Photosensitive transfer material and method for producing same

Abstract

Provided are: 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 off between the thermoplastic resin layer and the intermediate layer when the temporary support is peeled off, and has excellent peelability between the thermoplastic resin layer and the intermediate layer; and a method for producing the photosensitive transfer material. Provided are: a photosensitive transfer material having a temporary support, a thermoplastic resin layer containing a copolymerized polyester resin, an intermediate layer, and a photosensitive resin layer in this order; and a method for producing the photosensitive transfer material.

Description

Technical Field

[0001] The invention relates to a photosensitive transfer material and a method for making the same. Background Art

[0002] In the past, 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 having a desired pattern (hereinafter, also referred to as a "mask"), and then developed, thereby obtaining a desired pattern shape.

[0003] As a photosensitive transfer material, for example, Patent Document 1 discloses a pattern forming material having a cushion layer containing an ethylene-vinyl acetate copolymer resin as a thermoplastic resin, a barrier layer, and a photosensitive layer in this order on a support.

[0004] Patent Document 2 discloses a photosensitive transfer material including a photosensitive layer, an intermediate layer, an adhesive layer containing an adhesive such as an acrylic adhesive, and a temporary support in this order on a cover film.

[0005] Patent Document 3 discloses a transfer film including a thermoplastic resin layer containing an acrylic resin, a water-soluble resin layer, a photosensitive layer, and a protective film in this order on a temporary support.

[0006] Patent Document 1: Japanese Patent Application Publication No. 2007-178459

[0007] Patent Document 2: International Publication No. 2019 / 146380

[0008] Patent Document 3: Japanese Patent Application Publication No. 2022-168819

[0009] In patterning using dry film resist, high resolution is required. For example, in the manufacturing process of semiconductor package substrates, attempts are made to use fine patterns formed by dry film resists in a semi-additive process to form copper wiring patterns of less than 3 μm. In addition, for example, metal masks with tiny through holes used in the manufacture of OLEDs (Organic Light Emitting Diodes) require miniaturization with hole widths of less than 15 μm as OLEDs become more high-definition.

[0010] Among the exposure methods of dry film resists, there are three methods, for example, contact exposure, proximity exposure, and projection exposure. Among these exposure methods, the contact exposure method is an exposure method that uses a relatively cheap 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 exposure gap, the less blurring of the image, and a high-resolution image that is faithful to the mask can be obtained. Therefore, in order to form a high-resolution resist pattern, an attempt is made to shorten the exposure gap by peeling off and removing the temporary support before exposure, and then perform exposure.

[0011] 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 before exposure and then exposed, the mask is attached to the surface of the photosensitive resin layer exposed by peeling off the temporary support, and workability such as transportation may be reduced. In order to prevent adhesion between the photosensitive resin layer and the mask, for example, it is conceivable to set the photosensitive transfer material to a structure having other layers such as a thermoplastic resin layer and an intermediate layer between the temporary support and the photosensitive resin layer, so that it is not peeled off between the temporary support and the photosensitive resin layer when the temporary support is peeled off. Summary of the invention

[0012] The present invention has been accomplished in view of the above-mentioned circumstances.

[0013] The problem to be solved by one embodiment of the present invention is to provide a photosensitive transfer material having a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, wherein the thermoplastic resin layer and the intermediate layer are peeled off when the temporary support is peeled off, and the peelability between the thermoplastic resin layer and the intermediate layer is excellent.

[0014] Another embodiment of the present invention aims to provide a method for producing the above-mentioned photosensitive transfer material.

[0015] Specific means for solving the above-mentioned problems include the following embodiments.

[0016] <1> A photosensitive transfer material comprises a temporary support, a thermoplastic resin layer containing a copolyester resin, an intermediate layer and a photosensitive resin layer in this order.

[0017] <2> according to <1> The photosensitive transfer material, wherein:

[0018] The thermoplastic resin layer is a coating film.

[0019] <3> according to <1> or <2> The photosensitive transfer material, wherein:

[0020] The thermoplastic resin layer is in contact with the intermediate layer.

[0021] <4> according to <3> The photosensitive transfer material, wherein:

[0022] The peeling force between the thermoplastic resin layer and the intermediate layer is 100 mN / cm or less.

[0023] <5> according to <1> to <4> The photosensitive transfer material described in any one of the preceding claims, wherein

[0024] The copolyester 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.

[0025] <6> according to <1> to <5> The photosensitive transfer material described in any one of the preceding claims, wherein

[0026] The intermediate layer is a coating film containing polyvinyl alcohol.

[0027] <7> according to <1> to <6> The photosensitive transfer material described in any one of the preceding claims, wherein

[0028] The photosensitive resin layer contains a surfactant containing silicon.

[0029] <8> according to <1> to <7> The photosensitive transfer material described in any one of the preceding claims, wherein

[0030] The thermoplastic resin layer contains a surfactant containing silicon.

[0031] <9> A method for producing a photosensitive transfer material comprises the following steps: forming a thermoplastic resin layer containing a copolyester resin, an intermediate layer and a photosensitive resin layer in sequence on a temporary support by coating and drying.

[0032] <10> A method for manufacturing a photosensitive transfer material, comprising the following steps:

[0033] By coating and drying, a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer containing a copolymerized polyester resin are sequentially formed on the protective film; and

[0034] The temporary support is bonded to the thermoplastic resin layer by heat lamination.

[0035] Effects of the Invention

[0036] According to one embodiment of the present invention, a photosensitive transfer material can be provided, which has a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, and can be peeled off between the thermoplastic resin layer and the intermediate layer when the temporary support is peeled off, and has excellent peelability between the thermoplastic resin layer and the intermediate layer.

[0037] According to another embodiment of the present invention, a method for manufacturing the above-mentioned photosensitive transfer material is provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a schematic cross-sectional view showing an example of the structure of a photosensitive transfer material. DETAILED DESCRIPTION

[0039] The following description of the requirements may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments and can be implemented with appropriate modifications within the scope of the purpose of the present invention.

[0040] In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit, respectively.

[0041] In the numerical ranges recorded in stages in the present invention, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in the present invention, the upper limit or lower limit recorded in a certain numerical range can be replaced by the value shown in the embodiments.

[0042] In the present invention, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it refers to the total amount of the plurality of components present in the composition.

[0043] In the present invention, a combination of two or more preferred aspects is a more preferred aspect.

[0044] In the present invention, 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 can be achieved.

[0045] In the present invention, "transparent" means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more, preferably 90% or more.

[0046] In the present invention, the "transmittance" is a value measured using a spectrophotometer.

