuum drying are preferred. As a drying temperature, 80°C or higher is preferred, more preferably 90°C or higher. Furthermore, as an upper limit, 130°C or lower is preferred, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature.

[0627] Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular limitation on the upper limit, but it is preferably 600 seconds or less, more preferably 300 seconds or less.

[0628] [Protective film pressing method]

[0629] Furthermore, by attaching a protective film to a photosensitive composition layer, a transfer film with a protective film can be manufactured.

[0630] There are no particular limitations on the method of attaching the protective film to the photosensitive composition layer, and well-known methods can be cited.

[0631] As a device for attaching a protective film to a photosensitive composition layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[0632] The laminator is preferably equipped with any heatable roller, such as a rubber roller, and is capable of applying pressure and heating.

[0633] <Applications of Transfer Film>

[0634] By using the above-mentioned transfer film, the photosensitive composition layer can be transferred to the substrate.

[0635] The transfer film of this invention can be applied to various purposes. For example, it can be applied to etching resists and plated parts. More specifically, it can be used as an etching resist for forming wiring.

[0636] <Method for manufacturing laminates with conductor patterns>

[0637] The transfer film described above (Embodiments 1 to 4) can be used to manufacture laminates having conductor patterns. There are no particular limitations on the method for manufacturing laminates having conductor patterns as long as the transfer film described above is used; however, the following manufacturing method is preferred for manufacturing laminates having conductor patterns according to the present invention.

[0638] Specifically, a preferred embodiment is a method for manufacturing a laminate with a conductor pattern, comprising:

[0639] In the bonding process, the transfer film and the substrate are bonded together by contacting the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side with the conductive layer of the substrate having a conductive layer on the surface.

[0640] The exposure process involves patterning the photosensitive composition layer.

[0641] The developing process involves treating the exposed photosensitive composition layer to form a resist pattern; and

[0642] The etching process involves etching the conductive layer in areas where no resist pattern has been formed.

[0643] The method for manufacturing the laminate with conductor pattern further includes a temporary support peeling process between the bonding process and the exposure process, or between the exposure process and the developing process.

[0644] Furthermore, if the above-described bonding process is performed, a laminate containing a transfer film, a conductive layer, and a substrate can be obtained sequentially. The conductive layer preferably contains silver.

[0645] Furthermore, by performing the aforementioned developing process, a laminate with a resist pattern can be obtained. The laminate with the resist pattern sequentially comprises a substrate, a conductive layer, and a resist pattern. Specifically, the following manufacturing method is preferably employed to manufacture the laminate with the resist pattern.

[0646] Specifically, a preferred embodiment is a method for manufacturing a laminate with a conductor pattern, comprising:

[0647] In the bonding process, the transfer film and the substrate are bonded together by contacting the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side with the conductive layer of the substrate having a conductive layer on the surface.

[0648] The exposure process involves patterning the photosensitive composition layer; and

[0649] The developing process involves developing the exposed photosensitive composition layer to form a resist pattern.

[0650] The method for manufacturing the laminate with conductor pattern further includes a temporary support peeling process between the bonding process and the exposure process, or between the exposure process and the developing process.

[0651] The following describes the specific steps of the manufacturing methods for laminates with conductor patterns and laminates with resist patterns.

[0652] Furthermore, the steps that can be included in the manufacturing method of the laminate having the above-mentioned preferred conductor pattern and the manufacturing method of the laminate having the resist pattern will also be described.

[0653] [Stripping Process]

[0654] When the transfer film has a protective film, it is preferable to perform a peeling process of removing the protective film from the transfer film before performing the above-mentioned bonding process.

[0655] If a peeling process is performed, the surface of the photosensitive composition layer of the transfer film will be exposed.

[0656] There are no particular limitations on the method of peeling off the protective film; it can be done using known methods. For example, the protective film can be peeled off while it is being rolled up.

[0657] [Lamination Process]

[0658] The bonding process is a process of bonding a transfer film to a substrate having a conductive layer by contacting the surface of the photosensitive composition layer with the conductive layer of the substrate having a conductive layer on the surface.

[0659] If a bonding process is performed, a laminate containing a substrate, a conductive layer, a photosensitive composition layer, and a temporary support can be obtained (the substrate having the photosensitive composition layer).

[0660] A substrate with a conductive layer has a conductive layer on the substrate, and any layer can be formed as needed. That is, a substrate with a conductive layer is a conductive substrate that has at least a substrate and a conductive layer disposed on the substrate.

[0661] Examples of substrates include resin substrates, glass substrates, and semiconductor substrates.

