Method for producing laminate with conductor pattern

Abstract

To provide a method for producing a laminate with a conductor pattern that makes it possible to achieve both high resolution and deep focal depth.SOLUTION: A method for producing a laminate having a conductor pattern comprises: a step of bonding a transfer film having a temporary support and a photosensitive layer with a substrate to cause a photosensitive layer side of the transfer film contact with a metal layer of the substrate having the metal layer on its surface; a step of performing pattern exposure of the photosensitive layer using light emitted from a ring lighting device from the opposite side of a side having the substrate; a step of performing a development process on the exposed photosensitive layer to form a resist pattern; one of a step selected from steps of performing an etching process on the metal layer in regions where the resist pattern is not formed, and performing a plating process; a step of peeling off the resist pattern; and when including the step of performing the plating process, a step of removing the exposed metal layer in the peeling step.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a laminate having a conductor pattern. [Background technology]

[0002] In recent years, there has been a trend toward finer conductor patterns for printed wiring, circuit wiring, etc. For the formation of conductor patterns, a method using a photosensitive resin composition has been widely adopted, in which exposed metal that is not covered by a resin pattern is patterned.

[0003] In order to increase the resolution of a pattern in a method using a photosensitive resin composition, for example, a technique of performing maskless exposure has been known. However, because it is difficult to simultaneously improve sensitivity, resolution, and adhesion, photosensitive resin compositions for maskless exposure have also been studied. Specifically, as a photosensitive resin composition for maskless exposure, a photosensitive resin composition containing (a) an alkali-soluble polymer containing a carboxyl group, (b) an ethylenically unsaturated addition polymerizable monomer, (c) a photopolymerization initiator, (d) p-toluenesulfonic acid amide, and (e) an alkylene oxide compound represented by general formula (I) has been disclosed (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-190735 A

[0005] However, there is a limit to how much the resolution can be improved from the composition side, and the contrast of the image of the target pattern tends to decrease due to the influence of diffracted light that wraps around the periphery of the pattern during pattern exposure. In a method of patterning using a photosensitive resin composition, the focal depth of the irradiated light during pattern exposure on the photosensitive layer also greatly affects the improvement of the resolution. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of one embodiment of the present disclosure is to provide a method for manufacturing a laminate having a conductor pattern that allows both high resolution and a large depth of focus to be achieved. [Means for solving the problem]

[0007] Means for solving the above problems include the following aspects. <1> A method for manufacturing a laminate having a conductive pattern, comprising the steps of: laminating a transfer film having a temporary support and a photosensitive layer to a substrate such that the photosensitive layer side of the transfer film, which has a temporary support and a photosensitive layer, is in contact with the metal layer of the substrate having a metal layer on its surface; pattern-exposing the photosensitive layer from the side opposite the side having the substrate using light emitted from an annular illumination device; performing a development process on the exposed photosensitive layer to form a resist pattern; one of a process selected from a process of etching the metal layer in an area where the resist pattern is not formed and a process of plating; a process of peeling off the resist pattern; and, if a plating process is further performed, a process of removing the metal layer exposed by the peeling process. <2> The exposing step is a step of performing pattern exposure through a phase shift mask. <1> A method for producing a laminate having the conductive pattern according to claim 1. <3> The phase shift mask is a Levenson phase shift mask or a halftone phase shift mask; <2> A method for producing a laminate having the conductor pattern according to claim 1. <4> A step of peeling off the temporary support is provided between the laminating step and the exposing step. <1> ~ <3> 13. A method for producing a laminate having the conductor pattern according to any one of claims 1 to 12. <5> The transmittance of the photosensitive layer to the exposure wavelength is 65% or more. <1> ~ <4> 13. A method for producing a laminate having the conductor pattern according to any one of claims 1 to 12. <6> The thickness of the photosensitive layer is 1 μm to 3 μm. <1> ~ <5> 13. A method for producing a laminate having the conductive pattern according to any one of claims 1 to 12. <7> The aspect ratio of the conductor pattern is 3.0 or more. <1> ~ <6> 13. A method for producing a laminate having the conductor pattern according to any one of claims 1 to 12. <8> The photosensitive layer contains a sensitizer in an amount of 0.01% by mass to 5% by mass based on the total amount of the composition for forming the photosensitive layer. <1> ~ <7> 13. A method for producing a laminate having the conductive pattern according to any one of claims 1 to 12. <9> The transfer film has an intermediate layer between the temporary support and the photosensitive layer. <1> ~ <8> 13. A method for producing a laminate having the conductor pattern according to any one of claims 1 to 12. <10> The intermediate layer is a water-soluble resin layer. <9> A method for producing a laminate having the conductor pattern according to claim 1. <11> The transfer film has a thermoplastic resin layer between the temporary support and the intermediate layer. <9> or <10> A method for producing a laminate having the conductor pattern according to claim 1. <12> A method for producing a laminate having a conductive pattern, comprising the steps of: laminating a transfer film having a temporary support and a photosensitive layer to a substrate such that the photosensitive layer side of the transfer film, which has a temporary support and a photosensitive layer, is in contact with the metal layer of the substrate having a metal layer on its surface; exposing the photosensitive layer to a pattern through a phase shift mask from the side opposite to the side having the substrate; performing a development process on the exposed photosensitive layer to form a resist pattern; performing an etching process on the metal layer in an area where the resist pattern is not formed; and performing a plating process. A method for producing a laminate having a conductive pattern, comprising the steps of: laminating a transfer film having a temporary support and a photosensitive layer to a substrate such that the photosensitive layer side is in contact with the metal layer of the substrate having a metal layer on its surface; <13> The phase shift mask is a Levenson phase shift mask or a halftone phase shift mask; <12> A method for producing a laminate having the conductor pattern according to claim 1. <14> A step of peeling off the temporary support is provided between the laminating step and the exposing step. <12> or <13> A method for producing a laminate having the conductor pattern according to claim 1. <15> The transmittance of the photosensitive layer to the exposure wavelength is 65% or more. <12> ~ <14> 13. A method for producing a laminate having the conductor pattern according to any one of claims 1 to 12. <16> The thickness of the photosensitive layer is 1 μm to 3 μm. <12> ~ <15> 13. A method for producing a laminate having the conductive pattern according to any one of claims 1 to 12. <17> The aspect ratio of the conductor pattern is 3.0 or more. <12> ~ <16> 13. A method for producing a laminate having the conductor pattern according to any one of claims 1 to 12. <18> The photosensitive layer contains a sensitizer in an amount of 0.01% by mass to 5% by mass based on the total amount of the composition for forming the photosensitive layer. <12> ~ <17> 13. A method for producing a laminate having the conductive pattern according to any one of claims 1 to 12. <19> The transfer film has an intermediate layer between the temporary support and the photosensitive layer. <12> ~ <18> 13. A method for producing a laminate having the conductor pattern according to any one of claims 1 to 12. <20> The intermediate layer is a water-soluble resin layer. <19> A method for producing a laminate having the conductor pattern according to claim 1. <21> The transfer film has a thermoplastic resin layer between the temporary support and the intermediate layer. <19> or <20> A method for producing a laminate having the conductor pattern according to claim 1. Effect of the Invention

[0008] According to one embodiment of the present disclosure, a method for manufacturing a laminate having a conductor pattern that allows both high resolution and a large depth of focus to be achieved can be provided. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a transfer film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, embodiments of the present disclosure will be described in detail. Note that the present disclosure is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present disclosure.

[0011] In the present disclosure, a numerical range expressed using "~" means a range including the numerical values ​​described before and after "~" as the lower and upper limits. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0012] In the present disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0013] In the present disclosure, "transparent" means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more, and preferably 90% or more. In the present disclosure, the transmittance is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0014] In the present disclosure, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights detected by a gel permeation chromatography (GPC) analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names manufactured by Tosoh Corporation) in a solvent of THF (tetrahydrofuran) and a differential refractometer, and converted using polystyrene as a standard substance. In the present disclosure, unless otherwise specified, the ratio of polymer structural units is a mass ratio. In this disclosure, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).

[0015] In the present disclosure, "(meth)acrylic" refers to both or either of acrylic and methacrylic, and "(meth)acrylate" refers to both or either of acrylate and methacrylate.

[0016] In the present disclosure, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more.

[0017] In the present disclosure, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0018] In the present disclosure, the "solid content" of a composition means the components forming a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), means all components excluding the solvent. In addition, liquid components are also considered to be solid contents as long as they form a composition layer.

[0019] In the description of groups (atomic groups) in this disclosure, descriptions that do not indicate whether they are substituted or unsubstituted include those that have a substituent as well as those that do not have a substituent. For example, an "alkyl group" includes not only an alkyl group that does not have a substituent (an unsubstituted alkyl group) but also an alkyl group that has a substituent (a substituted alkyl group).

[0020] In the present disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

[0021] In the present disclosure, combinations of two or more preferred embodiments are more preferred embodiments.

[0022] In this disclosure, ordinal terms (eg, "first" and "second") are terms used to distinguish elements, and do not limit the number of elements or the relative importance of the elements.

[0023] <Method of manufacturing a laminate having a conductive pattern according to the first embodiment> The method for manufacturing a laminate having a conductive pattern according to the first embodiment of the present disclosure includes a step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate such that the photosensitive layer side of the transfer film is in contact with the metal layer of the substrate having a metal layer on its surface (hereinafter also referred to as the "bonding step"); a step of pattern-exposing the photosensitive layer using light emitted from an annular illumination device from the side opposite the substrate (hereinafter also referred to as the "first exposure step"); a step of developing the exposed photosensitive layer to form a resist pattern (hereinafter also referred to as the "developing step"); a step of etching the metal layer in an area where the resist pattern is not formed (hereinafter also referred to as the "etching step"); and a step of plating the metal layer (hereinafter also referred to as the "plating step"); a step of peeling off the resist pattern (hereinafter also referred to as the "peeling step"); and, if the method further includes a plating step, a step of removing the metal layer exposed by the peeling step (hereinafter also referred to as the "removing step").

[0024] In the method for manufacturing a laminate having a conductive pattern according to the first embodiment, the mechanism by which high resolution and a large depth of focus can be achieved at the same time is presumed to be as follows. In the exposure process, by using an annular illumination device, the zeroth order and plus or minus first order diffracted light passes through the pupil plane of the projection lens, and the contrast of the image on the photosensitive layer can be increased by two-beam interference. As a result, it is believed that both high resolution and deep depth of focus can be achieved. In another embodiment, the phase of light or the transmittance of light can be controlled by using a phase shift mask, which is believed to result in both high resolution and a deep depth of focus.

[0025] Each step of the method for producing a laminate having a conductive pattern according to the present disclosure will be described in detail below.

[0026] [Lamination process] The lamination step according to the present disclosure is a step of laminating a transfer film and a substrate such that the photosensitive layer side of the transfer film having a temporary support and a photosensitive layer is in contact with the metal layer of the substrate having a metal layer on its surface. By contacting the photosensitive layer with the metal layer in the lamination step, a substrate with a photosensitive layer having the substrate, the metal layer, the photosensitive layer, and the temporary support in this order can be obtained. The transfer film in the present disclosure has at least a temporary support and a photosensitive layer, and may have other layers (an intermediate layer, a thermoplastic resin layer, described later) between the temporary support and the photosensitive layer, as described later, and may have a protective film on the side opposite the temporary support of the photosensitive layer. For example, in the case of an embodiment having a laminated structure of temporary support / photosensitive layer / protective film, when a protective layer is present on the side opposite the temporary support of the photosensitive layer, in the lamination step, the protective film is peeled off in advance, and then the transfer film and the substrate are laminated so that the exposed photosensitive layer and the metal layer of the substrate having a metal layer on its surface are in contact with each other. This is also true for the second embodiment described later.

[0027] A substrate having a metal layer on its surface (hereinafter also referred to as a "substrate with a metal layer") has a substrate and a metal layer, and preferably has a substrate and a metal layer disposed on the substrate surface.

[0028] Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate. The substrate may be a substrate described in paragraph

[0140] of WO 2018 / 155193.

[0029] The resin substrate is preferably a resin substrate that transmits visible light. Examples of resins that constitute the resin substrate that transmits visible light include epoxy resin, polyamide, polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polyimide, and polycarbonate.

[0030] The substrate may also be made of glass epoxy resin, which is obtained, for example, by impregnating glass fiber cloth with epoxy resin and subjecting it to a thermal curing treatment.

[0031] The substrate may also be a silicon wafer.

[0032] The thickness of the substrate is not particularly limited, but is preferably 5 μm to 200 μm, and more preferably 10 μm to 100 μm.

[0033] The thickness of the substrate can be measured, for example, by the following method. A cross section of the substrate in a direction perpendicular to the main surface (i.e., thickness direction) is observed using a scanning electron microscope (SEM). Based on the obtained observation image, the thickness of the substrate is measured at 10 points. The measured values ​​are arithmetically averaged to obtain the average thickness of the substrate.

[0034] The metal layer is a layer containing a metal, and the metal is not particularly limited, and any known metal can be used. The metal layer is preferably a conductive layer. Metals include, for example, copper, chromium, lead, nickel, gold, silver, tin, and zinc.

[0035] The metal may be a metal containing one type of metal element, a metal mixture containing two or more types of metal elements, or an alloy containing at least one type of metal element.