[0047] As the spectrophotometer, for example, a spectrophotometer (model: U-3310) manufactured by Hitachi, Ltd. can be used. However, the spectrophotometer is not limited to this.

[0048] In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) unless otherwise specified.

[0049] The values ​​measured by GPC are as follows: TSKgel (registered trademark) GMHxL, TSKgel (registered trademark) G4000HxL or TSKgel (registered trademark) G2000HxL [all trade names manufactured by TOSOH CORPORATION] is used as the column, tetrahydrofuran (THF) is used as the eluent, a differential refractometer is used as the detector, and polystyrene is used as the standard substance, and the above-mentioned polystyrene conversion value is measured by the GPC analysis device.

[0050] In the present invention, unless otherwise specified, the ratio of the structural units of the polymer compound is a mass ratio.

[0051] In the present invention, the glass transition temperature (Tg) is a value measured using a differential scanning calorimeter.

[0052] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC-60) manufactured by SHIMADZU CORPORATION can be used. However, the differential scanning calorimeter is not limited to this.

[0053] In the present invention, unless otherwise specified, hue is a value measured using a colorimeter.

[0054] As the colorimeter, for example, a colorimeter (model: CR-221) manufactured by MINOLTA CO., LTD. can be used. However, the colorimeter is not limited to this.

[0055] In the present invention, “(meth)acrylic acid” is a term including both “acrylic acid” and “methacrylic acid”, “(meth)acrylate” is a term including both “acrylate” and “methacrylate”, and “(meth)acryloyloxy” is a term including both “acryloyloxy” and “methacryloyloxy”.

[0056] In the present invention, "alkali-soluble" means that the solubility in 100 g of a 1.0 mass % sodium carbonate aqueous solution at a liquid temperature of 22°C is 0.1 g or more.

[0057] In the present invention, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22° C. and a pH of 7.0 is 0.1 g or more. For example, a "water-soluble resin" refers to a resin that satisfies the above solubility conditions.

[0058] In the present invention, the "solid content" in the composition refers to the components that form the layer formed using the composition, and when the composition contains a solvent, it refers to all components excluding the solvent. In addition, if it is a component that forms a layer, liquid components other than the solvent are also regarded as solid components.

[0059] In the present invention, "solvent" refers to water and organic solvents.

[0060] In the present invention, "n-" means normal, "s-" means secondary, and "t-" means tertiary.

[0061] In the present invention, “light” refers to, for example, ultraviolet light, visible light, and infrared light.

[0062] In the present invention, “ultraviolet light” refers to light in a wavelength range of 200 nm to less than 400 nm, “visible light” refers to light in a wavelength range of 400 nm to less than 780 nm, and “infrared light” refers to light in a wavelength range of 780 nm to less than 1000 nm.

[0063] [Photosensitive transfer material]

[0064] The photosensitive transfer material according to the present invention comprises a temporary support, a thermoplastic resin layer containing a copolyester resin, an intermediate layer, and a photosensitive resin layer in this order.

[0065] The photosensitive transfer material of the present invention has a thermoplastic resin layer and an intermediate layer between a temporary support and a photosensitive resin layer, and the thermoplastic resin layer and the intermediate layer are peeled off when the temporary support is peeled off, and the peelability between the thermoplastic resin layer and the intermediate layer is excellent.

[0066] In patterning using dry film resist, high resolution is required. In the contact exposure method, which is one of the exposure methods of dry film resist, the shorter the exposure gap, the less blurring of the image, and a high-resolution image that is faithful to the mask can be obtained. As an attempt to obtain a high-resolution resist pattern by shortening the light gap, an attempt has been made to expose after peeling off a temporary support before exposure. 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 before exposure and then exposed, the mask is attached to the surface of the photosensitive resin layer exposed by peeling off the temporary support, and sometimes the transport becomes difficult, and the workability is reduced.

[0067] The photosensitive transfer material involved in the present invention has a thermoplastic resin layer and an intermediate layer in sequence from the temporary support side between the temporary support and the photosensitive resin layer. The thermoplastic resin layer contains a copolyester resin, so when the temporary support is peeled off, it is peeled off between the thermoplastic resin layer and the intermediate layer, and the peelability between the thermoplastic resin layer and the intermediate layer is excellent.

[0068] Compared with the photosensitive transfer material involved in the present invention, the pattern forming material described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-178459) has a buffer layer (so-called thermoplastic resin layer) and a barrier layer (so-called intermediate layer) between the temporary support and the photosensitive layer. When the temporary support is peeled off, the buffer layer (so-called thermoplastic resin layer) and the barrier layer (so-called intermediate layer) are peeled off. However, the buffer layer is a layer containing ethylene-vinyl acetate copolymer resin and does not contain copolyester resin. It is believed that the pattern forming material described in Patent Document 1 has poor peelability between the buffer layer and the barrier layer because the buffer layer containing ethylene-vinyl acetate copolymer resin has high adhesion (for example, refer to Comparative Example 4 described later).

[0069] The photosensitive transfer material described in Patent Document 2 (International Publication No. 2019 / 146380) is peeled off 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 copolyester resin. It is speculated that the adhesive layer of the photosensitive transfer material described in Patent Document 2 has high adhesiveness, and the buffer layer and the barrier layer have poor peelability.

[0070] In the transfer film described in Patent Document 3 (Japanese Patent Application Publication No. 2022-168819), a thermoplastic resin layer and a water-soluble resin layer are provided between the temporary support and the photosensitive layer, but the thermoplastic resin layer is a layer containing an acrylic resin and does not contain a copolyester resin. It is believed that when the transfer film described in Patent Document 3 is peeled off from the temporary support, it is not peeled off between the thermoplastic resin layer and the water-soluble resin layer, but peeled off between the temporary support and the thermoplastic resin layer (for example, refer to Comparative Example 1 described later).

[0071] In the photosensitive transfer material involved in the present invention, if an attempt is made to peel off the temporary support before exposure, the thermoplastic resin layer is removed in addition to the temporary support, so that the exposure gap becomes shorter than when only the temporary support is removed, thereby enabling formation of a higher-resolution resist pattern.

[0072] Furthermore, in the photosensitive transfer material involved in the present invention, since the photosensitive resin layer will not be exposed due to the peeling of the temporary support body, even when exposure is performed by contact exposure, the mask and the photosensitive resin layer will not come into contact, and the workability will not be reduced due to the mask sticking to the exposed surface of the photosensitive resin layer.

[0073] Furthermore, in the photosensitive transfer material according to the present invention, the releasability between the thermoplastic resin layer and the intermediate layer is excellent, so that operations such as transportation can be performed well, and for example, the productivity of the substrate with a pattern can be improved.