[0662] Preferred substrate materials are described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, and this content is incorporated herein by reference. The preferred materials for the resin substrate are cyclic olefin polymers and polyimide. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0663] From the viewpoint of conductivity and fine line formation, the conductive layer is preferably selected from at least one layer chosen from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. The conductive layer also preferably contains silver; for conductive substrates with a conductive layer containing silver, the transfer film of the present invention (Embodiments 1 to 4) is preferably used.

[0664] Furthermore, a single conductive layer or two or more conductive layers can be disposed on the substrate. When two or more conductive layers are disposed, conductive layers of different materials are preferred.

[0665] As a preferred embodiment of the conductive layer, for example, it is described in paragraph

[0141] of International Publication No. 2018 / 155193, and this content is incorporated herein by reference.

[0666] The conductive layer can be a transparent conductive layer that can form a transparent electrode through the processes described later. The transparent conductive layer is preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as fine metal wires such as metal mesh and metal nanowires.

[0667] Examples of fine metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred, and silver nanowires are even more preferred.

[0668] There is no particular limitation on the thickness of the conductive layer, but it is preferably 50 nm or more, and more preferably 100 nm or more. The upper limit is preferably 10 μm or less, and more preferably 2 μm or less.

[0669] In the above bonding process, it is preferable to press the conductive layer and the photosensitive composition layer in such a way that their surfaces come into contact.

[0670] There are no particular limitations on the above-mentioned pressing method, and known transfer methods and lamination methods can be used. Among them, it is preferable to overlap the surface of the photosensitive composition layer onto a substrate having conductive parts and apply pressure and heat using rollers or the like.

[0671] It can be laminated using well-known laminators such as vacuum laminators and automatic cutting laminators.

[0672] There are no particular limitations on the lamination temperature, but it is preferred, for example, to be 70 to 130°C.

[0673] [Exposure Process]

[0674] The exposure process is the process of exposing a pattern to the photosensitive composition layer.

[0675] By performing an exposure process and a development process described later, a resist pattern that protects at least a portion of the conductive layer can be formed on the conductive layer on the substrate.

[0676] In addition, "pattern exposure" here refers to exposure in a patterned manner, that is, exposure with exposed and non-exposed areas.

[0677] There are no particular restrictions on the positional relationship between the exposed and unexposed areas in pattern exposure, and it can be adjusted appropriately.

[0678] Exposure can be performed from the side of the photosensitive composition layer opposite to the substrate, or from the substrate side of the photosensitive composition layer.

[0679] As the light source for pattern exposure, any light source capable of illuminating at least a wavelength range sufficient to cure the photosensitive composition layer (e.g., 365 nm or 405 nm) can be appropriately selected. The dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. Furthermore, the dominant wavelength is the wavelength with the highest intensity.

[0680] As light sources, examples include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0681] The preferred exposure level is 5–200 mJ / cm. 2 More preferably 10–200 mJ / cm 2 .

[0682] Preferred methods of light source, exposure amount and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and these contents are incorporated herein by reference.

[0683] [Temporary support stripping process]

[0684] The temporary support peeling process is a 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.

[0685] 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.

[0686] [Developing process]

[0687] The developing process is a process of developing the exposed photosensitive composition layer to form a resist pattern. If the developing process is performed, a laminate with a resist pattern can be obtained, which sequentially has a substrate, a conductive layer, and a resist pattern.

[0688] The development of the above-mentioned photosensitive composition layer can be performed using a developing solution.

[0689] As a developing solution, an alkaline aqueous solution is preferred. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0690] Examples of development methods include, for instance, immersion development, spray development, spin development, and immersion development.

[0691] As a preferred developer used in this specification, for example, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271 can be cited as an example. As a preferred developing method, for example, the developing method described in paragraph

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

[0692] It is also preferable to perform a rinsing process to remove residual developer from the substrate with the conductive layer after development and before transferring to the next process. Water or the like can be used in the rinsing process.

[0693] After development and / or rinsing, a drying process can be performed to remove excess liquid from the substrate with the conductive layer.

[0694] [Etching Process]

[0695] In the etching process, the conductive layer located in the area where no resist pattern is configured is etched.

[0696] Through an etching process, a conductor pattern corresponding to the pattern of the resist is formed, thereby obtaining a laminate with a conductor pattern.

[0697] 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 such as plasma etching.

[0698] For wet etching, the etching solution can be appropriately selected as acidic or alkaline depending on the object being etched.

[0699] Examples of acidic etching solutions include, for example, aqueous solutions of individual 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 of acidic components and salts selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may also be a combination of multiple acidic components.

[0700] Examples of alkaline etching solutions include aqueous solutions of a single alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), as well as aqueous solutions of a mixture of an alkaline component and a salt (such as potassium permanganate). The alkaline component can also be a combination of multiple alkaline components.

