Photosensitive transfer material and method for manufacturing same

Abstract

Provided are: a photosensitive transfer material having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, wherein the peel force Fa between the temporary support and thermoplastic resin layer and the peel force Fb between the thermoplastic resin layer and intermediate layer satisfy the relationship in formula (1); and a method for manufacturing the photosensitive transfer material.　(1) Fa ≥ 150 mN / cm > Fb

Description

Photosensitive transfer material and method for manufacturing the same

[0001] This disclosure relates to a photosensitive transfer material and a method for producing the same.

[0002] Conventionally, photosensitive transfer materials, also known as dry film resists, have been widely used because they allow for the easy formation of resist patterns on various substrates. With photosensitive transfer materials, a photosensitive resin layer formed on any substrate by transfer can be exposed to a photomask (hereinafter simply referred to as "mask") having a desired pattern, and then developed to obtain the required pattern shape.

[0003] A photosensitive transfer material suitable for the fabrication of color filters is known, comprising a temporary support, a thermoplastic resin layer, and a photosensitive resin layer in that order, wherein the thermoplastic resin layer expands upon energy application (see Patent Document 1). Furthermore, as a photosensitive transfer material capable of fabricating color filters with reduced development load, a photosensitive transfer material comprising a temporary support on which a thermoplastic resin layer, an alkali-soluble intermediate layer, and an alkali-soluble photosensitive resin layer containing a pigment are provided in that order, wherein the difference Δγ between the dispersion component γm of the surface energy of the intermediate layer and the dispersion component γp of the surface energy of the thermoplastic resin layer is 10 egr / cm². ２ The above-mentioned photosensitive transfer material is known (see Patent Document 2).

[0004] Patent Document 1: Japanese Unexamined Patent Publication No. 2008-164842 Patent Document 2: Japanese Unexamined Patent Publication No. 2004-151506

[0005] Patterning using dry film resists requires high resolution. For example, in the manufacturing of OLEDs (Organic Light Emitting Diodes) using fine metal masks (FMMs), the increasing resolution of OLEDs necessitates the miniaturization of fine metal masks with minute through-holes, requiring hole widths of 15 μm or less.

[0006] Incidentally, there are three methods for exposing dry film resists: contact exposure, proximity exposure, and projection exposure. Of these exposure methods, contact exposure is a method that uses a relatively inexpensive exposure machine, offers high productivity, and provides relatively high resolution. In contact exposure, the shorter the distance from the mask to the resist, i.e., the exposure gap, the less blurring there is in the image, and the higher the resolution image that is faithful to the mask. Therefore, in order to form high-resolution resist patterns, attempts have been made to shorten the exposure gap by peeling off the temporary support before exposure.

[0007] However, in the case of a photosensitive transfer material having a photosensitive resin layer on the surface of a temporary support, for example, if the temporary support is peeled off and removed before exposure, the mask may stick to the surface of the photosensitive resin layer exposed by the peeling off of the temporary support, leading to mask contamination and a decrease in workability such as handling.

[0008] This disclosure has been made in view of the circumstances described above. One embodiment of this disclosure aims to solve the problem of providing a photosensitive transfer material having a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, and which can be stably peeled off between the thermoplastic resin layer and the intermediate layer when peeling off the temporary support. Another embodiment of this disclosure aims to solve the problem of providing a method for manufacturing the above-mentioned photosensitive transfer material.

[0009] The following embodiments are specific means for solving the above problems: <1> A photosensitive transfer material having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, wherein the peel force Fa between the temporary support and the thermoplastic resin layer and the peel force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship of formula (1): Fa ≥ 150 mN / cm > Fb (1) <2> The photosensitive transfer material according to <1>, wherein the thermoplastic resin layer comprises a copolymerized polyester resin. <3> The photosensitive transfer material according to <1> or <2>, wherein the temporary support has an easy-adhesion layer, and the easy-adhesion layer and the thermoplastic resin layer are in contact. <4> The photosensitive transfer material according to any one of <1> to <3>, wherein the intermediate layer is a coating film containing a polyvinyl alcohol-based resin. <5> The photosensitive transfer material according to any one of <1> to <4>, wherein the thermoplastic resin layer comprises a surfactant containing silicon. <6> A method for producing a photosensitive transfer material, comprising the steps of forming a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer on a temporary support in this order by coating and drying, wherein the peel force Fa between the temporary support and the thermoplastic resin layer and the peel force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship in formula (1): Fa ≥ 150 mN / cm > Fb (1) <7> A method for producing a photosensitive transfer material, comprising the steps of forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer on a protective film in this order by coating and drying, and bonding a temporary support to the thermoplastic resin layer by heat lamination, wherein the peel force Fa between the temporary support and the thermoplastic resin layer and the peel force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship in formula (1): Fa ≥ 150 mN / cm > Fb (1)

[0010] According to one embodiment of the present disclosure, a photosensitive transfer material is provided having a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, wherein the thermoplastic resin layer and the intermediate layer can be stably peeled off when the temporary support is peeled off. According to another embodiment of the present disclosure, a method for manufacturing the above-mentioned photosensitive transfer material is provided.

[0011] Figure 1 is a schematic cross-sectional view showing an example of the composition of a photosensitive transfer material.

[0012] The following provides a detailed description of this disclosure. While the requirements described below may be based on typical embodiments of this disclosure, this disclosure is not limited to such embodiments and may be modified as appropriate within the scope of the purposes of this disclosure.

[0013] In this disclosure, a numerical range indicated using "~" means a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0014] In this disclosure, when referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, it means the total amount of all multiple components present in the composition unless otherwise specified.

[0015] In this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0016] In this disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0017] In this disclosure, "transparent" means that the average transmittance of visible light with wavelengths of 400 nm to 700 nm is 80% or more, and preferably 90% or more. In this disclosure, "transmittance" is a value measured using a spectrophotometer. As a spectrophotometer, for example, a spectrophotometer manufactured by Hitachi, Ltd. (model number: U-3310) can be used. However, the spectrophotometer is not limited to this.

[0018] In this disclosure, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC). The GPC measurement is performed using a GPC analyzer with TSKgel® GMHxL, TSKgel® G4000HxL, or TSKgel® G2000HxL (all product names of Tosoh Corporation) as the column, tetrahydrofuran (THF) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance, and the above polystyrene-converted values ​​are measured.

[0019] In this disclosure, unless otherwise specified, the ratios of constituent units of polymer compounds are given by mass.

[0020] In this disclosure, the glass transition temperature (Tg) is a value measured using a differential scanning calorimeter. For example, a differential scanning calorimeter (model number: DSC-60) manufactured by Shimadzu Corporation can be used. However, the differential scanning calorimeter is not limited to this.

[0021] In this disclosure, unless otherwise specified, hue is a value measured using a colorimeter. For example, a colorimeter manufactured by Minolta, Inc. (model number: CR-221) can be used. However, the colorimeter is not limited to this.

[0022] In this disclosure, "(meth)acrylic" is a term that encompasses both "acrylic" and "methacrylic," "(meth)acrylate" is a term that encompasses both "acrylate" and "methacrylate," and "(meth)acryloxy" is a term that encompasses both "acryloxy" and "methacryloxy."

[0023] In this disclosure, "alkali soluble" means that the solubility in 100 g of a 1.0% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more.

[0024] In this disclosure, "water-soluble" means that the solubility in 100 g of water at a pH of 7.0 at a liquid temperature of 22°C is 0.1 g or more. For example, "water-soluble resin" means a resin that satisfies the above solubility conditions.

[0025] In this disclosure, "solids" in a composition means the components that form a layer using the composition, and if the composition contains a solvent, it means all components excluding the solvent. In addition, liquid components other than the solvent are also considered to be solids if they form a layer. In this disclosure, "solvent" means water and organic solvents.

[0026] In this disclosure, "n-" means normal, "s-" means secondary, and "t-" means tertiary.

[0027] In this disclosure, “light” means, for example, ultraviolet light, visible light, and infrared light. In this disclosure, “ultraviolet light” means light in the wavelength range of 200 nm to less than 400 nm, “visible light” means light in the wavelength range of 400 nm to less than 780 nm, and “infrared light” means light in the wavelength range of 780 nm to less than 1000 nm.

[0028] [Photosensitive Transfer Material] The photosensitive transfer material according to this disclosure comprises a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, wherein the peeling force Fa between the temporary support and the thermoplastic resin layer and the peeling force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship given by equation (1): Fa ≥ 150 mN / cm > Fb (1) The photosensitive transfer material according to this disclosure has a thermoplastic resin layer and an intermediate layer between the temporary support and the photosensitive resin layer, and when peeling off the temporary support, peeling occurs between the thermoplastic resin layer and the intermediate layer, and stable peeling is possible between the thermoplastic resin layer and the intermediate layer.

[0029] The present inventors have found that, when applying a photosensitive transfer material, if exposure is performed after peeling and removing the temporary support before exposure, a mask may adhere to the surface of the photosensitive resin layer exposed by peeling the temporary support, leading to contamination of the mask and reduced workability such as during conveyance. In order to prevent adhesion between the photosensitive resin layer and the mask, the inventors focused on, for example, configuring the photosensitive transfer material to have another layer such as a thermoplastic resin layer or an intermediate layer between the temporary support and the photosensitive resin layer, so that the surface of the photosensitive resin layer is not exposed when the temporary support is peeled off. That is, in order to adjust the adhesion balance so that the photosensitive resin layer is not exposed when peeling the temporary support among the constituent layers of the photosensitive transfer material, the inventors found that when the peeling force Fa between the temporary support and the thermoplastic resin layer and the peeling force Fb between the thermoplastic resin layer and the intermediate layer satisfy a specific relationship, it is effective for stably achieving peeling between the thermoplastic resin layer and the intermediate layer. The expression "stable peelability between the thermoplastic resin layer and the intermediate layer" means that when the temporary support is removed from the photosensitive transfer material, peeling occurs between the thermoplastic resin layer and the intermediate layer, and peeling at other interlayer interfaces is suppressed.

[0030] The photosensitive transfer material according to the present disclosure has a thermoplastic resin layer and an intermediate layer in this order from the temporary support side between the temporary support and the photosensitive resin layer, and the peeling force Fa between the temporary support and the thermoplastic resin layer and the peeling force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship of formula (1), whereby when peeling the temporary support, peeling occurs between the thermoplastic resin layer and the intermediate layer, and peeling between the thermoplastic resin layer and the intermediate layer can be stably achieved. Furthermore, while various manufacturing conditions for the photosensitive transfer material, conditions during peeling, and the like can be assumed, in any case, peeling can be caused to occur between the thermoplastic resin layer and the intermediate layer, and peeling at other interlayer interfaces can be suppressed.

[0031] In the photosensitive transfer material according to the present disclosure, if an attempt is made to peel off the temporary support before exposure, the thermoplastic resin layer is removed in addition to the temporary support. Therefore, compared with the case where only the temporary support is removed, the exposure gap when exposing the photosensitive resin layer is shortened, and formation of a higher-resolution resist pattern can be achieved. Further, in the photosensitive transfer material according to the present disclosure, since the photosensitive resin layer is not exposed by peeling off the temporary support, the mask does not come into contact with the photosensitive resin layer even when exposure is performed by a contact exposure method, and reduction in workability such as mask contamination and conveyance caused by the mask sticking to the exposed surface of the photosensitive resin layer is suppressed. Further, since the photosensitive transfer material according to the present disclosure can be stably peeled between the thermoplastic resin layer and the intermediate layer, for example, productivity of a patterned substrate or the like can be improved. In addition, manufacturing conditions for the photosensitive transfer material such as drying conditions for each layer can be flexibly set. Further, improvement in yield at the time of mask formation using the photosensitive transfer material can be achieved.

[0032] Further, the photosensitive transfer material according to the present disclosure, by including the thermoplastic resin layer, also has an effect that air bubbles (so-called lamination bubbles) are less likely to be mixed between the photosensitive transfer material and an object when the photosensitive transfer material is bonded to the object.

[0033] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a photosensitive transfer material. The photosensitive transfer material 10 shown in FIG. 1 includes a temporary support, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive resin layer 17, and a protective film 19 in this order.

[0034] The photosensitive transfer material according to the present disclosure may include layers other than the temporary support, the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer (so-called other layers). The temporary support, the thermoplastic resin layer, the intermediate layer, the photosensitive resin layer, and the other layers may each be a single layer, or may be multiple layers of two or more layers.

[0035] The photosensitive transfer material according to this disclosure comprises a temporary support, a thermoplastic resin layer (also simply referred to as the "thermoplastic resin layer"), an intermediate layer, and a photosensitive resin layer in this order, and it is preferable that the thermoplastic resin layer and the intermediate layer are in contact. The photosensitive transfer material according to this disclosure preferably further has a protective film on the photosensitive resin layer, and the structure of the photosensitive transfer material according to this disclosure is preferably a laminated structure of, for example, temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film.

[0036] The photosensitive transfer material according to this disclosure has a thermoplastic resin layer and an intermediate layer in contact, and the peel force Fa between the temporary support and the thermoplastic resin layer and the peel force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship given by equation (1): Fa ≥ 150 mN / cm > Fb (1)

[0037] It is preferable that the peel force Fa between the temporary support and the thermoplastic resin layer, and the peel force Fb between the thermoplastic resin layer and the intermediate layer satisfy equation (2): Fa ≥ 150 mN / cm and 80 > Fb (2) It is even more preferable that the peel force Fa between the temporary support and the thermoplastic resin layer, and the peel force Fb between the thermoplastic resin layer and the intermediate layer satisfy equation (3): Fa ≥ 200 mN / cm and 50 > Fb (3)

[0038] When the peeling force Fa between the temporary support and the thermoplastic resin layer, and the peeling force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship in the above formula, the balance of the peeling forces of the three layers becomes favorable, allowing for peeling between the thermoplastic resin layer and the intermediate layer when peeling off the temporary support, and enabling stable peeling between the thermoplastic resin layer and the intermediate layer.

[0039] The peel force Fa between the temporary support and the thermoplastic resin layer, and the peel force Fb between the thermoplastic resin layer and the intermediate layer in the photosensitive transfer material according to this disclosure are measured by the following method. The photosensitive transfer material is cut to a size of 30 mm x 100 mm, and if a protective film is present, the protective film is removed. The surface of the exposed photosensitive resin layer is attached to a 0.7 mm thick glass using double-sided tape (STT-125FK, manufactured by Soken Chemical Co., Ltd.). A 180° peel test is performed on the laminate attached to the glass using a Tensilon (Tensilon universal tester manufactured by A&D Co., Ltd.), in which the temporary support held at one end is peeled 180° toward the other end, under conditions of a temperature of 25°C and a peeling speed of 300 mm / min, and the peel force Fb is measured. At this time, the photosensitive transfer material after measuring the peel force Fb is observed to confirm that delamination has occurred between the thermoplastic resin layer and the intermediate layer.

