Photosensitive transfer material and method for producing the same

Abstract

To provide a photosensitive transfer material which has a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, is peeled between the thermoplastic resin layer and the intermediate layer when the temporary support is peeled, and is excellent in peelability between the thermoplastic resin layer and the intermediate layer, and a method for producing the same.SOLUTION: There are provided a photosensitive transfer material which has a temporary support, a thermoplastic resin layer containing a copolyester resin, an intermediate layer, and a photosensitive resin layer, in this order; and a method for producing the same.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a photosensitive transfer material and a method for producing the same. [Background technology]

[0002] Conventionally, photosensitive transfer materials, also called dry film resists, have been widely used because they can easily form resist patterns on various substrates. According to the photosensitive transfer material, a photosensitive resin layer provided on an arbitrary substrate by transfer is exposed through a photomask (hereinafter, also simply referred to as "mask") having a desired pattern, and then developed to obtain a required pattern shape.

[0003] As an example of a photosensitive transfer material, Patent Document 1 discloses a pattern-forming material having, on a support, a cushion layer made of an ethylene-vinyl acetate copolymer resin, which is a thermoplastic resin, a barrier layer, and a photosensitive layer, in that order. Patent Document 2 discloses a photosensitive transfer material having, in this order, a photosensitive layer, an intermediate layer, an adhesive layer containing an adhesive such as an acrylic adhesive, and a temporary support on a cover film. Patent Document 3 discloses a transfer film having, on a temporary support, a thermoplastic resin layer made of an acrylic resin, a water-soluble resin layer, a photosensitive layer, and a protective film in this order. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2007-178459 A [Patent Document 2] International Publication No. 2019 / 146380 [Patent Document 3] JP 2022-168819 A Summary of the Invention [Problem to be solved by the invention]

[0005] Patterning using dry film resist requires higher resolution. For example, in the manufacturing process of semiconductor package substrates, attempts are being made to form copper wiring patterns of 3 μm or less by using fine patterns formed with dry film resist in a semi-additive process. In addition, for example, metal masks with minute through-holes used in the manufacture of OLEDs (Organic Light Emitting Diodes) are required to be finer, with hole widths of 15 μm or less, as OLEDs become more precise.

[0006] Incidentally, there are three types of exposure methods for dry film resist, for example, contact exposure method, proximity exposure method, and projection exposure method. Among these exposure methods, the contact exposure method is an exposure method that uses a relatively inexpensive exposure machine, has high productivity, and can obtain a relatively high resolution. In the contact exposure method, the shorter the distance from the mask to the resist, i.e., the shorter the exposure gap, the less the image blurring and the higher the resolution of the image that is faithful to the mask can be obtained. Therefore, in order to form a high-resolution resist pattern, attempts have been made to shorten the exposure gap by peeling off and removing the temporary support before exposure.

[0007] However, for example, in the case of a photosensitive transfer material having a photosensitive resin layer on the surface of a temporary support, if the temporary support is peeled off and then exposed before exposure, the mask may stick to the surface of the photosensitive resin layer exposed by the peeling of the temporary support, which may reduce workability such as transport. In order to prevent adhesion between the photosensitive resin layer and the mask, for example, it is possible to configure 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 peeling between the temporary support and the photosensitive resin layer does not occur when the temporary support is peeled off.

[0008] The present disclosure has been made in consideration of the above-mentioned circumstances. The problem that one embodiment of the present disclosure aims to solve is to provide a photosensitive transfer material that has a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, and that peels off between the thermoplastic resin layer and the intermediate layer when the temporary support is peeled off, and that has excellent peelability between the thermoplastic resin layer and the intermediate layer. Another problem to be solved by another embodiment of the present disclosure is to provide a method for producing the above-mentioned photosensitive transfer material. [Means for solving the problem]

[0009] Specific means for solving the above problems include the following embodiments. <1> A photosensitive transfer material having, in this order, a temporary support, a thermoplastic resin layer containing a copolymer polyester resin, an intermediate layer, and a photosensitive resin layer. <2> The thermoplastic resin layer is a coating film. <1> 2. The photosensitive transfer material according to claim 1 . <3> The thermoplastic resin layer and the intermediate layer are in contact with each other. <1> or <2> 2. The photosensitive transfer material according to claim 1 . <4> The peel strength between the thermoplastic resin layer and the intermediate layer is 100 mN / cm or less. <3> 2. The photosensitive transfer material according to claim 1 . <5> The copolymer polyester resin 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. <1> ~ <4> 10. The photosensitive transfer material according to claim 9, <6> The intermediate layer is a coating film containing polyvinyl alcohol. <1> ~ <5> 10. The photosensitive transfer material according to claim 9, <7> The photosensitive resin layer contains a surfactant containing silicon. <1> ~ <6> 10. The photosensitive transfer material according to claim 9, <8> The thermoplastic resin layer contains a surfactant containing silicon. <1> ~ <7> 10. The photosensitive transfer material according to claim 9, <9> A method for producing a photosensitive transfer material, comprising a step of forming, on a temporary support, a thermoplastic resin layer containing a copolymer polyester resin, an intermediate layer, and a photosensitive resin layer by coating and drying in this order. <10> forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer containing a copolymer polyester resin on a protective film by coating and drying in this order; a step of bonding a temporary support to the thermoplastic resin layer by thermal lamination; A method for producing a photosensitive transfer material comprising the steps of: Effect of the Invention

[0010] According to one embodiment of the present disclosure, there is provided a photosensitive transfer material having a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, in which peeling occurs between the thermoplastic resin layer and the intermediate layer when the temporary support is peeled off, and which has excellent peelability between the thermoplastic resin layer and the intermediate layer. According to another embodiment of the present disclosure, there is provided a method for producing the above-mentioned photosensitive transfer material. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a photosensitive transfer material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present disclosure will be described in detail below. The following description of the requirements may be based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment, and can be modified as appropriate within the scope of the purpose of the present disclosure.

[0013] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in the present disclosure. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

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

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

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

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

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

[0019] In the present disclosure, the ratio of the constituent units of a polymer compound is a mass ratio unless otherwise specified.

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

[0021] In this disclosure, unless otherwise specified, the hue is a value measured using a color difference meter. As the color difference meter, for example, a color difference meter (model number: CR-221) manufactured by Minolta Co., Ltd. can be used. However, the color difference meter 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 the present disclosure, "alkali-soluble" means that the solubility in 100 g of a 1.0 mass % aqueous sodium carbonate solution at a liquid temperature of 22°C is 0.1 g or more.

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

[0025] In the present disclosure, the "solid content" of a composition means components that form a layer formed using the composition, and when the composition contains a solvent, means all components excluding the solvent. In addition, liquid components other than the solvent that form a layer are also considered to be solid contents. 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" refers to, for example, ultraviolet light, visible light, and infrared light. In this disclosure, "ultraviolet light" refers to light in the wavelength range of 200 nm or more and less than 400 nm, "visible light" refers to light in the wavelength range of 400 nm or more and less than 780 nm, and "infrared light" refers to light in the wavelength range of 780 nm or more and less than 1000 nm.

[0028] [Photosensitive transfer material] The photosensitive transfer material according to the present disclosure has, in this order, a temporary support, a thermoplastic resin layer containing a copolymer polyester resin, an intermediate layer, and a photosensitive resin layer. The photosensitive transfer material according to the present disclosure has a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, and when the temporary support is peeled off, the thermoplastic resin layer and the intermediate layer peel off, and the thermoplastic resin layer and the intermediate layer have excellent peelability.

[0029] Patterning using dry film resist requires high resolution. In the contact exposure method, which is one of the exposure methods for dry film resist, the shorter the exposure gap, the less blurring of the image and the higher the resolution of the image faithful to the mask. In an attempt to obtain a high-resolution resist pattern by shortening the light gap, exposure is performed after peeling off the temporary support before exposure. However, for example, in the case of a photosensitive transfer material having a photosensitive resin layer on the surface of the temporary support, if the temporary support is peeled off before exposure and then exposed, the mask may stick to the surface of the photosensitive resin layer exposed by peeling off the temporary support, making transportation difficult, and other workability may be reduced. The photosensitive transfer material according to the present disclosure has a thermoplastic resin layer and an intermediate layer, in that order from the temporary support side, between the temporary support and the photosensitive resin layer, and since the thermoplastic resin layer contains a copolymerized polyester resin, peeling occurs between the thermoplastic resin layer and the intermediate layer when the temporary support is peeled off, and the peelability between the thermoplastic resin layer and the intermediate layer is excellent.

[0030] In contrast to the photosensitive transfer material according to the present disclosure, the pattern-forming material described in Patent Document 1 (JP 2007-178459 A) has a cushion layer (so-called thermoplastic resin layer) and a barrier layer (so-called intermediate layer) between the temporary support and the photosensitive layer, and when the temporary support is peeled off, the cushion layer (so-called thermoplastic resin layer) and the barrier layer (so-called intermediate layer) are peeled off, but the cushion layer is a layer made of ethylene-vinyl acetate copolymer resin and does not contain a copolymer polyester resin. The pattern-forming material described in Patent Document 1 is considered to have poor peelability between the cushion layer and the barrier layer due to the high adhesiveness of the cushion layer made of ethylene-vinyl acetate copolymer resin (for example, see Comparative Example 4 described later). In the photosensitive transfer material described in Patent Document 2 (WO 2019 / 146380), peeling occurs between the adhesive layer and the intermediate layer when the temporary support is peeled off, but the adhesive layer is a layer containing an adhesive such as an acrylic adhesive, and is not a thermoplastic resin layer containing a copolymer polyester resin. It is presumed that the photosensitive transfer material described in Patent Document 2 has high adhesion of the adhesive layer and poor peelability between the cushion layer and the barrier layer. The transfer film described in Patent Document 3 (JP 2022-168819 A) has a thermoplastic resin layer and a water-soluble resin layer between the temporary support and the photosensitive layer, but the thermoplastic resin layer is a layer made of an acrylic resin and does not contain a copolymer polyester resin. It is considered that when the temporary support is peeled off from the transfer film described in Patent Document 3, the thermoplastic resin layer and the water-soluble resin layer do not peel off from each other, but peel off from the temporary support and the thermoplastic resin layer (for example, see Comparative Example 1 described later).

[0031] In the photosensitive transfer material according to the present disclosure, when an attempt is made to peel off the temporary support before exposure, the thermoplastic resin layer is removed in addition to the temporary support, and therefore the exposure gap is shorter than when only the temporary support is removed, making it possible to form a resist pattern with higher resolution. Furthermore, in the photosensitive transfer material according to the present disclosure, the photosensitive resin layer is not exposed by peeling off the temporary support, and therefore even when exposure is performed using a contact exposure method, the mask and the photosensitive resin layer do not come into contact with each other, and there is no reduction in workability due to the mask sticking to the exposed surface of the photosensitive resin layer. In addition, the photosensitive transfer material according to the present disclosure has excellent peelability between the thermoplastic resin layer and the intermediate layer, which allows operations such as transportation to be performed smoothly, and can improve the productivity of, for example, patterned substrates.

[0032] In addition, the photosensitive transfer material according to the present disclosure has a thermoplastic resin layer containing a copolymer polyester resin, which can have the effect of making it difficult for air bubbles (so-called lamination bubbles) to be mixed between the material and the target object when the material is attached to the target object. In contrast, for example, the photosensitive transfer material described in Patent Document 2 does not have a thermoplastic resin layer itself, and is formed by laminating a temporary support having an adhesive layer and an intermediate layer, so that air bubbles and / or foreign matter tend to be easily trapped between the adhesive layer and the intermediate layer when they are laminated. The trapped air bubbles and / or foreign matter can cause defects on the exposed surface of the intermediate layer when the temporary support is peeled off, and can be a cause of defects in the resist pattern.

[0033] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a photosensitive transfer material. A photosensitive transfer material 10 shown in FIG. 1 has a temporary support 11, 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 have 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 a multilayer consisting of two or more layers.

[0035] The photosensitive transfer material according to the present disclosure preferably has, in this order, a temporary support, a thermoplastic resin layer containing a copolymer polyester resin (also simply referred to as a "thermoplastic resin layer"), an intermediate layer, and a photosensitive resin layer, and the thermoplastic resin layer and the intermediate layer are in contact with each other. The photosensitive transfer material according to the present disclosure preferably further has a protective film on the photosensitive resin layer. For example, the photosensitive transfer material according to the present disclosure preferably has a configuration of temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film.

[0036] In the photosensitive transfer material according to the present disclosure, the thermoplastic resin layer and the intermediate layer are in contact with each other, and the peel strength between the thermoplastic resin layer and the intermediate layer (so-called interlayer peel strength) is preferably 100 mN / cm or less, more preferably 50 mN / cm or less, and even more preferably 25 mN / cm or less. The lower limit of the peel strength between the thermoplastic resin layer and the intermediate layer is not particularly limited, but may be, for example, 1 mN / cm or more, or 10 mN / cm or more.

[0037] The peel strength between the thermoplastic resin layer and the intermediate layer in the photosensitive transfer material according to the present disclosure is measured by the following method. The photosensitive transfer material and the Invar substrate are laminated together to obtain a laminate for evaluation in which the photosensitive resin layer, the intermediate layer, the thermoplastic resin layer, and the temporary support are arranged in this order on the surface of the Invar substrate. The photosensitive transfer material and the Invar substrate are laminated together using a roll laminator under 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 laminate obtained is then autoclaved under conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour. The laminate after the treatment is attached to a glass having a thickness of 0.7 mm using a double-sided tape. A 180° peel test is performed on the laminate attached to the glass using Tensilon to peel the thermoplastic resin layer and the intermediate layer at a peel speed of 300 mm / min, and the peel force is measured. As the Tensilon, for example, a Tensilon universal material testing machine RTF-1210 (model number) manufactured by A & D Co., Ltd. can be suitably used. However, the Tensilon is not limited to this.