[0701] [Resist Pattern Stripping Process]

[0702] The manufacturing method of a laminate with a conductor pattern may also include a resist pattern stripping process after the etching process to remove the residual resist pattern.

[0703] There are no particular limitations on the method for removing residual resist patterns; methods such as chemical removal are exemplified, but methods using a removal solution are preferred.

[0704] As a method for removing resist patterns, one example is to immerse a substrate with residual resist patterns in a removal solution at a temperature preferably 30 to 80°C, more preferably 50 to 80°C, under stirring for 1 to 30 minutes.

[0705] Examples of removal solutions include those obtained by dissolving an inorganic or organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic base components include sodium hydroxide and potassium hydroxide. Examples of organic base components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0706] Furthermore, it can also be removed using a removal liquid and by known methods such as spraying, scrubbing, and immersion.

[0707] [Other processes]

[0708] The manufacturing method of a laminate with a conductor pattern may include any process other than those described above (other processes).

[0709] For example, the process of reducing visible light reflectivity described in paragraph

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

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

[0710] <Process for reducing visible light reflectivity>

[0711] A method for manufacturing a laminate with a conductor pattern 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.

[0712] Oxidation is an example of a process to reduce visible light reflectivity. When the substrate has a conductive layer containing copper, copper is oxidized to produce copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectivity of the conductive layer.

[0713] Regarding the treatment of reducing visible light reflectivity, 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 are described, and the contents described in these publications are incorporated herein by reference.

[0714] <The process of forming an insulating film, and the process of forming a new conductive layer on the surface of the insulating film>

[0715] The manufacturing method of the laminate with conductor pattern also preferably includes a step of forming an insulating film on the surface of the conductor pattern and a step of forming a new conductive layer on the surface of the insulating film.

[0716] Through the above process, a second electrode pattern that is insulated from the first electrode pattern can be formed.

[0717] There are no particular limitations on the process of forming the insulating film, and known methods for forming permanent films can be cited. Furthermore, an insulating film with a desired pattern can also be formed using a photosensitive material with insulating properties and photolithography.

[0718] There are no particular limitations on the process of forming a new conductive layer on an insulating film. For example, a photosensitive material with conductivity can be used, and a new conductive layer with the desired pattern can be formed by photolithography.

[0719] In the manufacturing method of a laminate with a conductor pattern, it is preferable to use a substrate having multiple conductive layers on each of its two surfaces, and to form circuits sequentially or simultaneously on the conductive layers formed on the two surfaces of the substrate. With this structure, a laminate having a conductor pattern for a touch panel (a first conductor pattern formed on one surface of the substrate and a second conductor pattern formed on the other surface) can be formed. Furthermore, it is also preferable to form the laminate with this conductor pattern for a touch panel from both sides of the substrate by roll-to-roll.

[0720] Applications of laminates with conductor patterns

[0721] The laminate with conductor patterns manufactured by the above-described manufacturing method can be applied to various devices. Examples of devices equipped with the laminate with conductor patterns manufactured by the above-described manufacturing method include display devices, printed circuit boards, semiconductor packages, and input devices; touch panels are preferred, and capacitive touch panels are more preferred. Furthermore, the above-described input devices can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[0722] Example

[0723] The present invention will now be described in further detail with reference to embodiments.

[0724] The materials, quantities, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0725] <Making of Transfer Film>

[0726] The transfer films used in the examples and comparative examples were prepared according to the materials and steps shown below.

[0727] [Temporary support]

[0728] The temporary support used was the following temporary support A.

[0729] • Temporary support A: Polyethylene terephthalate film (16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16μm, haze: 0.4%)

[0730] [Composition for forming photosensitive composition layers]

[0731] The photosensitive composition layer forming compositions used in the various embodiments and comparative examples were obtained by following the steps below.

[0732] First, pre-treatment composition A1 and pre-treatment composition B1 were prepared using raw materials that had undergone ion removal treatment. Pre-treatment composition A1 and pre-treatment composition B1 were then subjected to ion removal treatment according to the steps described later, thereby obtaining composition A and composition B. Next, compounds I1 to I4 were added to composition A or composition B in such a manner that the content of each ion in the formed photosensitive composition layer was as shown in the table below, thereby obtaining photosensitive composition layer forming compositions A1 to A7 and B1 to B7 used in each example.

[0733] • I1: Potassium phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0734] • I2: Potassium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0735] • I3: Potassium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0736] • I4: Potassium nitrate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0737] Furthermore, the method for determining the content of each ion in the photosensitive composition layer is as described above.