[0040] Next, the peel force Fa between the temporary support and the thermoplastic resin layer is measured by the following method. After measuring the peel force between the thermoplastic resin layer and the intermediate layer, the exposed surface of the thermoplastic resin layer is attached to a 0.7 mm thick glass using double-sided tape (STT-125FK, manufactured by Soken Chemical Co., Ltd.). A 180° peel test is performed on the laminate attached to the glass using a Tensilon (Tensilon universal tester manufactured by A&D Co., Ltd.), in which the temporary support, held at one end, is peeled 180° toward the other end, under conditions of a temperature of 25°C and a peeling speed of 300 mm / min, and the peel force Fa is measured. As the Tensilon, for example, the RTF-1210 (model number), a Tensilon universal material tester manufactured by A&D Co., Ltd., can be suitably used. However, the Tensilon is not limited to this.

[0041] The components of the photosensitive transfer material relating to this disclosure will be described in detail below.

[0042] <Temporary Support> The photosensitive transfer material according to this disclosure has a temporary support. The temporary support is a member that supports the transfer layer and is ultimately removed by peeling. In this disclosure, "transfer layer" means a layer other than the temporary support in the photosensitive transfer material, which is placed on an object by bonding the photosensitive transfer material to the object in the use of the photosensitive transfer material. In one embodiment, the transfer layer is a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer.

[0043] The temporary support is preferably a film, and more preferably a resin film. The temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat. Specific examples of temporary supports include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. Polyethylene terephthalate film is preferred as the temporary support. The film used as the temporary support is preferably free from deformation such as wrinkles and scratches.

[0044] From the viewpoint of enabling pattern exposure through a temporary support, it is preferable that the temporary support has high transparency. For example, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, and more preferably 70% or more. The transmittance is calculated as the ratio of the amount of light emitted from the temporary support to the amount of light incident on the temporary support (= emitted light amount / incident light amount × 100; %).

[0045] From the viewpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable that the haze of the temporary support be small. Specifically, the haze value of the temporary support is preferably 5% or less, more preferably 2% or less, even more preferably 0.5% or less, and particularly preferably 0.1% or less. The lower limit of the haze value of the temporary support may be 0.01% or 0.001%. The haze value is measured using a haze meter [e.g., NDH400 haze meter manufactured by Nippon Denshoku Industries, Ltd.].

[0046] From the viewpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable to have a small number of coarse particles, foreign matter, and defects in the temporary support. The total number of particles with a diameter of 1 μm or more, foreign matter, and defects in the temporary support should be 50 per 10 mm. ２ The following is preferable: 10 pieces / 10 mm ２ More preferably, 3 pieces / 10 mm ２ More preferably, the following is true: 0 pieces / 10 mm ２ It is particularly preferable that this be the case.

[0047] From the viewpoint of resolution in pattern exposure via a temporary support, the thickness of the temporary support is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. Furthermore, the thickness of the temporary support is preferably 5 μm or more, and more preferably 10 μm or more. The thickness of the temporary support refers to the average thickness calculated by the arithmetic mean of the thicknesses of five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0048] Preferred temporary supports include, for example, a biaxially oriented polyethylene terephthalate film with a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film with a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film with a thickness of 9 μm.

[0049] Commercially available temporary supports can be used. Examples of commercially available temporary supports include Lumirror® 16QS62, Lumirror® 16KS40, Lumirror® 16FB40, Lumirror® #38-U48, Lumirror® #75-U34, and Lumirror® #25T60 (all manufactured by Toray Industries, Inc.), as well as Cosmoshine® A4100, Cosmoshine® A4160, Cosmoshine® A4300, Cosmoshine® A4360, and Cosmoshine® A8300 (all manufactured by Toyobo Co., Ltd.).

[0050] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Publication No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Publication No. 2016-27363, paragraphs 0041 to 0057 of International Publication No. 2012 / 081680, paragraphs 0029 to 0040 of International Publication No. 2018 / 179370, and paragraphs 0012 to 0032 of Japanese Patent Publication No. 2019-101405. The contents of the above publications are incorporated herein by reference.

[0051] From the viewpoint of handling, the temporary support may have a layer containing fine particles (also called a "lubricant layer"). The lubricant layer is preferably arranged as the outermost layer on one or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is not particularly limited, but is preferably, for example, 0.05 μm to 0.8 μm. The average thickness of the lubricant layer is not particularly limited, but is preferably, for example, 0.05 μm to 1.0 μm.

[0052] In the photosensitive transfer material according to this disclosure, the temporary support preferably has an easy-adhesion layer. The easy-adhesion layer is in contact with the thermoplastic resin layer. The easy-adhesion layer improves the adhesion when the surface of the temporary support and the thermoplastic resin layer are in direct contact, and can increase the peeling force Fa on the temporary support side so that the peeling surface in the subsequent process is guided to a desired interface (i.e., the interface between the thermoplastic resin layer and the intermediate layer). In other words, the easy-adhesion layer strengthens the adhesion on the temporary support side and optimizes the bonding state with the thermoplastic resin layer, making it easier to achieve the peeling force relationship shown in equation (1) during peeling.

[0053] The easily adhering layer is not necessarily limited to a specific material and may be formed by surface treatment of the temporary support (for example, surface modification by plasma treatment, corona discharge treatment, or ultraviolet irradiation), or it may be a layer formed on the temporary support by methods such as coating, spraying, vapor deposition, or roll coating, but a layer formed on the temporary support by methods such as coating, spraying, vapor deposition, or roll coating is preferred. Specifically, it is desirable to form a layer on the surface of the temporary support to a thickness of several tens of nanometers to several micrometers using a polyurethane-based, modified polyolefin-based, or other suitable polymer material that has an adhesion-promoting effect. Providing an easily adhering layer is preferable because it exhibits good mutual adhesion with the thermoplastic resin layer, while in the transfer process, it is easier to induce interfacial delamination with the subsequent intermediate layer and photosensitive resin layer, thus preventing excessive adhesive strength.

[0054] The presence of an easy-adhesion layer in the temporary support improves initial adhesion at the interface with the thermoplastic resin layer, reducing contact failures and localized bubble formation during the lamination process. Furthermore, sufficient peeling force is more easily generated between the temporary support and the thermoplastic resin layer during delamination, resulting in uniform and stable delamination between the thermoplastic resin layer and the intermediate layer. This improves the reproducibility of the manufacturing process and the accuracy of the final pattern for the entire transfer material.

[0055] <Thermoplastic Resin Layer> The photosensitive transfer material according to this disclosure has a thermoplastic resin layer. Preferably, the thermoplastic resin layer is a thermoplastic resin layer with high thermoplasticity. Preferably, the thermoplastic resin layer contains a polyester resin. Because the photosensitive transfer material has a thermoplastic resin layer with high thermoplasticity, it is preferable that, for example, when bonding to an object, it is difficult to introduce air bubbles between the material and the object, and that it tends to have excellent adhesion to the object. In addition, it is easier to appropriately balance the peel force between the thermoplastic resin layer and the adjacent layer, and when peeling, the relationship of peel force shown in formula (1) is easily achieved.

[0056] (Copolymerized polyester resin) The thermoplastic resin layer preferably contains copolymerized polyester resin. By including copolymerized polyester resin in the thermoplastic resin layer, the crystallinity and melting point are lower compared to polyester resins other than copolymerized polyester resin, and therefore the thermoplastic resin layer containing the copolymerized polyester resin layer tends to have high thermoplasticity.

[0057] In this disclosure, "copolymerized polyester resin" means a polyester resin in which at least one of the repeating units constituting the polyester resin, namely the dicarboxylic acid units and the diol component units, consists of multiple types of constituent units. The dicarboxylic acid units and diol component units constituting the copolymerized polyester resin may consist of one type of dicarboxylic acid unit and two or more types of diol component units, or may consist of two or more types of dicarboxylic acid units and one type of diol component unit, or may consist of two or more types of dicarboxylic acid units and two or more types of diol component units.

[0058] The copolymerized polyester resin may be a crystalline copolymerized polyester resin or an amorphous copolymerized polyester resin, but an amorphous copolymerized polyester resin is preferred.

[0059] Examples of dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid (orthophthalic acid), and 2,6-naphthalenedicarboxylic acid. Examples of diol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, bisphenol A, and ethylene oxide adducts of bisphenol A.

[0060] The copolymerized polyester resin preferably contains structural units derived from monomers having aromatic rings. When the copolymerized polyester resin contains structural units derived from monomers having aromatic rings, for example, when the temporary support is polyethylene terephthalate, the adhesion between the thermoplastic resin layer and the temporary support tends to improve due to π-electron interactions (π-π stacking). Furthermore, when the copolymerized polyester resin contains structural units derived from monomers having aromatic rings, the glass transition temperature (Tg) increases appropriately, which tends to further improve the peelability between the thermoplastic resin layer and the intermediate layer. Examples of monomers having aromatic rings include dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid (orthophthalic acid), and 2,6-naphthalenedicarboxylic acid. Other examples of monomers having aromatic rings include diol components such as bisphenol A and ethylene oxide adducts of bisphenol A.

[0061] Copolymerized polyester resins may contain constituent units derived from monomers other than dicarboxylic acids and diol components (hereinafter also referred to as "other monomers"). Examples of other monomers include monomers having three or more carboxyl groups, such as tricarboxylic acids and tetracarboxylic acids, and monomers having three or more hydroxyl groups, such as triol components and tetraol components. By copolymerizing small amounts of these monomers, branched copolymerized polyesters can be obtained, and the melt viscosity of the copolymerized polyester can be adjusted. Examples of tricarboxylic acids include trimellitic acid and 1,3,5-benzenetricarboxylic acid. Examples of triol components include glycerin and 1,2,4-butanetriol.

[0062] The total content of dicarboxylic acid units and diol components in the copolymerized polyester resin is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 99% by mass or more, relative to the total units constituting the copolymerized polyester resin. The upper limit of the total content of dicarboxylic acid units and diol components in the copolymerized polyester resin is not particularly limited, but for example, it may be 100% by mass relative to the total units constituting the copolymerized polyester resin.

[0063] From the viewpoint of excellent peelability between the thermoplastic resin layer and the intermediate layer, the copolymerized polyester resin preferably has a number average molecular weight in the range of 3,000 to 30,000 and a glass transition temperature in the range of -20°C to 80°C, more preferably has a number average molecular weight in the range of 4,000 to 20,000 and a glass transition temperature in the range of 10°C to 50°C, even more preferably has a number average molecular weight in the range of 5,000 to 10,000 and a glass transition temperature in the range of 20°C to 50°C, and particularly preferably has a number average molecular weight in the range of 6,000 to 10,000 and a glass transition temperature in the range of 30°C to 45°C.

[0064] When a thermoplastic resin layer contains two or more copolymerized polyester resins, the number-average molecular weight and glass transition temperature of the copolymerized polyester resins both represent weighted average values.

[0065] Commercially available copolymer polyester resins can be used. Examples of commercially available copolymer polyester resins include, for example, Byron® BX-1001 [Mn: 28000, Tg: -18℃, manufactured by Toyobo Co., Ltd.], Byron® GK-800 [Mn: 27000, Tg: 50℃, manufactured by Toyobo Co., Ltd.], Byron® 802 [Mn: 3000, Tg: 60℃, manufactured by Toyobo Co., Ltd.], Byron® 670 [Mn: 30000, Tg: 7℃, manufactured by Toyobo Co., Ltd.], Byron® GK-830 [Mn: 32000, Tg: 25℃, manufactured by Toyobo Co., Ltd.], Byron® GK-140 [Mn: 13000, Tg: 20℃, manufactured by Toyobo Co., Ltd.], and Byron® Examples include GK-780 [Mn: 11000, Tg: 36℃, manufactured by Toyobo Co., Ltd.], Byron® GK-810 [Mn: 6000, Tg: 46℃, manufactured by Toyobo Co., Ltd.], Byron® GK-590 [Mn: 7000, Tg: 15℃, manufactured by Toyobo Co., Ltd.], and Byron® GK-890 [Mn: 11000, Tg: 17℃, manufactured by Toyobo Co., Ltd.].

[0066] The thermoplastic resin layer may contain only one type of copolymerized polyester resin, or it may contain two or more types.

[0067] From the viewpoint of achieving superior peelability between the thermoplastic resin layer and the intermediate layer, the content of copolymerized polyester resin in the thermoplastic resin layer is preferably in the range of 10% to 100% by mass, more preferably in the range of 50% to 100% by mass, even more preferably in the range of 60% to 100% by mass, even more preferably in the range of 70% to 100% by mass, even more preferably in the range of 80% to 100% by mass, and even more preferably in the range of 90% to 100% by mass.

[0068] (Various Additives) The thermoplastic resin layer may contain known additives as needed, to the extent that it does not impair the effects of the present disclosure. Examples of additives include polymerization inhibitors, surfactants, and solvents.

[0069] The thermoplastic resin layer may contain a polymerization inhibitor. The polymerization inhibitor in the thermoplastic resin layer is the same as the polymerization inhibitor in the photosensitive resin layer described later, and the preferred embodiment is the same.

[0070] If the thermoplastic resin layer contains a polymerization inhibitor, it may contain only one polymerization inhibitor or two or more.

[0071] When the thermoplastic resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor in the thermoplastic resin layer is preferably in the range of 0.01% by mass or more and 10% by mass or less, more preferably in the range of 0.1% by mass or more and 1% by mass or less, and even more preferably in the range of 0.1% by mass or more and 0.5% by mass or less, based on the total mass of the thermoplastic resin layer.

[0072] The thermoplastic resin layer may contain a surfactant. The surfactant in the thermoplastic resin layer is the same as the surfactant in the photosensitive resin layer described later, and the preferred embodiments are also the same. For example, when the thermoplastic resin layer contains a surfactant, it is preferable that the thermoplastic resin layer contains a silicon-containing surfactant from the viewpoint of release properties between it and the intermediate layer. Furthermore, when the thermoplastic resin layer contains a surfactant, it is preferable that the surfactant is a silicon-containing surfactant from the viewpoint of improving environmental suitability.

[0073] If the thermoplastic resin layer contains a surfactant, it may contain only one type of surfactant or two or more types.

[0074] When the thermoplastic resin layer contains a surfactant, the surfactant content in the thermoplastic resin layer is preferably in the range of 0.001% by mass or more and 1% by mass or less, more preferably in the range of 0.01% by mass or more and 1% by mass or less, and even more preferably in the range of 0.1% by mass or more and 0.5% by mass or less, relative to the total mass of the thermoplastic resin layer.

[0075] The thermoplastic resin layer may contain a solvent. When a thermoplastic resin layer is formed using a composition containing a solvent, the solvent may remain in the thermoplastic resin layer.

[0076] Furthermore, the thermoplastic resin layer may contain known additives such as rust inhibitors, antioxidants, colorants, plasticizers, and polymerizable compounds.