[0038] Hereinafter, each component of the photosensitive transfer material according to the present disclosure will be described in detail.

[0039] <Temporary support> The photosensitive transfer material according to the present disclosure has a temporary support. The temporary support is a member that supports the transfer layer, and is ultimately removed by peeling. In the present disclosure, the term "transfer layer" refers to a layer other than the temporary support in the photosensitive transfer material, which is placed on the target by laminating the photosensitive transfer material and the target when using the photosensitive transfer material. In one embodiment, the transfer layer is a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer.

[0040] The temporary support is preferably a film, more preferably a resin film, which is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Specific examples of the temporary support include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film. The temporary support is preferably a polyethylene terephthalate film. The film used as the temporary support is preferably free from deformation such as wrinkles and scratches.

[0041] From the viewpoint of enabling pattern exposure through the 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 (=amount of emitted light / amount of incident light×100;%).

[0042] From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 5% or less, more preferably 2% or less, further 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 (eg, NDH400, a haze meter manufactured by Nippon Denshoku Industries Co., Ltd.).

[0043] From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferred that the temporary support contains fewer coarse particles, foreign matter and defects. The total number of particles, foreign objects, and defects with a diameter of 1 μm or more contained in the temporary support is 50 / 10 mm. 2 It is preferable that the number of pieces is less than 10 pieces / 10 mm. 2 More preferably, 3 pieces / 10 mm or less. 2 More preferably, 0 pieces / 10 mm or less. 2 It is particularly preferred that:

[0044] From the viewpoint of resolution in pattern exposure through the 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. 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 means an average thickness calculated by arithmetic average of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0045] Preferred temporary supports include, for example, a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm.

[0046] As the temporary support, a commercially available product can be used. Commercially available examples of the temporary support include Lumirror (registered trademark) 16KS40, Lumirror (registered trademark) 16FB40, Lumirror (registered trademark) #38-U48, Lumirror (registered trademark) #75-U34, and Lumirror (registered trademark) #25T60 (all manufactured by Toray Industries, Inc.), as well as Cosmoshine (registered trademark) A4100, Cosmoshine (registered trademark) A4160, Cosmoshine (registered trademark) A4300, Cosmoshine (registered trademark) A4360, and Cosmoshine (registered trademark) A8300 (all manufactured by Toyobo Co., Ltd.).

[0047] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of JP 2014-85643 A, paragraphs 0019 to 0026 of JP 2016-27363 A, paragraphs 0041 to 0057 of WO 2012 / 081680 A, paragraphs 0029 to 0040 of WO 2018 / 179370 A, and paragraphs 0012 to 0032 of JP 2019-101405 A. The contents of the above publications are incorporated herein by reference.

[0048] From the viewpoint of handling properties, the temporary support may have a layer containing fine particles (also called a "lubricant layer"). The lubricant layer is preferably disposed 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.

[0049] <Thermoplastic resin layer> The photosensitive transfer material according to the present disclosure has a thermoplastic resin layer containing a copolymer polyester resin. The copolymerized polyester resin contained in the thermoplastic resin layer has a lower crystallinity and melting point than polyester resins other than the copolymerized polyester resin, and therefore the thermoplastic resin layer containing the thermoplastic resin layer tends to have a high thermoplasticity. Since the photosensitive transfer material according to the present disclosure has a thermoplastic resin layer with high thermoplasticity, for example, when it is attached to an object, air bubbles are unlikely to be mixed between the photosensitive transfer material and the object, and the photosensitive transfer material tends to have excellent adhesion to the object.

[0050] (copolymer polyester resin) The thermoplastic resin layer contains a copolymer polyester resin. In the present disclosure, the term "copolymerized polyester resin" refers to a polyester resin in which at least one of the repeating units constituting the polyester resin, a dicarboxylic acid unit or a diol component unit, is composed of multiple types of constituent units. The dicarboxylic acid units and diol component units constituting the copolymerized polyester resin may be one type of dicarboxylic acid unit and two or more types of diol component units, two or more types of dicarboxylic acid units and one type of diol component units, or two or more types of dicarboxylic acid units and two or more types of diol component units.

[0051] The copolymer polyester resin may be a crystalline copolymer polyester resin or an amorphous copolymer polyester resin, but is preferably an amorphous copolymer polyester resin.

[0052] 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, and 2,6-naphthalenedicarboxylic acid. Examples of the diol component 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.

[0053] The copolymerized polyester resin preferably contains a structural unit derived from a monomer having an aromatic ring. When the copolymerized polyester resin contains a structural unit derived from a monomer having an aromatic ring, for example, when the temporary support is polyethylene terephthalate, the adhesion between the thermoplastic resin layer and the temporary support due to π-π stacking tends to be improved. In addition, when the copolymerized polyester resin contains a structural unit derived from a monomer having an aromatic ring, the glass transition temperature (Tg) is appropriately increased, so that the peelability between the thermoplastic resin layer and the intermediate layer tends to be further improved. Examples of the monomer having an aromatic ring include dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid. Examples of the monomer having an aromatic ring include diol components such as bisphenol A and ethylene oxide adducts of bisphenol A.

[0054] The copolymer polyester resin may contain a constituent unit derived from a monomer other than the dicarboxylic acid 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 a small amount of these monomers, a branched copolymer polyester can be obtained, and the melt viscosity of the copolymer polyester can be adjusted. Examples of tricarboxylic acids include trimellitic acid, 1,3,5-benzenetricarboxylic acid, etc. Examples of triol components include glycerin, 1,2,4-butanetriol, etc.

[0055] The total content of the dicarboxylic acid units and the diol component units in the copolymerized polyester resin is preferably 50 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 99 mass% or more, based on all units constituting the copolymerized polyester resin. The upper limit of the total content of the dicarboxylic acid units and the diol component units in the copolymerized polyester resin is not particularly limited, but may be, for example, 100% by mass based on all units constituting the copolymerized polyester resin.

[0056] From the viewpoint of excellent peelability between the thermoplastic resin layer and the intermediate layer, the copolymer polyester resin preferably has a number average molecular weight in the range of 3000 or more and 30,000 or less and a glass transition temperature in the range of -20°C or more and 80°C or less, more preferably a number average molecular weight in the range of 4000 or more and 20,000 or less and a glass transition temperature in the range of 10°C or more and 50°C or less, even more preferably a number average molecular weight in the range of 5000 or more and 10,000 or less and a glass transition temperature in the range of 20°C or more and 50°C or less, and particularly preferably a number average molecular weight in the range of 6000 or more and 10,000 or less and a glass transition temperature in the range of 30°C or more and 45°C or less.

[0057] When the thermoplastic resin layer contains two or more kinds of copolymerized polyester resins, the number average molecular weight and glass transition temperature of the copolymerized polyester resins each mean a weighted average value.

[0058] As the copolymer polyester resin, commercially available products can be used. Examples of commercially available copolymer polyester resins include VYLON (registered trademark) BX-1001 [Mn: 28,000, Tg: -18°C, manufactured by Toyobo Co., Ltd.], VYLON (registered trademark) GK-800 [Mn: 27,000, Tg: 50°C, manufactured by Toyobo Co., Ltd.], VYLON (registered trademark) 802 [Mn: 3,000, Tg: 60°C, manufactured by Toyobo Co., Ltd.], VYLON (registered trademark) 670 [Mn: 30,000, Tg: 7°C, manufactured by Toyobo Co., Ltd.], VYLON (registered trademark) GK-830 [Mn: 32,000, Tg: 25°C, manufactured by Toyobo Co., Ltd.], VYLON (registered trademark) GK-140 [Mn: 13,000, Tg: 20°C, manufactured by Toyobo Co., Ltd.], VYLON (registered trademark) Examples of such polyimide polymers include GK-780 (Mn: 11000, Tg: 36°C, manufactured by Toyobo Co., Ltd.), Vylon (registered trademark) GK-810 (Mn: 6000, Tg: 46°C, manufactured by Toyobo Co., Ltd.), Vylon (registered trademark) GK-590 (Mn: 7000, Tg: 15°C, manufactured by Toyobo Co., Ltd.), and Vylon (registered trademark) GK-890 (Mn: 11000, Tg: 17°C, manufactured by Toyobo Co., Ltd.).

[0059] The thermoplastic resin layer may contain only one type of copolymer polyester resin, or may contain two or more types of copolymer polyester resin.

[0060] From the viewpoint of achieving better peelability between the thermoplastic resin layer and the intermediate layer, the content of the copolymerized polyester resin in the thermoplastic resin layer is preferably in the range of 10% by mass or more and 100% by mass or less, more preferably in the range of 50% by mass or more and 100% by mass or less, and even more preferably in the range of 90% by mass or more and 100% by mass or less, relative to the total mass of the thermoplastic resin layer.

[0061] (Various additives) The thermoplastic resin layer may contain known additives as necessary, as long as the effects of the present disclosure are not impaired. The additives include, for example, a polymerization inhibitor, a surfactant, and a solvent.

[0062] The thermoplastic resin layer may contain a polymerization inhibitor. The polymerization inhibitor in the thermoplastic resin layer has the same meaning as the polymerization inhibitor in the photosensitive resin layer described below, and preferred embodiments are also the same.

[0063] When the thermoplastic resin layer contains a polymerization inhibitor, it may contain only one type of polymerization inhibitor, or may contain two or more types of polymerization inhibitors.

[0064] 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 mass% or more and 10 mass% or less, more preferably in the range of 0.1 mass% or more and 1 mass% or less, and even more preferably in the range of 0.1 mass% or more and 0.5 mass% or less, relative to the total mass of the thermoplastic resin layer.

[0065] The thermoplastic resin layer may contain a surfactant. The surfactant in the thermoplastic resin layer has the same meaning as the surfactant in the photosensitive resin layer described below, and the preferred embodiments are also the same. For example, when the thermoplastic resin layer contains a surfactant, the thermoplastic resin layer preferably contains a surfactant containing silicon from the viewpoint of peelability between the thermoplastic resin layer and the intermediate layer. Furthermore, when the thermoplastic resin layer contains a surfactant, from the viewpoint of improving environmental compatibility, the surfactant is preferably a silicon-containing surfactant.

[0066] When the thermoplastic resin layer contains a surfactant, it may contain only one type of surfactant, or may contain two or more types of surfactants.

[0067] When the thermoplastic resin layer contains a surfactant, the content of the surfactant in the thermoplastic resin layer is preferably in the range of 0.001 mass% or more and 1 mass% or less, more preferably in the range of 0.01 mass% or more and 1 mass% or less, and even more preferably in the range of 0.1 mass% or more and 0.5 mass% or less, relative to the total mass of the thermoplastic resin layer.

[0068] The thermoplastic resin layer may contain a solvent. When a thermoplastic resin layer is formed from a composition containing a solvent, the solvent may remain in the thermoplastic resin layer.

[0069] The thermoplastic resin layer may also contain known additives such as a rust inhibitor, an antioxidant, a colorant, a plasticizer, and a polymerizable compound.

[0070] The thermoplastic resin layer is preferably a coating film. In the present disclosure, the term "coated film" refers to a film formed by coating and drying. Since the copolymer 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. By using the coating method, a thermoplastic resin layer having high uniformity in thickness and smoothness can be obtained. The coating method is less likely to cause surface defects such as fish eyes, streaks, and unevenness, compared to, for example, the melt extrusion lamination method. When the thermoplastic resin layer is a coating film, defects in the resist pattern caused by the surface defects of the thermoplastic resin layer affecting the surface state of the intermediate layer are less likely to occur, and a resist pattern with high resolution tends to be obtained more easily.

[0071] <<Thickness of thermoplastic resin layer>> The thickness of the thermoplastic resin layer is preferably from 0.5 μm to 50 μm, more preferably from 1 μm to 20 μm, and further preferably from 3 μm to 10 μm. 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 the temporary support is peeled off, the thermoplastic resin layer and the intermediate layer tend to peel off, and the peelability between the thermoplastic resin layer and the intermediate layer tends to be excellent. In addition, it is possible to achieve the effect that it is more difficult for air bubbles (so-called lamination bubbles) to be mixed between the thermoplastic resin layer and the object when it is laminated to the object. The thickness of the thermoplastic resin refers to an average thickness calculated by arithmetic averaging of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0072] <Method of forming thermoplastic resin layer> The method for forming the thermoplastic resin layer is not particularly limited as long as the desired thermoplastic resin layer can be obtained. Examples of methods for forming a thermoplastic resin layer include a method in which a composition for forming a thermoplastic resin layer containing a thermoplastic resin including a copolymer polyester resin and any additives is prepared, the prepared composition for forming a thermoplastic resin layer is applied to a temporary support or an intermediate layer, and the applied composition for forming a thermoplastic resin layer is dried to form the layer.

[0073] 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 the viscosity. Examples of the solvent 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.

[0074] The solvent is preferably a solvent 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 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, and even more preferably 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.

[0075] 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. Ketone solvents include, for example, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, diisobutyl ketone, and diacetone alcohol. Ester solvents include, for example, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl lactate, ethyl lactate, and propyl lactate. Aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, Solvesso 100, Solvesso 150, and Solvesso 200.

[0076] When the thermoplastic resin layer-forming composition contains a solvent, it may contain only one type of solvent, or may contain two or more types of solvent.

[0077] When the composition for forming a thermoplastic resin layer contains a solvent, the content of the solvent when applying the composition for forming a thermoplastic resin layer is preferably 50 parts by mass to 1900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, per 100 parts by mass of the total solid content in the composition for forming a thermoplastic resin layer.

[0078] The method for preparing the composition for forming a thermoplastic resin layer is not particularly limited, and examples thereof include a method in which a solution is prepared in advance by dissolving each component in the above-mentioned solvent, and the obtained solutions are mixed in a predetermined ratio to prepare the composition for forming a thermoplastic resin layer. The composition for forming a thermoplastic resin layer is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the thermoplastic resin layer.