[0074] Furthermore, the photosensitive transfer material according to the present invention has a thermoplastic resin layer containing a copolyester resin, and thus can exhibit an effect that bubbles (so-called lamination bubbles) are less likely to be mixed between the material and the object when the material is bonded to the object.

[0075] In contrast, for example, the photosensitive transfer material described in Patent Document 2 does not have a thermoplastic resin layer itself, but is formed by laminating a temporary support having an adhesive layer and an intermediate layer, so bubbles and / or foreign matter tend to be easily caught between the adhesive layer and the intermediate layer during lamination. The caught bubbles and / or foreign matter may cause defects on the exposed surface of the intermediate layer when the temporary support is peeled off, which may be the main cause of defects in the resist pattern.

[0076] Figure 1 This is a schematic cross-sectional view showing an example of the structure of a photosensitive transfer material.

[0077] Figure 1 The photosensitive transfer material 10 shown includes 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.

[0078] The photosensitive transfer material according to the present invention may have layers (so-called other layers) other than the temporary support, the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer.

[0079] The temporary support, the thermoplastic resin layer, the intermediate layer, the photosensitive resin layer, and other layers may each be a single layer or may be a multilayer of two or more layers.

[0080] The photosensitive transfer material according to the present invention preferably comprises a temporary support, a thermoplastic resin layer containing a copolyester resin (also simply referred to as a "thermoplastic resin layer"), an intermediate layer, and a photosensitive resin layer in this order, wherein the thermoplastic resin layer is in contact with the intermediate layer.

[0081] The photosensitive transfer material of the present invention preferably further has a protective film on the photosensitive resin layer. For example, the structure of the photosensitive transfer material of the present invention is preferably temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film.

[0082] In the photosensitive transfer material of the present invention, the thermoplastic resin layer is in contact with the intermediate layer, and the peeling force between the thermoplastic resin layer and the intermediate layer (so-called interlayer peeling force) is preferably 100 mN / cm or less, more preferably 50 mN / cm or less, and further preferably 25 mN / cm or less. The lower limit of the peeling force 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.

[0083] The peeling force between the thermoplastic resin layer and the intermediate layer in the photosensitive transfer material according to the present invention was measured by the following method.

[0084] The photosensitive transfer material and the Invar alloy substrate are bonded to obtain an evaluation laminate having a photosensitive resin layer, an intermediate layer, a thermoplastic resin layer and a temporary support arranged in sequence on the surface of the Invar alloy substrate. The bonding of the photosensitive transfer material and the Invar alloy substrate is carried out using a roller laminator at a temperature of 100°C, a linear pressure of 0.5 MPa and a linear speed (so-called lamination speed) of 4 m / min. Next, the obtained laminate is subjected to an 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 treated laminate is attached to a glass having a thickness of 0.7 mm using a double-sided tape. For the laminate attached to the glass, a 180° peeling test between the thermoplastic resin layer and the intermediate layer is carried out using Tensilon at a peeling speed of 300 mm / min, and the peeling force is measured.

[0085] As the Tensilon, for example, RTF-1210 (model), which is a Tensilon universal material testing machine manufactured by A&D Company, Limited, can be preferably used. However, the Tensilon is not limited thereto.

[0086] Hereinafter, each structure of the photosensitive transfer material according to the present invention will be described in detail.

[0087] <Temporary Support Body>

[0088] The photosensitive transfer material according to the present invention has a temporary support.

[0089] The temporary support is a member that supports the transfer layer and is finally removed by peeling.

[0090] In the present invention, the "transfer layer" is a layer other than the temporary support in the photosensitive transfer material, and refers to a layer disposed on the object by laminating the photosensitive transfer material and the object during use of the photosensitive transfer material. In one embodiment, the transfer layer is a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer.

[0091] The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heating is preferred.

[0092] Specific examples of the temporary support include polyethylene terephthalate films (eg, biaxially stretched polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films.

[0093] As the temporary support, a polyethylene terephthalate film is preferable.

[0094] It is preferred that the film used as a temporary support has no deformation such as wrinkles or scratches.

[0095] From the viewpoint of enabling pattern exposure via the temporary support, the temporary support preferably has high transparency. For example, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more.

[0096] The transmittance is calculated as the ratio of the amount of light incident on the temporary support to the amount of light emitted from the temporary support (= amount of emitted light / amount of incident light×100; %).

[0097] From the viewpoint of pattern formation when pattern exposure is performed via a temporary support and the transparency of the temporary support, the temporary support preferably has a small haze value. Specifically, the temporary support preferably has a haze value of 5% or less, more preferably 2% or less, further preferably 0.5% or less, and particularly preferably 0.1% or less.

[0098] 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 (for example, a haze meter NDH400 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.).

[0099] From the viewpoint of pattern formability during pattern exposure via a temporary support and transparency of the temporary support, the number of coarse particles, foreign matter, and defects contained in the temporary support is preferably small.

[0100] The total number of particles, foreign matter and defects with a diameter of 1 μm or more contained in the temporary support is preferably 50 / 10 mm. 2 Below, more preferably 10 / 10mm 2 Below, more preferably 3 / 10mm 2 Below, especially preferably 0 / 10mm 2 .

[0101] From the viewpoint of resolution in pattern exposure via a temporary support, the thickness of the temporary support is preferably 200 μm or less, more preferably 100 μm or less, and further preferably 50 μm or less.

[0102] The thickness of the temporary support is an average thickness calculated by arithmetic average of thicknesses at five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0103] Preferred temporary supports include, for example, a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

[0104] As the temporary support, a commercially available product can be used.

[0105] Examples of commercially available temporary supports 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.] and Cosmo Shine (registered trademark) A4100, Cosmo Shine (registered trademark) A4160, Cosmo Shine (registered trademark) A4300, Cosmo Shine (registered trademark) A4360 and Cosmo Shine (registered trademark) A8300 [all manufactured by TOYOB0 CO., LTD.].

[0106] Preferred embodiments of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Application Publication No. 2016-27363, paragraphs 0041 to 0057 of International Publication No. 2012 / 081680, paragraphs 0029 to 0040 of International Publication No. 2018 / 179370, and paragraphs 0012 to 0032 of Japanese Patent Application Publication No. 2019-101405. The contents of the above publications are incorporated into this specification by reference.

[0107] From the viewpoint of handleability, the temporary support may have a layer containing fine particles (also referred to as a "lubricant layer").

[0108] The lubricant layer is preferably disposed as the outermost layer on one or both sides of the temporary support.