[0077] The thermoplastic resin layer is preferably a coated film. In this disclosure, "coated film" means a film formed by coating and drying. Since the copolymerized polyester resin contained in the thermoplastic resin layer has high solubility in organic solvents, the thermoplastic resin layer can be formed by a coating method. The coating method makes it possible to obtain a thermoplastic resin layer with high thickness uniformity and smoothness. Compared to, for example, the melt extrusion lamination method, the coating method is less likely to produce surface defects such as fisheyes, streaks, and unevenness. When the thermoplastic resin layer is a coated film, surface defects in the thermoplastic resin layer are less likely to affect the surface state of the intermediate layer, resulting in fewer defects in the resist pattern, and it tends to be easier to obtain a high-resolution resist pattern.

[0078] <<Thickness of the Thermoplastic Resin Layer>> The thickness of the thermoplastic resin layer is preferably 1 μm to 15 μm, more preferably 2 μm to 12 μm, and even more preferably 4 μm to 10 μm. A thickness of 1 μm or more tends to result in good transferability during lamination. A thickness of 15 μm or less makes it easier to satisfy equation (1) in terms of the peel force Fb between the thermoplastic resin and the intermediate layer. In other words, when the thickness of the thermoplastic resin layer is within the above range, the adhesion between the temporary support and the thermoplastic resin layer is good, and when peeling off the temporary support, peeling occurs between the thermoplastic resin layer and the intermediate layer, and the peelability between the thermoplastic resin layer and the intermediate layer tends to be superior, making it easier to achieve the peel force relationship shown in equation (1) during peeling. In addition, it is possible to have the effect of making it less likely to introduce air bubbles (so-called lamination bubbles) between the object and the object when bonding to the object. The thickness of the thermoplastic resin refers to the average thickness calculated by the arithmetic mean of the thicknesses of five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0079] <Method for forming a thermoplastic resin layer> The method for forming a thermoplastic resin layer is not particularly limited as long as the desired thermoplastic resin layer can be obtained. For example, a method for forming a thermoplastic resin layer may be prepared by preparing a thermoplastic resin layer-forming composition containing a thermoplastic resin including a copolymerized polyester resin and an optional additive, applying the prepared thermoplastic resin layer-forming composition to a temporary support or intermediate layer, and drying the applied thermoplastic resin layer-forming composition.

[0080] The composition for forming a thermoplastic resin layer preferably contains a solvent, from the viewpoint of facilitating the formation of the thermoplastic resin layer by adjusting its viscosity. Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone (MEK)), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., ethyl acetate), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0081] Preferably, the solvent is one containing at least one selected from the group consisting of alkylene glycol ether acetate solvents, ketone solvents, aromatic hydrocarbon solvents, and ester solvents. More preferably, the solvent is a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents, aromatic hydrocarbon solvents, and ester solvents. Even more preferably, the solvent is a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether acetate solvents, at least one selected from the group consisting of ketone solvents and ester solvents, and at least one selected from aromatic hydrocarbon solvents.

[0082] Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate [e.g., 1-methoxy-2-propyl acetate (MMPGAc)], diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. Examples of ketone solvents include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, diisobutyl ketone, and diacetone alcohol. Examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl lactate, ethyl lactate, and propyl lactate. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, Solvesso 100, Solvesso 150, and Solvesso 200.

[0083] If the thermoplastic resin layer forming composition contains a solvent, it may contain only one type of solvent or two or more types of solvents.

[0084] When the thermoplastic resin layer forming composition contains a solvent, the solvent content when applying the thermoplastic resin layer forming composition is preferably 50 to 1900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids in the thermoplastic resin layer forming composition.

[0085] The method for preparing the thermoplastic resin layer-forming composition is not particularly limited. For example, one method involves preparing a solution in which each component is dissolved in the solvent, and then mixing the resulting solution in a predetermined ratio to prepare the thermoplastic resin layer-forming composition. It is preferable to filter the thermoplastic resin layer-forming composition using a filter with a pore size of 0.2 μm to 30 μm before forming the thermoplastic resin layer.

[0086] The method for applying the thermoplastic resin layer-forming composition is not particularly limited and can be applied by known methods. Examples of application methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0087] As a drying method for the applied thermoplastic resin layer-forming composition, heat drying and vacuum drying are preferred. In this disclosure, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. The above methods can be applied individually or in combination. The drying temperature is preferably 70°C or higher, and more preferably 80°C or higher. The upper limit of the drying temperature is not particularly limited, but for example, it is preferably 180°C or lower, and more preferably 150°C or lower. The applied thermoplastic resin layer-forming composition may be dried by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. The upper limit of the drying time is not particularly limited, but for example, it is preferably 600 seconds or lower, and more preferably 300 seconds or lower. By setting the drying conditions of the thermoplastic resin layer-forming composition as described above, the peel force relationship shown in formula (1) is more easily achieved during peeling.

[0088] <Intermediate Layer> The photosensitive transfer material according to this disclosure has an intermediate layer. The photosensitive transfer material according to this disclosure has a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, and when the temporary support is peeled off, peeling occurs between the thermoplastic resin layer and the intermediate layer. For this reason, in order to obtain a high-resolution resist pattern, if the exposure gap is shortened by peeling off the temporary support and contact exposure is performed, the mask will be brought into close contact with the side of the intermediate layer opposite to the photosensitive resin layer. The photosensitive transfer material according to this disclosure has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer, and when exposure, the mask can be brought into contact with the intermediate layer. Therefore, compared to, for example, when peeling off the temporary support, peeling occurs between the temporary support and the thermoplastic resin layer and the mask is brought into contact with the thermoplastic resin layer, the mask tends to be less likely to adhere to the layer it is in contact with, and less likely to be affected by a decrease in workability.

[0089] (Water-soluble resin) The intermediate layer preferably contains a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol-based resins (e.g., polyvinyl alcohol), polyvinylpyrrolidone-based resins (e.g., polyvinylpyrrolidone), cellulose-based resins (e.g., hydroxypropyl methylcellulose), acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and resins that are copolymers thereof. From the viewpoint of suppressing the mixing of components between adjacent layers, the water-soluble resin contained in the intermediate layer is preferably a resin that is different from both the thermoplastic resin contained in the thermoplastic resin layer and the resin contained in the photosensitive resin layer (e.g., alkali-soluble resin).

[0090] The intermediate layer preferably contains polyvinyl alcohol, more preferably contains polyvinyl alcohol and polyvinylpyrrolidone, and even more preferably contains polyvinyl alcohol, polyvinylpyrrolidone, and hydroxypropyl methylcellulose, from the viewpoint of oxygen barrier properties and suppression of mixing of components between adjacent layers during application and storage after application. Furthermore, the inclusion of the above compounds in the intermediate layer makes it easier to achieve the peeling force relationship shown in formula (1) during peeling.

[0091] Examples of commercially available polyvinyl alcohol include Kuraray Poval (registered trademark) PVA 4-88LA [manufactured by Kuraray Co., Ltd.]. Examples of commercially available polyvinylpyrrolidone include polyvinylpyrrolidone K-30 [manufactured by Nippon Shokubai Co., Ltd.]. Examples of commercially available hydroxypropyl methylcellulose include Metroze (registered trademark) 60SH-03 [manufactured by Shin-Etsu Chemical Co., Ltd.].

[0092] The intermediate layer is preferably a coated film containing a water-soluble resin. When the intermediate layer contains a water-soluble resin, the peelability between the thermoplastic resin layer and the intermediate layer tends to be better. Also, because the intermediate layer contains a water-soluble resin, it can be formed by a coating method. With the coating method, an intermediate layer with high thickness uniformity and smoothness can be obtained. In addition, the coating method is less likely to cause surface defects such as fisheyes, streaks, and unevenness. When the intermediate layer is a coated film, defects in the resist pattern caused by surface defects in the intermediate layer are less likely to occur, and a higher resolution resist pattern tends to be easier to obtain.

[0093] The intermediate layer is more preferably a coating film containing a polyvinyl alcohol-based resin as a water-soluble resin, and more preferably a coating film containing polyvinyl alcohol, even more preferably a coating film containing polyvinyl alcohol and polyvinylpyrrolidone, and particularly preferably a coating film containing polyvinyl alcohol, polyvinylpyrrolidone, and hydroxypropyl methylcellulose.

[0094] If the intermediate layer contains a water-soluble resin, it may contain only one type of water-soluble resin or two or more types.

[0095] When the intermediate layer contains a water-soluble resin, the content of the water-soluble resin in the intermediate layer is not particularly limited, but from the viewpoint of oxygen barrier properties and suppressing the mixing of components between adjacent layers during coating and storage after coating, it is preferable that the content be in the range of 50% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, relative to the total mass of the intermediate layer.

[0096] (Various Additives) The intermediate layer may contain known additives as needed, to the extent that it does not impair the effects of the present disclosure. Examples of additives include surfactants, particles, and solvents.

[0097] The intermediate layer may contain a surfactant. The surfactant in the intermediate layer is the same as the surfactant in the photosensitive resin layer described later, and the preferred embodiment is the same.

[0098] If the intermediate layer contains a surfactant, it may contain only one type of surfactant or two or more types.

[0099] If the intermediate layer contains a surfactant, the surfactant content in the intermediate layer is preferably in the range of 0.001% by mass or more and 1% by mass or less, more preferably in the range of 0.01% by mass or more and 0.5% by mass or less, and even more preferably in the range of 0.05% by mass or more and 0.2% by mass or less, relative to the total mass of the intermediate layer.

[0100] The intermediate layer may contain particles. When the intermediate layer contains particles, for example, even when the mask is brought into contact with the intermediate layer during contact exposure, the intermediate layer is less likely to adhere to the mask. As a result, problems such as contamination caused by the intermediate layer adhering to the mask, and a decrease in workability, which are caused by the intermediate layer adhering to the mask, tend to be suppressed.

[0101] The particles are preferably inorganic particles. Metal oxide particles are preferred as inorganic particles. The metals in the metal oxide particles include metalloids such as B, Si, Ge, As, Sb, and Te.

[0102] The average primary particle diameter of the particles is not particularly limited, but is preferably 1 nm to 200 nm, and more preferably 3 nm to 80 nm, from the viewpoint of suppressing the increase in haze in the intermediate layer and obtaining a high-resolution resist pattern. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and taking the arithmetic mean of the measurement results. If the shape of the particles is not spherical, the longest side is used as the particle diameter.

[0103] The intermediate layer, if it contains inorganic particles, may contain only one type of particle with different metal types, sizes, etc., or it may contain two or more types. Furthermore, the intermediate layer may also contain organic particles.

[0104] If the intermediate layer contains particles, the particle content in the intermediate layer is not particularly limited, but is preferably in the range of 1% to 50% by mass, more preferably in the range of 5% to 40% by mass, and even more preferably in the range of 10% to 30% by mass, relative to the total mass of the intermediate layer.

[0105] <<Thickness of the Intermediate Layer>> The thickness of the intermediate layer is preferably 0.5 μm to 10 μm, more preferably 1 μm to 8 μm, and even more preferably 2 μm to 5 μm. A thickness of 0.5 μm or more results in good peel force Fb between the thermoplastic resin layer and the intermediate layer. A thickness of 10 μm or less tends to result in good transferability during lamination. Therefore, the relationship of peel force shown in formula (1) is more easily achieved during peeling. Furthermore, if the thickness of the intermediate layer is within the above range, for example, it is possible to suppress the mixing of components between adjacent layers during coating and storage after coating without reducing oxygen barrier properties, and to suppress the increase in the removal time of the intermediate layer during development. The thickness of the intermediate layer refers to the average thickness calculated by the arithmetic mean of the thicknesses of five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0106] <Method for forming the intermediate layer> The method for forming the intermediate layer is not limited as long as the desired intermediate layer can be obtained. Examples of methods for forming the intermediate layer include preparing an intermediate layer forming composition containing a water-soluble resin and an optional additive, applying the prepared intermediate layer forming composition to a thermoplastic resin layer or a photosensitive resin layer, and drying the applied intermediate layer forming composition.

[0107] The intermediate layer-forming composition preferably contains a solvent, from the viewpoint of facilitating the formation of the intermediate layer by adjusting its viscosity. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Among these, alcohols having 1 to 3 carbon atoms are preferred as the water-miscible organic solvent, methanol or ethanol is more preferred, and methanol is even more preferred.

[0108] If the intermediate layer-forming composition contains a solvent, it may contain only one type of solvent or two or more types of solvents.

[0109] When the intermediate layer forming composition contains a solvent, the solvent content when applying the intermediate layer forming composition is preferably 50 to 1900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids in the intermediate layer forming composition.

[0110] The method for preparing the intermediate layer-forming composition is not particularly limited. For example, one method involves preparing a solution in which each component is dissolved in the solvent, and then mixing the resulting solution in a predetermined ratio to prepare the intermediate layer-forming composition. It is preferable to filter the intermediate layer-forming composition using a filter with a pore size of 0.2 μm to 30 μm before forming the intermediate layer.

[0111] The method for coating the intermediate layer-forming composition is not particularly limited and can be done by known methods. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0112] Preferred drying methods for the applied intermediate layer-forming composition include heating and vacuum drying. Examples of drying methods include natural drying, heating, and vacuum drying. These methods can be applied individually or in combination. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. The upper limit of the drying temperature is not particularly limited, but for example, it is preferably 180°C or lower, and more preferably 150°C or lower. The applied intermediate layer-forming composition may be dried by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. The upper limit of the drying time is not particularly limited, but for example, it is preferably 600 seconds or lower, and more preferably 300 seconds or lower. Under the above drying conditions, the peeling force relationship shown in formula (1) is more easily achieved during peeling.

[0113] <Photosensitive Resin Layer> The photosensitive transfer material according to this disclosure has a photosensitive resin layer. According to the photosensitive transfer material according to this disclosure, for example, a pattern can be formed on the transfer object by transferring the photosensitive resin layer onto the transfer object and then performing exposure and development.

[0114] The photosensitive resin layer may be a positive-type photosensitive resin layer or a negative-type photosensitive resin layer, but a negative-type photosensitive resin layer is preferred. A negative-type photosensitive resin layer is a photosensitive resin layer in which the solubility of the exposed area in the developer decreases upon exposure. When the photosensitive resin layer is a negative-type photosensitive resin layer, the formed pattern corresponds to the cured layer.

[0115] (Polymer) The photosensitive resin layer preferably contains a polymer. The type of polymer is not particularly limited. A preferred polymer is, for example, an alkali-soluble resin. An example of an alkali-soluble resin is a known alkali-soluble resin used in etching resists. The alkali-soluble resin is preferably a binder polymer. The alkali-soluble resin is preferably an alkali-soluble resin having acid groups. A preferred alkali-soluble resin is polymer A, which will be described later.