[0079] The method for applying the composition for forming a thermoplastic resin layer is not particularly limited, and may be a known method, such as slit coating, spin coating, curtain coating, or inkjet coating.

[0080] As a method for drying the applied thermoplastic resin layer-forming composition, heat drying and reduced pressure drying are preferred. In the present disclosure, "drying" refers to removing at least a part of the solvent contained in the composition. Drying methods include, for example, natural drying, heat drying, and reduced pressure drying. For drying, the above-mentioned methods can be applied alone 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 is preferably, for example, 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 is preferably, for example, 600 seconds or less, and more preferably 300 seconds or less.

[0081] <Middle Class> The photosensitive transfer material according to the present disclosure has an intermediate layer. The photosensitive transfer material according to the present disclosure has a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, and peels off between the thermoplastic resin layer and the intermediate layer when the temporary support is peeled off. Therefore, in order to obtain a high-resolution resist pattern, if the exposure gap is shortened by peeling off the temporary support and then contact exposure is performed, a mask is attached to the surface of the intermediate layer opposite to the photosensitive resin layer side. The photosensitive transfer material according to the present disclosure has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer, and the mask can be brought into contact with the intermediate layer during exposure. Therefore, for example, compared to the case where the temporary support is peeled off between the temporary support and the thermoplastic resin layer and the mask is brought into contact with the thermoplastic resin layer when the temporary support is peeled off, the mask is less likely to adhere to the layer it contacts, and workability is less likely to decrease.

[0082] (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., hydroxypropylmethylcellulose), acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. In order to suppress mixing of components between adjacent layers, it is preferable that the water-soluble resin contained in the intermediate layer is a resin different from both the thermoplastic resin contained in the thermoplastic resin layer and the resin (e.g., an alkali-soluble resin) contained in the photosensitive resin layer.

[0083] From the viewpoints of oxygen barrier properties and suppressing mixing of components between adjacent layers during application and storage after application, 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.

[0084] The intermediate layer is preferably a coating 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. In addition, since the intermediate layer contains a water-soluble resin, it can be formed by a coating method. By using the coating method, an intermediate layer with high uniformity in thickness and smoothness can be obtained. In addition, the coating method is less likely to cause surface defects such as fish eyes, streaks, and unevenness. When the intermediate layer is a coating film, defects in the resist pattern caused by surface defects of the intermediate layer are less likely to occur, and a resist pattern with high resolution tends to be obtained more easily.

[0085] The intermediate layer is more preferably a coating film containing polyvinyl alcohol as a water-soluble resin, even more preferably a coating film containing polyvinyl alcohol and polyvinylpyrrolidone, and particularly preferably a coating film containing polyvinyl alcohol, polyvinylpyrrolidone, and hydroxypropylmethylcellulose.

[0086] When the intermediate layer contains a water-soluble resin, it may contain only one type of water-soluble resin, or may contain two or more types of water-soluble resin.

[0087] 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, for example, oxygen barrier properties and suppressing mixing of components between adjacent layers during application and storage after application, the content is preferably in the range of 50% by mass or more and 100% by mass or less, more preferably in the range of 70% by mass or more and 100% by mass or less, even more preferably in the range of 80% by mass or more and 100% by mass or less, and particularly preferably in the range of 90% by mass or more and 100% by mass or less, relative to the total mass of the intermediate layer.

[0088] (Various additives) The intermediate layer may contain known additives as necessary, as long as the effects of the present disclosure are not impaired. Additives include, for example, surfactants, particles and solvents.

[0089] The intermediate layer may include a surfactant. The surfactant in the intermediate layer has the same meaning as the surfactant in the photosensitive resin layer described below, and the preferred embodiments are also the same.

[0090] When the intermediate layer contains a surfactant, it may contain only one type of surfactant, or may contain two or more types of surfactants.

[0091] When the intermediate layer contains a surfactant, the content of the surfactant 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.

[0092] The intermediate layer may include particles. If 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 stick to the mask, which tends to suppress the occurrence of contamination due to the intermediate layer adhering to the mask and the deterioration of workability, which are caused by the intermediate layer sticking to the mask.

[0093] The particles are preferably inorganic particles. As the inorganic particles, metal oxide particles are preferred. The metals in the metal oxide particles include metalloids such as B, Si, Ge, As, Sb, and Te.

[0094] The average primary particle size of the particles is not particularly limited, but from the viewpoint of suppressing an increase in haze in the intermediate layer and obtaining a high-resolution resist pattern, it is preferably from 1 nm to 200 nm, and more preferably from 3 nm to 80 nm. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and taking the arithmetic mean of the measurement results. If the particle shape is not spherical, the longest side is used as the particle size.

[0095] When the intermediate layer contains inorganic particles as particles, it may contain only one type of particles having different metal species, sizes, etc., or may contain two or more types of particles. The intermediate layer may contain organic particles as the particles.

[0096] When the intermediate layer contains particles, the particle content in the intermediate layer is not particularly limited, but is, for example, preferably in the range of 1 mass % or more and 50 mass % or less, more preferably in the range of 5 mass % or more and 40 mass % or less, and even more preferably in the range of 10 mass % or more and 30 mass % or less, relative to the total mass of the intermediate layer.

[0097] <<Thickness of intermediate layer>> The thickness of the intermediate layer is preferably from 0.1 μm to 5 μm, and more preferably from 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, for example, the oxygen barrier property is not reduced, mixing of components between adjacent layers during coating and storage after coating can be suppressed, and an increase in the time required to remove the intermediate layer during development can be suppressed. The thickness of the intermediate layer refers to an average thickness calculated by arithmetic averaging of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0098] <Method of forming 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 an intermediate layer include a method in which a composition for forming an intermediate layer containing a water-soluble resin and any additives is prepared, the prepared composition for forming an intermediate layer is applied to a thermoplastic resin layer or a photosensitive resin layer, and the applied composition for forming an intermediate layer is dried to form the intermediate layer.

[0099] The composition for forming the intermediate layer preferably contains a solvent from the viewpoint of facilitating the formation of the intermediate layer by adjusting the 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, the water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol, and even more preferably methanol.

[0100] When the intermediate layer forming composition contains a solvent, it may contain only one type of solvent, or may contain two or more types of solvent.

[0101] When the composition for forming an intermediate layer contains a solvent, the content of the solvent when applying the composition for forming an intermediate layer is preferably 50 parts by mass to 1900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, per 100 parts by mass of the total solid content in the composition for forming an intermediate layer.

[0102] The method for preparing the composition for forming an intermediate layer is not particularly limited, and examples thereof include a method in which a solution is prepared in advance by dissolving each component in the above-mentioned solvent, and the obtained solutions are mixed in a predetermined ratio to prepare the composition for forming an intermediate layer. The composition for forming the intermediate layer is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the intermediate layer.

[0103] The method for applying the composition for forming the intermediate layer is not particularly limited, and may be a known method, for example, slit coating, spin coating, curtain coating, or inkjet coating.

[0104] As a method for drying the applied intermediate layer forming composition, heat drying and reduced pressure drying are preferred. Drying methods include, for example, natural drying, heat drying, and reduced pressure drying. For drying, the above-mentioned methods can be applied alone 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 is preferably, for example, 180° C. or lower, and more preferably 150° C. or lower. The applied composition for forming an intermediate layer 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 is preferably, for example, 600 seconds or less, and more preferably 300 seconds or less.

[0105] <Photosensitive resin layer> The photosensitive transfer material according to the present disclosure has a photosensitive resin layer. According to the photosensitive transfer material according to the present disclosure, for example, after a photosensitive resin layer is transferred onto a transfer-receiving body, a pattern can be formed on the transfer-receiving body by performing exposure and development.

[0106] The photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, but is preferably a negative photosensitive resin layer. The negative photosensitive resin layer is a photosensitive resin layer in which the solubility of the exposed portion in a developer is reduced by exposure to light. When the photosensitive resin layer is a negative photosensitive resin layer, the formed pattern corresponds to a cured layer.

[0107] (Polymer) The photosensitive resin layer preferably contains a polymer. The type of polymer is not particularly limited. A preferred example of the polymer is an alkali-soluble resin. Examples of the alkali-soluble resin include known alkali-soluble resins used in etching resists. The alkali-soluble resin is preferably a binder polymer. The alkali-soluble resin is preferably an alkali-soluble resin having an acid group. A preferred alkali-soluble resin is the polymer A described below.

[0108] The acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g, from the viewpoint of suppressing swelling of the photosensitive resin layer by the developer and thereby further improving the resolution. Also, the acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more, from the viewpoint of more excellent developability. The acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of 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 structural unit constituting polymer A and the content of the structural unit having an acid group.

[0109] The weight average molecular weight of polymer A is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, it is preferable that the weight average molecular weight of polymer A is 500,000 or less. The weight average molecular weight of polymer A is more preferably 100,000 or less, and further preferably 80,000 or less. On the other hand, it is preferable to set the weight average molecular weight of polymer A to 5,000 or more from the viewpoint of controlling the properties of development aggregates and the properties of the unexposed film in the photosensitive resin layer, such as edge fuse property and cut chip property, etc. The weight average molecular weight of polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fusing property refers to the degree of tendency of the photosensitive resin layer to protrude from the edge of a roll when the photosensitive transfer material is wound into a roll. The cut chip property refers to the degree of ease with which chips fly off when an unexposed film is cut with a cutter. If chips adhere to the surface of a photosensitive resin layer, they are transferred to a mask during an exposure process, causing defective products. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. The dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight). In the present disclosure, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured using gel permeation chromatography.

[0110] From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure, polymer A preferably has an aromatic hydrocarbon group, and more preferably has a structural unit having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of the structural unit having an aromatic hydrocarbon group in polymer A is preferably 20 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, particularly preferably 45 mass% or more, and most preferably 50 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 multiple types of polymer A are contained, the content of structural units having an aromatic hydrocarbon group is determined as a weight average value.

[0111] Examples of monomers that form structural units having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, the monomer that forms the structural unit having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.

[0112] Aralkyl groups include, for example, substituted or unsubstituted phenylalkyl groups. The aralkyl group is preferably a substituted or unsubstituted benzyl group.

[0113] An example of a monomer having a substituted or unsubstituted phenylalkyl group other than a benzyl group is phenylethyl (meth)acrylate.

[0114] Examples of monomers having a substituted or unsubstituted benzyl group include (meth)acrylates having a substituted or unsubstituted benzyl group [e.g., benzyl (meth)acrylate and chlorobenzyl (meth)acrylate]; and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol). Among these, the monomer having a substituted or unsubstituted benzyl group is preferably benzyl (meth)acrylate.

[0115] In an embodiment, when the monomer forming the structural unit having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the structural unit derived from benzyl (meth)acrylate is preferably 50 mass% to 95 mass%, more preferably 60 mass% to 90 mass%, even more preferably 70 mass% to 90 mass%, and particularly preferably 75 mass% to 90 mass%, based on the total mass of polymer A.

[0116] In an embodiment, when the monomer forming the structural unit having an aromatic hydrocarbon group in polymer A is styrene, the content of the structural unit derived from styrene is preferably 20 mass% to 60 mass%, more preferably 25 mass% to 60 mass%, even more preferably 30 mass% to 60 mass%, and particularly preferably 30 mass% to 55 mass%, based on the total mass of polymer A.

[0117] The polymer A having a structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one type of a first monomer described later and / or at least one type of a second monomer described later.

[0118] The polymer A having no structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described later, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described later.

[0119] The first monomer is a monomer having a carboxy group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half esters. Among these, (meth)acrylic acid is preferred as the first monomer.

[0120] The content of the structural units derived from the first monomer in polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass to 30% by mass, based on the total mass of polymer A.

[0121] The second monomer is a monomer which is non-acidic and has at least one ethylenically unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among these, as the second monomer, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferable, and methyl (meth)acrylate is more preferable.

[0122] The content of the structural units derived from the second monomer in polymer A is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 15% by mass to 45% by mass, based on the total mass of polymer A.

[0123] From the viewpoint of suppressing line width increase and deterioration of resolution when the focal position is shifted during exposure, polymer A preferably contains at least one type of structural unit selected from the group consisting of structural units having an aralkyl group and structural units derived from styrene. As the polymer A, for example, a copolymer containing benzyl methacrylate, styrene, and methacrylic acid, a copolymer containing styrene, methacrylic acid, and methyl methacrylate, and a copolymer containing benzyl methacrylate, styrene, methacrylic acid, and methyl methacrylate are preferable.

[0124] In one embodiment, polymer A is preferably a polymer containing 40% by mass to 60% by mass of structural units having an aromatic hydrocarbon group, 15% by mass to 25% by mass of structural units derived from a first monomer, and 20% by mass to 40% by mass of structural units derived from a second monomer.

[0125] The polymer A may have a branched structure and / or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain, or a monomer containing a group having an alicyclic structure in the side chain, it is possible to introduce a branched structure or an alicyclic structure into the side chain of polymer A. The alicyclic structure may be a monocyclic structure or a polycyclic structure.

[0126] Examples of monomers containing a group having a branched structure in the 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, as the monomer containing a group having a branched structure in the side chain, i-propyl(meth)acrylate, i-butyl(meth)acrylate, or t-butyl methacrylate is preferred, and i-propyl methacrylate or t-butyl methacrylate is more preferred.