[0036] The method for forming the metal layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion liquid in which metal fine particles are dispersed and sintering the applied film, a sputtering method, and a vapor deposition method.

[0037] The thickness of the metal layer is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more, and the upper limit of the thickness of the metal layer is preferably 2 μm or less.

[0038] One or more metal layers may be disposed on the substrate. When two or more metal layers are arranged, the metal layers may be the same or different, but from the viewpoint of electrical conductivity, it is preferable that the metal layers are made of different materials.

[0039] In the above lamination, it is preferable that the surface of the photosensitive layer of the transfer film (the surface opposite to the temporary support side) is brought into contact with the metal layer on the substrate and pressure-bonded. As the pressure bonding method, for example, a known transfer method and lamination method can be used. Among them, it is preferable to place the surface of the photosensitive layer on a substrate having a metal layer, and apply pressure and heat with a roll or the like.

[0040] For lamination, a known laminator such as a vacuum laminator or an autocut laminator can be used. The lamination temperature is not particularly limited, but is preferably from 70°C to 130°C, for example.

[0041] [Temporary support peeling process] In the method for producing a laminate having a conductive pattern according to the present disclosure, it is also preferable to provide a temporary support peeling step between the laminating step and the exposure step described below. The method for peeling off the temporary support is not particularly limited, and the same method as the cover film peeling method described in paragraphs

[0161] to

[0162] of JP-A-2010-072589 can be used.

[0042] [First exposure process] In the exposure step according to the present disclosure, the photosensitive layer is pattern-exposed using light emitted from an annular illumination device from the side opposite to the side having the substrate with the photosensitive layer. The term "pattern exposure" refers to a form of exposure in a pattern, in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in the pattern exposure can be appropriately adjusted.

[0043] (Ring illumination device) In the first exposure step according to the present disclosure, an annular illumination device is used. The annular illumination device is not particularly limited, and any known annular illumination device can be used. The shape of the aperture stop is not particularly limited as long as it is annular illumination, but 1 / 3 annular illumination, 1 / 2 annular illumination, or 2 / 3 annular illumination can be used. Among them, 1 / 2 annular illumination or 2 / 3 annular illumination is preferable, and 2 / 3 annular illumination is more preferable.

[0044] The light source of the annular illumination device is not particularly limited. Examples of light sources include various lasers such as an ArF excimer laser with a wavelength of 193 nm, a KrF excimer laser with a wavelength of 248 nm, a XeCl excimer laser with a wavelength of 308 nm, and a XeF excimer laser with a wavelength of 353 nm; semiconductor light sources such as light-emitting diodes (LEDs); and discharge lamps such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, and metal halide lamps. Among these, from the viewpoint of the exposure wavelength, ultra-high pressure mercury lamps and high pressure mercury lamps are preferred, and high pressure mercury lamps are more preferred.

[0045] The wavelength emitted from the light source of the annular illumination device is not particularly limited as long as it is a wavelength that can cure the exposed area, but it is preferable that the dominant wavelength includes 365 nm or 435 nm. The "dominant wavelength" refers to the wavelength of light emitted from the light source that has the greatest intensity. Furthermore, in the annular illumination device, in order to adjust the wavelength of the light emitted from the light source to fall within the above range, an optical filter such as a short wavelength cut filter or a band pass filter can be provided in the light path.

[0046] The exposure dose is not particularly limited, but is preferably 5 mJ / cm 2 ~400mJ / cm 2 and preferably 10 mJ / cm 2 ~300mJ / cm 2 It is more preferable that:

[0047] In the exposure step of the present disclosure, the light emitted from the light source of the annular illumination device is preferably irradiated onto the photosensitive layer through a mask. Examples of the mask include a normal mask patterned with a light-shielding layer containing chromium (Cr) on a quartz glass substrate, and a phase shift mask. Among them, it is preferable to use a phase shift mask from the viewpoint of achieving both high resolution and a deep focal depth.

[0048] (Phase shift mask) A phase shift mask is a mask that cancels diffracted light toward the periphery of a pattern during exposure by using light of the opposite phase. Phase shift masks include, for example, Levenson phase shift masks and attenuated phase shift masks.

[0049] Examples of Levenson phase shift masks include an engraved type in which a phase shift section is formed by engraving a transparent substrate by etching or the like, and a shifter-formed type in which a shift layer (also called a shifter layer) is provided on one of adjacent openings on a transparent substrate. Examples of half-tone phase shift masks include single-layer half-tone phase shift masks patterned with a semi-transparent layer containing chromium (Cr) or the like on a transparent substrate, and multi-layer half-tone phase shift masks patterned with a semi-transparent layer having, in that order, a layer containing silicon dioxide (SiO2) and a layer containing chromium (Cr) or the like on a transparent substrate. Among these, a half-tone phase shift mask is preferred from the viewpoint of improving the roughness of the pattern by making the boundaries and edges of the pattern clearer.

[0050] [Development process] In the development step, the exposed photosensitive layer is developed to form a resist pattern.

[0051] The development of the exposed photosensitive layer can be carried out using a developer. The developer is not particularly limited, and any known developer can be used. The developer may be, for example, the developer described in JP-A-5-72724.

[0052] The developer is preferably an alkaline aqueous solution. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0053] The pH of the alkaline aqueous solution is not particularly limited. The pH of the alkaline aqueous solution at 25° C. is, for example, preferably 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12. The pH can be measured using a known pH meter according to a method in accordance with JIS Z8802-1984. The pH measurement temperature is 25°C.

[0054] The temperature of the developer during development is not particularly limited, and is preferably, for example, 20°C to 40°C.

[0055] The content of the alkaline compound in the alkaline aqueous solution is not particularly limited, but is preferably 0.1% by mass to 5% by mass, and more preferably 0.1% by mass to 3% by mass, based on the total mass of the alkaline aqueous solution.

[0056] Examples of the development method include paddle development, shower development, spin development, and dip development.

[0057] The developing method is preferably the developing method described in paragraph

[0195] of WO 2015 / 093271.

[0058] After development, it is also preferable to carry out a rinsing treatment for removing the developer remaining on the metal layer-formed substrate before proceeding to the next step. Water or the like can be used for the rinsing treatment. After the development and / or rinsing process, a drying process may be carried out to remove excess liquid from the metal layer-formed substrate.

[0059] The position and size of the resist pattern formed on the metal layer-attached substrate are not particularly limited. The pattern width of the resist pattern is preferably 2.0 μm or less, more preferably 1.3 μm or less, and even more preferably 1.0 μm or less. The lower limit is preferably 0.8 μm or more.

[0060] The pattern width can be measured by the following method. The conductor pattern is observed with a scanning electron microscope (SEM), and the minimum width of the upper surface of the pattern where the conductor pattern can be formed without defects such as breaks, short circuits, or collapse is defined as the pattern width.

[0061] [Etching process] The etching process is a process of etching the metal layer in the area where the resist pattern is not formed. Specifically, in the etching process, the resist pattern obtained in the above steps is used as an etching resist to etch the metal layer. The etching step removes the metal layer at the openings of the resist pattern, forming the metal layer in a pattern shape similar to that of the resist pattern.

[0062] The etching method may be, for example, a known etching method. Specific examples of such methods include the method described in paragraphs

[0209] to

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

[0048] to

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

[0063] The etching solution used in the wet etching can be appropriately selected from acidic and alkaline etching solutions depending on the target to be etched.

[0064] Examples of the acidic etching solution include an acidic aqueous solution containing at least one acidic compound, and an acidic mixed aqueous solution of an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate.

[0065] The acidic compound contained in the acidic aqueous solution (that is, a compound that exhibits acidity when dissolved in water) includes at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid.

[0066] Examples of alkaline etching solutions include an alkaline aqueous solution containing at least one alkaline compound, and an alkaline mixed aqueous solution of an alkaline compound and a salt (such as potassium permanganate).

[0067] Examples of the alkaline compound contained in the alkaline aqueous solution (i.e., a compound that dissolves in water and exhibits alkalinity) include at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide, etc.).

[0068] It is preferable that the etching solution does not dissolve the resist pattern. The developer used in the developing step may also serve as the etching solution used in the etching treatment. In this case, the developing step and the etching step may be carried out simultaneously.

[0069] After the etching process, it is also preferable to carry out a rinsing process for removing the etching solution remaining on the metal layer-formed substrate before proceeding to the next step. Water or the like can be used for the rinsing process. After the etching process and / or the rinsing process, a drying process may be carried out to remove excess liquid from the substrate with the metal layer.

[0070] The resist pattern can be removed by a known method such as a spray method, a shower method, or a paddle method using a remover.

[0071] The stripping liquid may be, for example, a liquid in which an alkaline compound is dissolved in at least one selected from the group consisting of water, dimethylsulfoxide, and N-methylpyrrolidone.

[0072] Examples of alkaline compounds (compounds that exhibit alkalinity when dissolved in water) include alkaline inorganic compounds such as sodium hydroxide and potassium hydroxide, and alkaline organic compounds such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0073] The temperature of the stripping solution is preferably 30°C to 80°C, and more preferably 50°C to 80°C. A suitable method for stripping the resist pattern includes a method in which the resist pattern is immersed in a stirred stripping solution having a liquid temperature of 50° C. to 80° C. for 1 minute to 30 minutes.

[0074] It is preferable that the stripping solution does not dissolve the conductive pattern layer.

[0075] After the resist pattern is stripped, a rinse process may be carried out to remove the stripping solution. Water or the like can be used for the rinse process.

[0076] After the resist pattern stripping and / or rinsing process, a drying process for removing excess liquid may be carried out.

[0077] [Plating process] The plating process is a process in which plating is performed on the metal layer in the area where the resist pattern is not formed. More specifically, the plating process is a process of forming a plating layer by plating on the metal layer in the area where the resist pattern is not formed (the metal layer whose surface is exposed by the development process).

[0078] Examples of the plating method include electrolytic plating and electroless plating. Among them, electrolytic plating is preferred from the viewpoint of productivity. By the plating treatment step, a plating layer having a pattern shape similar to that of the area where the resist pattern is not formed (openings of the resist pattern) is obtained on the substrate with the metal layer.

[0079] An example of a component of a plating solution used in electroplating is a water-soluble copper salt. As the water-soluble copper salt, any water-soluble copper salt that is commonly used as a component of a plating solution can be used. The water-soluble copper salt is preferably at least one selected from the group consisting of inorganic copper salts, copper salts of alkanesulfonic acids, copper salts of alkanolsulfonic acids, and copper salts of organic acids. Inorganic copper salts include, for example, copper sulfate, copper oxide, copper chloride, and copper carbonate. Copper alkanesulfonates include, for example, copper methanesulfonate and copper propanesulfonate. Examples of copper alkanolsulfonates include copper isethionate and copper propanolsulfonate. Examples of the organic acid copper salts include copper acetate, copper citrate, and copper tartrate. Furthermore, as a component of the plating solution used in the electroplating, salts of other corresponding metals may be used in place of the copper mentioned above.

[0080] The plating solution may contain sulfuric acid, which makes it possible to adjust the pH and sulfate ion concentration of the plating solution.

[0081] The electroplating method and conditions are not particularly limited. The temperature of the plating solution used in electroplating is preferably 70° C. or less, and more preferably 10° C. to 40° C. The current density in electroplating is 0.1 A / dm 2 ~100A / dm 2 It is preferable that the current is 0.5A / dm 2 ~20A / dm 2It is more preferable that the current density is set to 1000 .mu.m or less. By increasing the current density, the productivity can be improved. By decreasing the current density, the uniformity of the thickness can be improved.

[0082] The thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm or more, and the upper limit is preferably 20 μm or less.

[0083] [Peeling process] The peeling step is a step of peeling off the remaining resist pattern to form a conductor pattern on the substrate. The method for removing the remaining resist pattern is not particularly limited, but examples thereof include a method of removing the remaining resist pattern by chemical treatment, and a method of removing the remaining resist pattern by using a remover is preferred. Alternatively, a stripping solution may be used to remove the film by a known method such as a spray method, a shower method, or a paddle method.

[0084] The stripping solution may be, for example, a stripping solution in which an inorganic or organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. The inorganic alkaline component may be, for example, sodium hydroxide or potassium hydroxide. The organic alkaline component may be, for example, a primary amine compound, a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt compound. The alkaline organic compound is preferably tetramethylammonium hydroxide or an alkanolamine compound.

[0085] The temperature of the removal liquid is preferably 30°C to 80°C, and more preferably 50°C to 80°C. A suitable method for stripping the resist pattern includes a method in which the resist pattern is immersed in a stirred stripping solution having a liquid temperature of 50° C. to 80° C. for 1 minute to 30 minutes.

[0086] The pH of the stripping solution used in the stripping treatment is preferably 11 or more, more preferably 12 or more, and even more preferably 13 or more. The upper limit is preferably 14 or less, and more preferably 13.8 or less. The pH can be measured using a known pH meter by a method conforming to JIS Z8802-1984. The pH measurement temperature is 25°C.