[0116] The acid value of polymer A is preferably 220 mg KOH / g or less, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g, from the viewpoint of further improving resolution by suppressing swelling of the photosensitive resin layer by the developer. Furthermore, from the viewpoint of superior developability, the acid value of polymer A is preferably 60 mg KOH / g or more, more preferably 120 mg KOH / g or more, even more preferably 150 mg KOH / g or more, and particularly preferably 170 mg KOH / g or more. The acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample. The acid value is calculated, for example, from the average content of acid groups in the compound. The acid value of polymer A is adjusted, for example, by the type of constituent units that make up polymer A and the content of constituent units having acid groups.

[0117] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. A weight-average molecular weight of polymer A is more preferably 100,000 or less, and even more preferably 80,000 or less. On the other hand, a weight-average molecular weight of polymer A of 5,000 or more is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film in the photosensitive resin layer, such as edge fusing and cut-tip properties. A weight-average molecular weight of polymer A is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fusing refers to the degree to which the photosensitive resin layer easily spills out from the end face of a roll when the photosensitive transfer material is wound into a roll. Cut-tip properties refer to the degree to which chips easily fly off when the unexposed film is cut with a cutter. If the chip adheres to the surface of the photosensitive resin layer, it will be transferred to the mask during the exposure process, causing defective products. The degree of dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. The degree of dispersion is the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight). In this disclosure, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) are measured using gel permeation chromatography.

[0118] Polymer A preferably has aromatic hydrocarbon groups, and more preferably has constituent units having aromatic hydrocarbon groups, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure. Examples of aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of constituent units having aromatic hydrocarbon groups in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of polymer A. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. When polymer A contains multiple types, the content of constituent units having aromatic hydrocarbon groups is determined as the weight average.

[0119] Examples of monomers that form structural units having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Among these, monomers having aralkyl groups or styrene are preferred as monomers that form structural units having aromatic hydrocarbon groups.

[0120] Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups. Preferably, the aralkyl group is a substituted or unsubstituted benzyl group.

[0121] Examples of monomers having phenylalkyl groups other than substituted or unsubstituted benzyl groups include phenylethyl (meth)acrylate.

[0122] Examples of monomers having substituted or unsubstituted benzyl groups include (meth)acrylates having substituted or unsubstituted benzyl groups [e.g., benzyl (meth)acrylate and chlorobenzyl (meth)acrylate]; and vinyl monomers having benzyl groups [e.g., vinylbenzyl chloride and vinylbenzyl alcohol]. Among these, benzyl (meth)acrylate is preferred as the monomer having substituted or unsubstituted benzyl groups.

[0123] In one embodiment, when the monomer forming the constituent unit having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the constituent unit derived from benzyl (meth)acrylate is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, even more preferably 70% to 90% by mass, and particularly preferably 75% to 90% by mass, based on the total mass of polymer A.

[0124] In one embodiment, when the monomer forming the constituent unit having an aromatic hydrocarbon group in polymer A is styrene, the content of the styrene-derived constituent unit is preferably 20% to 60% by mass, more preferably 25% to 60% by mass, even more preferably 30% to 60% by mass, and particularly preferably 30% to 55% by mass, based on the total mass of polymer A.

[0125] Polymer A having a constituent unit having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0126] Polymer A, which does not have a constituent unit having an aromatic hydrocarbon group, is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0127] The first monomer is a monomer having a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half-ester. Among these, (meth)acrylic acid is preferred as the first monomer.

[0128] The content of the constituent units derived from the first monomer in polymer A is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass, based on the total mass of polymer A.

[0129] The second monomer is non-acidic and has at least one ethylenically unsaturated group in its 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 alcohols such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred as the second monomer, with methyl (meth)acrylate being more preferred.

[0130] The content of the constituent units derived from the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and even more preferably 15% to 45% by mass, based on the total mass of polymer A.

[0131] From the viewpoint of suppressing line width thickening and resolution deterioration when the focal position shifts during exposure, polymer A preferably contains at least one constituent unit selected from the group consisting of constituent units having an aralkyl group and constituent units derived from styrene. As polymer A, for example, copolymers containing benzyl methacrylate, styrene, and methacrylic acid, copolymers containing styrene, methacrylic acid, and methyl methacrylate, and copolymers containing benzyl methacrylate, styrene, methacrylic acid, and methyl methacrylate are preferred.

[0132] In one embodiment, polymer A is preferably a polymer containing 40% to 60% by mass of constituent units having aromatic hydrocarbon groups, 15% to 25% by mass of constituent units derived from the first monomer, and 20% to 40% by mass of constituent units derived from the second monomer.

[0133] Polymer A may have a branched structure and / or an alicyclic structure in its side chains. A branched structure or an alicyclic structure can be introduced into the side chains of polymer A by using a monomer containing a group having a branched structure in its side chains, or a monomer containing a group having an alicyclic structure in its side chains. The alicyclic structure may be monocyclic or polycyclic.

[0134] Examples of monomers containing a group having a branched structure in its side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate are preferred monomers containing a group having a branched structure in its side chain, with i-propyl methacrylate or t-butyl methacrylate being more preferred.

[0135] Examples of monomers containing a group with an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Examples of monomers containing a group with an alicyclic structure in its side chain include (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms. More specific examples of monomers containing a group with an alicyclic structure in its side chain include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid-2-methyl-2-adamantyl, (meth)acrylic acid-2-ethyl-2-adamantyl, (meth) Examples include 3-hydroxy-1-adamantyl acrylic acid, 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, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among these, monomers containing a group having an alicyclic structure in its side chain include cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate, with cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate being more preferred.

[0136] The photosensitive resin layer may contain only one type of polymer A, or two or more types of polymer A. When the photosensitive resin layer contains two or more types of polymer A, it is preferable to use a mixture of two types of polymer A having aromatic hydrocarbon groups, or to use a mixture of polymer A having aromatic hydrocarbon groups and polymer A not having aromatic hydrocarbon groups. In the latter case, the content of polymer A having aromatic hydrocarbon groups 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.

[0137] The synthesis of polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring. The synthesis of polymer A may also be carried out by adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods.

[0138] The glass transition temperature (also called "Tg") of polymer A is preferably in the range of 30°C to 150°C. By using polymer A having a Tg of 150°C or less in the photosensitive resin layer, line width thickening or deterioration of resolution when the focal position shifts during exposure can be suppressed. From this viewpoint, the Tg of polymer A is more preferably 140°C or less, and even more preferably 135°C or less. Furthermore, using polymer A having a Tg of 30°C or higher is preferable from the viewpoint of improving edge fusing resistance. From this viewpoint, the Tg of polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0139] If the photosensitive resin layer contains an alkali-soluble resin, it may contain only one type of alkali-soluble resin or two or more types.

[0140] When the photosensitive resin layer contains an alkali-soluble resin, the content of the alkali-soluble resin in the photosensitive resin layer is not particularly limited, but for example, it is preferably 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass, relative to the total mass of the photosensitive resin layer. It is preferable from the viewpoint of controlling the development time to set the content of the alkali-soluble resin in the photosensitive resin layer to 90% by mass or less relative to the total mass of the photosensitive resin layer. On the other hand, it is preferable from the viewpoint of improving edge fusing resistance to set the content of the alkali-soluble resin in the photosensitive resin layer to 10% by mass or more relative to the total mass of the photosensitive resin layer.

[0141] The photosensitive resin layer may contain resins other than alkali-soluble resins. The resin other than alkali-soluble resins should be one in which the solubility in 100 g of a 1.0% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is less than 0.1 g. Examples of such resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (provided that the styrene content is 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0142] (Polymerizable Compounds) The photosensitive resin layer preferably contains a compound having polymerizable groups (a so-called polymerizable compound). A "polymerizable compound" refers to a compound that polymerizes under the action of a polymerization initiator, and is different from the polymers described above.

[0143] The polymerizable group is not particularly limited as long as it is a group that participates in the polymerization reaction. Examples of polymerizable groups include groups having an ethylenically unsaturated group, such as vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups. Examples of polymerizable groups include cationic polymerizable groups, such as epoxy groups and oxetane groups. Among these, groups having an ethylenically unsaturated group are preferred as polymerizable groups, and acryloyl groups or methacryloyl groups are more preferred.

[0144] From the viewpoint of providing superior photosensitivity of the photosensitive resin layer, a polymerizable compound having one or more ethylenically unsaturated groups (a so-called ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (a so-called polyfunctional ethylenically unsaturated compound) is more preferred. From the viewpoint of providing superior resolution and peelability, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably six or less, more preferably three or less, and even more preferably two or less.

[0145] From the viewpoint of achieving a better balance between the photosensitivity, resolution, and peelability of the photosensitive resin layer, it is preferable that the photosensitive resin layer contains a difunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and more preferably a difunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. From the viewpoint of excellent peelability, the ratio of the content of the difunctional ethylenically unsaturated compound to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more. The upper limit is not particularly limited and may be, for example, 100% by mass. That is, all polymerizable compounds may be difunctional ethylenically unsaturated compounds. As the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0146] The photosensitive resin layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a difunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the ethylenically unsaturated compounds described above.

[0147] In the photosensitive resin layer, the mass ratio of the ethylenically unsaturated compound B1 content to the ethylenically unsaturated compound content 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 superior resolution. The upper limit is not particularly limited, but for example, from the viewpoint of peelability, it is 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.

[0148] Examples of aromatic rings in ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and fused rings thereof. Aromatic hydrocarbon rings are preferred as the aromatic rings in ethylenically unsaturated compound B1, and benzene rings are more preferred. The aromatic rings in ethylenically unsaturated compound B1 may have substituents. Ethylenely unsaturated compound B1 may have only one aromatic ring or two or more.

[0149] Ethylene-unsaturated compound B1 is preferably a bisphenol structure, from the viewpoint of further improving resolution by suppressing swelling of the photosensitive resin layer due to the developer. Examples of bisphenol structures 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). Among these, the bisphenol A structure is preferred.

[0150] Examples of ethylenically unsaturated compounds B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be directly bonded to both ends of the bisphenol structure or bonded via one or more alkylene oxy groups. The alkylene oxy groups added to both ends of the bisphenol structure are preferably ethylene oxy groups or propylene oxy groups, with ethylene oxy groups being more preferred. The number of alkylene oxy groups added to the bisphenol structure is not particularly limited, but for example, it is preferably 4 to 16 per molecule, and more preferably 6 to 14. Ethyleneally unsaturated compounds B1 having a bisphenol structure are described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, and the contents described in this publication are incorporated herein by reference.

[0151] As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane [FA-324M, manufactured by Hitachi Chemical Co., Ltd.], 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane [BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.], and 2,2-bis(4-( Examples include methacryloxide dodecaethoxytetrapropoxy)phenyl)propane [FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.], 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane [BPE-1300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.], 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane [BPE-200, manufactured by Shin Nakamura Chemical Industry Co., Ltd.], and ethoxylated (10)bisphenol A diacrylate [NK ester A-BPE-10, manufactured by Shin Nakamura Chemical Industry Co., Ltd.].

[0152] As the ethylenically unsaturated compound B1, it is preferable to include a compound represented by the following formula (Bis) from the viewpoints of change in line width after standing time, change in line width due to development temperature, and sensitivity.

[0153]

[0154] In formula (Bis), R １ and R ２ each independently represent a hydrogen atom or a methyl group, and A is C ２ H ４ , B is C ３ H ６ , n １ and n ３ are each independently an integer of 1 to 39, and n １ + n ３ is an integer of 2 to 40, n ２ and n ４ are each independently an integer of 0 to 29, and n ２ + n ４ is an integer of 0 to 30, and the arrangement of repeating units of -(A-O)- and -(B-O)- may be random or block. When the arrangement of repeating units of -(A-O)- and -(B-O)- is a block, either of -(A-O)- or -(B-O)- may be on the bisphenol structure side. In one aspect, n １ + n ２ + n ３ + n ４ 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. Further, n ２ + n ４ 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.

[0155] When the photosensitive resin layer contains the ethylenically unsaturated compound B1, it may contain only one type of ethylenically unsaturated compound B1, or may contain two or more types thereof.

[0156] From the viewpoint of achieving superior resolution, the content of ethylenically unsaturated compound B1 in the photosensitive resin layer is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (the phenomenon in which components in the photosensitive resin layer seep out from the edges of the so-called photosensitive transfer material), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0157] The photosensitive resin layer may contain ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 described above. The ethylenically unsaturated compounds other than ethylenically unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. Examples of ethylenically unsaturated compounds other than ethylenically unsaturated compound B1 include compounds having one ethylenically unsaturated group in one molecule (so-called monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[0158] 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.

[0159] Examples of bifunctional ethylenically unsaturated compounds that do not have an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0160] Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate [A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], tricyclodecanedimethanol dimethacrylate [DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], 1,9-nonanediol diacrylate [A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], 1,6-hexanediol diacrylate [A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0161] 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.

[0162] Examples of commercially available polypropylene glycol di(meth)acrylate include Aronics® M-270 [manufactured by Toagosei Co., Ltd.].

[0163] Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available urethane di(meth)acrylates include 8UX-015A [manufactured by Taisei Fine Chemical Co., Ltd.], UA-32P [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], and UA-1100H [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.].

[0164] Examples of ethylenically unsaturated compounds with three or more functions 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 products thereof. "(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. In one embodiment, the photosensitive resin layer preferably contains the ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the ethylenically unsaturated compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compounds is preferably (total mass of ethylenically unsaturated compound B1) : (total mass of 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. In another embodiment, the photosensitive resin layer preferably contains the ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0165] Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds [e.g., KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.], alkylene oxide-modified (meth)acrylate compounds [e.g., KAYARAD® RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® 135 manufactured by Daicel Ornex], ethoxylated glycerin triacrylate [e.g., A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.], Aronics® TO-2349 [manufactured by Toagosei Co., Ltd.], and Aronics® Examples include M-520 [manufactured by Toagosei Co., Ltd.] and Arronix® M-510 [manufactured by Toagosei Co., Ltd.].

[0166] In addition, other ethylenically unsaturated compounds besides ethylenically unsaturated compound B1 include ethylenically unsaturated compounds having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942.

[0167] From the viewpoint of curability and resolution, the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth)acrylic compound, and more preferably contains a (meth)acrylate compound. From the viewpoint of curability, resolution and linearity, the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth)acrylic compound, and more preferably the content of the acrylic compound relative to the total mass of the (meth)acrylic compound contained in the photosensitive resin layer is 60% by mass or less.

[0168] The molecular weight of the ethylenically unsaturated compound containing ethylenically unsaturated compound B1 [or, if it has a distribution, the weight-average molecular weight (Mw)] is preferably 200 to 3000, more preferably 280 to 2200, and even more preferably 300 to 2200.

[0169] If the photosensitive resin layer contains polymerizable compounds, it may contain only one polymerizable compound or two or more polymerizable compounds.

[0170] When the photosensitive resin layer contains a polymerizable compound, the content of the polymerizable compound in the photosensitive resin layer is not particularly limited, but is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass, based on the total mass of the photosensitive resin layer.