[0127] Examples of monomers containing a group having an alicyclic structure in a side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Examples of monomers containing a group having an alicyclic structure in a side chain include (meth)acrylates having an alicyclic hydrocarbon group with a carbon number (i.e., carbon atom number) of 5 to 20. More specific examples of monomers containing a group having an alicyclic structure in the side chain include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, (1-adamantyl)(meth)acrylate, (2-adamantyl)(meth)acrylate, (3-methyl-1-adamantyl)(meth)acrylate, (3,5-dimethyl-1-adamantyl)(meth)acrylate, (3-ethyladamantyl)(meth)acrylate, (3-methyl-5-ethyl-1-adamantyl)(meth)acrylate, (3,5,8-triethyl-1-adamantyl (meth)acrylate, (3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, (2-methyl-2-adamantyl)(meth)acrylate, (2-ethyl-2-adamantyl)(meth)acrylate, Examples of the acrylates include 3-hydroxy-1-adamantyl acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, as the monomer containing a group having an alicyclic structure in a side chain, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is more preferred.

[0128] When the photosensitive resin layer contains the polymer A, it may contain only one type of the polymer A, or may contain two or more types of the 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 an aromatic hydrocarbon group, or a mixture of a polymer A having an aromatic hydrocarbon group and a polymer A not having an aromatic hydrocarbon group. In the latter case, the content of the polymer A having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the polymer A.

[0129] 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 the above-described monomer or monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. The synthesis of polymer A may be carried out while adding a part of the mixture dropwise to the reaction solution. After the reaction is completed, the solvent may be further added to adjust the concentration to the desired level. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

[0130] The glass transition temperature (also referred to as "Tg") of polymer A is preferably in the range of 30°C or higher and 150°C or lower. In the photosensitive resin layer, the polymer A having a Tg of 150° C. or less can be used to suppress line width thickening or deterioration of resolution caused by deviation of the focal position during exposure. From this viewpoint, the Tg of the polymer A is more preferably 140° C. or less, and further preferably 135° C. or less. Moreover, from the viewpoint of improving edge fuse resistance, it is preferable to use polymer A having a Tg of 30° C. or more. From this viewpoint, the Tg of polymer A is more preferably 40° C. or more, further preferably 50° C. or more, particularly preferably 60° C. or more, and most preferably 70° C. or more.

[0131] When the photosensitive resin layer contains an alkali-soluble resin, it may contain only one type of alkali-soluble resin, or may contain two or more types of alkali-soluble resin.

[0132] 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 is, for example, preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass to 60% by mass, relative to the total mass of the photosensitive resin layer. From the viewpoint of controlling the development time, it is preferable to set the content of the alkali-soluble resin in the photosensitive resin layer to 90 mass % or less based on the total mass of the photosensitive resin layer. On the other hand, it is preferable from the viewpoint of improving edge fuse resistance that the content of the alkali-soluble resin in the photosensitive resin layer is 10 mass % or more based on the total mass of the photosensitive resin layer.

[0133] The photosensitive resin layer may contain a resin other than the alkali-soluble resin. The resin other than the alkali-soluble resin may be a resin having a solubility of less than 0.1 g in 100 g of a 1.0% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C. Examples of resins other than such alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (with the styrene content being 40 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, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0134] (polymerizable compound) The photosensitive resin layer preferably contains a compound having a polymerizable group (so-called polymerizable compound). The "polymerizable compound" refers to a compound that is polymerized by the action of a polymerization initiator and is different from the above-mentioned polymer.

[0135] The polymerizable group is not particularly limited as long as it is a group that is involved in a polymerization reaction. Examples of the polymerizable group include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, a maleimide group, etc. Examples of the polymerizable group also include cationic polymerizable groups such as an epoxy group, an oxetane group, etc. Among these, as the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

[0136] As the polymerizable compound, from the viewpoint of achieving superior photosensitivity of the photosensitive resin layer, a compound having one or more ethylenically unsaturated groups (so-called ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (so-called polyfunctional ethylenically unsaturated compound) is more preferred. From the viewpoint of achieving better resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0137] From the viewpoint of achieving a better balance between the photosensitivity, resolution, and peelability of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and more preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. The content ratio of the bifunctional 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, from the viewpoint of excellent peelability. The upper limit is not particularly limited, and may be, for example, 100% by mass. That is, all of the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. As the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0138] 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 bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned ethylenically unsaturated compounds.

[0139] The mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, from the viewpoint of peelability.

[0140] Examples of the aromatic ring contained in the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; and condensed rings thereof. The aromatic ring contained in the ethylenically unsaturated compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring of the ethylenically unsaturated compound B1 may have a substituent. The ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0141] The ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of suppressing swelling of the photosensitive resin layer due to a developer and thereby further improving the resolution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). Among these, the bisphenol structure is preferably a bisphenol A structure.

[0142] Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure may be bonded to the two polymerizable groups directly or via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy or propyleneoxy, and more preferably ethyleneoxy. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, and more preferably 6 to 14, per molecule. The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP2016-224162A, the contents of which are incorporated herein by reference.

[0143] As the ethylenically unsaturated compound B1, a difunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane [FA-324M, 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.], 2,2-bis(4-( Examples of such ethoxylated bisphenol A diacrylate include 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0144] As the ethylenically unsaturated compound B1, from the viewpoints of the delay time line width change, the development temperature line width change, and the sensitivity, it is preferable to include a compound represented by the following formula (Bis).

[0145] [ka]

[0146] In formula (Bis), R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1 and n3 each independently represent an integer of 1 to 39, and n1+n3 is an integer of 2 to 40, n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 is an integer of 0 to 30, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. When the arrangement of the repeating units of -(AO)- and -(BO)- is block, either -(AO)- or -(BO)- may be on the bisphenol structure side. In one embodiment, n1+n2+n3+n4 is preferably an integer from 2 to 20, more preferably an integer from 2 to 16, and even more preferably an integer from 4 to 12. Furthermore, n2+n4 is preferably an integer from 0 to 10, more preferably an integer from 0 to 4, and even more preferably an integer from 0 to 2, and particularly preferably 0.

[0147] 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 of ethylenically unsaturated compounds B1.

[0148] The content of the ethylenically unsaturated compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (the phenomenon in which components in the photosensitive resin layer bleed out from the edge of the photosensitive transfer material), for example.

[0149] The photosensitive resin layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1. The ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 is not particularly limited and can be appropriately selected from known compounds. Examples of the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 include a compound having one ethylenically unsaturated group in one molecule (a so-called monofunctional ethylenically unsaturated compound), a difunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0150] 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.

[0151] Examples of difunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0152] Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0153] 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.

[0154] Examples of the urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Commercially available urethane di(meth)acrylates include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0155] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified versions of these. The term "(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 the term "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In an embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned 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 compound is preferably (total mass of the ethylenically unsaturated compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compound)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In an embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

[0156] Examples of alkylene oxide modified trifunctional or higher ethylenically unsaturated compounds include caprolactone modified (meth)acrylate compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide modified (meth)acrylate compounds (e.g., KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation), ethoxylated glycerin triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.) and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0157] Further, examples of the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 include the ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942.

[0158] From the viewpoints 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 viewpoints of curability, resolution and linearity, it is more preferable that the ethylenically unsaturated compound in the photosensitive resin layer contains a (meth)acrylic compound, and that the content of the acrylic compound relative to the total mass of the (meth)acrylic compound contained in the photosensitive resin layer is 60 mass% or less.

[0159] The molecular weight of the ethylenically unsaturated compound including the ethylenically unsaturated compound B1 (when the molecular weight has a distribution, the weight average molecular weight (Mw)) is preferably 200 to 3,000, more preferably 280 to 2,200, and further preferably 300 to 2,200.

[0160] When the photosensitive resin layer contains a polymerizable compound, it may contain only one type of polymerizable compound, or may contain two or more types of polymerizable compounds.

[0161] 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, for example, preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, relative to the total mass of the photosensitive resin layer.

[0162] When the photosensitive resin layer contains a polymer and a polymerizable compound, from the viewpoint of unevenness conformability, 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. In addition, 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.

[0163] (Polymerization initiator) The photosensitive resin layer preferably contains a polymerization initiator. The type of polymerization initiator is selected depending on the type of polymerization reaction. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.

[0164] The photosensitive resin layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to actinic rays such as ultraviolet light, visible light, or X-rays. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0165] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0166] From the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution, the photosensitive resin layer preferably contains at least one photoradical polymerization initiator selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0167] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783 may be used.

[0168] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate [DBE, CAS No. 10287-53-3], benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and benzophenone.

[0169] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], IRGACURE (registered trademark) OXE-03 [manufactured by BASF], 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad 379EG, manufactured by IGM Resins BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad 127, manufactured by IGM Resins BV], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad 369, manufactured by IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad 1173, manufactured by IGM Resins BV], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad 184, manufactured by IGM Resins BV], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: Omnirad 651, manufactured by IGM Resins BV] BV], 2,4,6-trimethylbenzoyl-diphenylphosphine oxide [trade name: Omnirad TPO H, IGM Resins BV], bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide [trade name: Omnirad 819, IGM Resins BV]Manufactured by DKSH Japan Co., Ltd.], oxime ester photoinitiator [trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.], 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole [trade name: B-CIM, manufactured by Hampford Chemical Industry 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 Examples of such oxime include 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

[0170] A photocationic polymerization initiator (so-called photoacid generator) is a compound that generates an acid when exposed to actinic rays. As the photocationic polymerization initiator, a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferred, but its chemical structure is not particularly limited. In addition, even if a photocationic polymerization initiator is not directly sensitive to actinic rays having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it responds to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.

[0171] As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of the pKa is not particularly limited, but is preferably, for example, −10.0 or more.

[0172] Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salt compounds and triarylsulfonium salt compounds, and quaternary ammonium salt compounds. The ionic photocationic polymerization initiator may be the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP 2014-85643 A. Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A may be used. As oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 A may be used.

[0173] When the photosensitive resin layer contains a polymerization initiator, it may contain only one type of polymerization initiator or may contain two or more types of polymerization initiators.

[0174] 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. The content of the polymerization initiator in the photosensitive resin layer is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

[0175] (dye) From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a dye, and more preferably 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 more and whose maximum absorption wavelength changes with an acid, a base, or a radical. Although the detailed mechanism is unclear, when the photosensitive resin layer contains dye N, the adhesion with adjacent layers (for example, intermediate layers) is improved, and the resolution is more excellent.

[0176] In the present disclosure, the dye's "maximum absorption wavelength changes due to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, a dye in a decolorized state is colored by an acid, a base, or a radical, and a dye in a colored state changes to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to develop a color upon exposure, or may be a compound that changes from a colored state to decolorize upon exposure. In this case, the dye may be one whose coloring or decoloring state changes as a result of an acid, base, or radical being generated and acting in the photosensitive layer upon exposure, or one whose coloring or decoloring state changes as a result of an acid, base, or radical changing the state (e.g., pH) in the photosensitive resin layer. The dye N may also be one whose coloring or decoloring state changes upon direct stimulation of an acid, base, or radical without exposure.

[0177] From the viewpoints of the visibility of exposed and unexposed areas, and of the resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical.

[0178] From the viewpoints of the visibility of exposed and unexposed areas and resolution, the photosensitive resin layer preferably contains, as dye N, both a dye whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator.

[0179] From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0180] An example of the color-developing mechanism of dye N in the present disclosure is a mode in which a photoradical polymerization initiator, a cationic photopolymerization 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 a radical, acid, or base generated from the photoradical polymerization initiator, the photocationic photopolymerization initiator, or the photobase generator.

[0181] From the viewpoint of visibility of exposed and non-exposed parts, the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm when colored, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm. Furthermore, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm when colored, or may have two or more maximum absorption wavelengths. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm when colored, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0182] The maximum absorption wavelength of dye N can be obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature: 25°C) in the wavelength range of 400 nm to 780 nm using a spectrophotometer (e.g., 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).

[0183] Examples of the dye that develops or loses color upon exposure to light include leuco compounds. Examples of dyes that are decolorized by exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. Among these, as the dye N, a leuco compound is preferable from the viewpoint of visibility of exposed and non-exposed areas.

[0184] Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (so-called triarylmethane dye), a leuco compound having a spiropyran skeleton (so-called spiropyran dye), a leuco compound having a fluoran skeleton (so-called fluoran dye), a leuco compound having a diarylmethane skeleton (so-called diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (so-called rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (so-called indolylphthalide dye), and a leucoauramine skeleton (so-called leucoauramine dye). As the leuco compound, a triarylmethane dye or a fluoran dye is preferable, and a leuco compound having a triphenylmethane skeleton (so-called triphenylmethane dye) or a fluoran dye is more preferable.

[0185] From the viewpoint of visibility of exposed and non-exposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring, whereby the lactone ring, the sultine ring, or the sultone ring of the leuco compound can be reacted with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound to a ring-closed state and thereby to lose color, or the leuco compound can be changed to a ring-opened state and thus to develop color. The leuco compound is preferably a compound which has a lactone ring, a sultine ring or a sultone ring and develops color by ring-opening the lactone ring, the sultine ring or the sultone ring by a radical or an acid, and more preferably a compound which has a lactone ring and develops color by ring-opening the lactone ring by a radical or an acid.

[0186] Specific examples of leuco compounds include p,p',p"-hexamethyltriaminotriphenylmethane (so-called leuco crystal violet), Pergascript Blue SRB (manufactured by Novartis Pharma), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methyl ... )-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N- diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2- 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0187] The colorant N may be, for example, a dye. Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), and 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-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0188] When the photosensitive resin layer contains a dye, it may contain only one type of dye, or may contain two or more types of dye.

[0189] When the photosensitive resin layer contains a dye, the content of the dye in the photosensitive resin layer is, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, even more preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %, relative to the total mass of the photosensitive resin layer. Furthermore, when the photosensitive resin layer contains dye N as a dye, the content of dye N in the photosensitive resin layer is, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, even more preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %, relative to the total mass of the photosensitive resin layer.

[0190] The content of dye N means the content of dye when all of the dye N contained in the photosensitive resin layer is in a color-developing state. In the following, a method for quantifying the content of dye N will be described using a dye that develops color by radicals as an example. Two types of solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF) is added to each of the obtained solutions, and radicals are generated by irradiating light of 365 nm to cause all dyes to develop color. Then, in an air 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 the dyes have developed color is measured by the same method as above, except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.