[0087] The temperature of the stripping solution during the stripping treatment is preferably higher than the temperature of the developer during the development treatment. Specifically, the value obtained by subtracting the temperature of the developer from the temperature of the stripper (temperature of the stripper-temperature of the developer) is preferably 10° C. or higher, and more preferably 20° C. or higher. The upper limit is preferably 100° C. or lower, and more preferably 80° C. or lower.

[0088] The pH of the stripping solution used in the stripping treatment is preferably higher than the pH of the developer used in the development treatment. Specifically, the value obtained by subtracting the pH of the developer from the pH of the stripper (pH of the stripper - pH of the developer) is preferably 1 or more, more preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.

[0089] It is preferable that the stripping solution does not dissolve the conductive pattern layer.

[0090] After the resist pattern is stripped with the stripper, it is also preferable to carry out a rinsing treatment to remove the stripper remaining on the substrate. Water or the like can be used for the rinsing treatment. After the resist pattern is stripped and / or rinsed with the stripping solution, a drying process may be carried out to remove excess liquid from the substrate.

[0091] [Removal process] In the case where the plating process step is included, the removing step is a step of removing the metal layer exposed in the peeling step to form a conductive pattern on the substrate. In the removal step, the plating layer formed in the plating step is used as an etching resist, and an etching process is performed on the metal layer in the area not protected by the plating layer.

[0092] The method for removing the part of the metal layer is not particularly limited, but it is preferable to use a known etching solution. Examples of known etching solutions include a ferric chloride solution, a cupric chloride solution, an ammonia alkali solution, a sulfuric acid-hydrogen peroxide mixture, and a phosphoric acid-hydrogen peroxide mixture.

[0093] When the removal step is performed, the metal layer exposed on the surface of the substrate is removed, leaving a plating layer (conductor pattern) having a pattern shape, thereby obtaining a laminate having a conductor pattern.

[0094] The upper limit of the pattern width of the conductor pattern to be formed is preferably 2.0 μm or less, more preferably 1.5 μm or less, and even more preferably 1.2 μm or less, and the lower limit is preferably 0.9 μm or more.

[0095] [Other processes] The method for producing a laminate having a conductive pattern may include any steps (other steps) other than the steps described above. For example, there may be mentioned a process for reducing visible light reflectance described in paragraph

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

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

[0096] (Step of reducing visible light reflectance) The method for producing a laminate having a conductive pattern may include a step of performing a treatment to reduce the visible light reflectance of some or all of the multiple metal layers of the substrate. Examples of treatments for reducing the visible light reflectance include oxidation treatments. When the substrate has a metal layer containing copper, the visible light reflectance of the metal layer can be reduced by oxidizing the copper to copper oxide and blackening the metal layer. Treatments for reducing visible light reflectance are described in paragraphs

[0017] to

[0025] of JP 2014-150118 A, and paragraphs

[0041] ,

[0042] ,

[0048] and

[0058] of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

[0097] (A process for forming an insulating film, and a process for forming a new conductive layer on the surface of the insulating film) The method for producing a laminate having a conductor pattern also preferably includes the steps of forming an insulating film on the surface of the circuit wiring, and forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and may be a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0098] In the method for producing a laminate having a conductive pattern, a substrate having a plurality of metal layers on both surfaces of the substrate is used, and circuits are formed on the metal layers formed on both surfaces of the substrate, either sequentially or simultaneously. With this configuration, a circuit wiring for a touch panel can be formed in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface of the substrate. It is also preferable to form the circuit wiring for a touch panel having such a configuration from both sides of the substrate by roll-to-roll.

[0099] <Applications of laminates having conductive patterns> The method for manufacturing a laminate having a conductive pattern can be applied to the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic wave shielding materials, and light control films; the manufacture of printed wiring boards and semiconductor packages; the manufacture of pillars and pins for interconnection between semiconductor chips and packages; the manufacture of metal masks; and the manufacture of tape substrates such as COF (ChiponFilm) and TAB (Tape Automated Bonding). The touch panel may be a capacitive touch panel. The method for producing a laminate having a conductive pattern according to the present disclosure can be used to form a conductive film or peripheral circuit wiring in a touch panel. The touch panel can be applied to a display device such as an organic electroluminescence (EL) display device or a liquid crystal display device.

[0100] <Method for manufacturing a laminate having a conductor pattern according to the second embodiment> A method for manufacturing a laminate having a conductive pattern according to a second embodiment of the present disclosure includes a step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate such that the photosensitive layer side of the transfer film is in contact with the metal layer of the substrate having a metal layer on its surface (hereinafter also referred to as a "bonding step"); a step of pattern-exposing the photosensitive layer through a phase shift mask from the side opposite to the side having the substrate (hereinafter also referred to as a "second exposure step"); a step of developing the exposed photosensitive layer to form a resist pattern (hereinafter also referred to as a "developing step"); a step of etching the metal layer in an area where the resist pattern is not formed (hereinafter also referred to as an "etching step") and a step of plating (hereinafter also referred to as a "plating step"); a step of peeling off the resist pattern (hereinafter also referred to as a "peeling step"); and, if a plating step is further included, a step of removing the metal layer exposed by the peeling step (hereinafter also referred to as a "removing step").

[0101] In the method for producing a laminate having a conductive pattern according to the second embodiment, the mechanism by which high resolution and a large depth of focus can be achieved at the same time is presumed to be as follows. By using a phase shift mask in the exposure process, diffracted light that tends to wrap around the periphery of the pattern during exposure is cancelled by light of the opposite phase, suppressing the spread of light in the intended target pattern and irradiating the photosensitive layer with sharp light, thereby increasing the contrast of the image. As a result, while the conventional method of exposure through a light-shielding mask having a pattern of a light-shielding film such as Cr had a small light intensity (contrast) of the pattern image, the contrast of the pattern image is increased, and it is presumed that it is possible to achieve both high resolution and deep depth of focus.

[0102] <Lamination process> The lamination step according to the present disclosure is a step of laminating a transfer film and a substrate such that the photosensitive layer side of the transfer film having a temporary support and a photosensitive layer is in contact with the metal layer of the substrate having a metal layer on its surface. By contacting the photosensitive layer with the metal layer in the lamination step, a substrate with a photosensitive layer having the substrate, the metal layer, the photosensitive layer, and the temporary support in this order can be obtained.

[0103] The configurations of the substrate and the metal layer, and the bonding method in the bonding step are the same as those in the first embodiment, and the preferred aspects are also the same.

[0104] <Temporary support peeling process> In the method for producing a laminate having a conductive pattern according to the present disclosure, it is also preferable to provide a temporary support peeling step between the laminating step and the exposure step described below. The method for peeling off the temporary support is the same as in the first embodiment, and the preferred aspects are also the same.

[0105] <Second Exposure Step> The second exposure step according to the present disclosure is a step of pattern-exposing the photosensitive layer through a phase shift mask from the side opposite to the side having the substrate.

[0106] The light source used for exposure is the same as in the first embodiment, and the preferred aspects are also the same.

[0107] The wavelength emitted from the light source is the same as in the first embodiment, and the preferred aspects are also the same.

[0108] The exposure dose is the same as in the first embodiment, and the preferred aspects are also the same.

[0109] (Phase shift mask) In the exposure step of the present disclosure, light emitted from a light source is irradiated onto a photosensitive layer through a phase shift mask. The phase shift mask is similar to that of the first embodiment, and the preferred aspects are also similar.

[0110] <Developing process> In the development step, the exposed photosensitive layer is developed to form a resist pattern. The developer and the like used in the development step, as well as the development method and the like, are the same as those in the first embodiment, and the preferred aspects are also the same.

[0111] <Etching process> The etching process is a process of etching the metal layer in the area where the resist pattern is not formed. The etching solution and the etching method used in the etching process are the same as those in the first embodiment, and the preferred aspects are also the same.

[0112] <Plating process> The plating process is a process of plating the metal layer in the area where the resist pattern is not formed. The plating process method and the like are the same as those in the first embodiment, and the preferred aspects are also the same.

[0113] <Peeling process> The stripping step is a step of stripping the remaining resist pattern. The stripping solution and the stripping method used in the stripping step are the same as those in the first embodiment, and the preferred aspects are also the same.

[0114] <Removal process> In the case where the plating process step is included, the removing step is a step of removing the metal layer exposed in the peeling step to form a conductive pattern on the substrate. The etching solution used in the removing step and the removing method are the same as those in the first embodiment, and the preferred aspects are also the same.

[0115] <Other processes> The method for producing a laminate having a conductive pattern may include any steps (other steps) other than the steps described above. The other steps are the same as those in the first embodiment, and the preferred aspects are also the same.

[0116] The transfer film used in the method for producing a laminate having a conductive pattern according to the present disclosure will be described in detail below.

[0117] [Transfer film] The transfer film used in the method for producing a laminate having a conductive pattern of the present disclosure has a temporary support and a photosensitive layer. The transfer film may have other layers in addition to the temporary support and the photosensitive layer. Examples of the other layers include a thermoplastic resin layer and an intermediate layer. The transfer film may further include other members (such as a protective film) described below.

[0118] An example of the embodiment of the transfer film is shown below, but the invention is not limited thereto. (1) "Temporary support / photosensitive layer" (2) "Temporary support / photosensitive layer / protective film" (3) "Temporary support / intermediate layer / photosensitive layer / protective film" (4) "Temporary support / thermoplastic resin layer / photosensitive layer / protective film" (5) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer / protective film" In each of the above configurations, the photosensitive layer may be either a negative photosensitive layer or a positive photosensitive layer, but is preferably a negative photosensitive layer. It is also preferable that the photosensitive layer is a colored resin layer. When a protective film is provided as in the above embodiments (2) to (5), in the lamination step of the present disclosure, the protective film is peeled off to expose the photosensitive layer, and the metal layer of the metal layer-attached substrate is laminated.

[0119] From the viewpoint of preventing the generation of air bubbles in the lamination step, the maximum waviness width of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit of the maximum waviness width is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.

[0120] The maximum width of the undulation of the transfer film is a value measured, for example, by the following procedure. The transfer film is cut in a direction perpendicular to the main surface to a size of 20 cm long x 20 cm wide to prepare a test sample. If the transfer film has a protective film, the protective film is peeled off. Next, the test sample is placed on a flat and horizontal stage so that the surface of the temporary support faces the stage. After being placed, the surface of the test sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) for a central 10 cm square range of the test sample to obtain a three-dimensional surface image, and the minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. The above operation is performed on 10 test samples, and the arithmetic average value can be regarded as the "maximum waviness width of the transfer film".

[0121] When the photosensitive layer of the transfer film further has other layers on the surface of the photosensitive layer opposite the temporary support, the total thickness of the other layers is preferably 0.1% to 30%, more preferably 0.1% to 20%, of the total thickness of the photosensitive layer.

[0122] From the viewpoint of superior adhesion, the transmittance of the photosensitive layer at 365 nm is preferably 65% ​​or more, more preferably 75% or more, and even more preferably 85% or more. The upper limit is preferably 99.9% or less, and more preferably 95% or less. In the present disclosure, the transmittance can be measured using a known transmittance measuring device (for example, spectrophotometer U-3310 manufactured by Hitachi, Ltd.).

[0123] An example of a specific embodiment of the transfer film will be described below. The transfer film 20 shown in FIG. 1 has a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive layer 17, and a protective film 19, in this order. The transfer film 20 shown in FIG. 1 has a protective film 19, but the protective film 19 may not be included. The transfer film 20 shown in FIG. 1 has a thermoplastic resin layer 13 and an intermediate layer 15, but it is not necessary to have the thermoplastic resin layer 13 or the intermediate layer 15, or the thermoplastic resin layer 13 and the intermediate layer 15.

[0124] Each member and component of the transfer film will be described in detail below.

[0125] [Temporary support] The transfer film has a temporary support. The temporary support is a support that supports the photosensitive layer and is removable in a temporary support removal step.

[0126] The temporary support may be a single layer, or a laminate in which two or more layers are laminated. Examples of the temporary support include a support consisting of only a substrate; a laminate comprising a substrate and a particle-containing layer disposed on one surface of the substrate; and a laminate comprising a substrate and a particle-containing layer disposed on both surfaces of the substrate.

[0127] Examples of the substrate constituting the temporary support include glass, a resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, the substrate constituting the temporary support is preferably a resin film.

[0128] Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, the resin film is preferably a PET film, and more preferably a biaxially stretched PET film.

[0129] When the temporary support includes a particle-containing layer, the layer may contain one type of binder polymer and one type of particles, or two or more types of binder polymer and particles.

[0130] The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected according to the purpose. The content of the particles in the particle-containing layer can be appropriately adjusted by the amount of the particles added to the composition for the particle-containing layer. In the present disclosure, the particles contained in the particle-containing layer are referred to as "added particles".

[0131] The additive particles are to be distinguished from impurities unexpectedly mixed in during the manufacturing process of the temporary support and particles formed during the manufacturing process of the temporary support. The additive particles are preferably particles having the property of not melting at 200°C.

[0132] In the temporary support, whether or not there are additive particles can be determined by, for example, the following method: Since additive particles usually have uniformity in shape and distribution, they can be determined by observation with an optical microscope.

[0133] The additive particles include, for example, inorganic particles and organic particles.

[0134] Examples of inorganic particles include particles of inorganic oxides such as silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina).

[0135] Examples of organic particles include particles of polymers such as acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene.