[0171] When the photosensitive resin layer contains a polymer and a polymerizable compound, from the viewpoint of conforming to uneven surfaces, the ratio of the total mass of the polymerizable compound (preferably an ethylenically unsaturated compound) to the total mass of the polymer (preferably an alkali-soluble resin) in the photosensitive resin layer is preferably 0.4 or more, more preferably 0.6 or more, and even more preferably 0.8 or more. Furthermore, the ratio of the total mass of the polymerizable compound (preferably an ethylenically unsaturated compound) to the total mass of the polymer (preferably an alkali-soluble resin) in the photosensitive resin layer is preferably 1.6 or less, more preferably 1.4 or less, and even more preferably 1.2 or less.

[0172] (Polymerization Initiator) The photosensitive resin layer preferably contains a polymerization initiator. The type of polymerization initiator is selected according to the type of polymerization reaction. Examples of polymerization initiators include thermal polymerization initiators and photopolymerization initiators. Other examples of polymerization initiators include radical polymerization initiators and cationic polymerization initiators.

[0173] The photosensitive resin layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to active light such as ultraviolet light, visible light, or X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0174] Examples of photo-radical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0175] The photosensitive resin layer preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives as a photoradical polymerization initiator, from the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of the 2,4,5-triarylimidazole dimer include the 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, the 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, the 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, the 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and the 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0176] As photoradical polymerization initiators, for example, those described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-14783 may be used.

[0177] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate [DBE, CAS No. 10287-53-3], benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and benzophenone.

[0178] Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE-03 [manufactured by BASF], and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad 379EG, manufactured by IGM Resins B. V. [Manufactured by Omnirad 907, IGM Resins B.V.], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [Trade name: Omnirad 907, IGM Resins B.V.], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [Trade name: Omnirad 127, IGM Resins B.V.], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [Trade name: Omnirad 369, IGM Resins B.V.], 2-hydroxy-2-methyl-1-phenylpropan-1-one [Trade name: Omnirad 1173, IGM Resins B.V.] [Manufactured by Omnirad], 1-hydroxycyclohexylphenyl ketone [Trade name: Omnirad 184, manufactured by IGM Resins B. V.], 2,2-dimethoxy-1,2-diphenylethane-1-one [Trade name: Omnirad 651, manufactured by IGM Resins B. V.], 2,4,6-trimethylbenzolyl-diphenylphosphine oxide [Trade name: Omnirad TPO H, manufactured by IGM Resins B. V.], bis(2,4,6-trimethylbenzolyl)phenylphosphine oxide [Trade name: Omnirad 819, manufactured by IGM Resins B. V.] [Manufactured by], oxime ester-based photopolymerization initiator [product name: Lunar 6, manufactured by DKSH Japan Co., Ltd.], 2,2'-bis(2-chlorophenyl)-4,4',5,5'-Tetraphenylbiimidazole [Trade name: B-IMD, manufactured by Kurogane Kasei Co., Ltd.], 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer [Trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) [Trade name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.], 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2 Examples include -(O-acetyloxime) [product name: TR-PBG-326, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.], TAZ-110 [product name: manufactured by Midori Chemical Co., Ltd.], TAZ-111 [product name: manufactured by Midori Chemical Co., Ltd.], and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) [product name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.], and 4,4'-bis(diethylamino)benzophenone [product name: SB-PI 701, obtained from Sanyo Trading Co., Ltd.].

[0179] A photocationic polymerization initiator (so-called photoacid generator) is a compound that generates acid upon receiving active light. While compounds that are sensitive to active light with a wavelength of 300 nm or higher, preferably 300 to 450 nm, and generate acid are preferred as photocationic polymerization initiators, their chemical structure is not particularly limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or higher can also be preferably used in combination with a sensitizer, provided they become sensitive to active light with a wavelength of 300 nm or higher and generate acid.

[0180] As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. The lower limit of pKa is not particularly limited, but for example, it is preferably -10.0 or higher.

[0181] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salt compounds and triarylsulfonium salt compounds, and quaternary ammonium salt compounds. As an ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643 may be used. Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494 may be used. Furthermore, as the oximesulfonate compound, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 may be used.

[0182] If the photosensitive resin layer contains a polymerization initiator, it may contain only one type of polymerization initiator or two or more types.

[0183] When the photosensitive resin layer contains a polymerization initiator, the content of the polymerization initiator in the photosensitive resin layer 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 resin layer. Furthermore, the content of the polymerization initiator in the photosensitive resin layer is preferably 15% by mass or less, and more preferably 8% by mass or less, based on the total mass of the photosensitive layer.

[0184] (Dye) The photosensitive resin layer preferably contains a dye from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. It is more preferable that the dye contains a dye (also called "dye N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical. Although the detailed mechanism is unknown, when the photosensitive resin layer contains dye N, the adhesion with adjacent layers (e.g., intermediate layers) is improved, resulting in superior resolution. Furthermore, the relationship of peeling force shown in formula (1) is more easily achieved during peeling.

[0185] In this disclosure, the phrase "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" may mean any of the following: a dye in a colored state becomes decolorized due to an acid, base, or radical; a dye in a decolorized state becomes colored due to an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue. Specifically, dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In this case, the dye may change its colored or decolorized state due to the generation and action of an acid, base, or radical within the photosensitive layer upon exposure, or it may be a dye that changes its colored or decolorized state due to a change in the state within the photosensitive resin layer (e.g., pH) due to an acid, base, or radical. Furthermore, dye N may be a dye that changes its colored or decolorized state upon direct stimulation by an acid, base, or radical without exposure.

[0186] From the viewpoint of visibility of exposed and unexposed areas, as well as resolution, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals.

[0187] From the viewpoint of visibility of the exposed and unexposed areas, as well as resolution, the photosensitive resin layer preferably contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator.

[0188] Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, it is preferable that the dye N is a dye that develops color in response to an acid, base, or radical.

[0189] An example of the color development mechanism of dye N in this disclosure is a method in which a photoradical polymerization initiator, a photocationic polymerization initiator (so-called photoacid generator), or a photobase generator is added to a photosensitive resin 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 radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator.

[0190] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or more, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm. Furthermore, dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or it may have two or more. If dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or more.

[0191] The maximum absorption wavelength of dye N can be obtained by measuring the transmission spectrum of a solution containing dye N (at a temperature of 25°C) in the range of wavelengths from 400 nm to 780 nm using a spectrophotometer (for example, a UV3100 manufactured by Shimadzu Corporation) in an atmospheric environment, and detecting the wavelength at which the light intensity is minimum (i.e., the maximum absorption wavelength).

[0192] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of dyes that decolorize upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. Among these, leuco compounds are preferred as dye N from the viewpoint of visibility between the exposed and unexposed areas.

[0193] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (so-called triarylmethane dyes), leuco compounds having a spiropyran skeleton (so-called spiropyran dyes), leuco compounds having a fluorane skeleton (so-called fluorane dyes), leuco compounds having a diarylmethane skeleton (so-called diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (so-called rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (so-called indolylphthalide dyes), and leuco compounds having a leucoauramine skeleton (so-called leucoauramine dyes). Triarylmethane dyes or fluorane dyes are preferred as leuco compounds, and leuco compounds having a triphenylmethane skeleton (so-called triphenylmethane dyes) or fluorane dyes are more preferred.

[0194] As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring from the viewpoint of visibility between the exposed and unexposed areas. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator, thereby changing the leuco compound to a closed state and decolorizing it, or changing the leuco compound to an open state and developing color. As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring, and the lactone ring, sultine ring, or sultone ring opens and develops color in response to radicals or acids, and more preferably a lactone ring, and the lactone ring opens and develops color in response to radicals or acids.

[0195] Specific examples of leuco compounds include p,p',p''-hexamethyltriaminotriphenylmethane (so-called leucocrystal violet, manufactured by Tokyo Chemical Industry Co., Ltd.), Pergascript Blue SRB (manufactured by Novartis Pharma), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino (N,N-)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N- Diethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2- Examples include methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0196] Examples of pigment N include dyes. Examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congo Red, Benzopulpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue - Naphthalene Sulfonate, Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.], Oil Blue #603 [manufactured by Orient Chemical Co., Ltd.], Oil Pink #312 [manufactured by Orient Chemical Co., Ltd.], Oil Red 5B [manufactured by Orient Chemical Co., Ltd.], Oil Scarlet #308 [manufactured by Orient Chemical Co., Ltd.] Examples include: Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by 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-p-N,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0197] If the photosensitive resin layer contains a dye, it may contain only one type of dye or two or more types of dyes.

[0198] When the photosensitive resin layer contains a dye, the dye content in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.1% to 1% by mass, based on the total mass of the photosensitive resin layer, from the viewpoint of visibility of the exposed and unexposed areas, pattern visibility after development, and resolution. Furthermore, when the photosensitive resin layer contains dye N as the dye, the dye N content in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.1% to 1% by mass, based on the total mass of the photosensitive resin layer, from the viewpoint of visibility of the exposed and unexposed areas, pattern visibility after development, and resolution.

[0199] The content of dye N refers to the amount of dye when all of the dye N contained in the photosensitive resin layer is brought into a colored state. Below, a method for quantifying the content of dye N is explained using a dye that develops color via radicals as an example. Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. To each of the obtained solutions, the photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF) is added, and radicals are generated by irradiating with 365 nm light, bringing all of the dye into a colored state. Then, under an atmospheric atmosphere, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is created. Next, the absorbance of the solution in which all of the dye has developed color is measured using the same method as above, except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye. The amount of dye contained in the photosensitive resin layer is calculated based on a calibration curve, using the absorbance of the solution containing the obtained photosensitive resin layer.

[0200] (Thermo-crosslinkable compounds) The photosensitive resin layer preferably contains a thermo-crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this disclosure, thermo-crosslinkable compounds having ethylenically unsaturated groups, as described later, will not be treated as ethylenically unsaturated compounds, but as thermo-crosslinkable compounds.

[0201] Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred as thermally crosslinkable compounds from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film.

[0202] Blocked isocyanate compounds react with hydroxyl and carboxyl groups. For example, if an alkali-soluble resin and / or ethylenically unsaturated compound has at least one of a hydroxyl and a carboxyl group, the hydrophilicity of the formed film decreases, and the function of the cured film of the photosensitive resin layer when used as a protective film tends to be enhanced. A blocked isocyanate compound refers to "a compound having a structure in which the isocyanate groups of an isocyanate are protected (so-called masked) with a blocking agent."

[0203] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, and more preferably 130°C to 150°C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate, as measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimetry meter." As the differential scanning calorimetry meter, for example, a differential scanning calorimetry meter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimetry meter is not limited to this.

[0204] Examples of blocking agents with a dissociation temperature of 100°C to 160°C include active methylene compounds [e.g., malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds [e.g., formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc., which have a structure represented by -C(=N-OH)- in the molecule]. From the viewpoint of storage stability, it is preferable that the blocking agent with a dissociation temperature of 100°C to 160°C includes an oxime compound.

[0205] Blocked isocyanate compounds are preferably those having an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and enhancing adhesion to the transfer target. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred from the viewpoint of making it easier to set the dissociation temperature within a favorable range and reducing development residue compared to compounds without an oxime structure.

[0206] The blocked isocyanate compound may have polymerizable groups. The polymerizable groups are not particularly limited and include known polymerizable groups, with radical polymerizable groups being preferred. Examples of polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, and epoxy groups such as glycidyl groups. Ethylenelycol unsaturated groups are preferred as polymerizable groups, (meth)acryloxy groups are more preferred, and acryloxy groups are even more preferred.

[0207] Commercially available blocked isocyanate compounds can be used. Examples of commercially available blocked isocyanate compounds include Karenz® AOI-BM, Karenz® MOI-BM, Karenz® MOI-BP, etc. (all manufactured by Showa Denko K.K.), and the block-type Duranate series (for example, Duranate® TPA-B80E and Duranate® WT32-B75P, manufactured by Asahi Kasei Chemicals Corporation). In addition, compounds having the following structure can also be used as blocked isocyanate compounds.

[0208]

[0209] If the photosensitive resin layer contains a thermally crosslinkable compound, it may contain only one thermally crosslinkable compound or two or more.

[0210] When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound in the photosensitive resin layer is not particularly limited, but is preferably 1% to 50% by mass, and more preferably 5% to 30% by mass, based on the total mass of the photosensitive resin layer.

[0211] (Other Components) The photosensitive resin layer may contain components other than those described above (also referred to as "other components") as necessary, to the extent that they do not impair the effects of the present disclosure. Examples of other components include polymerization inhibitors, surfactants, sensitizers, and various additives. If the photosensitive resin layer contains other components, it may contain only one type of other component or two or more types.

[0212] -Polymerization Inhibitor- The photosensitive resin layer may contain a polymerization inhibitor. A radical polymerization inhibitor is preferred as the polymerization inhibitor. Examples of radical polymerization inhibitors include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Other examples of radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. Phenothiazine, phenoxazine, or 4-methoxyphenol are preferred as radical polymerization inhibitors. Furthermore, in order to avoid impairing the sensitivity of the photosensitive resin layer, it is also preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0213] If the photosensitive resin layer contains a polymerization inhibitor, it may contain only one polymerization inhibitor or two or more.

[0214] If the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive resin layer is preferably 0.001% to 5.0% by mass, more preferably 0.01% to 3.0% by mass, and even more preferably 0.02% to 2.0% by mass, based on the total mass of the photosensitive resin layer.

[0215] Furthermore, the content of the polymerization inhibitor in the photosensitive resin layer is preferably 0.005% to 5.0% by mass, more preferably 0.01% to 3.0% by mass, and even more preferably 0.01% to 1.0% by mass, based on the total mass of the polymerizable compound.

[0216] - Surfactants - The photosensitive resin layer may contain surfactants. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Publication No. 2009-237362.

[0217] As the surfactant, nonionic surfactants or fluorinated surfactants are preferred. As the surfactant, from the viewpoint of improving environmental suitability, surfactants containing silicon (for example, silicone-based surfactants) are preferred.

[0218] Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), 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, Pluronic (trade name, registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 [all manufactured by BASF], Tetronic (trade name) 304, 701, 704, 901, 904, and 150R1 [all manufactured by BASF], and Solspers (trade name). Examples include 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin (trade name) D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin (trade name) E1010, Surfinol (trade name) 104, 400, and 440 (manufactured by Nisshin Chemical Industry Co., Ltd.), etc.

[0219] Examples of commercially available fluorine-based surfactants include Megafac (registered trademark) (product name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, 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, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 [all manufactured by DIC Corporation], Florard (product name) Examples include FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon (registered trademark) (product name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC Inc.), PolyFox (product name) PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA Corporation), and Futergent (product name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, and 245F (all manufactured by Neos Co., Ltd.).

[0220] As a fluorinated surfactant, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, in which the fluorine atom-containing functional group is cleaved and the fluorine atom volatilizes when heat is applied, can also be preferably used. Examples of such fluorinated surfactants include the Megafac (trade name) DS series manufactured by DIC Corporation [Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)], and specifically, Megafac (registered trademark) DS-21.