[0191] (Thermal crosslinkable compound) From the viewpoints of the strength of the resulting cured film and the adhesion of the resulting uncured film, the photosensitive resin layer preferably contains a thermally crosslinkable compound. In the present disclosure, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as an ethylenically unsaturated compound but as a thermally crosslinkable compound.

[0192] Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound. Among these, the thermally crosslinkable compound is preferably a blocked isocyanate compound from the viewpoints of the strength of the resulting cured film and the adhesion of the resulting uncured film.

[0193] Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the alkali-soluble resin and / or the ethylenically unsaturated compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when the film obtained by curing the photosensitive resin layer is used as a protective film. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0194] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably from 100°C to 160°C, and more preferably from 130°C to 150°C, for example. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of a blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

[0195] Examples of blocking agents having 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., compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime]. The blocking agent having a dissociation temperature of 100° C. to 160° C. preferably contains an oxime compound, for example, from the viewpoint of storage stability.

[0196] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoints of improving the brittleness of the film and improving the adhesive strength with the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by converting it into an isocyanurate. Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred from the viewpoints that the dissociation temperature can be set in a preferred range more easily and development residues can be reduced more easily than a compound not having an oxime structure.

[0197] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and includes known polymerizable groups, and is preferably a radically polymerizable group. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group. The polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0198] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E and Duranate (registered trademark) WT32-B75P, manufactured by Asahi Kasei Chemicals Corporation). In addition, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0199] [ka]

[0200] When the photosensitive resin layer contains a thermally crosslinkable compound, it may contain only one type of thermally crosslinkable compound, or may contain two or more types of thermally crosslinkable compounds.

[0201] 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, for example, preferably 1 mass % to 50 mass % and more preferably 5 mass % to 30 mass % relative to the total mass of the photosensitive resin layer.

[0202] (Other ingredients) The photosensitive resin layer may contain components (also referred to as "other components") other than the components described above, as necessary, to the extent that the effects of the present disclosure are not impaired. Examples of the other components include a polymerization inhibitor, a surfactant, a sensitizer, and various additives. When the photosensitive resin layer contains other components, it may contain only one type of other component, or may contain two or more types of other components.

[0203] -Polymerization inhibitor- The photosensitive resin layer may contain a polymerization inhibitor. The polymerization inhibitor is preferably a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. The radical polymerization inhibitor is preferably phenothiazine, phenoxazine, or 4-methoxyphenol. In order not to impair the sensitivity of the photosensitive resin layer, it is also preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0204] When the photosensitive resin layer contains a polymerization inhibitor, it may contain only one type of polymerization inhibitor, or may contain two or more types of polymerization inhibitors.

[0205] When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive resin layer is preferably 0.001 mass % to 5.0 mass %, more preferably 0.01 mass % to 3.0 mass %, and even more preferably 0.02 mass % to 2.0 mass %, relative to the total mass of the photosensitive resin layer.

[0206] Furthermore, the content of the polymerization inhibitor in the photosensitive resin layer is preferably 0.005% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.01% by mass to 1.0% by mass, relative to the total mass of the polymerizable compound.

[0207] -Surfactants- The photosensitive resin layer may contain a surfactant. Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0208] The surfactant is preferably a nonionic surfactant or a fluorine-based surfactant. As the surfactant, from the viewpoint of improving environmental compatibility, a surfactant containing silicon (for example, a silicone-based surfactant) is preferable.

[0209] Examples of 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 names) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (all manufactured by BASF), Tetronic (trade names) 304, 701, 704, 901, 904, and 150R1 (all manufactured by BASF), and Solsperse (trade name). 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin (trade name) D-6112, D-6112-W, and D-6315 (all manufactured by Takemoto Oil Co., Ltd.), Olfine (trade name) E1010, Surfynol (trade name) 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0210] Commercially available fluorine-based surfactants include, for example, Megafac (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-5 60, 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), Fluorad (product name) Examples of such a surfactant include FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Limited), Surflon (trade 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 Corporation), PolyFox (trade name) PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA), and Futergent (trade name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, and 245F (all manufactured by Neos Corporation).

[0211] As the fluorosurfactant, an acrylic compound having a molecular structure with a functional group containing a fluorine atom, which is cleaved when heated and volatilizes the fluorine atom, can also be preferably used. Examples of such fluorosurfactants include the Megafac (trade name) DS series manufactured by DIC Corporation [The Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016)], and specifically, Megafac (registered trademark) DS-21.

[0212] As the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound can also be preferably used.

[0213] As the fluorosurfactant, a block polymer can also be used.

[0214] As the fluorine-based surfactant, a fluorine-containing polymer compound containing a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a constituent unit derived from a (meth)acrylate compound having two or more (preferably, five or more) alkyleneoxy groups (preferably, ethyleneoxy groups and / or propyleneoxy groups) can also be preferably used.

[0215] As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Examples of such a fluorosurfactant include Megafac (trade name) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0216] As the fluorosurfactant, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental compatibility, as the fluorosurfactant, a substitute material for perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) is preferable.

[0217] Examples of surfactants containing silicon include silicone-based surfactants. Examples of silicone surfactants include linear polymers formed from siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or ends. Specific examples of silicone surfactants include 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, K Examples of such compounds include F-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials), and BYK307, BYK323, and BYK330 (all manufactured by BYK-Chemie).

[0218] When the photosensitive resin layer contains a surfactant, it may contain only one type of surfactant, or may contain two or more types of surfactants.

[0219] When the photosensitive resin layer contains a surfactant, the content of the surfactant in the photosensitive resin layer is not particularly limited, but is, for example, preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, relative to the total mass of the photosensitive resin layer.

[0220] -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.

[0221] When the photosensitive resin layer contains a sensitizer, it may contain only one type of sensitizer, or may contain two or more types of sensitizers.

[0222] When the photosensitive resin layer contains a sensitizer, the content of the sensitizer in the photosensitive resin layer is not particularly limited and can be appropriately set depending on the purpose. The content of the sensitizer in the photosensitive resin layer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer, from the viewpoints of improving the sensitivity to the light source and improving the curing speed through a balance between the polymerization rate and chain transfer.

[0223] -Various additives- The photosensitive resin layer may contain known additives, if necessary. Examples of additives include plasticizers, heterocyclic compounds, benzotriazole compounds, carboxybenzotriazole compounds, pyridine compounds (eg, isonicotinamide), purine bases (eg, adenine), and solvents. When the photosensitive resin layer contains an additive, it may contain only one type of additive, or may contain two or more types of additives.

[0224] 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.

[0225] Examples of the carboxybenzotriazole compound 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, examples of the carboxybenzotriazole compound include commercially available products such as CBT-1 (trade name, manufactured by Johoku Chemical Industry Co., Ltd.).

[0226] 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, for example, preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer. It is preferable to set the total content of the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin layer to 0.01% by mass or more based on the total mass of the photosensitive resin layer in order to impart storage stability to the photosensitive resin layer, while it is preferable to set the total content of the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin layer to 3% by mass or less based on the total mass of the photosensitive resin layer in order to maintain sensitivity and suppress decolorization of the dye.

[0227] The photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of WO 2018 / 179640.

[0228] The photosensitive resin layer may contain a solvent. When a photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

[0229] The photosensitive resin layer may further contain known additives such as metal oxide particles, antioxidants, rust inhibitors, dispersants, acid multipliers, development accelerators, conductive fibers, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents.

[0230] The additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of JP2014-85643A, the contents of which are incorporated herein by reference.

[0231] (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 ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents thereof to the following amounts.

[0232] The content of impurities 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, based on the total mass of the photosensitive resin layer. The content of impurities in the photosensitive resin layer may be, for example, 1 ppb by mass or more, or 0.1 ppm by mass or more, based on the total mass of the photosensitive resin layer.

[0233] Methods for keeping the content of impurities within the above range include, for example, selecting a raw material for the composition for forming the photosensitive resin layer (so-called photosensitive resin composition) that contains a small amount of impurities, preventing the inclusion of impurities when forming the photosensitive resin layer, and removing the impurities by washing. By such methods, the content of impurities can be kept within the above range.

[0234] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0235] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive resin layer is preferably small. The content of the above-mentioned compound in the photosensitive resin layer is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and even more preferably 4 mass ppm or less, based on the total mass of the photosensitive resin layer. The content of the above-mentioned compound in the photosensitive resin layer may be, for example, 10 mass ppb or more, or 100 mass ppb or more, based on the total mass of the photosensitive resin layer. The content of the above compounds can be controlled in the same manner as the content of the above metal impurities. The above compounds can be quantified by known measurement methods.

[0236] From the viewpoint of improving reliability and lamination properties, the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass.

[0237] (Residual monomer) The photosensitive resin layer may contain residual monomers corresponding to each of the structural units of the alkali-soluble resin described above. From the viewpoint of patterning property and reliability, the content of the residual monomer in the photosensitive resin layer is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, and even more preferably 500 mass ppm or less, based on the total mass of the alkali-soluble resin. The content of the residual monomer in the photosensitive resin layer may be, for example, 1 mass ppm or more, or 10 mass ppm or more, based on the total mass of the alkali-soluble resin.

[0238] From the viewpoint of patterning property and reliability, the content of the residual monomer in the photosensitive resin layer is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm or less, relative to the total mass of the photosensitive resin layer. Moreover, the content of the residual monomer in the photosensitive resin layer may be, for example, 0.1 mass ppm or more, or 1 mass ppm or more, relative to the total mass of the photosensitive resin layer.

[0239] The amount of remaining monomer when synthesizing an alkali-soluble resin by a polymer reaction is also preferably the above amount. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably the above amount.

[0240] The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

[0241] (Pigments) The photosensitive resin layer may be a colored layer containing a pigment. The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. When forming a black pattern, a black pigment is preferably selected as the pigment.

[0242] As the black pigment, any known black pigment (for example, an organic pigment or an inorganic pigment) can be appropriately selected as long as the effects of the present disclosure are not impaired. 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. From the viewpoint of surface resistance, the carbon black is preferably one at least partly coated with a resin. From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 μm to 0.1 μm, and more preferably 0.01 μm to 0.08 μm, in number average particle size. The particle size refers to the diameter of a circle with the same area as the area of ​​a pigment particle, calculated from the area of ​​the pigment particle in a photograph of the pigment particle taken with an electron microscope, and the number average particle size is the average value obtained by calculating the above particle size for 100 random particles and averaging the particle sizes of the 100 particles thus calculated.

[0243] As the white pigment, the white pigments described in paragraphs 0015 and 0114 of JP-A No. 2005-007765 can be used. Specifically, among the white pigments, inorganic pigments are preferably titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide, even more preferably titanium oxide, particularly preferably rutile or anatase titanium oxide, and most preferably rutile titanium oxide.

[0244] The surface of titanium oxide may be subjected to at least one treatment selected from the group consisting of silica treatment, alumina treatment, titania treatment, zirconia treatment, and organic treatment, which suppresses the catalytic activity of titanium oxide and improves heat resistance and fading resistance. As the surface treatment of titanium oxide, from the viewpoint of reducing the thickness of the photosensitive layer after heating, at least one of alumina treatment and zirconia treatment is preferred, and both alumina treatment and zirconia treatment are particularly preferred.

[0245] When the photosensitive resin layer is a colored layer, it is also preferable that the photosensitive resin layer further contains a chromatic pigment other than a black pigment and a white pigment from the viewpoint of transferability. When the photosensitive resin layer contains a chromatic pigment, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the viewpoint of superior dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), and Monastral Fast Blue. (CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Among these, CI Pigment Red 177 is preferred as a chromatic pigment.

[0246] When the photosensitive resin layer contains a pigment, the content of the pigment in the photosensitive resin layer is preferably in the range of more than 3 mass% to not more than 40 mass%, more preferably in the range of more than 3 mass% to not more than 35 mass%, even more preferably in the range of more than 5 mass% to not more than 35 mass%, and particularly preferably in the range of 10 mass% to not more than 35 mass%, relative to the total mass of the photosensitive resin layer.

[0247] When the photosensitive resin layer contains pigments other than black pigments (i.e., white pigments and chromatic pigments), the content of the pigments other than black pigments in the photosensitive resin layer relative to the content of the black pigment is preferably 30 mass % or less, more preferably 1 mass % to 20 mass %, and even more preferably 3 mass % to 15 mass %.

[0248] In the method for producing a photosensitive resin layer containing a black pigment, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition described below in the form of a pigment dispersion. The dispersion may be prepared by previously mixing the black pigment with the pigment dispersant, adding the mixture obtained to an organic solvent or vehicle, and dispersing the mixture using a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant may be used. The vehicle refers to the medium portion in which the pigment is dispersed when a pigment dispersion is prepared, and is liquid and includes a binder component that holds the black pigment in a dispersed state, and a solvent component (i.e., an organic solvent) that dissolves and dilutes the binder component. The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, a sand mill, etc. After dispersion by the dispersing machine, the mixture may be further finely pulverized by utilizing frictional force caused by mechanical grinding. For information on dispersers and fine grinding, see "Encyclopedia of Pigments" (Kunizo Asakura, 1st Edition, Asakura Publishing, 2000, pages 438 and 310).

[0249] <<Thickness of photosensitive resin layer>> From the viewpoints 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. 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 means an average thickness calculated by arithmetic average of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0250] For example, when the transfer layer is 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 viewpoints of resolution and unevenness followability.

[0251] <<Light transmittance>> From the viewpoint of superior adhesion, the transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and more preferably 50% or more. The upper limit of the transmittance of the photosensitive resin layer at a wavelength of 365 nm is not particularly limited, but is preferably, for example, 99.9% or less.