[0109] 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.

[0110] The average thickness of the lubricant layer is not particularly limited, but is preferably, for example, 0.05 μm to 1.0 μm.

[0111] <Thermoplastic Resin Layer>

[0112] The photosensitive transfer material according to the present invention has a thermoplastic resin layer containing a copolymerized polyester resin.

[0113] The copolyester resin contained in the thermoplastic resin layer has lower crystallinity and melting point than polyester resins other than the copolyester resin, so the thermoplastic resin layer containing the thermoplastic resin layer tends to have high thermoplasticity. The photosensitive transfer material involved in the present invention has a thermoplastic resin layer with high thermoplasticity, so that, for example, when attached to an object, bubbles are difficult to mix between the object and the photosensitive transfer material, and the photosensitive transfer material tends to have excellent adhesion to the object.

[0114] (Copolyester resin)

[0115] The thermoplastic resin layer includes a copolyester resin.

[0116] In the present invention, the "copolyester resin" refers to a polyester resin containing a plurality of structural units in at least one of the repeating units constituting the polyester resin, namely, the unit of a dicarboxylic acid and the unit of a diol component.

[0117] The dicarboxylic acid units and diol component units constituting the copolyester resin may be one type of dicarboxylic acid unit and two or more types of diol component units, or may be two or more types of dicarboxylic acid units and one type of diol component units, or may be two or more types of dicarboxylic acid units and two or more types of diol component units.

[0118] The copolyester resin may be a crystalline copolyester resin or an amorphous copolyester resin, but is preferably an amorphous copolyester resin.

[0119] Examples of the dicarboxylic acid 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-naphthalene dicarboxylic acid.

[0120] 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.

[0121] The copolyester resin preferably contains a structural unit derived from a monomer having an aromatic ring. If the copolyester resin contains a structural unit derived from a monomer having an aromatic ring, for example, when the temporary support is polyethylene terephthalate, the adhesion based on the π electron interaction (π-π stacking) between the thermoplastic resin layer and the temporary support tends to be improved. In addition, if the copolyester resin contains a structural unit derived from a monomer having an aromatic ring, the glass transition temperature (Tg) is moderately increased, so the peelability between the thermoplastic resin layer and the intermediate layer tends to be further improved.

[0122] Examples of monomers having an aromatic ring include dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid. Examples of monomers having an aromatic ring include diol components such as bisphenol A and ethylene oxide adducts of bisphenol A.

[0123] The copolyester resin may contain a structural unit derived from a monomer other than the dicarboxylic acid and the diol component (hereinafter also referred to as “other monomer”).

[0124] As other monomers, for example, monomers having three or more carboxyl groups such as tricarboxylic acid and tetracarboxylic acid and monomers having three or more hydroxyl groups such as triol components and tetraol components can be cited. If these monomers are copolymerized in a small amount, a copolyester having a branched chain can be obtained, thereby adjusting the melt viscosity of the copolyester.

[0125] Examples of the tricarboxylic acid include trimellitic acid and 1,3,5-benzenetricarboxylic acid, and examples of the triol component include glycerol and 1,2,4-butanetriol.

[0126] The total content of the dicarboxylic acid units and diol component units in the copolyester resin is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, particularly preferably 99% by mass or more, based on all units constituting the copolyester resin.

[0127] The upper limit of the total content of the dicarboxylic acid units and the diol component units in the copolyester resin is not particularly limited, but may be, for example, 100% by mass based on all the units constituting the copolyester resin.

[0128] The copolyester resin preferably has a number average molecular weight of 3,000 to 30,000 and a glass transition temperature of -20°C to 80°C, from the viewpoint of excellent releasability between the thermoplastic resin layer and the intermediate layer. It is more preferably a number average molecular weight of 4,000 to 20,000 and a glass transition temperature of 10°C to 50°C. It is further preferably a number average molecular weight of 5,000 to 10,000 and a glass transition temperature of 20°C to 50°C. It is particularly preferably a number average molecular weight of 6,000 to 10,000 and a glass transition temperature of 30°C to 45°C.

[0129] When the thermoplastic resin layer contains two or more copolyester resins, the number average molecular weight and glass transition temperature of the copolyester resins are weighted average values.

[0130] As the copolyester resin, a commercially available product can be used.

[0131] Examples of commercially available copolyester resins include BYRON (registered trademark) BX-1001 [Mn: 28000, Tg: -18°C, manufactured by TOYOBO CO., LTD.], BYRON (registered trademark) GK-800 [Mn: 27000, Tg: 50°C, manufactured by TOYOBO CO., LTD.], BYRON (registered trademark) 802 [Mn: 3000, Tg: 60°C, manufactured by TOYOBO CO., LTD.], BYRON (registered trademark) 670 [Mn: 30000, Tg: 7°C, manufactured by TOYOBO CO., LTD.], BYRON (registered trademark) GK-830 [Mn: 32000, Tg: 25°C, manufactured by TOYOBO CO., LTD.], BYRON (registered trademark) GK-140 [Mn: 13000, Tg: 20°C, manufactured by TOYOBO CO., LTD.], BYRON (registered trademark) GK-780 [Mn: 11000, Tg: 36°C, manufactured by TOYOBO CO., LTD.], BYRON (registered trademark) GK-810 [Mn: 6000, Tg: 46°C, manufactured by TOYOBO CO., LTD.], BYRON (registered trademark) GK-590 [Mn: 7000, Tg: 15°C, manufactured by TOYOBO CO., LTD.] and BYRON (registered trademark) GK-890 [Mn: 11000, Tg: 17°C, manufactured by TOYOBO CO., LTD.].

[0132] The thermoplastic resin layer may contain only one type of copolyester resin, or may contain two or more types.

[0133] From the viewpoint of achieving better releasability between the thermoplastic resin layer and the intermediate layer, the content of the copolyester 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 further 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.

[0134] (Various additives)

[0135] The thermoplastic resin layer may contain known additives as necessary within a range not impairing the effects of the present invention.

[0136] Examples of the additive include a polymerization inhibitor, a surfactant, and a solvent.

[0137] The thermoplastic resin layer may contain a polymerization inhibitor.

[0138] The polymerization inhibitor in the thermoplastic resin layer has the same meaning as the polymerization inhibitor in the photosensitive resin layer described later, and the preferred aspects are also the same.

[0139] When the thermoplastic resin layer contains a polymerization inhibitor, only one type of polymerization inhibitor may be contained, or two or more types may be contained.