[0738] (Ion removal treatment of raw materials)

[0739] The ion removal treatment of the raw materials used in the preparation of the composition for forming the photosensitive composition layer is described.

[0740] -Alkali-soluble resin-

[0741] For the alkali-soluble resin shown in the later section, ion removal treatment was performed according to the following steps. As an example, the treatment of copolymer A (styrene / methacrylic acid / methyl methacrylate = 52 / 29 / 19 (wt%)) will be described.

[0742] A copolymer A mixture was prepared by mixing 250 g of a propylene glycol-1-monomethyl ether (hereinafter also referred to as PGME) solution (solid content concentration 30.0%) with 250 g of acetone. The copolymer A mixture was then added dropwise to a mixture of 250 g of methanol and 2250 g of deionized water. After addition, the mixture was filtered to obtain a white solid, which was then dried at 50°C to remove the solvent. The dried white solid was dissolved in PGME to obtain a solution containing the aforementioned copolymer A after ion removal treatment (solid content concentration: 40% by mass).

[0743] The same treatment as described above was also performed on copolymer B (methacrylic acid / benzyl methacrylate = 20 / 80 (wt%)).

[0744] -Polymerizing compounds-

[0745] For the polymerizable compound shown in the latter section, ion removal treatment was performed according to the following steps. As an example, the treatment of NK Ester BPE-500 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.) will be described.

[0746] 50g of NK Ester BPE-500 was dissolved in 200g of ethyl acetate. Then, 100g of deionized water was added and the mixture was stirred for 5 minutes. After stirring, the aqueous and organic phases were separated by standing, and the organic phase was extracted. Deionized water (100g) was added to the extracted organic phase, and the organic phase was extracted using the same method as above. The organic phase was washed by repeating this process. After washing, hydroquinone monomethyl ether (0.02g) was added, and the solvent was removed under conditions of 50°C and 30 Torr, thus obtaining the deionized Ester BPE-500.

[0747] The same treatment was applied to the other polymeric compounds shown in the latter part.

[0748] -Photopolymerization initiator-

[0749] Ion removal treatment was performed on the photopolymerization initiator (2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, hereinafter also referred to as BIMD) shown in the latter part according to the following steps.

[0750] 10 g of BIMD was dissolved in 400 g of ethyl acetate. Then, 100 g of deionized water was added and the mixture was stirred for 5 minutes. After stirring, the aqueous and organic phases were separated by standing, and the organic phase was extracted. 100 g of deionized water was added to the extracted organic phase, and the organic phase was extracted using the same method as above. The organic phase was washed by repeating this process. After washing, the solvent was removed under conditions of 50°C and 30 Torr, thus obtaining ion-removed BIMD.

[0751] (Ion removal treatment of the composition before treatment)

[0752] Compositions A and B, before the addition of compounds I1 to I4, were subjected to the following ion removal treatment to obtain composition A. As an example, the method for obtaining composition A will be described.

[0753] The composition of the pre-treatment composition A1 supplied for treatment is as follows. Furthermore, the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used in the preparation of the pre-treatment composition A1 are alkali-soluble resins, polymerizable compounds, and photopolymerization initiators that have undergone the treatment described in the ion removal treatment of the above-mentioned raw materials.

[0754] -Alkali-soluble resin-

[0755] • Copolymer A (styrene / methacrylic acid / methyl methacrylate = 52 / 29 / 19 (wt%), weight average molecular weight: 70000): 9.84 parts by weight (solids)

[0756] -Polymerizing compounds-

[0757] • NK Ester BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 5.3 parts by weight

[0758] • NK Ester HD-N (1,6-hexanediol dimethacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 2.8 parts by weight

[0759] -Photopolymerization initiator-

[0760] • BIMD (manufactured by KUROGANE KASEI Co., Ltd.): 1.3 parts by weight

[0761] -Sensitizer-

[0762] · 4,4'-Bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.06 parts by weight

[0763] -Polymerization inhibitor-

[0764] • Phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.02 parts by weight

[0765] -pigment-

[0766] • Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.08 parts by weight

[0767] -solvent-

[0768] Methyl ethyl ketone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 38.3 parts by weight

[0769] • Propylene glycol monomethyl ether acetate (hereinafter also known as PGMEA) (manufactured by FUJIFILM Wako Pure Chemical Corporation): 16.6 parts by weight

[0770] •PGME (Product Name: MFG, Manufactured by NIPPON NYUKAZAI CO.,LTD.): 23.0 parts by weight

[0771] • Methanol (manufactured by FUJIFILM Wako Pure Chemical Corporation): 2.4 parts by weight

[0772] 8.0 g of zeolite adsorbent (described later) and 8.0 g of anion exchange resin (Amberlyst A21 manufactured by Rohm and Haas Company) were added to the untreated composition A1 (182 g) as metal ion adsorbents, and the mixture was stirred for 24 hours to perform ion adsorption treatment using the metal ion adsorbent and anion exchange resin. After stirring, the zeolite adsorbent and anion exchange resin were filtered out, thereby obtaining composition A for forming a photosensitive composition layer.