[0136] When the temporary support has a particle-containing layer, the additive particles contained in the particle-containing layer are preferably inorganic oxide particles.

[0137] The average particle size of the additive particles is not particularly limited, but is, for example, 0.1 μm to 10 μm. The average particle size is measured by cutting a slice having a thickness of 100 nm with an ultramicrotome and using a transmission electron microscope (TEM).

[0138] The thickness of the temporary support is preferably 25 μm or more, more preferably 50 μm or more, and even more preferably 75 μm or more, from the viewpoint of suppressing deformation of the substrate to be laminated with the transfer film. The upper limit of the thickness is not particularly limited, and is, for example, 200 μm.

[0139] The temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning used films and the like, forming them into chips, and then forming the chips into films as raw materials. Specific examples of recycled products include the Ecouse series from Toray Industries.

[0140] In order to improve the adhesion between the temporary support and the photosensitive layer, the surface of the temporary support which comes into contact with the photosensitive layer may be subjected to a surface modification treatment. Examples of surface modification treatments include treatments using UV irradiation, corona discharge, plasma, and the like.

[0141] The exposure dose for UV irradiation was 10 mJ / cm2 ~2000mJ / cm 2 is preferred, and 50 mJ / cm 2 ~1000mJ / cm 2 is more preferred. As long as the exposure amount is within the above range, the lamp output and illuminance are not particularly limited. Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs), all of which emit light in the 150 nm to 450 nm wavelength band.

[0142] [Photosensitive layer] The transfer film has a photosensitive layer. The photosensitive layer is preferably a negative photosensitive layer in which the solubility of the exposed portion in a developer is reduced by exposure and the non-exposed portion is removed by development. However, the photosensitive layer is not limited to a negative photosensitive layer, and may be a positive photosensitive layer in which the solubility of the exposed portion in a developer is increased by exposure and the exposed portion is removed by development.

[0143] The photosensitive layer can be obtained, for example, by applying a composition for forming a photosensitive layer and drying it.

[0144] The photosensitive layer preferably contains a resin, a polymerizable compound, and a polymerization initiator. As described later, it is also preferable that the resin contains an alkali-soluble resin (such as polymer A, which is an alkali-soluble resin) as a part or all of the resin. That is, in one embodiment, the photosensitive layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

[0145] Each component will be described in turn below.

[0146] <Polymer A (resin)> Examples of the polymer A include (meth)acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and acid-modified epoxy acrylate resin obtained by reacting epoxy acrylate resin with acid anhydride. However, the polymer A is preferably a (meth)acrylic resin. In the present disclosure, the (meth)acrylic resin refers to a resin having a structural unit derived from a (meth)acrylic compound. In the (meth)acrylic resin, the content of the structural unit derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on the total mass of the (meth)acrylic resin.

[0147] As the polymer A, a polymer having a constitutional unit derived from a (meth)acrylic compound and a constitutional unit derived from a styrene compound is also preferred.

[0148] The polymer A is preferably an alkali-soluble resin. The acid value of polymer A is preferably 250 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g, from the viewpoint of suppressing swelling of the photosensitive layer by a developer and thereby achieving superior resolution. There is no particular lower limit for the acid value of polymer A. From the viewpoint of superior developability, the acid value of polymer A is preferably 60 mgKOH / g or more, more preferably 80 mgKOH / g or more, and even more preferably 120 mgKOH / g or more. The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample. The acid value can be calculated, for example, from the average content of acid groups in a compound. The acid value of polymer A can be adjusted by adjusting the type of structural unit constituting polymer A and the content of structural units containing acid groups.

[0149] The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. In terms of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight is more preferably 100,000 or less, and further preferably 60,000 or less.

[0150] On the other hand, a weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of the development aggregates and the properties of the unexposed film, such as edge fuse property and cut chip property, when the film is made into a photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fuse property refers to the degree of ease with which the photosensitive layer protrudes from the end face of the roll when the film is wound into a roll as a photosensitive resin laminate. Cut chip property refers to the degree of ease with which chips fly off when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the photosensitive resin laminate, they are transferred to a mask in a subsequent exposure process, etc., causing defective products. The photosensitive resin laminate is a laminate obtained by laminating a transfer film and a circuit board.

[0151] The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In the present disclosure, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight). In the present disclosure, the weight average molecular weight and the number average molecular weight are values ​​measured using gel permeation chromatography.

[0152] In the photosensitive layer, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure, it is preferable that the polymer A contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. When multiple types of polymer A are included, it is preferable that the average content of the structural unit derived from the monomer having an aromatic hydrocarbon group is within the above range.

[0153] Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer).

[0154] From the viewpoint of further improving the resolution, the polymer A preferably contains 1 mmol / g to 6 mmol / g, more preferably 3 mmol / g to 6 mmol / g, of structural units derived from at least one selected from the group consisting of styrene and styrene derivatives. The polymer A may contain only structural units derived from styrene, may contain only structural units derived from styrene derivatives, or may contain structural units derived from styrene and structural units derived from styrene derivatives.

[0155] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, with a substituted or unsubstituted benzyl group being preferred.

[0156] An example of the monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0157] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth)acrylate, the content of the constitutional unit derived from benzyl (meth)acrylate is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass, based on the total mass of the polymer A.

[0158] The polymer A containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one type of a first monomer described below and / or at least one type of a second monomer described below.

[0159] Polymer A which does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described later, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described later.

[0160] The first monomer is a monomer having a carboxy group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.

[0161] The content of the constitutional unit derived from the first monomer in polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass to 30% by mass, based on the total mass of polymer A.

[0162] A content of 5% by mass or more is preferable from the viewpoints of achieving good developability, controlling edge fusing properties, etc. A content of 50% by mass or less is preferable from the viewpoints of high resolution and foot shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

[0163] The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, the second monomer is preferably methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate.

[0164] The content of the constitutional units derived from the second monomer in polymer A is preferably from 5 to 60% by mass, more preferably from 15 to 50% by mass, and even more preferably from 17 to 45% by mass, based on the total mass of polymer A.

[0165] When the polymer A contains a structural unit derived from a monomer having an aralkyl group and / or a structural unit derived from a monomer containing styrene, it is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure. For example, a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene, a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from a copolymer derived from a styrene, and the like are preferable.

[0166] In one embodiment, polymer A is preferably a polymer containing 25% to 55% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from a first monomer, and 15% to 45% by mass of structural units derived from a second monomer. In another embodiment, polymer A is preferably a polymer containing 70% to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, and 10% to 25% by mass of structural units derived from a first monomer.

[0167] The polymer A may have a linear structure, a branched structure, or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. The group having an alicyclic structure may be monocyclic or polycyclic.

[0168] Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

[0169] Specific examples of monomers containing a group having an alicyclic structure in a side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Specific examples of monomers containing a group having an alicyclic structure in a side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-2-(meth)acrylate, 2 ... acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0170] Among these, the monomer containing a group having an alicyclic structure in its side chain is preferably cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate, more preferably cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.

[0171] The polymer A contained in the photosensitive layer may be one type or two or more types.

[0172] When two or more types of polymer A are included, it is preferable to include two types of polymer A containing structural units derived from a monomer having an aromatic hydrocarbon group, or to include a polymer A containing structural units derived from a monomer having an aromatic hydrocarbon group and a polymer A not containing structural units derived from a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of polymer A containing structural units derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of polymer A.

[0173] From the viewpoints of sensitivity and resolution, it is preferable that the polymer A has a crosslinkable group.

[0174] From the viewpoints of developability, sensitivity, and resolution, the crosslinkable group is preferably a polymerizable group.

[0175] The polymerizable group is not particularly limited as long as it is a group that is involved in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated bond, such as a vinyl group, a (meth)acryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group, such as an epoxy group and an oxetane group.

[0176] Polymer A preferably has an ethylenically unsaturated bond, and more preferably has an acryloyl group or a methacryloyl group.

[0177] Polymer A is preferably an alkali-soluble resin having a crosslinkable group, more preferably an acrylic resin having an ethylenically unsaturated bond, and even more preferably an acrylic resin containing a structural unit having an ethylenically unsaturated group.

[0178] The synthesis of polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0179] The glass transition temperature Tg of the polymer A is preferably 30°C to 135°C. By using the polymer A having a Tg of 135°C or less, it is possible to suppress line width thickening and deterioration of resolution when the focal position is shifted during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. In addition, it is preferable to use the polymer A having a Tg of 30°C or more from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40°C or more, further preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0180] The photosensitive layer may contain, as the polymer A, a resin other than those mentioned above.

[0181] Other resins include acrylic 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, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0182] As the polymer A, an alkali-soluble resin described in the section on the thermoplastic resin layer below may be used.

[0183] The content of polymer A is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass to 60% by mass, based on the total mass of the photosensitive layer. It is preferable that the content of polymer A is 90% by mass or less based on the total mass of the photosensitive layer, because the development time can be controlled. On the other hand, it is preferable that the content of polymer A is 10% by mass or more based on the total mass of the photosensitive layer, because the edge fuse resistance is improved.

[0184] <Polymerizable compound> The photosensitive layer preferably contains a polymerizable compound having a polymerizable group. In the present disclosure, the term "polymerizable compound" refers to a compound that is polymerized by the action of a polymerization initiator described later and is different from the polymer A described above.

[0185] The polymerizable group contained in the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, a (meth)acryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group such as an epoxy group and an oxetane group.

[0186] As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and a (meth)acryloyl group is more preferable.

[0187] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the photosensitive layer is superior.

[0188] From the viewpoint of obtaining superior resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0189] The photosensitive layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and more preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule, in that the photosensitive layer has a better balance between photosensitivity, resolution, and peelability.

[0190] The content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. The upper limit of the content of the bifunctional ethylenically unsaturated compound is not particularly limited, and may be 100% by mass. That is, all of the polymerizable compounds may be bifunctional ethylenically unsaturated compounds.

[0191] Moreover, the ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group.

[0192] (Polymerizable compound B1) The photosensitive layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the above-mentioned polymerizable compounds B.

[0193] In the photosensitive layer, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of better resolution. The upper limit is not particularly limited, but is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, from the viewpoint of peelability.

[0194] The aromatic ring of the polymerizable compound B1 includes, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocycles such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof, and is preferably aromatic hydrocarbon ring, more preferably benzene ring.The aromatic ring may have a substituent.

[0195] The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0196] The polymerizable compound B1 preferably has a bisphenol structure, from the viewpoint of improving the resolution by suppressing swelling of the photosensitive layer due to a developer.

[0197] Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0198] An example of the polymerizable compound B1 having a bisphenol structure is a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0199] Both ends of the bisphenol structure may be directly bonded to the two polymerizable groups, or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy or propyleneoxy, more preferably ethyleneoxy. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.

[0200] The polymerizable compound B1 having a bisphenol structure is described in paragraphs

[0072] to

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

[0201] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, ethoxylated bisphenol A dimethacrylate (NK Ester BPE-500, average repeat number of ethylene oxide chain: 10, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, Hitachi Chemical Co., Ltd.), and ethoxylated bisphenol A dimethacrylate (NK Ester BPE-500, average repeat number of ethylene oxide chain: 10, Shin-Nakamura Chemical Co., Ltd.). Examples of such ethoxylated bisphenol A dimethacrylate include NK Ester BPE-1300N, having an average ethylene oxide chain repeat number of 30, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated bisphenol A dimethacrylate (NK Ester BPE-200, having an average ethylene oxide chain repeat number of 4, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated bisphenol A dimethacrylate (NK Ester BPE-100, having an average ethylene oxide chain repeat number of 2.6, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated bisphenol A diacrylate (NK Ester A-BPE-10, having an average ethylene oxide chain repeat number of 10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0202] As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0203] [ka]

[0204] In the general formula (B1), R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer of 1 to 39, and n1+n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 represents an integer of 0 to 30. The arrangement of the structural units -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenol group side.

[0205] In one embodiment, n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

[0206] The photosensitive layer may contain one type of polymerizable compound B1, or two or more types of polymerizable compounds.

[0207] The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive layer from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which photosensitive resin oozes out from the edge of a transfer member).

[0208] The photosensitive layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1. The polymerizable compound other than the polymerizable compound B1 is not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound without aromatic ring, and a trifunctional or higher ethylenically unsaturated compound can be mentioned.

[0209] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0210] Examples of difunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0211] Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.); Examples of the monomer unit include ethanol 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.

[0212] Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0213] Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0214] The content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on the total mass of the negative photosensitive layer, from the viewpoint of better resolution and resist strippability. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive layer forming composition seeps out from the edge of the transfer member).

[0215] The content of the bifunctional ethylenically unsaturated compound is preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the polymerizable compound having an ethylenically unsaturated group, from the viewpoint of better resolution and resist strippability. The upper limit is preferably 100% by mass or less, more preferably 90% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive layer forming composition seeps out from the edge of the transfer film).

[0216] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified versions of these.

[0217] Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0218] In one embodiment, the photosensitive layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compounds is preferably (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compounds)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

[0219] In one embodiment, the photosensitive layer preferably contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

[0220] Examples of alkylene oxide modified trifunctional or higher ethylenically unsaturated compounds include caprolactone modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), 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.).