[0252] <Method of forming photosensitive resin layer> The method for forming the 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 a method in which a composition for forming a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, etc. is prepared, the prepared composition for forming a photosensitive resin layer is applied to an intermediate layer or a protective film, and the applied composition for forming a photosensitive resin layer is dried to form the layer.

[0253] The photosensitive resin layer forming composition preferably contains a solvent from the viewpoint of facilitating the formation of the photosensitive resin layer by adjusting the viscosity. Examples of the solvent 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.

[0254] The solvent is preferably a solvent 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 ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (e.g., 1-methoxy-2-propanol (MFG)), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0255] Specific examples of the alkylene glycol ether acetate solvent have been described above, and therefore, description thereof will be omitted here.

[0256] As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of JP-A-2018-177889 may be used, the contents of which are incorporated herein by reference.

[0257] When the photosensitive resin layer forming composition contains a solvent, it may contain only one type of solvent, or may contain two or more types of solvent.

[0258] When the composition for forming a photosensitive resin layer contains a solvent, the content of the solvent when applying the composition for forming a photosensitive resin layer is preferably 50 parts by mass to 1900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, per 100 parts by mass of the total solid content in the composition for forming a photosensitive resin layer.

[0259] The method for preparing the composition for forming a photosensitive resin layer is not particularly limited, and examples thereof include a method in which a solution is prepared in advance by dissolving each component in the above-mentioned solvent, and the obtained solutions are mixed in a predetermined ratio to prepare the composition for forming a photosensitive resin layer. The composition for forming a photosensitive resin layer is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming a photosensitive resin layer.

[0260] The method for applying the photosensitive resin layer-forming composition is not particularly limited, and any known method may be used. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0261] As a method for drying the applied photosensitive resin layer-forming composition, heat drying and reduced pressure drying are preferred. Drying methods include, for example, natural drying, heat drying, and reduced pressure drying. For drying, the above-mentioned methods can be applied alone 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 is preferably, for example, 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 is preferably, for example, 600 seconds or less, and more preferably 300 seconds or less.

[0262] <Protective film> The photosensitive transfer material according to the present 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 (eg, polypropylene film and polyethylene film), polyester films (eg, polyethylene terephthalate film), polycarbonate films, cellulose triacetate films, and polystyrene films. The protective film is preferably a polypropylene film, a polyethylene film, or a polyethylene terephthalate film.

[0263] The thickness of the protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, further preferably from 5 μm to 40 μm, and particularly preferably from 15 μm to 30 μm. The thickness of the protective film means an average thickness calculated by arithmetic average of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0264] 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 is preferably, for example, 0.001 μm or more.

[0265] The arithmetic mean roughness Ra value of the surface of the protective film is measured by the following method. A three-dimensional optical profiler (New View7300, manufactured by Zygo) is used to measure the surface of the protective film, and a surface profile of the protective film is obtained. The Microscope Application of MetroPro ver8.3.2 is used as the measurement and analysis software. Next, the Surface Map screen is displayed in the above analysis software, and histogram data is obtained in the Surface Map screen. The arithmetic mean roughness Ra of the protective film surface is calculated from the obtained histogram data.

[0266] <Other layers> The photosensitive transfer material according to the present disclosure may have other layers. The other layers include, for example, a refractive index adjustment layer (so-called contrast enhancement layer). The contrast enhancement layer is described in paragraph 0134 of WO 2018 / 179640. In addition, other layers are described in paragraphs 0194 to 0196 of JP2014-85643A, the contents of which are incorporated herein by reference.

[0267] <Method of manufacturing photosensitive transfer material> The method for producing the photosensitive transfer material according to the present disclosure is not particularly limited. The photosensitive transfer material according to the present disclosure can be produced by a known method. The photosensitive transfer material according to the present disclosure is preferably produced by a method (hereinafter also referred to as "production method A") including a step of forming, on a temporary support, a thermoplastic resin layer containing a copolymer polyester resin, an intermediate layer, and a photosensitive resin layer by coating and drying in that order (hereinafter also referred to as "step A1"), or a method (hereinafter also referred to as "production method B") including a step of forming, on a protective film, a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer containing a copolymer polyester resin by coating and drying in that order (hereinafter also referred to as "step B1"), and a step of bonding a temporary support to the thermoplastic resin layer by thermal lamination (hereinafter also referred to as "step B2"). According to the production method A and the production method B, the photosensitive transfer material according to the present disclosure can be produced more simply.

[0268] Hereinafter, the manufacturing method A and the manufacturing method B will be described, but a description of the points common to those described in the section on the photosensitive transfer material according to the present disclosure will be omitted.

[0269] (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 containing a copolymer polyester resin, an intermediate layer, and a photosensitive resin layer on a temporary support by coating and drying them in that order. The manufacturing method A may include a step other than the step A1. An example of a step other than step A1 is a step of attaching a protective film to the photosensitive resin layer formed in step A1 by thermal lamination (hereinafter, also referred to as "step A2").

[0270] -Process A1- Step A1 is a step of forming a thermoplastic resin layer containing a copolymer polyester resin, an intermediate layer, and a photosensitive resin layer on a temporary support by coating and drying in this order. The method for forming a thermoplastic resin layer on a temporary support, the method for forming an intermediate layer on a thermoplastic resin layer, and the method for forming a photosensitive resin layer on an intermediate layer are as described above in the sections "Method for forming a thermoplastic resin layer," "Method for forming an intermediate layer," and "Method for forming a photosensitive resin layer," respectively.

[0271] -Process A2- Step A2 is a step of attaching a protective film to the photosensitive resin layer formed in step A1 by thermal lamination. The means for thermal lamination is not particularly limited, and any known laminator can be used. The laminator is preferably a device equipped with any heatable roller such as a rubber roller and capable of applying pressure and heat. The temperature of the thermal lamination is not particularly limited, but is preferably from 20°C to 100°C, and more preferably from 25°C to 60°C, for example.

[0272] (Manufacturing method B) Manufacturing method B is a method for manufacturing a photosensitive transfer material, which includes a step of forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer containing a copolymer polyester resin on a protective film by coating and drying in that order (i.e., step B1), and a step of bonding a temporary support to the thermoplastic resin layer by thermal lamination (i.e., step B2). The manufacturing method B may include steps other than step B1 and step B2.

[0273] -Process B1- Step B1 is a step of forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer containing a copolymer polyester resin on a protective film by coating and drying in this order. The method for forming a photosensitive resin layer on a protective film, the method for forming an intermediate layer on a photosensitive resin layer, and the method for forming a thermoplastic resin layer on an intermediate layer are as described above in the sections "Method for forming a photosensitive resin layer," "Method for forming an intermediate layer," and "Method for forming a thermoplastic resin layer," respectively.

[0274] -Process B2- Step B2 is a step of bonding a temporary support to the thermoplastic resin layer formed in step B1 by thermal lamination. The means for thermal lamination is not particularly limited, and any known laminator can be used. The laminator is preferably a device equipped with any heatable roller such as a rubber roller and capable of applying pressure and heat. The temperature of the thermal lamination is not particularly limited, but is preferably from 20°C to 100°C, and more preferably from 25°C to 60°C, for example.

[0275] The photosensitive transfer material produced as described above may be wound up to prepare a roll-shaped photosensitive transfer material and store it. The roll-shaped photosensitive transfer material can be provided as it is to a lamination step with a substrate in a roll-to-roll system.

[0276] [Method of manufacturing patterned substrate] The manufacturing method of the patterned substrate according to the present disclosure (hereinafter also simply referred to as the "manufacturing method according to the present disclosure") includes, in this order, a step of laminating a photosensitive transfer material and a substrate so that the transfer layer side of the photosensitive transfer material according to the present disclosure is in contact with the substrate (hereinafter also referred to as the "lamination step"); a step of removing the temporary support from the laminate by peeling 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 producing a patterned substrate according to the present disclosure uses the photosensitive transfer material according to the present disclosure, and therefore can form a high-resolution resist pattern.

[0277] The manufacturing method according to the present disclosure may include steps (so-called other steps) other than the laminating step, the pressing step, the temporary support removing step, the exposure step, and the developing step. Other steps include, for example, a protective film removing step and a pressure applying step.

[0278] <Protection film removal process> When the photosensitive transfer material according to the present disclosure has a protective film, the manufacturing method according to the present disclosure preferably includes a step of removing the protective film from the photosensitive transfer material (a so-called protective film removing step) before the lamination step. The photosensitive transfer material according to the present disclosure has been described above, and therefore will not be described here. The method for removing the protective film from the photosensitive transfer material according to the present disclosure is not particularly limited, and any known method can be applied.

[0279] <Lamination process> The manufacturing method according to the present disclosure includes a step of laminating a photosensitive transfer material according to the present disclosure to a substrate so that the transfer layer side of the photosensitive transfer material is in contact with the substrate (i.e., lamination step). When the photosensitive transfer material and the substrate are bonded together, the transfer layer in contact with the substrate will be, for example, a layer in contact with the protective film (e.g., a photosensitive resin layer) if the photosensitive transfer material according to the present disclosure has a protective film. According to the lamination step, a laminate of the photosensitive transfer material and the substrate is obtained.

[0280] A known method can be applied to attach the photosensitive transfer material to the substrate. In the lamination step, the photosensitive transfer material and the substrate are preferably bonded together by pressure. For example, it is preferable to overlap the transfer layer side of the photosensitive transfer material with the substrate, and apply pressure and heat using a roll or other means to pressure-bond the photosensitive transfer material to the substrate.

[0281] A known lamination method can be used to bond the substrate and the photosensitive transfer material by pressure. Examples of the lamination method include a method using a known laminator such as a vacuum laminator or an autocut laminator. The lamination temperature is not particularly limited, but is preferably from 70°C to 130°C, for example.

[0282] The substrate is not particularly limited, and any known substrate can be used. In one embodiment, the substrate may be a substrate having a metal layer, and preferably has a metal layer on the surface of the substrate. The substrate may have any layer other than the metal layer as necessary. Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the substrate is described, for example, in paragraph 0140 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0283] Examples of the base material constituting the substrate include metals (e.g., Invar, an iron-nickel alloy), glass, silicon, and films. The base material constituting the substrate may be transparent.

[0284] Examples of the transparent glass substrate include tempered glass, such as Gorilla Glass from Corning Inc. In addition, the transparent glass substrate may be made of the materials described in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492.

[0285] When a film substrate is used as the substrate, it is preferable to use a film substrate having small optical distortion and / or high transparency. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0286] When the film is produced by a roll-to-roll method, the substrate is preferably a film substrate.

[0287] The metal layer of the substrate may be a conductive layer used for general circuit wiring or touch panel wiring. From the viewpoints of electrical conductivity and fine line formability, 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, more preferably a metal layer, and even more preferably a copper layer or a silver layer.

[0288] The substrate may have a single metal layer, or may have two or more metal layers. When there are two or more metal layers, it is preferable that the metal layers are made of different materials.

[0289] Materials for the metal layer include, for example, metals and conductive metal oxides. Metals include, for example, Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au. Examples of conductive metal oxides include indium tin oxide (ITO), indium zinc oxide (IZO), and SiO2.

[0290] In one embodiment, the substrate may be a metal substrate. The photosensitive transfer material of the present disclosure can suppress the generation of lamination bubbles during thermal lamination by the thermoplastic resin layer, and can be removed together with the temporary support during pattern exposure, so that the exposure gap can be shortened. Therefore, the photosensitive transfer material of the present disclosure can be particularly suitably used for microfabrication of metal substrates for deposition masks having fine irregularities on the surface. The metal substrate has a first side and a second side opposite the first side.

[0291] The metal substrate may have a single-layer structure or a multi-layer structure. Examples of metal elements contained in the metal substrate include Cu, Ni, Fe, Cr, Mn, and Co. The metal substrate preferably contains at least one metal element selected from the group consisting of Cu, Ni, Fe, Cr, Mn, and Co, more preferably contains at least one metal element selected from the group consisting of Cu, Fe, and Ni, and even more preferably contains Cu. The metal substrate may contain elements other than metal elements, such as B, C, N, O, P, S, and Cl. An example of a preferred metal substrate is a copper substrate. Part or all of the metal substrate may be an alloy. Examples of alloys include nickel-cobalt (Ni-Co) alloys and iron-nickel (Fe-Ni) alloys. In one embodiment, the metal substrate preferably comprises an iron-nickel (Fe-Ni) alloy.

[0292] The first surface of the metal substrate may have a roughness Rmax of 0.5 μm to 5.0 μm.The second surface of the metal layer may have a roughness Rmax of 0.5 μm to 5.0 μm.

[0293] The thickness of the metal substrate is preferably 30 μm to 500 μm, more preferably 40 μm to 400 μm, and further preferably 50 μm to 300 μm. The thickness of the metal layer refers to an average thickness calculated by arithmetic averaging of thicknesses measured at five points by cross-sectional observation using a scanning electron microscope (SEM).

[0294] <Pressing process> The manufacturing method according to the present disclosure preferably includes a step of pressurizing the laminate of the photosensitive transfer material and the substrate (a so-called pressurizing step). By applying pressure to the bonded body, the adhesion between the transfer layer and the substrate increases, and the ability of the transfer layer to conform to the irregularities on the surface of the substrate tends to improve.

[0295] The laminate to be pressed has a substrate, a transfer layer, and a temporary support in this order. The method of pressurizing the laminated body includes, for example, a method of subjecting the laminated body to autoclaving, for example, under the conditions of a pressure of 0.45 MPa, a temperature of 50° C., and a treatment time of 1 hour.

[0296] <Temporary support removal process> The manufacturing method according to the present disclosure includes a step of removing the temporary support from the laminate by peeling between the thermoplastic resin layer and the intermediate layer (that is, a temporary support removing step). If the temporary support is removed prior to the exposure step, the exposure gap becomes shorter, which tends to facilitate the production of a high-resolution resist pattern. Furthermore, the blur of the optical image is reduced, which tends to further improve the mask fidelity and line width uniformity of the resulting resist pattern. Furthermore, if the temporary support is removed prior to the exposure step, the effects of pinholes originating from the temporary support can be eliminated, and therefore a defect-free resist pattern tends to be obtained.