[0140] 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 % to 10 mass % with respect to the total mass of the thermoplastic resin layer, more preferably in the range of 0.1 mass % to 1 mass %, and further preferably in the range of 0.1 mass % to 0.5 mass %.

[0141] The thermoplastic resin layer may contain a surfactant.

[0142] The surfactant in the thermoplastic resin layer has the same meaning as the surfactant in the photosensitive resin layer described later, and the preferred aspects are also the same.

[0143] For example, when the thermoplastic resin layer contains a surfactant, the thermoplastic resin layer preferably contains a surfactant containing silicon from the viewpoint of the peelability between the thermoplastic resin layer and the intermediate layer.

[0144] Furthermore, when the thermoplastic resin layer contains a surfactant, the surfactant is preferably a surfactant containing silicon from the viewpoint of improving environmental suitability.

[0145] When the thermoplastic resin layer contains a surfactant, it may contain only one type of surfactant or two or more types of surfactant.

[0146] 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 % to 1 mass %, more preferably in the range of 0.01 mass % to 1 mass %, and further preferably in the range of 0.1 mass % to 0.5 mass %, relative to the total mass of the thermoplastic resin layer.

[0147] The thermoplastic resin layer may contain a solvent.

[0148] When the thermoplastic resin layer is formed from a composition containing a solvent, the solvent may remain in the thermoplastic resin layer.

[0149] Furthermore, the thermoplastic resin layer may contain known additives such as a rust preventive, an antioxidant, a colorant, a plasticizer, and a polymerizable compound.

[0150] The thermoplastic resin layer is preferably a coating film.

[0151] In the present invention, the "coating film" refers to a film formed by coating and drying.

[0152] The copolyester resin contained in the thermoplastic resin layer has high solubility in organic solvents, so the thermoplastic resin layer can be formed by a coating method. According to the coating method, a thermoplastic resin layer with high uniformity of thickness and smoothness can be obtained. Compared with the melt extrusion lamination method, the coating method is less likely to produce surface defects such as fish eyes, stripes, and unevenness. If the thermoplastic resin layer is a coating film, it is less likely to produce defects in the resist pattern caused by the surface defects of the thermoplastic resin layer affecting the surface state of the intermediate layer, and it tends to be easier to obtain a high-resolution resist pattern.

[0153] <<Thickness of Thermoplastic Resin Layer>>

[0154] The thickness of the thermoplastic resin layer is preferably 0.5 μm to 50 μm, more preferably 1 μm to 20 μm, and further preferably 3 μm to 10 μm.

[0155] If the thickness of the thermoplastic resin layer is within the above range, the adhesion between the temporary support and the thermoplastic resin layer becomes good, and when the temporary support is peeled off, the thermoplastic resin layer and the intermediate layer are peeled off, and the peelability between the thermoplastic resin layer and the intermediate layer is more excellent. In addition, it is possible to exert an effect that bubbles (so-called laminating bubbles) are less likely to be mixed between the temporary support and the object when the temporary support is attached.

[0156] The thickness of the thermoplastic resin refers to an average thickness calculated by arithmetic average of thicknesses at five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0157] <Method for Forming Thermoplastic Resin Layer>

[0158] The method for forming the thermoplastic resin layer is not particularly limited as long as the intended thermoplastic resin layer can be obtained.

[0159] As a method for forming a thermoplastic resin layer, for example, the following method can be mentioned: a thermoplastic resin containing a copolyester resin and a thermoplastic resin layer-forming composition containing any additives is prepared, the prepared thermoplastic resin layer-forming composition is applied to a temporary support or an intermediate layer, and the applied thermoplastic resin layer-forming composition is dried.

[0160] 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.

[0161] 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 thereof.

[0162] The solvent is preferably a solvent containing at least one selected from the group consisting of an alkylene glycol ether acetate solvent, a ketone solvent, an aromatic hydrocarbon solvent and an ester solvent, more preferably a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent, an aromatic hydrocarbon solvent and an ester solvent, and further preferably a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether acetate solvent, at least one selected from the group consisting of a ketone solvent and an ester solvent, and at least one selected from the group consisting of an aromatic hydrocarbon solvent.

[0163] Examples of the alkylene glycol ether acetate solvent 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.

[0164] Examples of the ketone solvent include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, diisobutyl ketone, and diacetone alcohol.

[0165] Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl lactate, ethyl lactate, and propyl lactate.

[0166] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, SOLVESSO 100, SOLVESSO 150, and SOLVESSO 200.

[0167] When the thermoplastic resin layer-forming composition contains a solvent, it may contain only one kind of solvent or two or more kinds of solvents.

[0168] When the thermoplastic resin layer-forming composition contains a solvent, the content of the solvent when the thermoplastic resin layer-forming composition is applied is preferably 50 to 1900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin layer-forming composition.

[0169] The method for preparing the thermoplastic resin layer-forming composition is not particularly limited, and an example thereof includes a method of preparing a solution obtained by dissolving each component in the above-mentioned solvent in advance and mixing the obtained solution at a predetermined ratio to prepare the thermoplastic resin layer-forming composition.

[0170] The thermoplastic resin layer-forming composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the thermoplastic resin layer.

[0171] The method for applying the thermoplastic resin layer-forming composition is not particularly limited, and the composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0172] As a method for drying the applied thermoplastic resin layer-forming composition, heating drying and reduced-pressure drying are preferred. In the present invention, "drying" means removing at least a part of the solvent contained in the composition.

[0173] Examples of the drying method include natural drying, heat drying, and reduced-pressure drying.

[0174] For drying, the above-mentioned methods can be applied alone or in combination of two or more.

[0175] The drying temperature is preferably 70° C. or higher, more preferably 80° C. or higher.

[0176] The upper limit of the drying temperature is not particularly limited, but is, for example, preferably 180° C. or lower, and more preferably 150° C. or lower.

[0177] The applied thermoplastic resin layer-forming composition may be dried while continuously changing the temperature.

[0178] The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The upper limit of the drying time is not particularly limited, but is, for example, preferably 600 seconds or shorter, and more preferably 300 seconds or shorter.

[0179] <Middle Layer>

[0180] The photosensitive transfer material according to the present invention has an intermediate layer.

[0181] The photosensitive transfer material of the present invention has a temporary support, a thermoplastic resin layer, an intermediate layer and a photosensitive resin layer in sequence, and is peeled 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 it is desired to perform contact exposure after shortening the exposure gap by peeling off the temporary support, the mask is made to be closely fitted to the surface of the side opposite to the photosensitive resin layer side of the intermediate layer. The photosensitive transfer material of the present invention has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer, and during exposure, the mask can be brought into contact with the intermediate layer, so that, for example, compared with peeling off between the temporary support and the thermoplastic resin layer when the temporary support is peeled off and the mask is brought into contact with the thermoplastic resin layer, it tends to be difficult to adhere to the layer in contact with the mask, and it is not easy to reduce the workability.