[0221] In addition, a polymerizable compound having an acid group (such as a carboxy group) may be used as the polymerizable compound. The acid group may form an acid anhydride group. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0222] As the polymerizable compound having an acid group, for example, the polymerizable compounds having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 may be used.

[0223] The photosensitive layer may contain one type of polymerizable compound or two or more types of polymerizable compounds.

[0224] The content of the polymerizable compound is preferably from 10% by mass to 70% by mass, more preferably from 15% by mass to 70% by mass, and further preferably from 20% by mass to 70% by mass, based on the total mass of the photosensitive layer.

[0225] The molecular weight (weight average molecular weight when the polymerizable compound has a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0226] <Polymerization initiator> The photosensitive layer also preferably contains a polymerization initiator.

[0227] The polymerization initiator is selected depending on the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0228] The photosensitive layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to active light such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used.

[0229] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0230] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0231] From the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution, the photosensitive layer preferably contains at least one photoradical polymerization initiator selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different.

[0232] Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0233] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP2011-95716A and paragraphs

[0064] to

[0081] of JP2015-14783A may be used.

[0234] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0235] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins), BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester photoinitiator (trade name: Lunar 6, DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Examples of such oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.).

[0236] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. As the photocationic polymerization initiator, a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and generates an acid is preferred, but the chemical structure is not limited. In addition, even if a photocationic polymerization initiator is not directly sensitive to actinic rays having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it responds to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.

[0237] As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of the pKa is not particularly set, but is preferably, for example, -10.0 or more.

[0238] The photocationic polymerization initiator includes an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.

[0239] Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0240] As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs

[0114] to

[0133] of JP2014-085643A may be used.

[0241] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs

[0083] to

[0088] of JP 2011-221494 A may be used. As oxime sulfonate compounds, compounds described in paragraphs

[0084] to

[0088] of WO 2018 / 179640 may be used.

[0242] The photosensitive layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

[0243] The photosensitive layer may contain one type of polymerization initiator, or two or more types of polymerization initiators.

[0244] The content of the polymerization initiator (preferably photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the photosensitive layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the negative-type photosensitive layer.

[0245] <Dye> From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the photosensitive layer preferably contains a dye (also referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes depending on an acid, a base, or a radical. When dye N is contained, the adhesion to adjacent layers (e.g., intermediate layers) is improved, resulting in better resolution, although the detailed mechanism is unclear.

[0246] In the present disclosure, the dye's "maximum absorption wavelength changes due to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, a dye in a decolorized state is colored by an acid, a base, or a radical, and a dye in a colored state changes to a colored state of another hue.

[0247] Specifically, the dye N may be a compound that changes from a decolorized state to a colored state by exposure, or may be a compound that changes from a colored state to a decolored state by exposure. In this case, the dye may be a dye whose colored or decolored state changes when an acid, base, or radical is generated and acts in the photosensitive layer by exposure, or a dye whose colored or decolored state changes when the state (e.g., pH) in the photosensitive layer changes due to an acid, base, or radical. Alternatively, the dye may be a dye whose colored or decolored state changes when it is directly stimulated by an acid, base, or radical without exposure.

[0248] Among these, from the viewpoints of visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical.

[0249] When the photosensitive layer is a negative photosensitive layer, it is preferable that the photosensitive layer contains both a dye whose maximum absorption wavelength changes due to radicals as dye N, and a photoradical polymerization initiator, from the viewpoints of visibility of exposed and non-exposed areas and resolution.

[0250] From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0251] An example of the color-developing mechanism of dye N is a mode in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the photocationic photopolymerization initiator, or the photobase generator.

[0252] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm upon color development of 550 nm or more, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm.

[0253] Furthermore, dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm when it develops color, or may have two or more maximum absorption wavelengths. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm when it develops color, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

[0254] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimal (maximum absorption wavelength).

[0255] Examples of the dye that develops or loses color upon exposure to light include leuco compounds.

[0256] Examples of dyes that are decolorized by exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

[0257] As the dye N, a leuco compound is preferable from the viewpoint of visibility of exposed and non-exposed areas.

[0258] Examples of the leuco compound include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes).

[0259] Among these, dye N is preferably a triarylmethane dye or a fluoran dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluoran dye.

[0260] From the viewpoint of visibility of the exposed and non-exposed parts, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, the sultine ring, or the sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby changing the leuco compound to a ring-closed state to cause discoloration, or changing the leuco compound to a ring-open state to cause color development. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which is colored by opening the lactone ring, the sultine ring, or the sultone ring with a radical or an acid, and more preferably a compound having a lactone ring, which is colored by opening the lactone ring with a radical or an acid.

[0261] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the pigments N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), and Examples of the pigments that can be used include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0262] Specific examples of the leuco compound among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)- 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0263] From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals.

[0264] As dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalenesulfonate is preferred.

[0265] The dye N contained in the photosensitive layer may be of one type or of two or more types.

[0266] From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, even more preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %, relative to the total mass of the photosensitive layer.

[0267] The content of dye N means the content of dye when all of dye N contained in the total mass of the photosensitive layer is in a color-developing state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example. Prepare solutions by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. Add a photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Co., Ltd.) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals and make all the dyes colored. Then, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere, and create a calibration curve. Next, the absorbance of the solution in which all the dye has been colored is measured in the same manner as above, except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. The content of the dye contained in the photosensitive layer is calculated based on the calibration curve from the absorbance of the solution containing the photosensitive layer obtained. The photosensitive layer 3g is the same as the total solid content 3g in the composition for forming the photosensitive layer.

[0268] <Thermal crosslinkable compound> From the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film, the photosensitive layer preferably contains a thermally crosslinkable compound. In addition, in the present disclosure, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound but as a thermally crosslinkable compound.

[0269] Examples of the thermally crosslinkable compound include an epoxy compound, an oxetane compound, a methylol compound, and a blocked isocyanate compound. Among these, from the viewpoints of the strength of the resulting cured film and the adhesion of the resulting uncured film, a blocked isocyanate compound is preferred.

[0270] Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound or the like has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when a film obtained by curing a negative type photosensitive layer is used as a protective film.

[0271] The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0272] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably from 100°C to 160°C, and more preferably from 130°C to 150°C.

[0273] The dissociation temperature of a blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of a blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter."

[0274] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0275] Examples of blocking agents having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime).

[0276] Among them, examples of blocking agents having a dissociation temperature of 100° C. to 160° C. include storage-stable blocking agents. From the viewpoint of the chemical property, at least one selected from oxime compounds is preferred.

[0277] The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesive strength to the transfer target.

[0278] A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by converting it into an isocyanurate.

[0279] Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred from the viewpoints that it is easier to set the dissociation temperature in a preferred range and to reduce development residues than a compound not having an oxime structure.

[0280] The blocked isocyanate compound may have a polymerizable group.

[0281] The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radically polymerizable group being preferred.

[0282] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyl group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group.

[0283] Among these, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloyl group is more preferable, and an acryloyl group is even more preferable.

[0284] As the blocked isocyanate compound, commercially available products can be used.

[0285] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation).

[0286] In addition, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0287] [ka]

[0288] The photosensitive layer may contain one type of thermally crosslinkable compound, or two or more types of compounds. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass, based on the total mass of the photosensitive layer.

[0289] <Surfactant> From the viewpoint of thickness uniformity, the photosensitive layer preferably contains a surfactant.

[0290] Examples of the surfactant include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0291] The surfactant may be a hydrocarbon surfactant, a fluorine surfactant, or a silicone surfactant. From the viewpoint of improving environmental compatibility, it is preferable that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon surfactant or a silicone surfactant.

[0292] Commercially available fluorine-based surfactants include, for example, Megafac (registered trademark) 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-33. 0, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Co., Ltd.), and U-120E (Unichem Co., Ltd.).

[0293] Also suitable for use as the fluorosurfactant are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is broken and the fluorine atom volatilizes. Examples of such fluorosurfactants include the Megafac (registered trademark) DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016)), such as Megafac (registered trademark) DS-21.

[0294] As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

[0295] Furthermore, as the fluorosurfactant, a block polymer can also be used.

[0296] In addition, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used.

[0297] As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0298] From the viewpoint of improving environmental compatibility, it is preferable that the fluorosurfactant be a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0299] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, and the like.

[0300] Specific examples of hydrocarbon surfactants 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 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), Paionin D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0301] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, modified siloxane polymers in which organic groups have been introduced into the side chains or ends, and polymers having a structural unit having a hydrophilic group in the side chain and a structural unit having a siloxane bond-containing group in the side chain.

[0302] Among them, the silicone surfactant is preferably a polymer having a structural unit having a hydrophilic group in a side chain and a structural unit having a siloxane bond-containing group in a side chain. The polymer may be a random copolymer or a block copolymer.

[0303] Examples of the structural unit having a hydrophilic group in the side chain include structural units derived from the following monomers.

[0304] [ka]

[0305] R 4 is a hydrogen atom or a methyl group, R 5 is a hydrogen atom or a methyl group, n is an integer from 1 to 4; m is an integer from 1 to 100.

[0306] Examples of the structural unit having a siloxane bond-containing group in the side chain include structural units derived from the following monomers.

[0307] [ka] R is independently an alkyl group having 1 to 3 carbon atoms; R 1 is a hydrogen atom or a methyl group, L 1 is a divalent organic group or a single bond.

[0308] Examples of the structural unit having a siloxane bond-containing group in the side chain include structural units derived from the following monomers.

[0309] [ka]

[0310] R1 is a hydrogen atom or a methyl group; R2 is an alkylene group having 1 to 10 carbon atoms; R3 is an alkyl group having 1 to 4 carbon atoms; n is an integer from 5 to 50.

[0311] Specific examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), X-22-4952, X-22-4272, and 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-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-1 25, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Examples of such compounds include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0312] The surfactant is preferably a nonionic surfactant.

[0313] The photosensitive layer may contain one type of surfactant, or two or more types of surfactants. When the photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, more preferably 0.01% by mass to 1.0% by mass, and further preferably 0.05% by mass to 0.80% by mass, based on the total mass of the photosensitive layer.

[0314] <Sensitizer> The photosensitive layer may contain a sensitizer.

[0315] The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0316] The photosensitive layer may contain one type of sensitizer, or two or more types of sensitizers. When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving the sensitivity when annular illumination or a phase shift mask is used, and improving the curing rate by balancing the polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, based on the total mass of the composition for forming the photosensitive layer.

[0317] <Other additives> The photosensitive layer may contain known additives, if necessary, in addition to the above components. Examples of additives include radical polymerization inhibitors, chain transfer agents, plasticizers, heterocyclic compounds (such as triazoles), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), and purine bases (such as adenine).

[0318] The photosensitive layer may contain one type of each additive, or two or more types of additives.

[0319] The photosensitive layer may contain a radical polymerization inhibitor.

[0320] Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive layer, nitrosophenylhydroxyamine aluminum salt is preferable.

[0321] When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.02% by mass to 2.0% by mass, based on the total mass of the photosensitive layer. The content of the polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.01% by mass to 1.0% by mass, based on the total mass of the polymerizable compounds.

[0322] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0323] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of carboxybenzotriazoles that can be used include commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name).

[0324] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and the suppression of decolorization of the dye are more excellent.

[0325] The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.

[0326] Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs

[0097] to

[0103] and paragraphs

[0111] to

[0118] of WO 2018 / 179640.

[0327] The photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, UV absorbers, thickeners, crosslinkers, and organic or inorganic suspending agents.

[0328] Additives contained in the photosensitive layer are described in paragraphs

[0165] to

[0184] of JP2014-085643A, the contents of which are incorporated herein by reference.

[0329] The thickness of the photosensitive layer is generally 0.1 μm to 300 μm, preferably 0.2 μm to 100 μm, more preferably 0.5 μm to 50 μm, further preferably 1 μm to 16 μm, particularly preferably 1 μm to 10 μm, and most preferably 1 μm to 3 μm, which can improve the developability of the photosensitive layer and the resolution.

[0330] The aspect ratio of the conductor pattern is preferably 2.1 or more, more preferably 2.5 or more, and even more preferably 3.0 or more. The upper limit of the aspect ratio of the conductor pattern may be 10 or less, and is preferably 5 or less. In the present disclosure, the aspect ratio of a conductor pattern is calculated by the following formula (1). Aspect ratio of conductor pattern = Thickness of photosensitive layer (μm) / Pattern width (μm) Formula (1) The thickness of the photosensitive layer can be determined in the same manner as the method for measuring the thickness of the substrate, and the pattern width can be determined in the same manner as the method for measuring the pattern width obtained after the development step.

[0331] <Impurities, etc.> The photosensitive layer may contain a certain amount of impurities.

[0332] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so the following contents are preferable.

[0333] The content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, by mass.

[0334] Methods for keeping the amount of impurities within the above range include selecting raw materials for the composition that contain a small amount of impurities, preventing impurities from being mixed in during the preparation of the photosensitive layer, and removing the impurities by washing. By such methods, the amount of impurities can be kept within the above range.

[0335] Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0336] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably small. The content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass.

[0337] The lower limit of the content is preferably 10 ppb, more preferably 100 ppb, based on the total mass of the photosensitive layer, on a mass basis. The content of these compounds can be controlled in the same manner as for the metal impurities described above. They can also be quantified by known measurement methods.