[0297] The method for removing the temporary support is not particularly limited. In the manufacturing method according to the present disclosure, the photosensitive transfer material according to the present disclosure described above is used as the photosensitive transfer material, so that the thermoplastic resin layer and the intermediate layer are peeled off smoothly, and the temporary support is removed from the laminate together with the thermoplastic resin layer.

[0298] <Exposure process> The manufacturing method according to the present disclosure includes a step of pattern-exposing a transfer layer including an intermediate layer and a photosensitive resin layer through a mask (i.e., an exposure step). The term "pattern exposure" refers to a form of pattern-wise exposure, i.e., exposure in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in the pattern exposure is not particularly limited and is appropriately adjusted depending on, for example, the shape of the desired pattern.

[0299] According to the exposure step, exposed and unexposed areas are formed in the photosensitive resin layer. For example, when the photosensitive resin layer is a negative type, the exposed portion of the photosensitive resin layer on the substrate is cured in the pattern exposure, and finally becomes a cured film.On the other hand, the non-exposed portion of the photosensitive resin layer on the substrate is not cured in the pattern exposure, and is dissolved and removed by the developer in the development process described below.The non-exposed portion can form an opening of the cured film after the development process.

[0300] The light used for the pattern exposure is preferably applied to the transfer layer in a direction from the transfer layer toward the substrate.

[0301] The light source for pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range capable of curing the photosensitive resin layer (for example, 365 nm or 405 nm). The dominant wavelength of the exposure light for the pattern exposure is preferably 365 nm. "Dominant wavelength" refers to the wavelength with the highest intensity.

[0302] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose was 5 mJ / cm 2 ~200mJ / cm 2 and preferably 10 mJ / cm 2 ~200mJ / cm 2 It is more preferable that:

[0303] Since the exposure step is carried out after the temporary support removal step, the exposure gap is reduced by removing the temporary support, and a more faithful pattern can be obtained on the mask.

[0304] In the exposure step, the transfer layer may be pattern-exposed with a mask in contact with the transfer layer, or the transfer layer may be pattern-exposed with a mask close to the transfer layer without contacting the transfer layer. The "transfer layer" as used herein includes the intermediate layer and the photosensitive resin layer. In the temporary support removal step, the thermoplastic resin layer and the intermediate layer are peeled off to remove the temporary support, so that the mask comes into contact with the intermediate layer without coming into contact with the photosensitive resin layer. As a result, even if the transfer layer is exposed to pattern light while the mask is in contact with the transfer layer, the transportability is unlikely to decrease due to the sticking between the mask and the photosensitive resin layer, and stable production is possible.

[0305] The exposure may be carried out, for example, under any environment, such as under atmospheric pressure, under reduced pressure, or under vacuum.

[0306] Examples of the exposure method include a contact exposure method, a proximity exposure method, and a projection exposure method. Among these, the contact exposure method is preferable as the exposure method. The contact exposure method is a method in which a mask is brought into contact with the surface of an object to be exposed. The contact exposure method uses a relatively inexpensive exposure machine, has high productivity, and can obtain a high resolution. In the contact exposure method, the shorter the distance from the mask to the photosensitive resin layer, i.e., the shorter the exposure gap, the less the image blurring and the higher the resolution of the image faithful to the mask. In the manufacturing method of the present disclosure, the exposure step is performed after the temporary support removal step, so the exposure gap is shortened by removing the temporary support. Therefore, there is a tendency to easily obtain a high-resolution image faithful to the mask.

[0307] Examples of the mask include a chrome mask, an emulsion mask, and a film mask.

[0308] <Developing process> The manufacturing method according to the present disclosure includes a step of developing the pattern-exposed transfer layer to form a pattern (developing step). The pattern-exposed transfer layer is developed to form a pattern. The pattern is formed by removal of either the exposed or unexposed areas of the transfer layer. When the photosensitive resin layer contained in the transfer layer is of a negative type, the non-exposed areas of the transfer layer are removed, and the exposed areas of the transfer layer form a resin pattern.

[0309] The development can be carried out using a developer. The developer is preferably an aqueous alkaline solution. Examples of alkaline compounds contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). The pH of the alkaline aqueous solution at 25°C is preferably 8-13, more preferably 9-12, and even more preferably 10-12. The content of the alkaline compound in the alkaline aqueous solution is preferably 0.1% by mass to 5% by mass, and more preferably 0.1% by mass to 3% by mass, based on the total mass of the alkaline aqueous solution.

[0310] In the present disclosure, examples of developers that can be suitably used include the developers described in paragraph 0194 of WO 2015 / 093271.

[0311] Examples of the developing method include paddle development, shower development, shower and spin development, and dip development. Shower development is a developing method in which a developing solution is sprayed onto an object by showering. In the present disclosure, examples of the development method that can be suitably used include the development method described in paragraph 0195 of WO 2015 / 093271.

[0312] Any developer solution and residue remaining after the development step is preferably removed. Methods for removing the developer and residues include, for example, shower treatment and AirKnife treatment. In the shower process, the object is sprayed with a shower of liquid such as water and a cleaning agent. Residue may be removed using a brush. EXAMPLES

[0313] The present disclosure will be described in more detail below with reference to examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure should not be interpreted as being limited by the following examples. Unless otherwise specified, "%" is by mass. In the following examples, the weight average molecular weight of the resin is a weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0314] [Production of photosensitive transfer material] <Example 1> The photosensitive transfer material of Example 1 having a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a protective film in this order was produced by the following procedure.

[0315] Composition A was prepared, containing the components listed in the "thermoplastic resin layer" column of Table 1. Composition A was applied onto a temporary support (trade name: Lumirror (registered trademark) 16KS40, thickness: 16 μm, biaxially stretched PET film, manufactured by Toray Industries, Inc.) using a slit nozzle, and then dried at 80° C. for 2 minutes to form a thermoplastic resin layer. The thickness (i.e., average thickness) of the thermoplastic resin layer is as shown in Table 1.

[0316] Composition B was prepared, containing the components shown in the "Intermediate Layer" column of Table 1. Composition B was applied onto the thermoplastic resin layer using a slit nozzle, and then dried at 90°C for 2 minutes to form an intermediate layer. The thickness (i.e., average thickness) of the intermediate layer is as shown in Table 1.

[0317] A composition C was prepared containing the components shown in the "photosensitive resin layer" column of Table 1. The composition C was applied onto the intermediate layer using a slit nozzle, and then dried at 80°C for 2 minutes to form a photosensitive resin layer. The thickness (i.e., average thickness) of the photosensitive resin layer is as shown in Table 1.

[0318] Finally, a protective film (product name: Lumirror (registered trademark) 16KS40, thickness: 16 μm, biaxially stretched PET film, manufactured by Toray Industries, Inc.) was attached to the exposed surface of the photosensitive resin layer by thermal lamination.

[0319] In this manner, the photosensitive transfer material of Example 1 was obtained.

[0320] <Examples 2 to 4> The same procedure as in Example 1 was carried out except that the compositions A, B and C were as shown in Table 1, to obtain photosensitive transfer materials of Examples 2 to 4.

[0321] <Example 5> A photosensitive transfer material of Example 5 having a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a protective film in this order was produced by the following procedure.

[0322] Composition C was prepared, containing the components listed in the "Photosensitive resin layer" column of Table 1. Composition C was applied onto a protective film (product name: Lumirror (registered trademark) 16KS40, thickness: 16 μm, biaxially stretched PET film, manufactured by Toray Industries, Inc.) using a slit nozzle, and then dried at 80° C. for 2 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer is as listed in Table 1.

[0323] Composition B was prepared, containing the components shown in the "Intermediate Layer" column of Table 1. Composition B was applied onto the photosensitive resin layer using a slit nozzle, and then dried at 90°C for 2 minutes to form an intermediate layer. The thickness of the intermediate layer is as shown in Table 1.

[0324] Composition A was prepared, containing the components shown in the "thermoplastic resin layer" column of Table 1. Composition A was applied onto the intermediate layer using a slit nozzle, and then dried at 80°C for 2 minutes to form a thermoplastic resin layer. The thickness of the thermoplastic resin layer is as shown in Table 1.

[0325] Finally, a temporary support (trade name: Lumirror (registered trademark) 16KS40, thickness: 16 μm, biaxially stretched PET film, manufactured by Toray Industries, Inc.) was attached to the exposed surface of the thermoplastic resin layer by thermal lamination.

[0326] In this manner, a photosensitive transfer material of Example 5 was obtained.

[0327] <Comparative Examples 1, 2 and 4> The same procedure as in Example 1 was carried out except that the compositions A, B and C were as shown in Table 2, to obtain photosensitive transfer materials of Comparative Examples 1, 2 and 4.

[0328] <Comparative Example 3> A photosensitive transfer material of Comparative Example 3 having a temporary support, an intermediate layer, a photosensitive resin layer, and a protective film in this order was produced by the following procedure.

[0329] Composition B was prepared, containing the components shown in the "Intermediate layer" column of Table 2. Composition B was applied onto a temporary support (model number: 16KS40, thickness: 16 μm, biaxially stretched PET film, manufactured by Toray Industries, Inc.) using a slit nozzle, and then dried at 90° C. for 2 minutes to form an intermediate layer. The thickness of the intermediate layer is as shown in Table 2.

[0330] Composition C was prepared, containing the components shown in the "Photosensitive resin layer" column of Table 2. Composition C was applied onto the intermediate layer using a slit nozzle, and then dried at 80°C for 2 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer is as shown in Table 2.

[0331] Finally, a protective film (model number: 16KS40, thickness: 16 μm, biaxially oriented PET film, manufactured by Toray Industries, Inc.) was attached to the exposed surface of the photosensitive resin layer by thermal lamination.

[0332] In this manner, a photosensitive transfer material of Comparative Example 3 was obtained.

[0333] [Table 1]

[0334] [Table 2]

[0335] In Tables 1 and 2, "-" in the composition column means that the corresponding component is not used. In Tables 1 and 2, "normal order" in the application order column means that composition A, composition B, and composition C are applied in that order onto the temporary support (however, in the case of Comparative Example 3, composition B and composition C are applied in that order onto the temporary support), and "reverse order" means that composition C, composition B, and composition A are applied in that order onto the protective film. In the "normal order", a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer are formed in this order on a temporary support by coating and drying, and then a protective film is attached to the photosensitive resin layer by thermal lamination. In the "reverse order", a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer are formed in this order on a protective film by coating and drying, and then a temporary support is attached to the photosensitive resin layer by thermal lamination.

[0336] The following abbreviations shown in Tables 1 and 2 have the following meanings, respectively. "Vylon BX-1001": Amorphous copolymer polyester resin manufactured by Toyobo Co., Ltd., Tg: -18°C, Mn: 28000, hydroxyl value: 8KOHmg / g, acid value: less than 2KOHmg / g "Vylon GK-800": Amorphous copolymer polyester resin manufactured by Toyobo Co., Ltd., Tg: 50°C, Mn: 27000, hydroxyl value: 7KOHmg / g, acid value: less than 2KOHmg / g "Vylon 802": Amorphous copolymer polyester resin manufactured by Toyobo Co., Ltd., Tg: 60°C, Mn: 3000, hydroxyl value: 37KOHmg / g, acid value: less than 1KOHmg / g "Polymer 1": benzyl methacrylate (BzMA) / methacrylic acid (MAA) / acrylic acid (AA) = 78 / 14.5 / 7.5 [mass ratio], Mw: 14000, solid content: 40 mass% "Evaflex EV45X": Ethylene-vinyl acetate copolymer resin manufactured by Mitsui Dow Polychemicals Co., Ltd. "A-DCP": NK Ester A-DCP, tricyclodecane dimethanol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd. "8UX-015A": 8UX-015A, UV-curable urethane acrylate manufactured by Taisei Fine Chemical Co., Ltd. "TO-2349": Aronix TO-2349 manufactured by Toagosei Co., Ltd. "CBT-1": CBT-1, carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd. "F-552": Megafac F-552 manufactured by DIC Corporation, fluorosurfactant, solid content: 30% by mass (methyl ethyl ketone solution) "EXP-S-315": EXP-S-315 manufactured by DIC Corporation, silicone surfactant, solid content: 30% by mass (methyl ethyl ketone solution) "MMPGAc": 1-methoxy-2-propyl acetate "MEK": Methyl ethyl ketone "MFG": 1-methoxy-2-propanol

[0337] "PVA": PVA 205, polyvinyl alcohol, manufactured by Kuraray Co., Ltd. "PVP": K-30, polyvinylpyrrolidone, manufactured by Nippon Shokubai Co., Ltd. "HPMC": Metolose 60SH-03, hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd. "Snowtex OYL": Colloidal silica manufactured by Nissan Chemical Co., Ltd., silica particles dispersed in water "F-444": Megafac F-444, a fluorosurfactant manufactured by DIC Corporation "EXP-S-506": EXP-S-506 manufactured by DIC Corporation, a silicone-based surfactant "MeOH": Methanol

[0338] "M / B": Ratio of the total mass of polymerizable compounds to the total mass of polymer "Polymer 2": styrene (St) / methyl methacrylate (MMA) / methacrylic acid (MAA) = 52 / 19 / 29 [mass ratio], Mw: 60,000, Tg: 131°C, solid content: 30% by mass "BPE-500": NK Ester BPE-500, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane manufactured by Shin-Nakamura Chemical Co., Ltd. "Aronix M-270": Aronix M-270, polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. "B-CIM": 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole manufactured by Hampford "EAB-F": 4,4'-bis(diethylamino)benzophenone obtained from Sanyo Trading Co., Ltd. "Phenidone 1% MEK solution": A 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": Leuco Crystal Violet manufactured by Tokyo Chemical Industry Co., Ltd., a dye that develops color when exposed to radicals

[0339] [evaluation] The photosensitive transfer materials of Examples 1 to 5 and Comparative Examples 1 to 4 were used to carry out the following evaluations.