[0773] -Metal ion adsorbent-

[0774] The metal ion adsorbent material used for the above-mentioned ion removal treatment is obtained according to the following steps.

[0775] According to the synthesis method described in Japanese Patent Publication No. 42-008129, 100g of Mizuga Sieves Y-500 (synthetic zeolite) manufactured by MIZUSAWA INDUSTRIAL CHEMICALS, LTD. was added to an aqueous solution prepared by dissolving 300g of ammonium sulfate in 1500g of ion-exchanged water, and the mixture was treated by stirring at 100°C for 30 minutes.

[0776] The synthetic zeolite was recovered by filtering it through a Teflon (registered trademark) filter. The recovered zeolite was further treated in the same manner as described above using an aqueous solution obtained by dissolving 300g of ammonium sulfate in 1500g of ion-exchanged water. The synthetic zeolite was then recovered and washed with water until no sulfate ions were detected in the washing solution. The washed synthetic zeolite was then further heat-treated at 550°C for 3 hours.

[0777] Furthermore, heat-treated synthetic zeolite was added to an aqueous solution prepared by dissolving 300g of ammonium sulfate in 6000g of ion-exchange water. The mixture was stirred at 100°C for 30 minutes while being treated, and the zeolite was filtered out and recovered. The recovered synthetic zeolite was subjected to two more water washings and heat treatments (550°C). After two repeated treatments, it was thoroughly washed with water and further heated at 850°C for 3 hours. Through this process, sodium ions in the synthetic zeolite were replaced with ammonium ions, thereby obtaining a metal ion adsorbent composed of ultra-stable zeolite.

[0778] Regarding composition B, the same treatment as described above was applied to composition B1 before treatment. The composition of composition B1 before treatment is as follows. In addition, the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used in the preparation of composition B1 before treatment were alkali-soluble resin, polymerizable compound, and photopolymerization initiator that underwent the treatment described in the above-mentioned ion removal treatment of raw materials.

[0779] -Alkali-soluble resin-

[0780] • Copolymer B (methacrylic acid / benzyl methacrylate = 20 / 80 (wt%), weight average molecular weight: 30000): 10.69 parts by weight (30% solids)

[0781] -Polymerizing compounds-

[0782] • Dipentaerythritol hexaacrylate: 4.28 parts by weight

[0783] • ATM-4E (ethoxylated pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 3.21 parts by weight

[0784] -Photopolymerization initiator-

[0785] • BIMD (manufactured by KUROGANE KASEI Co., Ltd.): 1.07 parts by weight

[0786] -Sensitizer-

[0787] ·1-Phenylacetyl-3-(4-Biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline: 0.04 parts by weight

[0788] -pigment-

[0789] • Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.11 parts by weight

[0790] -solvent-

[0791] • Methyl ethyl ketone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 36.4 parts by weight

[0792] •PGMEA (manufactured by FUJIFILM Wako Pure Chemical Corporation): 16.6 parts by weight

[0793] •PGME (Product Name: MFG, Manufactured by NIPPON NYUKAZAI CO.,LTD.): 24.9 parts by weight

[0794] • Methanol (manufactured by FUJIFILM Wako Pure Chemical Corporation): 2.4 parts by weight

[0795] (Preparation of compositions for forming photosensitive composition layers)

[0796] The ion content was adjusted by adding compounds I1 to I4 to compositions A or B obtained according to the above steps, such that the ion content in the photosensitive composition layer was as shown in the following section, thereby obtaining photosensitive composition layer forming compositions A1 to A7 and B1 to B7 used in the examples. However, for photosensitive composition layer forming composition A1 with an ion content of 0.00 ppm by mass, the aforementioned compounds were not added.

[0797] Furthermore, the photosensitive composition layer forming composition AC1 used in Comparative Example 1 contained the aforementioned compounds I1 to I4 in such a manner that the content of ions in the photosensitive composition layer was as shown in the following paragraph. Otherwise, it was obtained by the same method as the photosensitive composition layer forming compositions A1 to A7.

[0798] In Comparative Example 2, the photosensitive composition layer forming composition BC1 contained the above-mentioned compounds I1 to I4 in such a way that the content of ions in the photosensitive composition layer was as shown in the following paragraph. Otherwise, it was obtained by the same method as the photosensitive composition layer forming compositions B1 to B7.