[0338] From the viewpoint of improving the sensitivity of the photosensitive layer, the water content of the photosensitive layer is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and even more preferably 0.3% by mass or more, based on the total amount of the photosensitive layer. The upper limit of the water content is not particularly limited, and is, for example, 1.0% by mass.

[0339] <Pigments> The photosensitive layer may be a colored resin layer containing a pigment.

[0340] In some cases, in order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc. is attached to the liquid crystal display window. A colored resin layer can be used to form such a light-shielding layer.

[0341] The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. Among them, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0342] As the black pigment, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as long as the effects of the present disclosure are not impaired. Among them, from the viewpoint of optical density, for example, carbon black, titanium oxide, titanium carbide, iron oxide, and graphite are suitable as black pigments, and carbon black is particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a part of the surface of which is coated with a resin is preferred.

[0343] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably from 0.001 μm to 0.1 μm, more preferably from 0.01 μm to 0.08 μm, in terms of number average particle size.

[0344] Here, the particle size refers to the diameter of a circle whose area is equal to the area of ​​a pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope, and the number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the particle sizes of the 100 particles thus calculated.

[0345] As a pigment other than the black pigment, the white pigment described in paragraphs

[0015] and

[0114] of JP-A-2005-007765 can be used. Specifically, among the white pigments, the inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide, and even more preferably titanium oxide. As the inorganic pigment, rutile or anatase titanium oxide is more preferable, and rutile titanium oxide is particularly preferable.

[0346] The surface of titanium oxide may be subjected to a silica treatment, an alumina treatment, a titania treatment, a zirconia treatment, or an organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, etc.

[0347] From the viewpoint of reducing the thickness of the photosensitive layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

[0348] In addition, when the photosensitive layer is a colored resin layer, it is also preferable from the viewpoint of transferability that the photosensitive layer further contains a chromatic pigment other than a black pigment and a white pigment. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of superior dispersibility.

[0349] Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Red 146 ... Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow Examples of pigments that can be used include CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and 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. Of these, CI Pigment Red 177 is preferred.

[0350] When the photosensitive layer contains a pigment, the content of the pigment is preferably more than 3 mass% and not more than 40 mass%, more preferably more than 3 mass% and not more than 35 mass%, even more preferably more than 5 mass% and not more than 35 mass%, and particularly preferably 10 mass% or more and not more than 35 mass%.

[0351] When the photosensitive layer contains pigments other than the black pigment (white pigment and chromatic pigments), the content of the pigments other than the black pigment is preferably 30% by mass or less, more preferably 1% by mass to 20% by mass, and even more preferably 3% by mass to 15% by mass, relative to the black pigment.

[0352] In addition, when the photosensitive layer contains a black pigment and is formed from a composition for forming a photosensitive layer, it is preferable that the black pigment (preferably carbon black) is introduced into the composition for forming a photosensitive layer in the form of a pigment dispersion.

[0353] The dispersion may be prepared by adding a mixture of a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant may be used. The vehicle refers to the medium portion in which the pigment is dispersed when the pigment dispersion is prepared, and 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.

[0354] Examples of dispersants include urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, their modifications, amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups, and their salts. Oil-based dispersants include water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters. The form of the dispersant may be selected from the items described in paragraphs

[0021] to

[0065] of JP 2021-012355 A.

[0355] A preferred dispersant is, for example, a basic polymer type dispersant. A preferred basic polymer type dispersant is, for example, a polymer containing a nitrogen atom. The nitrogen atom may be contained in the main chain of the polymer. The nitrogen atom may be contained in the side chain of the polymer. The nitrogen atom may be contained in the main chain and the side chain of the polymer. The basic polymer type dispersant is preferably a polymer containing a nitrogen atom in the side chain. Since the surface of carbon black is generally acidic, when carbon black is used as a pigment, a basic polymer type dispersant is particularly preferred as the dispersant.

[0356] Examples of the polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in the side chain) include a polymer containing at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group. For example, a polymer containing a quaternary ammonium base is preferred. The atomic group is preferably introduced into the side chain of the polymer. For example, a polymer containing at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group in the side chain is preferred, and a polymer containing a quaternary ammonium base in the side chain is more preferred. Examples of the counter ion of the quaternary ammonium cation in the quaternary ammonium base include a carboxylate ion. Examples of the carboxylate ion include an aliphatic carboxylate ion and an aromatic carboxylate ion.

[0357] The polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in a side chain) is preferably a polymer containing a structural unit derived from styrene and a structural unit derived from a maleimide derivative, and more preferably a copolymer of styrene and a maleimide derivative. The maleimide derivative has a structure in which at least one hydrogen atom of the maleimide is substituted with a substituent. Examples of the maleimide derivative include maleimide derivatives containing at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group. The maleimide derivative is preferably a maleimide derivative containing a quaternary ammonium base.

[0358] The dispersant may be a commercially available dispersant, for example, BYK-2012 (BYK Japan Co., Ltd.).

[0359] The photosensitive layer may contain a dispersion aid (also called a pigment dispersion aid) in addition to the pigment. The dispersion aid may be selected from known dispersion aids.

[0360] Examples of the dispersing aid include compounds having an organic dye residue. Examples of the organic dye include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, and the like. The compound having an organic dye residue may have an acidic substituent, a basic substituent, or a neutral substituent. Examples of the acidic substituent include a sulfo group, a carboxy group, and a phosphoric acid group. Examples of the basic substituent include a sulfonamide group and an amino group. Examples of the neutral substituent include a phenyl group and a phthalimidoalkyl group. The embodiment of the dispersion aid may be selected from the items described in paragraphs

[0067] to

[0084] of JP2021-012355A.

[0361] A preferred dispersing aid is, for example, a compound having a phthalocyanine residue. Specifically, the dispersing aid is preferably a phthalocyanine pigment derivative having an acidic substituent or a salt thereof, more preferably a phthalocyanine pigment derivative having at least one acidic substituent selected from the group consisting of a sulfo group, a carboxy group, and a phosphoric acid group or a salt thereof, and even more preferably a phthalocyanine pigment derivative having a sulfo group or a salt thereof. Phthalocyanine pigment derivatives are described, for example, in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A. These publications are incorporated herein by reference.

[0362] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details of dispersing machines and fine pulverization, see the description in "Encyclopedia of Pigments" (written by Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0363] [Middle layer] The transfer film preferably includes an intermediate layer between the temporary support and the photosensitive layer. In addition, when the transfer film includes a thermoplastic resin layer described later between the temporary support and the photosensitive layer, the transfer film preferably includes an intermediate layer between the thermoplastic resin layer and the photosensitive layer.

[0364] By providing the intermediate layer, it is possible to suppress mixing of the components when the compositions for forming a plurality of layers are applied and during storage after application.

[0365] The intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin. The intermediate layer may be an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in JP-A-5-072724. It is preferable that the intermediate layer is an oxygen barrier layer, since the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved.

[0366] The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred.

[0367] Each component that the intermediate layer may contain will be described below.

[0368] The intermediate layer preferably contains a resin. The resin preferably contains a water-soluble resin as a part or the whole. Examples of resins that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

[0369] In addition, as the water-soluble resin, a copolymer of (meth)acrylic acid / vinyl compound can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / allyl (meth)acrylate is preferable, and a copolymer of methacrylic acid / allyl methacrylate is more preferable.

[0370] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol %) of each is, for example, preferably from 90 / 10 to 20 / 80, and more preferably from 80 / 20 to 30 / 70.

[0371] The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more, and the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersity (Mw / Mn) of the water-soluble resin is preferably 1-10, and more preferably 1-5.

[0372] In order to further improve the interlayer mixing suppression ability of the intermediate layer, it is preferable that the resin contained in the intermediate layer is different from the resin contained in the layer disposed on one side of the intermediate layer and the resin contained in the layer disposed on the other side of the intermediate layer. For example, when the photosensitive layer contains polymer A and the thermoplastic resin layer contains a thermoplastic resin (alkali-soluble resin), it is preferable that the resin contained in the intermediate layer is different from polymer A and the thermoplastic resin (alkali-soluble resin).

[0373] The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in order to further improve the oxygen barrier property and the ability to inhibit interlayer mixing.

[0374] The water-soluble resin contained in the intermediate layer may be of one type or of two or more types. The content of the water-soluble resin is not particularly limited, but from the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppression ability, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the intermediate layer. The upper limit is not particularly limited, but for example, it is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.

[0375] The intermediate layer may contain known additives such as a surfactant, if necessary.

[0376] The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not deteriorated, and the interlayer mixing suppression ability is excellent. Furthermore, the increase in the removal time of the intermediate layer during development can be suppressed.

[0377] [Thermoplastic resin layer] The transfer film preferably includes a thermoplastic resin layer between the temporary support and the intermediate layer. By providing the transfer film with a thermoplastic resin layer, the conformability to the substrate during the bonding process between the transfer film and the substrate is improved, and the inclusion of air bubbles between the substrate and the transfer film can be suppressed, thereby ensuring adhesion between the thermoplastic resin layer and an adjacent layer (e.g., a temporary support).

[0378] The thermoplastic resin layer contains a resin. The resin contains a thermoplastic resin as a part or the whole. That is, in one embodiment, it is also preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.

[0379] <Alkali-soluble resin> The thermoplastic resin is preferably an alkali-soluble resin. Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0380] As the alkali-soluble resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin is preferred. Here, the acrylic resin means a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides.

[0381] The acrylic resin preferably contains, in total, 50% by mass or more of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic acid amide, relative to the total mass of the acrylic resin. In particular, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid esters is preferably 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass, based on the total mass of the acrylic resin.

[0382] The alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with the carboxy group being preferred.

[0383] From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0384] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins. For example, the alkali-soluble resin is a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph

[0025] of JP-A-2011-095716, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs

[0033] to

[0052] of JP-A-2010-237589, and the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs

[0053] to

[0068] of JP-A-2016-224162.

[0385] The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 12% by mass to 30% by mass, based on the total mass of the acrylic resin.

[0386] As the alkali-soluble resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred.

[0387] The alkali-soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples of the reactive group include ethylenically unsaturated groups, polycondensable groups such as hydroxyl groups and carboxyl groups, and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0388] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 50,000.

[0389] The alkali-soluble resin contained in the thermoplastic resin layer may be one type or two or more types.

[0390] From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, even more preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0391] <Dye> The thermoplastic resin layer preferably contains a dye, and more preferably contains a dye (also simply referred to as "dye B") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm when colored and whose maximum absorption wavelength changes in response to an acid, a base, or a radical.

[0392] A preferred embodiment of dye B is the same as the preferred embodiment of dye N described above, except for the points described below.

[0393] From the viewpoints of visibility of exposed and unexposed areas and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to an acid.

[0394] From the viewpoints of visibility and resolution of exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye B whose maximum absorption wavelength changes in response to acid, and a compound that generates an acid when exposed to light, as described below.

[0395] The thermoplastic resin layer may contain one type or two or more types of dye B. From the viewpoint of visibility of exposed and non-exposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, further preferably 0.2 mass% to 5 mass%, and particularly preferably 0.25 mass% to 3.0 mass%, based on the total mass of the thermoplastic resin layer.

[0396] Here, the content of dye B means the content of dye when all of dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example. Prepare solutions by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. Add a photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Co., Ltd.) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals and make all the dyes colored. Then, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere, and create a calibration curve. Next, the absorbance of the solution in which all the dye has been colored is measured in the same manner as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. The amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve from the absorbance of the solution containing the thermoplastic resin layer obtained. The thermoplastic resin layer 3g is the same as the 3g of solid content of the composition for forming a thermoplastic resin layer.

[0397] <Compounds that generate acids, bases, or radicals when exposed to light> The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical when exposed to light (also simply referred to as "compound C").

[0398] Compound C is preferably a compound that generates an acid, a base, or a radical upon exposure to actinic rays such as ultraviolet light and visible light.

[0399] As the compound C, a known photoacid generator, photobase generator, or photoradical polymerization initiator (photoradical generator) can be used.

[0400] (Photoacid generator) From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator.

[0401] Examples of the photoacid generator include the above-mentioned cationic photopolymerization initiators that may be contained in the photosensitive layer, and preferred embodiments are also the same except for the points described below.

[0402] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and from the viewpoints of sensitivity, resolution, and adhesion, it is more preferable that the photoacid generator contains an oxime sulfonate compound. As the photoacid generator, a photoacid generator having the following structure is also preferred.

[0403] [ka]

[0404] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0405] As the photoradical polymerization initiator, the photoradical polymerization initiators which may be contained in the photosensitive layer described above can be mentioned, and the preferred embodiments are also the same.

[0406] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator.

[0407] The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- Examples include 1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0408] The compound C contained in the thermoplastic resin layer may be one type or two or more types. The content of compound C is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of exposed and non-exposed areas.

[0409] <Plasticizer> The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.

[0410] The plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or polymer and has a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.

[0411] The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0412] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0413] Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound contained in the photosensitive layer.