[0182] (Water-soluble resin)

[0183] The intermediate layer preferably contains a water-soluble resin.

[0184] Examples of the water-soluble resin include polyvinyl alcohol resins (e.g., polyvinyl alcohol), polyvinyl pyrrolidone resins (e.g., polyvinyl pyrrolidone), cellulose resins (e.g., hydroxypropyl methylcellulose), acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and resins that are copolymers thereof.

[0185] From the viewpoint of suppressing mixing of components between adjacent layers, the water-soluble resin contained in the intermediate layer is preferably a resin different from both the thermoplastic resin contained in the thermoplastic resin layer and the resin (for example, alkali-soluble resin) contained in the photosensitive resin layer.

[0186] From the viewpoint of oxygen barrier properties and suppression of mixing of components between adjacent layers during coating and storage after coating, the intermediate layer preferably contains polyvinyl alcohol, more preferably contains polyvinyl alcohol and polyvinyl pyrrolidone, and further preferably contains polyvinyl alcohol, polyvinyl pyrrolidone and hydroxypropyl methylcellulose.

[0187] The intermediate layer is preferably a coating film containing a water-soluble resin.

[0188] If the intermediate layer contains a water-soluble resin, the peeling property between the thermoplastic resin layer and the intermediate layer tends to be more excellent. In addition, since the intermediate layer contains a water-soluble resin, it can be formed by a coating method. According to the coating method, an intermediate layer with high uniformity of thickness and smoothness can be obtained. In addition, the coating method is not easy to produce surface defects such as fish eyes, stripes, and unevenness. If the intermediate layer is a coating film, it is difficult to produce defects in the resist pattern caused by the surface defects of the intermediate layer, and it tends to be easier to obtain a high-resolution resist pattern.

[0189] The intermediate layer is more preferably a coating film containing polyvinyl alcohol as the water-soluble resin, further preferably a coating film containing polyvinyl alcohol and polyvinyl pyrrolidone, and particularly preferably a coating film containing polyvinyl alcohol, polyvinyl pyrrolidone and hydroxypropyl methylcellulose.

[0190] When the intermediate layer contains a water-soluble resin, the intermediate layer may contain one type of water-soluble resin or may contain two or more types of water-soluble resin.

[0191] 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 suppression of mixing of components between adjacent layers during coating and storage after coating, the content of the water-soluble resin is preferably in the range of 50 mass % to 100 mass %, more preferably in the range of 70 mass % to 100 mass %, further preferably in the range of 80 mass % to 100 mass %, and particularly preferably in the range of 90 mass % to 100 mass % relative to the total mass of the intermediate layer.

[0192] (Various additives)

[0193] The intermediate layer may contain known additives as necessary within a range not impairing the effects of the present invention.

[0194] Examples of the additive include surfactants, particles, and solvents.

[0195] The intermediate layer may contain a surfactant.

[0196] The surfactant in the intermediate layer has the same meaning as the surfactant in the photosensitive resin layer described later, and the preferred aspects are also the same.

[0197] When the intermediate layer contains a surfactant, it may contain only one type of surfactant or may contain two or more types of surfactant.

[0198] When the intermediate layer contains a surfactant, the content of the surfactant in the intermediate layer is preferably in the range of 0.001 mass % to 1 mass %, more preferably in the range of 0.01 mass % to 0.5 mass %, and further preferably in the range of 0.05 mass % to 0.2 mass %, relative to the total mass of the intermediate layer.

[0199] The intermediate layer may contain particles.

[0200] If the intermediate layer contains particles, the intermediate layer is less likely to adhere to the mask even when the mask and the intermediate layer are brought into contact during contact exposure, for example. Therefore, the generation of contamination caused by the intermediate layer adhering to the mask, the decrease in workability, etc., tends to be suppressed.

[0201] The particles are preferably inorganic particles.

[0202] As the inorganic particles, metal oxide particles are preferred.

[0203] The metal in the metal oxide particles also includes semimetals such as B, Si, Ge, As, Sb, and Te.

[0204] The average primary particle size of the particles is not particularly limited, but is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of suppressing an increase in the haze of the intermediate layer and obtaining a high-resolution resist pattern.

[0205] The average primary particle size of the particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particles is not spherical, the longest side is used as the particle size.

[0206] When the intermediate layer contains inorganic particles as particles, the intermediate layer may contain only one type of particles different in metal type, size, etc., or may contain two or more types of particles.

[0207] Also, the intermediate layer may contain organic particles as particles.

[0208] When the intermediate layer contains particles, the content of the particles in the intermediate layer is not particularly limited, but is preferably in the range of 1 mass % to 50 mass %, more preferably in the range of 5 mass % to 40 mass %, and further preferably in the range of 10 mass % to 30 mass %, relative to the total mass of the intermediate layer.

[0209] <<Thickness of the middle layer>>

[0210] The thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm.

[0211] When the thickness of the intermediate layer is within the above range, for example, mixing of components between adjacent layers during coating and storage after coating can be suppressed without reducing oxygen barrier properties, and an increase in the time required to remove the intermediate layer during development can be suppressed.

[0212] The thickness of the intermediate layer refers to an average thickness calculated by arithmetic average of thicknesses at five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0213] <Method for Forming Intermediate Layer>

[0214] The method for forming the intermediate layer is not limited as long as the target intermediate layer can be obtained.

[0215] As a method for forming the intermediate layer, for example, the following method can be cited: preparing an intermediate layer forming composition containing a water-soluble resin and any additives, applying the prepared intermediate layer forming composition to a thermoplastic resin layer or a photosensitive resin layer, and drying the applied intermediate layer forming composition.

[0216] The intermediate layer-forming composition preferably contains a solvent from the viewpoint of facilitating the formation of the intermediate layer by adjusting the viscosity.

[0217] The solvent is preferably at least one selected from water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0218] Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin.

[0219] Among these, as the water-miscible organic solvent, alcohols having 1 to 3 carbon atoms are preferred, methanol or ethanol is more preferred, and methanol is further preferred.

[0220] When the intermediate layer forming composition contains a solvent, it may contain only one kind of solvent or two or more kinds of solvents.

[0221] When the intermediate layer forming composition contains a solvent, the content of the solvent when the intermediate layer forming composition is applied is preferably 50 to 1900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the intermediate layer forming composition.