[0340] 1. Peelability between thermoplastic resin layer and intermediate layer 1-1. Manufacturing of laminate for evaluation (1) Examples 1 to 5 and Comparative Examples 1, 2 and 4 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 into a size of 30 mm x 100 mm, and the protective film was peeled off. Using a roll laminator, the photosensitive transfer material was laminated to an Invar substrate under 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, and a photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support were arranged in this order on the surface of the Invar substrate. As a result, a laminate for evaluation was obtained.

[0341] (2) Comparative Example 3 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 into a size of 30 mm x 100 mm, and the protective film was peeled off. Using a roll laminator, the photosensitive transfer material was laminated to an Invar substrate under 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, and a photosensitive resin layer, an intermediate layer, and a temporary support were arranged in this order on the surface of the Invar substrate. As a result, a laminate for evaluation was obtained.

[0342] 1-2.Evaluation test The obtained laminate was subjected to autoclave treatment under conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour. The laminate after the treatment was attached to a 0.7 mm thick glass using double-sided tape. A 180° peel test was performed on the laminate attached to the glass at a peel speed of 300 mm / min using a Tensilon to peel off the temporary support, and the peel force was measured. In addition, the laminate after the peel test was observed to confirm the peel interface. Then, the peelability between the thermoplastic resin layer and the intermediate layer was evaluated according to the following evaluation criteria. In the following evaluation criteria, "5," "4," and "3" are practically acceptable levels, with "5" being the most preferable.

[0343] -Evaluation criteria- 5: Peeling occurred between the thermoplastic resin layer and the intermediate layer, and the interlayer peel strength was 25 mN / cm or less. 4: Peeling has occurred between the thermoplastic resin layer and the intermediate layer, and the interlayer peel strength is in the range of more than 25 mN / cm and not more than 50 mN / cm. 3: Peeling has occurred between the thermoplastic resin layer and the intermediate layer, and the interlayer peel strength is in the range of more than 50 mN / cm and not more than 100 mN / cm. 2: Peeling occurred between the thermoplastic resin layer and the intermediate layer, and the interlayer peel strength exceeded 100 mN / cm. 1: Peeling occurs between layers other than between the thermoplastic resin layer and the intermediate layer.

[0344] The results of confirming the peel interface (in the table, indicated as "peeling interface when the temporary support is peeled off") are shown in Table 3. In the table, "between the thermoplastic resin layer / intermediate layer" means that peeling occurred between the thermoplastic resin layer and the intermediate layer, "between the temporary support / thermoplastic resin layer" means that peeling occurred between the temporary support and the thermoplastic resin layer, and "between the temporary support / intermediate layer" means that peeling occurred between the temporary support and the intermediate layer. In addition, when peeling occurred between the thermoplastic resin layer and the intermediate layer, the measured peel force (in the table, indicated as "Peel force between thermoplastic resin layer / intermediate layer (mN / cm)") and the evaluation results of the peelability between the thermoplastic resin layer and the intermediate layer (in the table, indicated as "Peelability between thermoplastic resin layer / intermediate layer") are shown in Table 3.

[0345] 2. Laminated foam 2-1. Manufacturing of laminate for evaluation A laminate for evaluation was obtained in the same manner as in "1-1 Production of laminate for evaluation" in "1. Peelability between thermoplastic resin layer and intermediate layer" above.

[0346] 2-2.Evaluation test The obtained laminate was observed using an optical microscope with a 10x objective lens to check for the presence or absence of air bubbles (so-called lamination bubbles) left between the Invar substrate and the photosensitive resin layer during lamination using a roll laminator. 2 In addition, when lamination bubbles were observed, the size and amount per unit area of ​​the lamination bubbles were measured. Evaluation was then performed according to the following evaluation criteria. The evaluation results are shown in Table 3. In the following evaluation criteria, "5", "4" and "3" are practically acceptable levels, with "5" being the most preferable. Note that the "major axis" of the lamination foam in the following evaluation criteria refers to the longest axis of the lamination foam.

[0347] -Evaluation criteria- 5: No lamination bubbles were observed. 4: No lamination bubbles with a major axis exceeding 100 μm were observed, and lamination bubbles with a major axis of 100 μm or less were observed. 2 The number of hits is confirmed to be in the range of 1 to 5. 3: No lamination bubbles with a major axis exceeding 100 μm were observed, and lamination bubbles with a major axis of 100 μm or less were observed. 2 The hits are found in the range of more than 5 and less than 50. 2: The lamination bubble with a major axis of 100 μm or more is 10,000 μm 2 The number of lamination bubbles is in the range of 1 to 5 per 10000 μm, or no lamination bubbles with a major axis of 100 μm or less are observed. 2 More than 50 hits confirmed. 1: The lamination bubble with a major axis of over 100 μm is 10,000 μm 2 More than five hits confirmed.

[0348] 3. Attachment to the exposure mask 3-1. Manufacturing of laminate for evaluation (1) Examples 1 to 5 and Comparative Examples 1, 2 and 4 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 90 mm x 90 mm, and the protective film was peeled off. Using a roll laminator, the photosensitive transfer material was laminated to an Invar substrate under 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, and a photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support were arranged in this order on the surface of the Invar substrate. As a result, a laminate for evaluation was obtained.

[0349] (2) Comparative Example 3 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 90 mm x 90 mm, and the protective film was peeled off. Using a roll laminator, the photosensitive transfer material was laminated to an Invar substrate under 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, and a photosensitive resin layer, an intermediate layer, and a temporary support were arranged in this order on the surface of the Invar substrate. As a result, a laminate for evaluation was obtained.

[0350] 3-2.Evaluation test The obtained laminate was subjected to autoclave treatment under the conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour. The temporary support was peeled off from the laminate after the treatment, and the surface exposed by the peeling (i.e., the exposed surface of the thermoplastic resin layer or the intermediate layer) was placed in contact with a glass exposure mask (specifically, a blue plate glass for full-surface solid exposure), and then a load of 1.96 N was applied to 63 mm x 63 mm for 60 seconds. After measuring the static friction coefficient according to JIS K 7125:1999, the contact surface of the exposure mask (i.e., the contact surface with the above-mentioned exposed surface) was observed. Then, the adhesion to the exposure mask was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3. In the following evaluation criteria, "3" and "2" are practically acceptable levels, with "3" being the most preferable.

[0351] -Evaluation criteria- 3: No dirt was found on the exposure mask, and the static friction coefficient was 1.0 or less. 2: No contamination was found on the exposure mask, and the static friction coefficient was greater than 1.0. 1: A part of the transfer layer is transferred to the exposure mask, and contamination of the exposure mask is observed.

[0352] The "transfer layer" in the above "3. Adhesion to exposure mask" and the below "4. Resolution" refers to the following layer. Examples 1 to 5 and Comparative Examples 3 and 4: Photosensitive resin layer and intermediate layer Comparative Examples 1 and 2: Photosensitive resin layer, intermediate layer, and thermoplastic resin layer

[0353] 4. Resolution 4-1. Manufacturing of laminate for evaluation A laminate for evaluation was obtained in the same manner as in "3-1. Production of laminate for evaluation" in "3. Attachment to exposure mask" above.

[0354] 4-2.Evaluation test The obtained laminate was subjected to autoclave treatment under conditions of a pressure of 0.45 MPa, a temperature of 50°C, and a treatment time of 1 hour. The temporary support was peeled off from the laminate after the treatment, and an exposure mask was attached to the surface exposed by the peeling (i.e., the exposed surface of the thermoplastic resin layer or the intermediate layer). The exposure mask has a plurality of square light-shielding parts. The dimensions of each light-shielding part vary in 1 μm increments within a range of 1 μm length×1 μm width to 20 μm length×20 μm width. Using a high-pressure mercury lamp exposure machine (model number: MAP-1200L, main wavelength: 365 nm, manufactured by Dainihon Kaken Co., Ltd.), the transfer layer after the operation of peeling off the temporary support was irradiated with light from the exposure mask side. The exposure dose was adjusted so that the diameter of the resist pattern obtained after development in the part corresponding to the 20 μm pattern of the exposure mask becomes the pattern diameter of the mask (i.e., 20 μm).

[0355] Next, a development process was performed. A 1.0 mass % sodium carbonate aqueous solution with a liquid temperature of 28°C was used as the developer. The development time was twice the minimum development time. The "minimum development time" refers to the shortest time required for the photosensitive resin layer in the unexposed parts to be completely dissolved by the development process. The development method was shower development. Specifically, the shortest time required for the photosensitive resin layer in the unexposed parts to be completely dissolved by shower development was first obtained, and then shower development was performed on the pattern-exposed photosensitive resin layer for twice the minimum development time. After development, an AirKnife process was performed to remove the developer, and then a shower process was performed for 30 seconds using pure water with a liquid temperature of 25°C, and then an AirKnife process was performed. As a result, a laminate substrate having a resist pattern was obtained. The obtained laminate substrate having a resist pattern was observed using a scanning electron microscope (SEM) to confirm the size of the minimum hole diameter that can be resolved. Then, the resolution was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3. In the following evaluation criteria, "3" and "2" are practically acceptable levels, with "3" being the most preferable.

[0356] -Evaluation criteria- 3: The minimum resolvable hole diameter is 3 μm or less. 2: The minimum resolvable hole diameter is in the range of more than 3 μm and not more than 5 μm. 1: The minimum resolvable hole diameter exceeds 5 μm.

[0357] [Table 3]

[0358] In Table 3, "-" in the column for type of thermoplastic resin means that no thermoplastic resin was used, and "-" in the columns for Tg and Mn of copolymer polyester resin means that no copolymer polyester resin was used and there is no corresponding item. In Table 3, the value shown in the column of Tg of copolymerized polyester resin is a weighted average value of the Tg of the copolymerized polyester resin contained in the thermoplastic resin layer. In Table 3, the value shown in the column of Mn of the copolymerized polyester resin is the weighted average value of Mn of the copolymerized polyester resin contained in the thermoplastic resin layer.

[0359] In Table 3, the column "Peel force between thermoplastic resin layer and intermediate layer" states "Cannot be measured" means that peeling occurred between the thermoplastic resin layer and the intermediate layer during the peel test, and measurement was not possible.

[0360] From the results shown in Table 3, it was confirmed that the photosensitive transfer material according to the present disclosure peels off between the thermoplastic resin layer and the intermediate layer when the temporary support is peeled off, and that the photosensitive transfer material has excellent peelability between the thermoplastic resin layer and the intermediate layer. It has also been confirmed that the photosensitive transfer material according to the present disclosure is less likely to trap air bubbles between the substrate and the photosensitive resin layer when laminated onto the substrate. It was also confirmed that in the photosensitive transfer material according to the present disclosure, the intermediate layer, which is the layer that comes into contact with the mask during contact exposure, is less likely to stick to the mask. Moreover, it was confirmed that the photosensitive transfer material according to the present disclosure has excellent resolution.

[0361] On the other hand, in the case of the photosensitive transfer materials of Comparative Example 1 and Comparative Example 2, which have a thermoplastic resin layer containing an acrylic resin, when the temporary support is peeled off, peeling occurs between the temporary support and the thermoplastic resin layer, and it was confirmed that the thermoplastic resin layer, which is the layer that comes into contact with the mask during contact exposure, tends to stick to the mask. When the photosensitive transfer material of Comparative Example 3, which does not have a thermoplastic resin layer, was subjected to an operation of peeling off the temporary support, peeling occurred between the temporary support and the intermediate layer. It was confirmed that the photosensitive transfer material of Comparative Example 3 is less likely to trap air bubbles between the substrate and the photosensitive resin layer when laminated onto the substrate. The photosensitive transfer material of Comparative Example 4, which had a thermoplastic resin layer containing an ethylene-vinyl acetate copolymer resin, peeled off between the thermoplastic resin layer and the intermediate layer when the temporary support was peeled off, but it was confirmed that the peelability between the thermoplastic resin layer and the intermediate layer was significantly inferior compared to the photosensitive transfer materials of the Examples. [Explanation of symbols]

[0362] 10: photosensitive transfer material, 11: temporary support, 13: thermoplastic resin layer, 15: intermediate layer, 17: photosensitive resin layer, 19: protective film

Claims

1. A photosensitive transfer material having, in this order, a temporary support, a thermoplastic resin layer containing a copolymer polyester resin, an intermediate layer, and a photosensitive resin layer.

2. The photosensitive transfer material according to claim 1 , wherein the thermoplastic resin layer is a coating film.

3. 2. The photosensitive transfer material according to claim 1, wherein the thermoplastic resin layer and the intermediate layer are in contact with each other.

4. 4. The photosensitive transfer material according to claim 3, wherein a peel strength between the thermoplastic resin layer and the intermediate layer is 100 mN / cm or less.

5. 2. The photosensitive transfer material according to claim 1, wherein the copolymer polyester resin 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.

6. 2. The photosensitive transfer material according to claim 1, wherein the intermediate layer is a coating film containing polyvinyl alcohol.

7. The photosensitive transfer material according to claim 1 , wherein the photosensitive resin layer contains a surfactant containing silicon.

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

9. A method for producing a photosensitive transfer material, comprising a step of forming, on a temporary support, a thermoplastic resin layer containing a copolymer polyester resin, an intermediate layer, and a photosensitive resin layer by coating and drying in this order.

10. forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer containing a copolymer polyester resin on a protective film by coating and drying in this order; a step of bonding a temporary support to the thermoplastic resin layer by thermal lamination; A method for producing a photosensitive transfer material comprising the steps of:

Images