[0414] In the transfer film, when the thermoplastic resin layer and the photosensitive layer are laminated in direct contact with each other, it is preferable that both the thermoplastic resin layer and the negative photosensitive layer contain the same (meth)acrylate compound. By containing the same (meth)acrylate compound in the thermoplastic resin layer and the photosensitive layer, the diffusion of components between the layers is suppressed, and the storage stability is improved.

[0415] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and an adjacent layer.

[0416] In addition, as the (meth)acrylate compound used as a plasticizer, from the viewpoints of the 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.

[0417] Furthermore, as the (meth)acrylate compound used as a plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferred.

[0418] The plasticizer contained in the thermoplastic resin layer may be of one type or of two or more types. From the viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0419] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that may be contained in the negative photosensitive layer described above.

[0420] The sensitizer contained in the thermoplastic resin layer may be of one type or of two or more types. The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoints of improving sensitivity to the light source and visibility of exposed and non-exposed areas, it is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the thermoplastic resin layer.

[0421] <Additives, etc.> In addition to the above components, the thermoplastic resin layer may contain known additives such as a surfactant, if necessary.

[0422] In addition, the thermoplastic resin layer is described in paragraphs

[0189] to

[0193] of JP2014-085643A, the contents of which are incorporated herein by reference.

[0423] The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion with adjacent layers. The upper limit is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less, from the viewpoint of developability and resolution.

[0424] [Protective film] The transfer film may have a protective film. As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film.

[0425] Furthermore, as the protective film, a resin film made of the same material as the above-mentioned temporary support may be used.

[0426] Among these, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0427] The thickness of the protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, further preferably from 5 μm to 40 μm, and particularly preferably from 15 μm to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of being relatively inexpensive.

[0428] In addition, the number of fish eyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 It is preferable that:

[0429] "Fish eyes" are foreign matter, unmelted material, and oxidized deterioration products of the material that become trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0430] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The following is even more preferred:

[0431] This makes it possible to suppress defects caused by the transfer of unevenness due to particles contained in the protective film to the photosensitive layer or the conductor layer.

[0432] From the viewpoint of providing winding properties, the arithmetic mean roughness Ra of the surface of the protective film 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, while it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0433] The protective film may be a recycled product. Examples of recycled products include used films and the like that are cleaned and cut into chips, and the chips are used to make films. A specific example of a recycled product is the Ecouse series from Toray Industries.

[0434] In order to suppress defects during transfer, the surface roughness Ra of the protective film on 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, while it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0435] [Transfer film manufacturing method] The method for producing the transfer film is not particularly limited, and any known method can be used. The method for producing the transfer film will be described with reference to Fig. 1. Examples of the method for producing the transfer film 20 include a method including a step of applying a composition for forming a thermoplastic resin layer on the surface of the temporary support 11 to form a coating film, and further drying the coating film to form the thermoplastic resin layer 13, a step of applying a composition for forming an intermediate layer on the surface of the thermoplastic resin layer 13 to form a coating film, and further drying the coating film to form the intermediate layer 15, and a step of applying a composition for forming a photosensitive layer on the surface of the intermediate layer 15 to form a coating film, and further drying the coating film to form the photosensitive layer 17. In FIG. 1, a protective film 19 is further pressed onto the photosensitive layer 17 of the laminate produced by the above-mentioned production method, whereby a transfer film 20 can be produced.

[0436] The method for producing the transfer film preferably includes a step of providing a protective film 19 so as to be in contact with the surface of the photosensitive layer 17 opposite to the side having the temporary support 11, thereby producing a transfer film 20 including the temporary support 11, the thermoplastic resin layer 13, the intermediate layer 15, the photosensitive layer 17, and the protective film 19. The thermoplastic resin layer 13, the intermediate layer 15, and the photosensitive layer 17 correspond to the transfer layer 12.

[0437] After the transfer film 20 is manufactured by the above manufacturing method, a transfer film in a roll form may be produced and stored by winding up the transfer film 20. The transfer film in a roll form can be subjected to a step of laminating it to a substrate with a metal layer by a roll-to-roll method described later, and when the transfer film has a protective film, the transfer film is provided in its original form by the roll-to-roll method, and the protective film is peeled off before being subjected to a step of laminating it to a substrate with a metal layer.

[0438] In addition, the above-mentioned transfer film 20 may be manufactured by forming the photosensitive layer 17 and the intermediate layer 15 on the protective film 19, and then forming the thermoplastic resin layer 13 on the surface of the intermediate layer 15.

[0439] <Method of forming thermoplastic resin layer> The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and any known method can be used. For example, the thermoplastic resin layer can be formed by applying a composition for forming a thermoplastic resin layer on the temporary support and drying it as necessary.

[0440] The thermoplastic resin layer forming composition preferably contains various components forming the above-mentioned thermoplastic resin layer and a solvent. In the thermoplastic resin layer forming composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the above-mentioned thermoplastic resin layer.

[0441] The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used. Examples of the solvent include the same solvents contained in the composition for forming the photosensitive layer described below, and the preferred embodiments are also the same.

[0442] The content of the solvent is preferably from 50 parts by mass to 1,900 parts by mass, and more preferably from 100 parts by mass to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition for forming a thermoplastic resin layer.

[0443] The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0444] <Method of forming intermediate layer> The method for forming the intermediate layer can be a known method, for example, the intermediate layer can be formed by applying the composition for forming the intermediate layer and drying it as necessary. The composition for forming the intermediate layer preferably contains various components for forming the intermediate layer and a solvent. In the composition for forming the intermediate layer, the preferred range of the content of each component relative to the total solid content of the composition for forming the intermediate layer is the same as the preferred range of the content of each component relative to the total mass of the intermediate layer.

[0445] The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0446] Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0447] The solvent contained in the composition for forming an intermediate layer may be one type or two or more types. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the intermediate layer forming composition.

[0448] The method for forming the intermediate layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0449] <Method of forming photosensitive layer> The photosensitive layer can be formed by a known method. For example, in terms of excellent productivity, it is desirable to form the photosensitive layer by a coating method using a photosensitive forming composition containing the components constituting the photosensitive layer described above (e.g., polymer A, a polymerizable compound, a polymerization initiator, etc.) and a solvent.

[0450] Specifically, the method for producing the transfer film is preferably a method in which a photosensitive composition is applied onto the intermediate layer to form a coating film, and the coating film is dried at a predetermined temperature to form the photosensitive layer. The amount of remaining solvent is adjusted by the drying treatment of the coating film.

[0451] The photosensitive composition preferably contains the above-mentioned various components forming the photosensitive layer and a solvent. In the photosensitive composition, the preferred range of the content of each component relative to the total solid content of the photosensitive composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive layer.

[0452] The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used.Specific examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0453] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0454] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0455] Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0456] As the solvent, the solvents described in paragraphs

[0092] to

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

[0014] of JP-A-2018-177889 may be used, the contents of which are incorporated herein by reference.

[0457] The solvent contained in the photosensitive forming composition may be one type alone or two or more types.

[0458] The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0459] Examples of methods for applying the photosensitive forming composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0460] As a method for drying the coating of the composition for forming the photosensitive layer, heat drying and reduced pressure drying are preferred.

[0461] The drying temperature is preferably 80° C. or higher, and more preferably 90° C. or higher. The upper limit is preferably 130° C. or lower, and more preferably 120° C. or lower. Drying can also be performed by continuously changing the temperature.

[0462] The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. Although there is no particular upper limit, the drying time is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0463] Furthermore, a transfer film can be produced by laminating a protective film onto the photosensitive layer. do.

[0464] The method for attaching the protective film to the photosensitive layer is not particularly limited, and any known method can be used.

[0465] Examples of a device for laminating the protective film to the photosensitive layer include known laminators such as a vacuum laminator and an autocut laminator.

[0466] The laminator is preferably equipped with any heatable roller, such as a rubber roller, and is capable of applying pressure and heat. EXAMPLES

[0467] The present disclosure will be described in detail below with reference to examples. However, the present disclosure is not limited to the following examples. In the following description, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass".

[0468] <Preparation of Photosensitive Layer Forming Composition> The components shown in Table 1 were mixed in the amounts (mass %) shown in Table 1 to prepare compositions 1 to 10 for forming photosensitive layer, respectively.

[0469] [Table 1]

[0470] The components used to prepare the photosensitive layer-forming composition are as follows.

[0471] [Resin (Polymer A)] Using the polymerizable monomers shown in Table 2, polymers A1 to A4 were synthesized.

[0472] [Table 2]

[0473] Details of the polymerizable monomer are as follows. St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ·MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) GB: Glycidyl butyrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) GMA: Glycidyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0474] -Synthesis of polymer A1- 85 parts by mass of propylene glycol monomethyl ether was charged into a flask and heated to 90°C under a nitrogen stream. A solution of 40 parts by mass of St, 25 parts by mass of MAA, and 5 parts by mass of MMA dissolved in 20 parts by mass of propylene glycol monomethyl ether, and a solution of 7 parts by mass of a polymerization initiator (product name "V-601", Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in 45 parts by mass of propylene glycol monomethyl ether were simultaneously dropped into this liquid over 3 hours. After the dropwise addition was completed, 1.0 part by mass of V-601 was added three times every hour. Then, the reaction was continued for another 3 hours. The mixture was diluted with 60 parts by mass of PGMEA and 22 parts by mass of propylene glycol monomethyl ether. Under an air stream, the reaction liquid was heated to 100°C, and 0.7 parts by mass of tetraethylammonium bromide and 0.3 parts by mass of p-methoxyphenol were added. 30 parts by mass of GB was dropped into this over 20 minutes. This was reacted at 100° C. for 7 hours to obtain a solution containing polymer A1 (solid content concentration: 30.0% by mass).

[0475] -Synthesis of polymer A2- 85 parts by mass of propylene glycol monomethyl ether was charged into a flask and heated to 90°C under a nitrogen stream. A solution of 40 parts by mass of St, 25 parts by mass of MAA, and 5 parts by mass of MMA dissolved in 20 parts by mass of propylene glycol monomethyl ether, and a solution of 7 parts by mass of V-601 dissolved in 45 parts by mass of propylene glycol monomethyl ether were simultaneously dropped into this liquid over 3 hours. After the dropwise addition was completed, 1.0 part by mass of V-601 was added three times every hour. Then, the reaction was continued for another 3 hours. The mixture was diluted with 60 parts by mass of PGMEA and 12 parts by mass of propylene glycol monomethyl ether. Under an air stream, the reaction liquid was heated to 100°C, and 0.7 parts by mass of tetraethylammonium bromide and 0.3 parts by mass of p-methoxyphenol were added. 15 parts by mass of GB and 15 parts by mass of GMA were dropped into this liquid over 20 minutes. This was reacted at 100° C. for 7 hours to obtain a solution containing polymer A2 (solid content concentration: 30.0% by mass).

[0476] -Synthesis of polymer A3- 85 parts by mass of propylene glycol monomethyl ether was charged into a flask and heated to 90°C under a nitrogen stream. A solution of 40 parts by mass of St, 25 parts by mass of MAA, and 5 parts by mass of MMA dissolved in 20 parts by mass of propylene glycol monomethyl ether, and a solution of 7 parts by mass of V-601 dissolved in 45 parts by mass of propylene glycol monomethyl ether were simultaneously dropped into this liquid over 3 hours. After the dropwise addition was completed, 1.0 part by mass of V-601 was added three times every hour. Then, the reaction was continued for another 3 hours. The reaction solution was diluted with 60 parts by mass of PGMEA and 12 parts by mass of propylene glycol monomethyl ether. Under an air stream, the reaction solution was heated to 100°C, and 0.7 parts by mass of tetraethylammonium bromide and 0.3 parts by mass of p-methoxyphenol were added. 30 parts by mass of GMA were dropped into this over 20 minutes. This was reacted at 100°C for 7 hours to obtain a solution containing polymer A3 (solid content concentration 30.0% by mass).

[0477] -Synthesis of polymer A4- 115 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was placed in a three-neck flask and heated to 90° C. under a nitrogen atmosphere. A solution containing 40 parts by mass of St, 25 parts by mass of MAA, 35 parts by mass of MMA, 4 parts by mass of V-601, and 115 parts by mass of PGMEA was added dropwise over 2 hours to the flask solution maintained at 90° C.±2° C. After the dropwise addition was completed, the solution in the flask was stirred at 90° C.±2° C. for 2 hours to obtain a solution containing polymer A4, which is an alkali-soluble resin (solid content concentration 30.0% by mass).

[0478] [Polymerizable compound] ·BPE-500: Product name "NK Ester BPE-500", ethoxylated bisphenol A dimethacrylate, average repeat number of ethylene oxide chains: 10, manufactured by Shin-Nakamura Chemical Co., Ltd. ·M-270: Product name "Aronix M-270", polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. BPE-100: Product name "NK Ester BPE-100", ethoxylated bisphenol A dimethacrylate, average repeat number of ethylene oxide chains 2.6, manufactured by Shin-Nakamura Chemical Co., Ltd. The above BPE-500 and BPE-100 correspond to the polymerizable compound B1.

[0479] [Polymerization initiator] B-CIM: Product name: B-CIM (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Kurogane Chemical Industry Co., Ltd.

[0480] [Sensitizer] SB-PI 701: 4,4'-bis(diethylamino)benzophenone, sold by Sanyo Trading Co., Ltd.