[0221] As a fluorinated surfactant, polymers 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 can also be preferably used.

[0222] Block polymers can also be used as fluorine-based surfactants.

[0223] As a fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which includes 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) alkylene oxy groups (preferably ethylene oxy groups and / or propylene oxy groups).

[0224] As fluorinated surfactants, fluorinated polymers having ethylenically unsaturated groups in their side chains can also be used. Examples of such fluorinated surfactants include Megafac (trade name) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0225] As the fluorine-based surfactant, a compound having a linear perfluoroalkyl group with 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental suitability, perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) is preferred as the fluorine-based surfactant.

[0226] Examples of silicon-containing surfactants include silicone-based surfactants. Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into the side chains or terminals. A specific example of a silicone-based surfactant is DOWSIL (trade name) 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 Toray Dow Corning Co., Ltd.], X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, Other examples include KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (manufactured by Momentive Performance Materials), EFS-131, EFS-132, EFS-241, EFS-321, EFS-322, EFS-323-S, EFS-331, EFS-341, EFS-521, EFS-701, EFS-801, and EFS-821-S (manufactured by DIC Corporation), and BYK307, BYK323, BYK330, and BYK345 (manufactured by BIC Chemie Japan).

[0227] If the photosensitive resin layer contains a surfactant, it may contain only one type of surfactant or two or more types.

[0228] When the photosensitive resin layer contains a surfactant, the amount of surfactant in the photosensitive resin layer is not particularly limited, but is preferably 0.001% to 10% by mass, and more preferably 0.01% to 3% by mass, relative to the total mass of the photosensitive resin layer.

[0229] - Sensitizer - The photosensitive resin layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers 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.

[0230] If the photosensitive resin layer contains a sensitizer, it may contain only one type of sensitizer or two or more types.

[0231] When the photosensitive resin layer contains a sensitizer, the amount of sensitizer in the photosensitive resin layer is not particularly limited and can be set appropriately depending on the purpose. From the viewpoint of improving sensitivity to a light source and improving the curing speed by balancing polymerization rate and chain transfer, the amount of sensitizer in the photosensitive resin layer is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0232] - Chain transfer agent - The photosensitive resin layer may contain a chain transfer agent. The chain transfer agent is not particularly limited, and known chain transfer agents can be used.

[0233] If the photosensitive resin layer contains a chain transfer agent, it may contain only one type of chain transfer agent or two or more types.

[0234] When the photosensitive resin layer contains a chain transfer agent, the content of the chain transfer agent in the photosensitive resin layer is not particularly limited and can be set as appropriate depending on the purpose.

[0235] - Various Additives - The photosensitive resin layer may contain known additives as needed. Examples of additives include plasticizers, heterocyclic compounds, benzotriazole compounds, carboxybenzotriazole compounds, pyridine compounds (e.g., isonicotinamide), purine bases (e.g., adenine), and solvents. If the photosensitive resin layer contains additives, it may contain only one type of additive or two or more types.

[0236] Examples of benzotriazole compounds 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.

[0237] Examples of carboxybenzotriazole compounds 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. In addition, commercially available carboxybenzotriazole compounds such as CBT-1 (trade name, manufactured by Johoku Chemical Industry Co., Ltd.) can also be used.

[0238] When the photosensitive resin layer contains a benzotriazole compound and / or a carboxybenzotriazole compound, the total content of the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin layer is not particularly limited, but is preferably 0.01% to 3% by mass, and more preferably 0.05% to 1% by mass, relative to the total mass of the photosensitive resin layer. Setting the total content of the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin layer to 0.01% by mass or more relative to the total mass of the photosensitive resin layer is preferable from the viewpoint of imparting storage stability to the photosensitive resin layer. On the other hand, setting the total content of the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin layer to 3% by mass or less relative to the total mass of the photosensitive resin layer is preferable from the viewpoint of maintaining sensitivity and suppressing dye decolorization.

[0239] The photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of plasticizers and heterocyclic compounds include those described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0240] The photosensitive resin layer may contain a solvent. When a photosensitive resin layer is formed using a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

[0241] Furthermore, the photosensitive resin layer may contain known additives such as metal oxide particles, antioxidants, rust inhibitors, dispersants, acid builders, development accelerators, conductive fibers, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.

[0242] The additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese Patent Publication No. 2014-85643, and the contents of this publication are incorporated herein by reference.

[0243] (Impurities, etc.) The photosensitive resin layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are easily incorporated as impurities, so it is preferable to have the following content levels.

[0244] The impurity content in the photosensitive resin layer is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive resin layer. Furthermore, the impurity content in the photosensitive resin layer may be, for example, 1 ppb by mass or more, or 0.1 ppm by mass or more, relative to the total mass of the photosensitive resin layer.

[0245] Methods to keep the impurity content within the above range include, for example, selecting raw materials with a low impurity content for the composition for forming the photosensitive resin layer (so-called photosensitive resin composition), preventing the inclusion of impurities when forming the photosensitive resin layer, and removing them by washing. By such methods, the impurity content can be kept within the above range.

[0246] Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0247] In the photosensitive resin layer, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably low. The content of the above compounds in the photosensitive resin layer is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, based on the total mass of the photosensitive resin layer. Furthermore, the content of the above compounds in the photosensitive resin layer may be, for example, 10 ppb by mass or more, or 100 ppb by mass or more, based on the total mass of the photosensitive resin layer. The content of the above compounds can be suppressed by the same method as the content of metal impurities. Furthermore, the above compounds can be quantified by known measurement methods.

[0248] From the viewpoint of improving reliability and lamination, the water content in the photosensitive resin layer is preferably 0.01% to 1.0% by mass, and more preferably 0.05% to 0.5% by mass.

[0249] (Residual monomers) The photosensitive resin layer may contain residual monomers corresponding to each constituent unit of the alkali-soluble resin described above. From the viewpoint of patternability and reliability, the residual monomer content in the photosensitive resin layer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. Furthermore, the residual monomer content in the photosensitive resin layer may be, for example, 1 ppm by mass or more, or 10 ppm by mass or more, relative to the total mass of the alkali-soluble resin.

[0250] From the viewpoint of patternability and reliability, the residual monomer content in the photosensitive resin layer is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive resin layer. Furthermore, the residual monomer content in the photosensitive resin layer may be, for example, 0.1 ppm by mass or more, or 1 ppm by mass or more, relative to the total mass of the photosensitive resin layer.

[0251] It is also preferable that the amount of monomer remaining after synthesizing an alkali-soluble resin by polymer reaction be the amount described above. For example, when synthesizing an alkali-soluble resin by reacting a carboxylic acid side chain with glycidyl acrylate, it is preferable that the amount of glycidyl acrylate is the amount described above.

[0252] The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0253] (Pigment) The photosensitive resin layer may be a colored layer containing a pigment. The pigment can be appropriately selected according to the desired hue, and can be selected from black pigment, white pigment, and chromatic pigments other than black and white. When forming a black pattern, black pigment is preferably selected as the pigment.

[0254] As the black pigment, any known black pigment (e.g., organic or inorganic pigment) can be appropriately selected, as long as it does not impair the effects of this disclosure. From the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite. Among these, carbon black is particularly preferred as the black pigment. As carbon black, from the viewpoint of surface resistance, carbon black in which at least a part of the surface is coated with resin is preferred. From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 μm to 0.1 μm in number-average particle size, and more preferably 0.01 μm to 0.08 μm. Particle size refers to the diameter of a circle with the same area as the pigment particle when the area of ​​the pigment particle is determined from a photographic image of the pigment particle taken with an electron microscope, and the number-average particle size is the average value obtained by determining the above particle size for any 100 particles and averaging the obtained particle sizes of 100 particles.

[0255] As the white pigment, the white pigment described in paragraphs 0015 and 0114 of Japanese Patent Publication No. 2005-007765 can be used. Specifically, among the white pigments, titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, titanium dioxide or zinc oxide is more preferred, titanium dioxide is even more preferred, rutile-type or anatase-type titanium dioxide is particularly preferred, and rutile-type titanium dioxide is most preferred.

[0256] The surface of titanium dioxide may be subjected to at least one treatment selected from the group consisting of silica treatment, alumina treatment, titania treatment, zirconia treatment, and organic matter treatment. This suppresses the catalytic activity of titanium dioxide and improves heat resistance and fading properties. As for the surface treatment of titanium dioxide, at least one of alumina treatment and zirconia treatment is preferred from the viewpoint of reducing the thickness of the photosensitive layer after heating, and both alumina treatment and zirconia treatment are particularly preferred.

[0257] If the photosensitive resin layer is a colored layer, it is preferable that the photosensitive resin layer further contains chromatic pigments other than black and white pigments from the viewpoint of transferability. If the photosensitive resin layer contains chromatic pigments, the particle size of the chromatic pigments is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the viewpoint of better dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO [Color Index (also called "C.I.") 42595], Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolight Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Faster Pink B Supra (C.I. Pigment Red 81), Monastral First Blue (C.I. Pigment Blue 15), Monolight First Black B (C.I. Pigment Black 1), and Carbon, C. Examples include I. Pigment Red 97, C. I. Pigment Red 122, C. I. Pigment Red 149, C. I. Pigment Red 168, C. I. Pigment Red 177, C. I. Pigment Red 180, C. I. Pigment Red 192, C. I. Pigment Red 215, C. I. Pigment Green 7, C. I. Pigment Blue 15:1, C. I. Pigment Blue 15:4, C. I. Pigment Blue 22, C. I. Pigment Blue 60, C. I. Pigment Blue 64, and C. I. Pigment Violet 23. Among these, C. I. Pigment Red 177 is preferred as a chromatic pigment.

[0258] When the photosensitive resin layer contains a pigment, the pigment content in the photosensitive resin layer is preferably in the range of more than 3% by mass and 40% by mass or less, more preferably in the range of more than 3% by mass and 35% by mass or less, even more preferably in the range of more than 5% by mass and 35% by mass or less, and particularly preferably in the range of 10% by mass or more and 35% by mass or less, based on the total mass of the photosensitive resin layer.

[0259] When the photosensitive resin layer contains pigments other than black pigment (i.e., white pigment and chromatic pigment), the content of pigments other than black pigment in the photosensitive resin layer is preferably 30% by mass or less, more preferably 1% to 20% by mass, and even more preferably 3% to 15% by mass, relative to the content of black pigment.

[0260] In a method for producing a photosensitive resin layer containing a black pigment, it is preferable that the black pigment (preferably carbon black) is introduced into the photosensitive resin composition described later in the form of a pigment dispersion. The dispersion may be prepared by pre-mixing the black pigment and a pigment dispersant to obtain a mixture, adding it to an organic solvent or vehicle, and dispersing it in a disperser. The pigment dispersant can be selected according to the pigment and solvent, and for example, commercially available dispersants can be used. The vehicle refers to the medium portion in which the pigment is dispersed when it is a pigment dispersion, and is liquid, containing a binder component that holds the black pigment in a dispersed state, and a solvent component (i.e., an organic solvent) that dissolves and dilutes the binder component. The disperser is not particularly limited, and examples of known dispersers include kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. After dispersion by the disperser, the material may be further finely ground using the frictional force of mechanical grinding. For information on dispersers and fine grinding, please refer to the "Dictionary of Pigments" (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438 and 310).

[0261] <<Thickness of the Photosensitive Resin Layer>> From the viewpoint of developability and resolution, the thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 5 μm or less. Furthermore, the thickness of the photosensitive resin layer is preferably 0.5 μm or more, and more preferably 1 μm or more. The thickness of the photosensitive resin layer refers to the average thickness calculated by the arithmetic mean of the thicknesses of five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0262] For example, when the transfer layer consists of a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer, the ratio of the average thickness of the photosensitive resin layer to the average thickness of the transfer layer is preferably 10% to 50%, more preferably 15% to 35%, and even more preferably 20% to 30%, from the viewpoint of resolution and ability to follow uneven surfaces.

[0263] <<Light Transmittance>> The light transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, preferably 30% or more, and more preferably 50% or more, from the viewpoint of superior adhesion. The upper limit of the light transmittance of the photosensitive resin layer at a wavelength of 365 nm is not particularly limited, but for example, it is preferably 99.9% or less.

[0264] <Method for forming a photosensitive resin layer> The method for forming a photosensitive resin layer is not limited as long as the desired photosensitive resin layer can be obtained. Examples of methods for forming a photosensitive resin layer include preparing a photosensitive resin layer forming composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, etc., applying the prepared photosensitive resin layer forming composition to an intermediate layer or protective film, and drying the applied photosensitive resin layer forming composition.

[0265] The composition for forming a photosensitive resin layer preferably contains a solvent, from the viewpoint of facilitating the formation of the photosensitive resin layer by adjusting the viscosity. Examples of solvents include alkylene glycol ether solvents [e.g., 1-methoxy-2-propanol (MFG)], alkylene glycol ether acetate solvents [e.g., 1-methoxy-2-propyl acetate (MMPGAc)], alcohol solvents (e.g., methanol and ethanol), ketone solvents [e.g., acetone and methyl ethyl ketone (MEK)], aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0266] Preferably, the solvent is one containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents; more preferably, 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; and even more preferably, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, at least one selected from the group consisting of ketone solvents and cyclic ether solvents and at least one selected from alcohol solvents. Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether [e.g., 1-methoxy-2-propanol (MFG)], propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0267] Specific examples of alkylene glycol ether acetate solvents have already been described, so we will omit further explanation here.

[0268] As solvents, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvent described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and the contents of these are incorporated herein.

[0269] If the photosensitive resin layer forming composition contains a solvent, it may contain only one type of solvent or two or more types of solvents.

[0270] When the photosensitive resin layer forming composition contains a solvent, the solvent content when applying the photosensitive resin layer forming composition is preferably 50 to 1900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solids in the photosensitive resin layer forming composition.

[0271] The method for preparing the photosensitive resin layer forming composition is not particularly limited. For example, one method involves preparing a solution in which each component is dissolved in the solvent, and then mixing the resulting solution in a predetermined ratio to prepare the photosensitive resin layer forming composition. It is preferable to filter the photosensitive resin layer forming composition using a filter with a pore size of 0.2 μm to 30 μm before forming the photosensitive resin layer.

[0272] The method for applying the photosensitive resin layer-forming composition is not particularly limited and can be applied by known methods. Examples of application methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0273] Preferred drying methods for the applied photosensitive resin layer-forming composition include heating and vacuum drying. Examples of drying methods include natural drying, heating, and vacuum drying. These methods can be applied individually or in combination. The drying temperature is preferably 70°C or higher, and more preferably 80°C or higher. The upper limit of the drying temperature is not particularly limited, but for example, it is preferably 180°C or lower, and more preferably 150°C or lower. The applied photosensitive resin layer-forming composition may be dried by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. The upper limit of the drying time is not particularly limited, but for example, it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0274] <Protective Film> The photosensitive transfer material according to this disclosure preferably has a protective film. Examples of materials constituting the protective film include resin films and paper. From the viewpoint of strength and flexibility, the protective film is preferably a resin film. Examples of protective films include polyolefin films (e.g., polypropylene films and polyethylene films), polyester films (e.g., polyethylene terephthalate films), polycarbonate films, cellulose triacetate films, and polystyrene films. The protective film is preferably a polypropylene film, a polyethylene film, or a polyethylene terephthalate film.