[0799] [Protective film]

[0800] The protective film used is the following protective film A.

[0801] • Protective film A: Polypropylene film (thickness: 12μm, haze: 0.2%)

[0802] [Steps for making transfer film]

[0803] The fabrication of the transfer film used in Example 1 will be described in a representative manner.

[0804] Using a slit nozzle, the photosensitive composition layer forming composition shown in the table below is applied to one surface of the temporary support A to a dried film thickness of 5 μm, and then dried at 100°C for 2 minutes to form the photosensitive composition layer 1.

[0805] Next, the photosensitive composition layer 1 and the protective film A are bonded together to obtain the transfer film used in Example 1.

[0806] Regarding the transfer films used in other embodiments and comparative examples, the type of composition for forming the photosensitive composition layer and the content of ions were changed as described in Table 1 below. Otherwise, the transfer films were prepared in the same manner as in Example 1.

[0807] <Evaluation>

[0808] Following the steps below, a substrate (conductive substrate) having a conductive layer on its surface was obtained, and the adhesion and residue generation of the photosensitive composition layer formed using the transfer films of each embodiment and comparative example were evaluated.

[0809] [Preparation of Silver Nanowire Dispersion]

[0810] 60 parts by mass of ethylene glycol and 2.5 parts by mass of polyvinylpyrrolidone (PVP) at room temperature (25°C) were added to a container, and the temperature was raised to 135°C over 10 minutes while stirring at 500 rpm (rotation per minute). Stirring was then continued at 135°C. Ten minutes after reaching 135°C, a sodium chloride solution (0.006 parts by mass, 0.1 mmol) previously dissolved in 0.6 parts by mass of ethylene glycol in another container was added. Three minutes after adding the sodium chloride solution, a silver nitrate solution (0.85 parts by mass, 5.0 mmol) previously dissolved in 7.65 parts by mass of ethylene glycol in another container) was added. After adding the silver nitrate solution, the stirring speed was changed to 100 rpm, and heating was stopped at 135°C for 3.0 hours. The mixture was then allowed to cool naturally to room temperature (25°C).

[0811] After the solution temperature in the container reached room temperature (25°C), the reacted slurry was transferred to centrifuge tubes, washed with distilled water, and centrifuged at 3,000 rpm for 5 minutes. After removing the supernatant, methanol was added to the remaining precipitate to form a slurry, which was then centrifuged at 2,500 rpm for 5 minutes. After removing the supernatant, methanol was added again to the remaining precipitate to form a slurry, which was then centrifuged at 1,500 rpm for 10 minutes. After removing the supernatant, water was added to the remaining precipitate, and the mixture was stirred at 500 rpm for 10 minutes to obtain a silver nanowire dispersion.

[0812] The average major axis length and average minor axis length of the obtained silver nanowires were determined by the following method. The results showed that the average major axis length was 10 μm, the average minor axis length (average diameter) was 70 nm, and the average aspect ratio was 140.

[0813] The average major axis length and average minor axis length of silver nanowires were determined using a transmission electron microscope (TEM; JEOL Ltd., JEM-2000FX). Among the magnified metal nanowires observed, 300 nanowires were randomly selected, and their major axis length and minor axis length (diameter) were measured. The arithmetic mean of these measurements was taken as the average major axis length and average minor axis length (average diameter) of the metal nanowires.

[0814] Fabrication of conductive substrates

[0815] The silver nanowire dispersion obtained according to the above steps was coated on one side of a polyethylene terephthalate substrate (thickness 40 μm) and dried at 80°C for 2 minutes to form a transparent conductive layer containing silver nanowires with a thickness of 200 nm on the substrate, thereby fabricating a substrate (conductive substrate) with a layer containing silver nanowires.

[0816] [Fitness Assessment]

[0817] The fit assessment is carried out according to the following steps.

[0818] First, the protective film is peeled off from the transfer film, exposing the photosensitive composition layer of the transfer film. Next, under lamination conditions of 90°C roller temperature, 0.8 MPa linear pressure, and 3.0 m / min linear speed, the transparent conductive layer of the conductive substrate and the photosensitive composition layer of the transfer film are bonded together in an opposing manner, thereby obtaining a laminate. The laminate sequentially comprises a substrate, a transparent conductive layer, a photosensitive composition layer, and a temporary support.

[0819] The temporary support was peeled off from the obtained laminate, and the photosensitive composition layer of the laminate was cross-cut into 100 squares of 1 mm × 1 mm. For the cross-cut laminate, a tape peel test was performed using Cellotape (registered trademark) No. 405 manufactured by NICHIBAN CO., LTD., and the adhesion was evaluated according to the following criteria. As an evaluation, A to C are preferred, B is more preferred, and A is particularly preferred.