[0481] [Chain transfer agent] Compound A: N-phenylcarbamoylmethyl-N-carboxymethylaniline, Fujifilm Wako Pure Chemical Industries, Ltd.

[0482] [Pigment] LCV: Leuco Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd., a dye that changes color when exposed to radicals

[0483] [Rust inhibitor] CBT-1: Product name "CBT-1", Carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.

[0484] [Polymerization inhibitor] TDP-G: Product name "TDP-G", phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0485] [Surfactants] F-552: Product name: "Megafac (registered trademark) F-552", manufactured by DIC Corporation EXP.S-315: Product name "EXP.S-315", silicone surfactant, manufactured by DIC Corporation KP-124: Product name "KP-124", silicone surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.

[0486] [Preparation of composition for forming intermediate layer] An intermediate layer forming composition was prepared using the following components. PVA (Polyvinyl Alcohol): Product name "Kuraray Poval PVA-205", manufactured by Kuraray Co., Ltd. PVP (Polypyrrolidone): Product name: Polyvinylpyrrolidone K-30, manufactured by Nippon Shokubai Co., Ltd. HPMC (hydroxypropyl methylcellulose): Product name: "Metolose 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd. The PVA, PVP, and HPMC components were mixed in a ratio (mass ratio) of 67.5 / 31.5 / 1, and then a solvent (a mixed solvent of ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a ratio (mass ratio) of 40 / 60) was added to prepare a composition for forming an intermediate layer.

[0487] [Preparation of Thermoplastic Resin Layer-Forming Composition] The components shown in Table 4 were mixed in the amounts (mass %) shown in Table 4 to prepare a composition for forming a thermoplastic resin layer.

[0488] [Table 3]

[0489] The components used to prepare the thermoplastic resin layer-forming composition are as follows: Note that a description of the above-mentioned components will be omitted.

[0490] [Thermoplastic resin A5] Using the polymerizable monomers shown in Table 5, thermoplastic resin A5 was synthesized.

[0491] [Table 4]

[0492] Details of the polymerizable monomer are as follows. MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) BzMA: benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) AA: Acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0493] -Synthesis of thermoplastic resin A5- A solution containing thermoplastic resin A5 (solid content concentration: 30% by mass) was obtained in the same manner as for polymer A4, except that the monomer used was changed to that in Table 5. The acid value of thermoplastic resin A5 was 155 mgKOH / g.

[0494] [Plasticizer] A-DCP: Product name "NK Ester A-DCP", tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. 8UX-015: Product name "8UX-015A", multifunctional urethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd. TO-2349: Product name "Aronix TO-2349", a multifunctional acrylate compound with a carboxy group, manufactured by Toagosei Co., Ltd.

[0495] <<Preparation of transfer film>> -Example 1, Example 3 to Example 11, Example 14 to Example 21, Comparative Example 1, Comparative Example 2- The intermediate layer-forming composition was applied onto a temporary support (polyethylene terephthalate film, product name "16KS40 manufactured by Toray Industries, Inc.", thickness: 16 μm) so that the layer thickness after drying would be 1 μm. The coating of the intermediate layer-forming composition was dried at 90° C. for 120 seconds to form an intermediate layer. A composition for forming a photosensitive layer shown in Tables 6 and 7 was applied onto the intermediate layer using a slit nozzle so that the layer thickness after drying would be the thickness shown in Tables 6 and 7. The coating of the composition for forming a photosensitive layer was dried at 80° C. for 120 seconds to form a photosensitive layer. A transfer film having a temporary support, an intermediate layer, and a photosensitive layer in this order was obtained.

[0496] Example 2 The thermoplastic layer-forming composition was applied onto a temporary support (polyethylene terephthalate film, product name "16KS40 manufactured by Toray Industries, Inc.", thickness: 16 μm) using a slit nozzle so that the layer thickness after drying would be 5 μm. The coating of the thermoplastic resin layer-forming composition was dried at 90° C. for 120 seconds to form a thermoplastic resin layer. The intermediate layer-forming composition was applied onto the thermoplastic resin layer using a slit nozzle so that the layer thickness after drying would be 1 μm. The coating of the intermediate layer-forming composition was dried at 90° C. for 120 seconds to form an intermediate layer. A composition for forming a photosensitive layer shown in Table 1 was applied onto the intermediate layer using a slit nozzle so that the layer thickness after drying would be 3 μm. The coating of the composition for forming a photosensitive layer was dried at 80° C. for 120 seconds to form a photosensitive layer. A transfer film having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive layer in this order was obtained.

[0497] -Examples 12 and 13- Photosensitive layer-forming composition 1 was applied onto a temporary support (polyethylene terephthalate film, product name "16KS40 manufactured by Toray Industries, Inc.", thickness: 16 μm) so that the layer thickness after drying would be 3 μm. The coating of photosensitive layer-forming composition 1 was dried at 80° C. for 120 seconds to form a photosensitive layer. A transfer film having a temporary support and a photosensitive layer in this order was obtained.

[0498] <Preparation of the substrate> A Cu sputtering process was performed on the surface of a silicon wafer with a thickness of 0.7 mm to a thickness of 200 nm, thereby obtaining a substrate having a metal layer.

[0499] <Preparation of Laminate> The photosensitive layer side of the transfer film and the metal layer were adhered to the substrate and pressed to obtain a laminate. The pressing was performed using a heat roll at 100° C. under a pressure of 0.7 MPa at a speed of 0.5 m / min. (Laminating step)

[0500] <<Resolution evaluation>> -Example 1, Example 3 to Example 10, Example 14, Example 15- The temporary support was peeled off from the obtained laminate to expose the intermediate layer. (Temporary Support Peeling Step) The photosensitive layer was exposed to a pattern at an arbitrary exposure dose using a halftone phase shift mask with a wiring pattern inscribed with a pitch (line (L) + space (s)) of 0.5 um intervals, and a 2 / 3 annular illumination source with a high pressure mercury lamp as the light source. (Exposure process) The exposure dose was determined using a Stouffer 41-step tablet, and when developed for 1.5 times the shortest development time, the exposure dose resulting in 12 remaining steps was used as the center, and was varied in 5% increments within a range of ±50%. The minimum pattern width remaining after development was measured, and the film thickness of the photosensitive layer relative to the minimum pattern width was taken as the aspect ratio to evaluate the resolution.

[0501] Example 2 In Example 2, the same treatment as in Example 1 was carried out, except that the thermoplastic resin layer was exposed by peeling off the temporary support.

[0502] -Examples 11 and 12- In Examples 11 and 12, the same treatment as in Example 1 was carried out, except that the temporary support was not peeled off.

[0503] Example 13 In Example 13, the same treatment as in Example 1 was carried out, except that the photosensitive layer was exposed by peeling off the temporary support.

[0504] Example 16 In Example 16, the same process as in Example 1 was carried out, except that no halftone phase shift mask was used in the exposure.

[0505] Example 17 In Example 17, the same treatment as in Example 16 was carried out, except that the temporary support was not peeled off.

[0506] Example 18 In Example 18, the same procedures as in Example 17 were performed, except that the 2 / 3 ring illumination was changed to 1 / 2 ring illumination.

[0507] - Example 19 - In Example 19, the same procedures as in Example 1 were performed, except that ring illumination was not used.

[0508] - Example 20 - In Example 20, the same procedures as in Example 19 were performed, except that the temporary support was not peeled off.

[0509] - Example 21 - In Example 21, the same procedures as in Example 20 were performed, except that the halftone phase shift mask was changed to a Levenson phase shift mask.

[0510] - Comparative Example 1 - In Comparative Example 1, the same procedures as in Example 21 were performed, except that the Levenson phase shift mask was not used.

[0511] - Comparative Example 2 - In Comparative Example 2, the same procedures as in Comparative Example 1 were performed, except that the temporary support was peeled off.

[0512] <<DOF (Depth of Field) Evaluation>> For Examples 1 to 21 and Comparative Examples 1 to 2, with the condition where the minimum pattern width was obtained in the above "Resolution Evaluation" as the focus of 0 μm, the lens focus of the projection exposure apparatus was changed in the vertical direction by ±24 μm in 2-μm increments, and pattern exposure was performed. The obtained patterns were measured using an electron microscope, and the range where the line width variation from the focus of 0 μm was within ±15% was evaluated as the focus margin (DOF margin).

[0513] The evaluation results are shown in Tables 6 and 7. In Tables 6 and 7, "Transmittance of the photosensitive layer" means the transmittance of the photosensitive layer at the main wavelength (365 nm) of the light used for pattern exposure.

[0514] [Table 5]

[0515] [Table 6]

[0516] As shown in Tables 6 and 7, Examples 1 to 21, which used annular illumination or a halftone phase shift or Levenson phase shift mask, were shown to achieve both high resolution and deep depth of focus compared to Comparative Examples 1 and 2, which did not use annular illumination or a phase shift mask. It was also shown that the combined use of annular illumination and a halftone phase-shift mask makes it easier to achieve both high resolution and a deep depth of focus compared to the use of either annular illumination or a phase-shift mask. [Explanation of symbols]

[0517] 11: Temporary support 12: Transfer layer 13: Thermoplastic resin layer 15: Middle class 17: Photosensitive layer 19: Protective film 20: Transfer film

Claims

1. a step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate such that the photosensitive layer side of the transfer film is in contact with the metal layer of the substrate having a metal layer on a surface thereof; exposing the photosensitive layer to a pattern using light emitted from an annular illumination device from a side opposite to the side having the substrate; a step of performing a development process on the exposed photosensitive layer to form a resist pattern; any one of a step of performing an etching process and a step of performing a plating process on the metal layer in an area where the resist pattern is not formed; stripping the resist pattern; When the method further comprises the step of performing the plating treatment, the method further comprises the step of removing the metal layer exposed by the peeling step.

2. The method for producing a laminate having a conductive pattern according to claim 1 , wherein the step of exposing is a step of performing pattern exposure through a phase shift mask.

3. 3. The method for producing a laminate having a conductor pattern according to claim 2, wherein the phase shift mask is a Levenson phase shift mask or an attenuated phase shift mask.

4. The method for producing a laminate having a conductor pattern according to claim 1 , further comprising a step of peeling off a temporary support between the laminating step and the exposing step.

5. 3. The method for producing a laminate having a conductor pattern according to claim 1, wherein the transmittance of the photosensitive layer to the exposure wavelength is 65% or more.

6. 3. The method for producing a laminate having a conductive pattern according to claim 1, wherein the photosensitive layer has a thickness of 1 μm to 3 μm.

7. 3. The method for producing a laminate having a conductor pattern according to claim 1, wherein the conductor pattern has an aspect ratio of 3.0 or more.

8. 3. The method for producing a laminate having a conductive pattern according to claim 1, wherein the photosensitive layer contains 0.01% by mass to 5% by mass of a sensitizer based on the total amount of a composition for forming a photosensitive layer.

9. The method for producing a laminate having a conductor pattern according to claim 1 or 2, wherein the transfer film has an intermediate layer between the temporary support and the photosensitive layer.

10. The method for producing a laminate having a conductor pattern according to claim 9 , wherein the intermediate layer is a water-soluble resin layer.

11. The method for producing a laminate having a conductor pattern according to claim 9 , wherein the transfer film has a thermoplastic resin layer between the temporary support and the intermediate layer.

12. a step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate such that the photosensitive layer side of the transfer film is in contact with the metal layer of the substrate having a metal layer on a surface thereof; exposing the photosensitive layer to a pattern through a phase shift mask from a side opposite to the side having the substrate; a step of performing a development process on the exposed photosensitive layer to form a resist pattern; any one of a step of performing an etching process and a step of performing a plating process on the metal layer in an area where the resist pattern is not formed; stripping the resist pattern; When the method further comprises the step of performing the plating treatment, the method further comprises the step of removing the metal layer exposed by the peeling step.

13. The method for producing a laminate having a conductor pattern according to claim 12, wherein the phase shift mask is a Levenson phase shift mask or an attenuated phase shift mask.

14. The method for producing a laminate having a conductor pattern according to claim 12 or 13, further comprising a step of peeling off a temporary support between the laminating step and the exposing step.

15. The method for producing a laminate having a conductor pattern according to claim 12 or 13, wherein the transmittance of the photosensitive layer to an exposure wavelength is 65% or more.

16. The method for producing a laminate having a conductive pattern according to claim 12 or 13, wherein the photosensitive layer has a thickness of 1 μm to 3 μm.

17. The method for producing a laminate having a conductor pattern according to claim 12 or 13, wherein the conductor pattern has an aspect ratio of 3.0 or more.

18. The method for producing a laminate having a conductive pattern according to claim 12 or 13, wherein the photosensitive layer contains 0.01% by mass to 5% by mass of a sensitizer based on the total amount of a composition for forming a photosensitive layer.

19. The method for producing a laminate having a conductor pattern according to claim 12 or 13, wherein the transfer film has an intermediate layer between the temporary support and the photosensitive layer.

20. The method for producing a laminate having a conductor pattern according to claim 19, wherein the intermediate layer is a water-soluble resin layer.

21. The method for producing a laminate having a conductor pattern according to claim 19 , wherein the transfer film has a thermoplastic resin layer between the temporary support and the intermediate layer.

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