[0275] The thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, even more preferably 5 μm to 40 μm, and particularly preferably 15 μm to 30 μm. The thickness of the protective film refers to the average thickness calculated by the arithmetic mean of the thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0276] The arithmetic mean roughness Ra value of the surface of the protective film on the photosensitive resin layer side (hereinafter also referred to as the "surface of the protective film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less, from the viewpoint of superior resolution. The lower limit of the arithmetic mean roughness Ra value of the surface of the protective film is not particularly limited, but for example, it is preferably 0.001 μm or more.

[0277] The arithmetic mean roughness Ra value of the protective film surface is measured by the following method: A 3D optical profiler (New View 7300, Zygo) is used to measure the surface of the protective film and obtain its surface profile. MetroPro ver 8.3.2 Microscope Application is used as the measurement and analysis software. Next, the Surface Map screen is displayed in the analysis software, and histogram data is obtained from the Surface Map screen. The arithmetic mean roughness Ra of the protective film surface is calculated from the obtained histogram data.

[0278] <Other Layers> The photosensitive transfer material according to this disclosure may have other layers. Examples of other layers include a refractive index adjusting layer (a so-called contrast enhancement layer). A contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018 / 179640. Other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Publication No. 2014-85643. The contents of these publications are incorporated herein by reference.

[0279] <Method for Manufacturing Photosensitive Transfer Material> The method for manufacturing the photosensitive transfer material according to this disclosure is not particularly limited. The photosensitive transfer material according to this disclosure is preferably manufactured by a method (hereinafter also referred to as "manufacturing method A") which includes a step of forming a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer on a temporary support in this order by coating and drying (hereinafter also referred to as "step A1"), or by a method (hereinafter also referred to as "manufacturing method B") which includes a step of forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer on a protective film in this order by coating and drying (hereinafter also referred to as "step B1"), and a step of bonding a temporary support to the thermoplastic resin layer by heat lamination (hereinafter also referred to as "step B2"). According to manufacturing methods A and B, the photosensitive transfer material according to this disclosure can be manufactured more easily.

[0280] The following describes manufacturing methods A and B. Matters common to those described in the section on photosensitive transfer materials relating to this disclosure will be omitted from the explanation.

[0281] (Manufacturing Method A) Manufacturing Method A is a method for manufacturing a photosensitive transfer material, which includes a step (i.e., step A1) of forming a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer on a temporary support in that order by coating and drying. Manufacturing Method A may include steps other than step A1. An example of a step other than step A1 is a step (hereinafter also referred to as "step A2") of bonding a protective film to the photosensitive resin layer formed in step A1 by thermal lamination.

[0282] -Step A1- Step A1 involves forming a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer on a temporary support in that order by coating and drying. The methods for forming the thermoplastic resin layer on the temporary support, the method for forming the intermediate layer on the thermoplastic resin layer, and the method for forming the photosensitive resin layer on the intermediate layer are as described in the sections "Method for forming the thermoplastic resin layer," "Method for forming the intermediate layer," and "Method for forming the photosensitive resin layer" above.

[0283] -Step A2- Step A2 is a step in which a protective film is bonded to the photosensitive resin layer formed in Step A1 by thermal lamination. The means of thermal lamination are not particularly limited, and a known laminator can be used. The laminator is preferably a device that is equipped with any heatable roller, such as a rubber roller, and is capable of pressurizing and heating. The temperature of thermal lamination is not particularly limited, but is preferably 20°C to 100°C, and more preferably 25°C to 60°C.

[0284] (Manufacturing Method B) Manufacturing Method B is a method for manufacturing a photosensitive transfer material, comprising the steps of forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer on a protective film in that order by coating and drying (i.e., step B1), and bonding a temporary support to the thermoplastic resin layer by heat lamination (i.e., step B2). Manufacturing Method B may include steps other than steps B1 and B2.

[0285] -Step B1- Step B1 involves forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer on a protective film by coating and drying them in that order. The methods for forming the photosensitive resin layer on the protective film, the method for forming the intermediate layer on the photosensitive resin layer, and the method for forming the thermoplastic resin layer on the intermediate layer are as described in the sections "Method for forming the photosensitive resin layer," "Method for forming the intermediate layer," and "Method for forming the thermoplastic resin layer" above.

[0286] -Step B2- Step B2 is a step in which a temporary support is bonded to the thermoplastic resin layer formed in Step B1 by thermal lamination. The means of thermal lamination are not particularly limited, and a known laminator can be used. The laminator is preferably a device that is equipped with any heatable roller, such as a rubber roller, and is capable of pressurizing and heating. The temperature of thermal lamination is not particularly limited, but is preferably 20°C to 100°C, and more preferably 25°C to 60°C.

[0287] The photosensitive transfer material manufactured as described above may be wound up to produce a roll of photosensitive transfer material, which can then be stored. The roll of photosensitive transfer material can be supplied in its original form for the lamination process with the substrate using a roll-to-roll method.

[0288] [Method for Manufacturing a Patterned Substrate] The method for manufacturing a patterned substrate according to this disclosure (hereinafter also simply referred to as the "manufacturing method according to this disclosure") includes, in this order: a step of bonding a photosensitive transfer material and a substrate so that the transfer layer side of the photosensitive transfer material according to this disclosure is in contact with the substrate (hereinafter also referred to as the "bonding step"), a step of removing a temporary support from the bonded body by peeling it between the thermoplastic resin layer and the intermediate layer (hereinafter also referred to as the "temporary support removal step"), a step of pattern-exposing the transfer layer, including the intermediate layer and the photosensitive resin layer, through an exposure mask (hereinafter also referred to as the "exposure step"), and a step of developing the pattern-exposed transfer layer to form a pattern (hereinafter also referred to as the "development step"). The method for manufacturing a patterned substrate according to this disclosure uses the photosensitive transfer material according to this disclosure, and therefore a high-resolution resist pattern can be formed.

[0289] The manufacturing method relating to this disclosure may include steps other than the lamination step, pressurization step, temporary support removal step, exposure step, and development step (so-called other steps). Examples of other steps include the protective film removal step and the pressurization step.

[0290] <Protective Film Removal Step> If the photosensitive transfer material according to this disclosure has a protective film, the manufacturing method according to this disclosure preferably includes a step of removing the protective film from the photosensitive transfer material (a so-called protective film removal step) before the lamination step. The photosensitive transfer material according to this disclosure is as described above, so its explanation is omitted here. The method for removing the protective film from the photosensitive transfer material according to this disclosure is not particularly limited, and known methods can be applied.

[0291] <Lamination Process> The manufacturing method according to the present disclosure includes a step of laminating a photosensitive transfer material and a substrate (i.e., a lamination process) such that the transfer layer side of the photosensitive transfer material according to the present disclosure is in contact with the substrate. When laminating the photosensitive transfer material and the substrate, the transfer layer in contact with the substrate is, for example, the layer in contact with the protective film (e.g., the photosensitive resin layer) if the photosensitive transfer material according to the present disclosure has a protective film. The lamination process yields a laminate of the photosensitive transfer material and the substrate.

[0292] Known methods can be applied to bond the photosensitive transfer material to the substrate. In the bonding process, it is preferable to press the photosensitive transfer material and the substrate together. For example, it is preferable to overlap the transfer layer side of the photosensitive transfer material with the substrate and press the photosensitive transfer material and the substrate together by applying pressure and heat using means such as a roll.

[0293] A known lamination method can be applied to the method of bonding the substrate and the photosensitive transfer material. Examples of lamination methods include using a known laminator such as a vacuum laminator or an auto-cut laminator. The lamination temperature is not particularly limited, but is preferably, for example, 70°C to 130°C.

[0294] The substrate is not particularly limited, and any known substrate can be used. In some embodiments, the substrate may be a substrate having a metal layer, and it is preferable that the substrate has a metal layer on its surface. The substrate may have any layer other than the metal layer as needed. Examples of substrates include resin substrates, glass substrates, and semiconductor substrates. Preferred embodiments of the substrate are described, for example, in paragraph 0140 of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0295] Examples of substrates that make up the substrate include metal (e.g., Invar, an iron-nickel alloy), glass, silicon, and film. The substrate that makes up the substrate may be transparent.

[0296] Examples of transparent glass substrates include tempered glass such as Corning's Gorilla Glass. Additionally, materials described in Japanese Patent Publication No. 2010-86684, 2010-152809, and 2010-257492 can be used as transparent glass substrates.

[0297] When using a film substrate, it is preferable to use a film substrate that has low optical distortion and / or high transparency. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymers.

[0298] When manufacturing using a roll-to-roll method, the substrate is preferably a film substrate.

[0299] Examples of metal layers in the substrate include conductive layers used in general circuit wiring or touch panel wiring. From the viewpoint of conductivity and fine wire formation, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, with a metal layer being more preferred, and a copper layer or a silver layer being even more preferred.

[0300] The substrate may have a single metal layer or two or more metal layers. If there are two or more metal layers, it is preferable that the metal layers be made of different materials.

[0301] Examples of materials for the metal layer include metals and conductive metal oxides. Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ２ These are some examples.

[0302] In some embodiments, the substrate may be a metal substrate. The photosensitive transfer material of this disclosure can suppress the generation of lamination bubbles by the thermoplastic resin layer during thermal lamination, and the thermoplastic resin layer can be removed together with the temporary support during pattern exposure, thus enabling a shorter exposure gap. For this reason, the photosensitive transfer material of this disclosure can be used particularly suitably for microfabrication of metal substrates for vapor deposition masks having fine irregularities on their surface. The metal substrate has a first surface and a second surface located opposite the first surface.

[0303] The structure of the metal substrate may be a single-layer structure or a multi-layer structure. Examples of metal elements included in the metal substrate include Cu, Ni, Fe, Cr, Mn, and Co. Preferably, the metal substrate contains at least one metal element selected from the group consisting of Cu, Ni, Fe, Cr, Mn, and Co, more preferably at least one metal element selected from the group consisting of Cu, Fe, and Ni, and even more preferably Cu. The metal substrate may also contain elements other than metal elements. Examples of elements other than metal elements include B, C, N, O, P, S, and Cl. A copper substrate is an example of a preferred metal substrate. Part or all of the metal substrate may be an alloy. Examples of alloys include nickel-cobalt (Ni-Co) alloy and iron-nickel (Fe-Ni) alloy. In some embodiments, it is preferable that the metal substrate contains an iron-nickel (Fe-Ni) alloy.

[0304] The roughness Rmax of the first surface of the metal substrate may be 0.5 μm to 5.0 μm. The roughness Rmax of the second surface of the metal layer may be 0.5 μm to 5.0 μm.

[0305] The thickness of the metal substrate is preferably 30 μm to 500 μm, more preferably 40 μm to 400 μm, and even more preferably 50 μm to 300 μm. The thickness of the metal layer refers to the average thickness calculated by the arithmetic mean of the thicknesses measured at five locations by cross-sectional observation using a scanning electron microscope (SEM).

[0306] <Pressurization Step> The manufacturing method according to this disclosure preferably includes a step of pressurizing the bond between the photosensitive transfer material and the substrate (a so-called pressurization step). Pressurizing the bond increases the adhesion between the transfer layer and the substrate, and tends to improve the ability of the transfer layer to follow the irregularities on the surface of the substrate.

[0307] The bonded structure to be pressed comprises a substrate, a transfer layer, and a temporary support in that order. One method for pressing the bonded structure is to autoclave it. An example of autoclave treatment conditions is a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour.

[0308] <Temporary Support Removal Step> The manufacturing method according to this disclosure includes a step of removing a temporary support from the laminate by delaminating it between the thermoplastic resin layer and the intermediate layer (i.e., a temporary support removal step). Removing the temporary support prior to the exposure step tends to shorten the exposure gap, making it easier to obtain a high-resolution resist pattern. Furthermore, blurring of the optical image tends to be reduced, and the mask fidelity and line width uniformity of the obtained resist pattern tend to be further improved. In addition, removing the temporary support prior to the exposure step tends to eliminate the influence of pinholes originating from the temporary support, making it easier to obtain a resist pattern without defects.

[0309] The method for removing the temporary support is not particularly limited. In the manufacturing method according to this disclosure, the photosensitive transfer material described above is used as the photosensitive transfer material, so the thermoplastic resin layer and the intermediate layer are peeled off well, and the temporary support is removed from the laminate together with the thermoplastic resin layer.

[0310] <Exposure Process> The manufacturing method according to this disclosure includes a process of pattern exposure (i.e., exposure process) of a transfer layer including an intermediate layer and a photosensitive resin layer through a mask. "Pattern exposure" means exposure in a patterned manner, that is, exposure in a manner in which exposed areas and unexposed areas exist. The positional relationship between the exposed areas and unexposed areas in pattern exposure is not particularly limited and can be adjusted as appropriate, for example, according to the shape of the desired pattern.

[0311] During the exposure process, exposed and unexposed areas are formed in the photosensitive resin layer. For example, if the photosensitive resin layer is negative type, the exposed areas of the photosensitive resin layer on the substrate during pattern exposure are cured and ultimately become a cured film. On the other hand, the unexposed areas of the photosensitive resin layer on the substrate during pattern exposure do not harden and are dissolved and removed by the developer in the development process described later. After the development process, the unexposed areas may form openings in the cured film.

[0312] It is preferable that the light used for pattern exposure is irradiated onto the transfer layer in a direction from the transfer layer toward the substrate.

[0313] As a light source for pattern exposure, any light source capable of irradiating light in a wavelength range that can cure the photosensitive resin layer (for example, 365 nm or 405 nm) can be appropriately selected and used. The dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. "Dominant wavelength" means the wavelength with the highest intensity.

[0314] Examples of light sources include semiconductor light sources such as various lasers and light-emitting diodes (LEDs); and discharge lamps such as ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure dose is 5 mJ / cm². ２ ~200 mJ / cm ２ Preferably, it is 10 mJ / cm ２ ~200 mJ / cm ２ It is preferable that it be so.

[0315] Since the exposure process is performed after the temporary support removal process, the exposure gap is reduced by the removal of the temporary support, allowing for a more faithful pattern to be obtained from the mask.

[0316] In the exposure process, the transfer layer may be pattern-exposed with the mask in contact with the transfer layer, or the transfer layer may be pattern-exposed with the mask close to the transfer layer without contacting it. The "transfer layer" here includes the intermediate layer and the photosensitive resin layer. In the temporary support removal process, the temporary support is removed by peeling it between the thermoplastic resin layer and the intermediate layer, so the mask comes into contact with the intermediate layer without coming into contact with the photosensitive resin layer. As a result, even when the transfer layer is pattern-exposed with the mask in contact with the transfer layer, a decrease in transportability due to adhesion between the mask and the photosensitive resin layer is less likely to occur, enabling stable production.