[0222] The method for preparing the intermediate layer forming composition is not particularly limited, and an example thereof includes a method of preparing a solution in which each component is dissolved in the above-mentioned solvent in advance and mixing the obtained solution at a predetermined ratio to prepare the intermediate layer forming composition.

[0223] The composition for forming an intermediate layer is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the intermediate layer.

[0224] The coating method of the intermediate layer forming composition is not particularly limited, and the composition may be coated by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0225] As a method for drying the applied intermediate layer-forming composition, heating drying and reduced-pressure drying are preferred.

[0226] Examples of the drying method include natural drying, heat drying, and reduced-pressure drying.

[0227] For drying, the above-mentioned methods can be applied alone or in combination of two or more.

[0228] The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher.

[0229] The upper limit of the drying temperature is not particularly limited, but is, for example, preferably 180° C. or lower, and more preferably 150° C. or lower.

[0230] The applied intermediate layer-forming composition may be dried while continuously changing the temperature.

[0231] The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The upper limit of the drying time is not particularly limited, but is, for example, preferably 600 seconds or shorter, and more preferably 300 seconds or shorter.

[0232] <Photosensitive Resin Layer>

[0233] The photosensitive transfer material according to the present invention has a photosensitive resin layer.

[0234] According to the photosensitive transfer material of the present invention, for example, after the photosensitive resin layer is transferred onto the transfer target, exposure and development are performed, thereby forming a pattern on the transfer target.

[0235] 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.

[0236] The negative photosensitive resin layer refers to a photosensitive resin layer in which the solubility of the exposed portion to a developer is reduced by exposure. When the photosensitive resin layer is a negative photosensitive resin layer, the formed pattern corresponds to a cured layer.

[0237] (polymer)

[0238] The photosensitive resin layer preferably contains a polymer.

[0239] The type of polymer is not particularly limited.

[0240] As a preferable polymer, an alkali-soluble resin is mentioned, for example.

[0241] Examples of the alkali-soluble resin include known alkali-soluble resins used for etching resists.

[0242] The alkali-soluble resin is preferably a binder polymer.

[0243] The alkali-soluble resin is preferably an alkali-soluble resin having an acid group.

[0244] Preferred alkali-soluble resins include polymer A described below.

[0245] From the viewpoint of further improving the resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and further preferably less than 190 mgKOH / g. Furthermore, from the viewpoint of better developability, the acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more.

[0246] The acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of a sample.

[0247] The acid value is calculated, for example, from the average content of acid groups in the compound.

[0248] The acid value of the polymer A is adjusted according to, for example, the type of structural unit constituting the polymer A and the content of the structural unit having an acid group.

[0249] The weight average molecular weight of polymer A is preferably 5,000 to 500,000.

[0250] From the viewpoint of improving resolution and developability, the weight average molecular weight of polymer A is preferably 500,000 or less. The weight average molecular weight of polymer A is more preferably 100,000 or less, and even more preferably 80,000 or less.

[0251] On the other hand, from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as the edge melting property and the chipping property in the photosensitive resin layer, the weight average molecular weight of the polymer A is preferably set to 5,000 or more. The weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.

[0252] The edge melting property refers to the degree to which the photosensitive resin layer is likely to flow out from the end surface of the roll when the photosensitive transfer material is wound into a roll shape.

[0253] Cutting properties refer to the ease with which cutting chips fly when the unexposed film is cut with a cutter. If cutting chips adhere to the surface of the photosensitive resin layer, they will be transferred to the mask during the exposure process, etc., causing defective products.

[0254] The dispersity of 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. Dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight). In the present invention, weight average molecular weight (Mw) and number average molecular weight (Mn) are measured using gel permeation chromatography.

[0255] From the viewpoint of suppressing degradation of line width and resolution when the focus position is shifted during exposure, the polymer A preferably has an aromatic hydrocarbon group, and more preferably contains a structural unit having an aromatic hydrocarbon group.

[0256] Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.

[0257] The content ratio of the structural unit having an aromatic hydrocarbon group in the polymer A is preferably 20 mass % or more, more preferably 30 mass % or more, further preferably 40 mass % or more, particularly preferably 45 mass % or more, and most preferably 50 mass % or more, based on the total mass of the polymer A.

[0258] The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less.

[0259] When a plurality of polymers A are included, the content ratio of the structural unit having an aromatic hydrocarbon group is calculated as a weight average value.

[0260] 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 dimers, and styrene trimers).

[0261] Among these, as the monomer forming the structural unit having an aromatic hydrocarbon group, a monomer having an aralkyl group or styrene is preferred.

[0262] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups.

[0263] The aralkyl group is preferably a substituted or unsubstituted benzyl group.

[0264] As a monomer which has a phenylalkyl group other than a substituted or unsubstituted benzyl group, phenylethyl (meth)acrylate is mentioned, for example.

[0265] Examples of the monomer having a substituted or unsubstituted benzyl group include (meth)acrylates having a substituted or unsubstituted benzyl group (e.g., benzyl (meth)acrylate and benzyl (meth)acrylate chloride); and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol).

[0266] Among these, as the monomer having a substituted or unsubstituted benzyl group, benzyl (meth)acrylate is preferred.

[0267] In one embodiment, when the monomer forming the structural unit having an aromatic hydrocarbon group in the polymer A is benzyl (meth)acrylate, the content ratio of the structural unit derived from benzyl (meth)acrylate is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass based on the total mass of the polymer A.

[0268] In one embodiment, when the monomer forming the structural unit having an aromatic hydrocarbon group in the polymer A is styrene, the content ratio of the structural unit derived from styrene is preferably 20% by mass to 60% by mass, more preferably 25% by mass to 60% by mass, further preferably 30% by mass to 60% by mass, and particularly preferably 30% by mass to 55% by mass, based on the total mass of the polymer A.

[0269] The polymer A containing a structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group and at least one first monomer described below and / or at least one second monomer described below.

[0270] The polymer A not containing a structural unit having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one first monomer described below, and more preferably by copolymerizing at least one first monomer and at least one second monomer described below.

[0271] The first monomer is a monomer having a carboxyl group in the molecule.

[0272] Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester.

[0273] Among these, (meth)acrylic acid is preferred as the first monomer.

[0274] The content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and further preferably 15 to 30 mass %, based on the total mass of the polymer A.

[0275] The second monomer is a non-acidic monomer having at least one ethylenically unsaturated group in the molecule.

[0276] As the second monomer, for example, there can be mentioned (meth)acrylic acid esters 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.

[0277] Among these, as the second monomer, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is more preferred.