[0820] A: The number of squares stripped is 0.

[0821] B: The number of squares to be peeled off is 1 to 5.

[0822] C: The number of squares to be peeled off is 6 to 10.

[0823] D: The number of stripped squares is 11 or more.

[0824] [Evaluation of Developer Residue Generation]

[0825] A glass mask (duty cycle 1:1) with a line and space pattern of 3μm to 50μm in linewidth was fitted with the laminate obtained according to the above steps without peeling off the temporary support, and then exposed.

[0826] The exposure conditions were determined as follows.

[0827] The exposure was set as follows: after exposure using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.) through the aforementioned glass mask, the exposure was left for 1 hour, and during development, the residual pattern width in the 50μm line / 50μm blank pattern area was in the range of 49.0 to 51.0μm.

[0828] After exposure and a 1-hour resting period, the temporary support was peeled off, and then a resin pattern (resist pattern) was formed by development. For development, a 1.0% potassium carbonate aqueous solution (developer) at 30°C was used for 30 seconds via spray development.

[0829] The spatial portion of the obtained resist pattern was observed using an ultra-high resolution scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) at an accelerating voltage of 2.0 kV and a magnification of 5000x to check for the presence or absence of development residue (residue in the photosensitive composition layer), and the formation of development residue was evaluated according to the following criteria. As an evaluation, A to C are preferred, B is more preferred, and A is particularly preferred.

[0830] A: No development residue was observed within the 10μm space.

[0831] B: Development residue was observed in the 10μm space, but not in the 15μm space.

[0832] C: Development residue was observed in the 15μm space, but not in the 25μm space.

[0833] D: Development residue was observed within a 25μm space.

[0834] <Results>

[0835] The composition of the photosensitive composition layer forming composition used in each embodiment and comparative example, as well as the results of the adhesion evaluation and the evaluation of the generation of developing residue, are shown in the table.

[0836] In the table, the column “Composition for forming photosensitive composition layer” indicates which of the photosensitive composition compositions A and B obtained by performing the above-mentioned ion removal treatment was used.

[0837] In the table, the ion content in the "Ion Content of Photosensitive Composition Layer" column represents the ion content determined by the method described above, and is the content of each ion relative to the total mass of the photosensitive composition layer. Specifically, the "Phosphate Ion" column indicates the content of phosphate ions, the "Iodide Ion" column indicates the content of iodide ions, the "Bromide Ion" column indicates the content of bromide ions, and the "Nitrate Ion" column indicates the content of nitrate ions.

[0838] [Table 1]

[0839]

[0840] The results in Table 1 confirm that the examples in which the ion content relative to the total mass of the photosensitive composition layer is a specified amount exhibit excellent adhesion and suppress residue formation. On the other hand, the comparative examples in which the ion content is not a specified amount show poor adhesion or fail to suppress residue formation.

[0841] As can be seen from the comparison of Examples 1, 3, 4 and 6 with Examples 2, 5 and 7, and the comparison of Examples 8, 10, 11 and 13 with Examples 9, 12 and 14, when the content of phosphate ions relative to the total mass of the photosensitive composition layer is 0.1 to 7.0 ppm by mass, the adhesion is better or the generation of residue is further suppressed.

[0842] The comparison of Examples 1, 3, 4 and 6 with Examples 2, 5 and 7, and the comparison of Examples 8, 10, 11 and 13 with Examples 9, 12 and 14, show that when the content of nitrate ions relative to the total mass of the photosensitive composition layer is 0.1 to 7.0 ppm by mass, the adhesion is better or the generation of residue is further suppressed.

[0843] The comparison of Examples 1, 3, 4 and 6 with Examples 2, 5 and 7, and the comparison of Examples 8, 10, 11 and 13 with Examples 9, 12 and 14, show that when the content of iodide ions relative to the total mass of the photosensitive composition layer is 3.0 to 10.0 ppm by mass, the adhesion is better or the generation of residue is further suppressed.

[0844] The comparison of Examples 1, 3, 4 and 6 with Examples 2, 5 and 7, and the comparison of Examples 8, 10, 11 and 13 with Examples 9, 12 and 14, show that when the bromide ion content is 6.0 to 10.0 ppm by mass relative to the total mass of the photosensitive composition layer, the adhesion is better or the generation of residue is further suppressed.