[0317] Exposure may be carried out in any of the following environments, for example, under atmospheric pressure, reduced pressure, or in a vacuum.

[0318] Examples of exposure methods include contact exposure, proximity exposure, and projection exposure. Among these, contact exposure is preferred. Contact exposure is a method in which a mask is brought into contact with the surface of the object to be exposed. Contact exposure uses a relatively inexpensive exposure machine, offers high productivity, and provides high resolution. In contact exposure, the shorter the distance from the mask to the photosensitive resin layer, i.e., the exposure gap, the less blurring there is in the image, and the higher the resolution image that is faithful to the mask can be obtained. In the manufacturing method of this disclosure, the exposure process is performed after the temporary support removal process, so the exposure gap is shortened by the removal of the temporary support. For this reason, it is easier to obtain a high-resolution image that is faithful to the mask.

[0319] Examples of masks include chrome masks, emulsion masks, and film masks.

[0320] <Development Process> The manufacturing method according to this disclosure includes a step of developing a pattern-exposed transfer layer to form a pattern (i.e., a development process). A pattern is formed by developing a pattern-exposed transfer layer. The pattern is formed by removing the exposed or unexposed parts of the transfer layer. If the photosensitive resin layer contained in the transfer layer is of the negative type, the unexposed parts of the transfer layer are removed, and a resin pattern is formed by the exposed parts of the transfer layer.

[0321] Development can be carried out using a developing solution. An alkaline aqueous solution is preferred as the developing solution. Examples of alkaline compounds contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). The pH of the alkaline aqueous solution at 25°C is preferably 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12. The content of alkaline compounds in the alkaline aqueous solution is preferably 0.1% to 5% by mass, and more preferably 0.1% to 3% by mass, based on the total mass of the alkaline aqueous solution.

[0322] In this disclosure, examples of preferred developers include the developer described in paragraph 0194 of International Publication No. 2015 / 093271.

[0323] Examples of development methods include paddle development, shower development, shower and spin development, and dip development. Shower development is a development method in which a developer is sprayed onto the object by showering. In this disclosure, a preferred development method is, for example, the development method described in paragraph 0195 of International Publication No. 2015 / 093271.

[0324] It is preferable to remove any developer solution and residue remaining after the developing process. Methods for removing the developer solution and residue include, for example, shower treatment and AirKnife treatment. In shower treatment, a liquid such as water and a cleaning agent is sprayed onto the object using a shower. The residue may be removed using a brush.

[0325] The present disclosure will be further described below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not deviate from the spirit of the present disclosure. Therefore, the scope of the present disclosure should not be interpreted as being limited by the examples shown below. Unless otherwise specified, "%" is based on mass. In the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight obtained in polystyrene terms by gel permeation chromatography (GPC) as described above. The theoretical acid value was used for the acid value.

[0326] Table 1 shows the temporary supports used in the examples and comparative examples. The types of temporary supports are as listed above.

[0327]

[0328] In Table 1, temporary supports with an easy-adhesion layer (i.e., a resin layer) are those that have an easy-adhesion surface coating as described in the manufacturer's catalog. In Table 1, the corona treatment was 2.8 kW / m². ２ It was carried out under these conditions.

[0329] [Preparation of Thermoplastic Resin Layer Forming Compositions] The compositions of thermoplastic resin layer forming compositions C1 to C5 are shown in Table 2. In Table 2, the numerical values ​​represent parts by mass, and blank spaces indicate that the compound is not present.

[0330]

[0331] The details of the abbreviations listed in Table 2 are as follows: • Polymer A-1: ​​Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid = 55 / 11.7 / 4.5 / 28.8 (molar ratio), Mw = 90,000, solids = 30% by mass • Polymer A-2: Styrene / acrylic acid = 63 / 37 (molar ratio) copolymer, Mw = 8,000, solids = 30% by mass・Byron BX-1001: Copolymerized polyester resin, Tg -18℃, manufactured by Toyobo Co., Ltd. ・Byron GK-800: Copolymerized polyester resin, Tg 50℃, manufactured by Toyobo Co., Ltd. ・Byron 802: Copolymerized polyester resin, Tg 60℃, manufactured by Toyobo Co., Ltd. ・D620: Polyester-based plasticizer, manufactured by Mitsubishi Chemical Corporation ・BPE-500: 2,2-bis(4-(meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ・Phenothiazinepril: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd. ・CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd. ・F-780F 30% MEK solution: 30% methyl ethyl ketone solution of fluorine-based surfactant, Megafac® F-780F, manufactured by DIC Corporation; EFS-801: Silicone-based surfactant, manufactured by DIC Corporation; MMPGAc: 1-methoxy-2-propyl acetate; MEK: methyl ethyl ketone

[0332] [Preparation of Intermediate Layer Forming Compositions] The compositions of intermediate layer forming compositions P1 and P2 are shown in Table 3. In Table 3, the numerical values ​​represent parts by mass, and blank spaces indicate that the compound is not present.

[0333]

[0334] Details of the abbreviations listed in Table 3 are shown below: • PVA: Polyvinyl alcohol, Kuraray Poval PVA 4-88LA, manufactured by Kuraray Co., Ltd. • PVP: Polyvinylpyrrolidone, Polyvinylpyrrolidone K-30, manufactured by Nippon Shokubai Co., Ltd. • HPMC: Hydroxypropyl methylcellulose, Metroze 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd. • F-444: Fluorine-based surfactant, Megafac® F-444, manufactured by DIC Corporation • BYK-345: Silicone-based surfactant, manufactured by Bic Chemie Japan Co., Ltd. • MeOH: Methanol

[0335] [Preparation of Photosensitive Resin Layer Forming Compositions] The compositions of photosensitive resin layer forming compositions R1 and R2 are shown in Table 4. In Table 4, the numerical values ​​represent parts by mass, and blank spaces indicate that the compound is not present.

[0336]

[0337] Details of the abbreviations listed in Table 4, other than those mentioned above, are shown below. • Polymer A-3: Resin with the following structure, Mw = 60,000, solids content = 30% by mass

[0338]

[0339] In the above resins, the number in the lower right corner of the parentheses represents the mass ratio.

[0340] • BPE-500: 2,2-bis(4-(meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin Nakamura Chemical Industry Co., Ltd. • Aronix M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. • B-IMD: (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Kurogane Kasei Co., Ltd. • SB-PI 701: 4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd. Phenothiazine: Manufactured by Kawaguchi Chemical Co., Ltd. Phenidone 1% MEK solution: Methyl ethyl ketone solution containing 1% by mass of phenidone Compound A: N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. LCV: Leucocrystal violet, a dye that develops color upon radical reaction, manufactured by Tokyo Chemical Industry Co., Ltd. CBT-1: Carboxybenzotriazole compound (manufactured by Johoku Chemical Industry Co., Ltd.) F-552 30% MEK solution: 30% methyl ethyl ketone solution of fluorine-based surfactant, Megafac® F-552, manufactured by DIC Corporation MFG: 1-Methoxy-2-propanol

[0341] <Example 1> (Manufacturing of photosensitive transfer material) The photosensitive transfer material of Example 1 was manufactured by following the procedure below, having a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a protective film in that order.

[0342] A composition C1 containing the components listed in the "Thermoplastic Resin Layer" column of Table 5 was prepared. After applying composition C1 onto a temporary support A1 using a slit nozzle, a thermoplastic resin layer was formed by drying composition C1 at 100°C for 2 minutes. The thickness (i.e., average thickness) of the thermoplastic resin layer was 8.0 μm.

[0343] A composition P1 containing the components listed in the "Intermediate Layer" column of Table 5 was prepared. After applying composition P1 onto a thermoplastic resin layer using a slit nozzle, an intermediate layer was formed by drying composition P1 at 100°C for 2 minutes. The thickness (i.e., average thickness) of the intermediate layer was 2.0 μm.

[0344] A composition R1 containing the components listed in the "Photosensitive Resin Layer" column of Table 5 was prepared. After applying composition R1 onto the intermediate layer using a slit-shaped nozzle, a photosensitive resin layer was formed by drying composition R1 at 80°C for 2 minutes. The film thickness (i.e., average thickness) of the photosensitive resin layer was 2.0 μm.

[0345] Finally, a protective film [model number: 16KS40, thickness: 16 μm, biaxially oriented PET film, manufactured by Toray Industries, Inc.] was laminated to the exposed surface of the photosensitive resin layer using thermal lamination.

[0346] Based on the above, the photosensitive transfer material of Example 1 was obtained.

[0347] <Example 2, Comparative Example 1> The same procedure as in Example 1 was followed, except that the compositions of the temporary support A1, composition C1, composition P1, and composition R1 were those listed in Table 5, to obtain the photosensitive transfer materials for Example 2 and Comparative Example 1.

[0348] 1. Measuring the peel force between the thermoplastic resin layer and the intermediate layer: A photosensitive transfer material was cut to a size of 30 mm x 100 mm, and the protective film was removed. The photosensitive resin layer was attached to a 0.7 mm thick glass using double-sided tape (STT-125FK, manufactured by Soken Chemical Co., Ltd.). A 180° peel test was performed on the laminate attached to the glass using a Tensilon (Tensilon universal tester, manufactured by A&D Co., Ltd.), in which a temporary support held at one end was peeled 180° toward the other end, under conditions of a temperature of 25°C and a peeling speed of 300 mm / min, and the peel force was measured. The laminate after the peel test was also observed, and the peel force between the thermoplastic resin layer and the intermediate layer was defined as the peel force between the thermoplastic resin layer and the intermediate layer if the layer was peeled.

[0349] 2. Measurement of peel force between the temporary support and the thermoplastic resin layer After measuring the peel force between the thermoplastic resin layer and the intermediate layer, the temporary support and the thermoplastic resin layer were attached to a 0.7 mm thick glass using double-sided tape (STT-125FK, manufactured by Soken Chemical Co., Ltd.). A 180° peel test was performed on the laminate attached to the glass using a Tensilon (Tensilon universal testing machine manufactured by A&D Co., Ltd.), in which the temporary support, held at one end, was peeled 180° toward the other end, under conditions of a temperature of 25°C and a peeling speed of 300 mm / min, and the peel force was measured.

[0350] (Evaluation) The following evaluations were performed using each photosensitive transfer material from the examples and comparative examples. The evaluation results are shown in Table 5.

[0351] 1. Peelability between the thermoplastic resin layer and the intermediate layer 1-1. Manufacturing of evaluation laminates (1) Examples 1 and 2, and Comparative Example 1 An Invar substrate was prepared as a metal substrate. The surface roughness Rmax of the Invar substrate was 0.80 μm. The average thickness of the Invar substrate was 50 μm. The photosensitive transfer material was cut to a size of 30 mm × 100 mm and the protective film was peeled off. Using a roll laminator, the photosensitive transfer material and the Invar substrate were bonded together under the conditions of a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called lamination speed) of 4 m / min. The photosensitive resin layer, intermediate layer, thermoplastic resin layer, and temporary support were arranged on the surface of the Invar substrate in this order. An evaluation laminate was obtained as described above.

[0352] 1-2. Evaluation Test The obtained laminate was autoclaved under the conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a processing time of 1 hour. The treated laminate was attached to 0.7 mm thick glass using double-sided tape (STT-125FK, manufactured by Soken Chemical Co., Ltd.). A 180° peel test was performed on the laminate attached to the glass using Tensilon, under the conditions of a temperature of 25°C and a peeling speed of 300 mm / min, and this test was performed 20 times. The laminate after the peel test was also observed to confirm the peel interface. Then, the peelability between the thermoplastic resin layer and the intermediate layer was evaluated according to the evaluation criteria below. In the evaluation criteria below, "A" and "B" are practically acceptable levels, and "A" is preferred.

[0353] -Evaluation Criteria- A: In all 20 trials, delamination occurs between the thermoplastic resin layer and the intermediate layer, and there is no residue of the thermoplastic resin layer in the intermediate layer. B: In all 20 trials, delamination occurs between the thermoplastic resin layer and the intermediate layer, but there is some residue of the fractured thermoplastic resin layer in the intermediate layer. C: In one or more of the 20 trials, delamination occurs at an interface other than between the thermoplastic resin layer and the intermediate layer across the entire surface. D: In all 20 trials, delamination occurs at an interface other than between the thermoplastic resin layer and the intermediate layer across the entire surface.

[0354] <Examples 3-7, Comparative Example 2> The same procedure as in Example 1 was followed to prepare the photosensitive transfer materials for Examples 3-7 and Comparative Example 2, except that the compositions of the temporary support A1, composition C1, composition P1, and composition R1 were those listed in Table 5.

[0355] A laminate is prepared and evaluated in the same manner as in Example 1. In Table 5, ">300" indicates a value greater than 300 mN / cm.

[0356]

[0357] As shown in Table 5, the photosensitive transfer material according to this disclosure satisfies formula (1) when the temporary support is peeled off, resulting in separation between the thermoplastic resin layer and the intermediate layer, and the peelability between the thermoplastic resin layer and the intermediate layer is stable.

[0358] On the other hand, it was confirmed that the photosensitive transfer materials of Comparative Examples 1 and 2, which did not satisfy formula (1) for peeling force, sometimes did not peel between the thermoplastic resin layer and the intermediate layer, and that the peelability between the thermoplastic resin layer and the intermediate layer was also unstable.

[0359] The disclosure of Japanese Patent Application No. 2025-046049, filed on 19 March 2025, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, wherein the peel force Fa between the temporary support and the thermoplastic resin layer and the peel force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship given by formula (1): Fa ≥ 150 mN / cm > Fb (1) 2. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer comprises a copolymerized polyester resin.

3. The photosensitive transfer material according to claim 1, wherein the temporary support has an easy-adhesion layer, and the easy-adhesion layer and the thermoplastic resin layer are in contact.

4. The photosensitive transfer material according to claim 1, wherein the intermediate layer is a coated film containing a polyvinyl alcohol-based resin.

5. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer comprises a surfactant containing silicon.

6. A method for producing a photosensitive transfer material, comprising the step of forming a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer on a temporary support in this order by coating and drying, wherein the peeling force Fa between the temporary support and the thermoplastic resin layer and the peeling force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship given by formula (1): Fa ≥ 150 mN / cm > Fb (1) 7. A method for producing a photosensitive transfer material, comprising the steps of: forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer on a protective film in that order by coating and drying; and bonding a temporary support to the thermoplastic resin layer by heat lamination, wherein the peel force Fa between the temporary support and the thermoplastic resin layer and the peel force Fb between the thermoplastic resin layer and the intermediate layer satisfy the relationship given by formula (1): Fa ≥ 150 mN / cm > Fb (1)

Images