[0845] The lines and spaces of the substrate after evaluation of the development residue in each embodiment were sprayed with a 30% by mass aqueous solution of ferric nitrate (pH: 0.6) at 40°C for 120 seconds. Afterwards, the resist was removed by immersion in a 3% by mass aqueous solution of sodium hydroxide at 50°C. Furthermore, the transparent conductive layer (containing silver nanowires) could be etched using the 30% by mass aqueous solution of ferric nitrate at 40°C.

[0846] Through the above steps, a laminate with a transparent conductive layer patterned as a conductor pattern in the form of lines and spaces was obtained. Scanning electron microscopy revealed that the patterned transparent conductive layer, corresponding to the lines and spaces of the photosensitive composition layer of the laminate with the obtained conductor pattern where no development residue was observed, exhibited no peeling or defects, indicating a good pattern.

[0847] Symbol Explanation

[0848] 10-Transfer film, 11-Temporary support, 13-Intermediate layer, 15-Photosensitive composition layer, 17-Composition layer, 19-Protective film.

Claims

1. A transfer film having a temporary support and a photosensitive composition layer, the photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenic unsaturated group, and a photopolymerization initiator, the content of phosphate ions in the photosensitive composition layer is 10.0 mass ppm or less with respect to the total mass of the photosensitive composition layer.

2. The transfer film according to claim 1, wherein, the content of phosphate ions is 0.1 mass ppm to 7.0 mass ppm with respect to the total mass of the photosensitive composition layer.

3. A transfer film having a temporary support and a photosensitive composition layer, the photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenic unsaturated group, and a photopolymerization initiator, the content of nitrate ions in the photosensitive composition layer is 10.0 mass ppm or less with respect to the total mass of the photosensitive composition layer.

4. The transfer film according to claim 3, wherein, the content of nitrate ions is 0.1 mass ppm to 7.0 mass ppm with respect to the total mass of the photosensitive composition layer.

5. A transfer film having a temporary support and a photosensitive composition layer, the photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenic unsaturated group, and a photopolymerization initiator, the content of iodide ions in the photosensitive composition layer is 2.0 mass ppm to 20.0 mass ppm with respect to the total mass of the photosensitive composition layer.

6. The transfer film according to claim 5, wherein, the content of iodide ions is 3.0 mass ppm to 10.0 mass ppm with respect to the total mass of the photosensitive composition layer.

7. A transfer film having a temporary support and a photosensitive composition layer, the photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenic unsaturated group, and a photopolymerization initiator, the content of bromide ions in the photosensitive composition layer is 4.0 mass ppm to 20.0 mass ppm with respect to the total mass of the photosensitive composition layer.

8. The transfer film according to claim 7, wherein, the content of bromide ions is 6.0 mass ppm to 10.0 mass ppm with respect to the total mass of the photosensitive composition layer.

9. The transfer film according to any one of claims 1 to 8, wherein, the temporary support is a biaxially-stretched polyethylene terephthalate film.

10. The transfer film according to any one of claims 1 to 8, wherein, the haze of the temporary support is 0.1% to 0.5%.

11. The transfer film according to any one of claims 1 to 8, wherein, the photosensitive composition layer further contains a colorless compound.

12. The transfer film according to any one of claims 1 to 8, wherein, the photosensitive composition layer further contains a polymerization inhibitor.

13. The transfer film according to any one of claims 1 to 8, wherein, the photosensitive composition layer further contains a sensitizer.

14. A laminate having, in this order, the transfer film according to any one of claims 1 to 8, a conductive layer, and a substrate.

15. The laminate according to claim 14, wherein the conductive layer contains silver.

16. A method for producing a laminate having a resist pattern, the method comprising: a laminating step of laminating a transfer film according to any one of claims 1 to 8 and a substrate having a conductive layer on a surface thereof, in such a manner that the surface of the photosensitive composition layer of the transfer film on the side opposite to the temporary support side is brought into contact with the conductive layer of the substrate; an exposure step of performing pattern exposure on the photosensitive composition layer; and a developing step of forming a resist pattern by performing developing treatment on the photosensitive composition layer after exposure.

17. A method for producing a laminate having a conductor pattern, the method comprising: a laminating step of laminating a transfer film according to any one of claims 1 to 8 and a substrate having a conductive layer on a surface thereof, in such a manner that the surface of the photosensitive composition layer of the transfer film on the side opposite to the temporary support side is brought into contact with the conductive layer of the substrate; an exposure step of performing pattern exposure on the photosensitive composition layer; a developing step of forming a resist pattern by performing developing treatment on the photosensitive composition layer after exposure; and an etching step of performing etching treatment on the conductive layer in a region where a resist pattern is not formed.

18. The method for producing a laminate according to claim 17, wherein the method further comprises a temporary support peeling step of peeling the temporary support between the laminating step and the exposure step or between the exposure step and the developing step. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​

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