[0278] The content of the structural unit derived from the second monomer in the polymer A is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, based on the total mass of the polymer A.

[0279] From the viewpoint of suppressing degradation of line width and resolution when the focus position is shifted during exposure, the polymer A preferably contains at least one structural unit selected from a structural unit having an aralkyl group and a structural unit derived from styrene.

[0280] Preferred examples of the polymer A include 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.

[0281] In one embodiment, the polymer A preferably contains 40 to 60% by mass of a structural unit having an aromatic hydrocarbon group, 15 to 25% by mass of a structural unit derived from the first monomer, and 20 to 40% by mass of a structural unit derived from the second monomer.

[0282] The polymer A may have a branched structure and / or an alicyclic structure in a side chain.

[0283] By using a monomer containing a group having a branched structure in a side chain or a monomer containing a group having an alicyclic structure in a side chain, a branched structure or an alicyclic structure can be introduced into the side chain of polymer A. The alicyclic structure may be a monocyclic structure or a polycyclic structure.

[0284] Examples of the monomer containing a group having a branched structure in a side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, tert-pentyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate.

[0285] Among these, as the monomer containing a group having a branched structure in a side chain, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl (meth)acrylate is preferred, and isopropyl (meth)acrylate or tert-butyl (meth)acrylate is more preferred.

[0286] As the monomer containing a group having an alicyclic structure in the side chain, for example, there can be mentioned a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Furthermore, as the monomer containing a group having an alicyclic structure in the side chain, for example, there can be mentioned a (meth)acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (i.e., the number of carbon atoms).

[0287] More specific examples of the monomer containing a group having an alicyclic structure in a 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(meth)acrylate -2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-menthoindene-5-yl (meth)acrylate, octahydro-4,7-menthoindene-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.

[0288] Among these, as a 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.

[0289] When the photosensitive resin layer contains the polymer A, the polymer A may be contained only one kind, or two or more kinds may be contained.

[0290] When the photosensitive resin layer contains two or more polymers A, it is preferred to use a mixture of two polymers A having an aromatic hydrocarbon group, or to use a mixture of a polymer A having an aromatic hydrocarbon group and a polymer A having no 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, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the polymer A.

[0291] 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 of one or more monomers described above diluted with a solvent such as acetone, methyl ethyl ketone or isopropanol, followed by heating and stirring.

[0292] The synthesis of the polymer A may be performed while adding dropwise a part of the mixture to the reaction solution.

[0293] After the reaction is completed, a solvent may be further added to adjust the concentration to a desired level.

[0294] As a synthesis method, bulk polymerization, suspension polymerization or emulsion polymerization may be used in addition to solution polymerization.

[0295] The glass transition temperature (also referred to as "Tg") of the polymer A is preferably in the range of 30°C or higher and 150°C or lower.

[0296] By using polymer A having a Tg of 150° C. or less in the photosensitive resin layer, it is possible to suppress degradation of line width or resolution when the focus position is shifted during exposure. From this viewpoint, Tg of polymer A is more preferably 140° C. or less, and further preferably 135° C. or less.

[0297] Furthermore, from the viewpoint of improving edge melting resistance, it is preferred to use a polymer A having a Tg of 30°C or higher. From this viewpoint, the Tg of the polymer A is more preferably 40°C or higher, further preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0298] When the photosensitive resin layer contains an alkali-soluble resin, the photosensitive resin layer may contain only one type of alkali-soluble resin or may contain two or more types of alkali-soluble resin.

[0299] 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 preferably 10% to 90% by mass, more preferably 30% to 70% by mass, and further preferably 40% to 60% by mass, relative to the total mass of the photosensitive resin layer.

[0300] From the viewpoint of controlling the development time, the content of the alkali-soluble resin in the photosensitive resin layer is preferably set to 90% by mass or less relative to the total mass of the photosensitive resin layer.

[0301] On the other hand, from the viewpoint of improving edge melting resistance, the content of the alkali-soluble resin in the photosensitive resin layer is preferably set to 10% by mass or more based on the total mass of the photosensitive resin layer.

[0302] The photosensitive resin layer may contain a resin other than the alkali-soluble resin.

[0303] The resin other than the alkali-soluble resin may be any resin having a solubility of less than 0.1 g in 100 g of a 1.0 mass % sodium carbonate aqueous solution at a liquid temperature of 22°C.

[0304] Examples of such resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (copolymers having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0305] (Polymerizable compound)

[0306] 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 polymer A described above.

[0307] The polymerizable group is not particularly limited as long as it is a group that participates in a polymerization reaction.

[0308] 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, and a maleimide group. Examples of the polymerizable group include cationic polymerizable groups such as an epoxy group and an oxetanyl group.

[0309] Among these, as the polymerizable group, a group having an ethylenically unsaturated group is preferred, and an acryloyl group or a methacryloyl group is more preferred.

[0310] As the polymerizable compound, from the viewpoint of better photosensitivity of the photosensitive resin layer, a compound having one or more ethylenically unsaturated groups (so-called ethylenically unsaturated compounds) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (so-called multifunctional ethylenically unsaturated compounds) is more preferred.

[0311] From the viewpoint of achieving better resolution and releasability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0312] 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.

[0313] From the viewpoint of excellent stripping property, the content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and further preferably more than 55% by mass. The upper limit is not particularly limited, for example, it can be 100% by mass. That is, the polymerizable compound can be all bifunctional ethylenically unsaturated compounds.

[0314] As the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0315] 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.

[0316] From the viewpoint of better resolution, the mass ratio of the content of the ethylenically unsaturated compound B1 in the photosensitive resin layer to the content of the ethylenically unsaturated compound is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit is not particularly limited, but, for example, from the viewpoint of peelability, it is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0317] Examples of the aromatic ring possessed by the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring, and aromatic heterocyclic rings 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.

[0318] The aromatic ring of the ethylenically unsaturated compound B1 is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring.

[0319] The aromatic ring of the ethylenically unsaturated compound B1 may have a substituent.

[0320] The ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0321] From the viewpoint of further improving the resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the ethylenically unsaturated compound B1 preferably has a bisphenol structure.

[0322] 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).

[0323] Among these, the bisphenol structure is preferably a bisphenol A structure.

[0324] 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.

[0325] Both ends of the bisphenol structure and the two polymerizable groups may be bonded directly or through one or more alkyleneoxy groups.

[0326] As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferred, and an ethyleneoxy group is more preferred.

[0327] The number of the alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14, per molecule, for example.

[0328] The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in the publication are incorporated into the present specification.

[0329] As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0330] 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-(methacryloxydodecethoxytetrapropoxy)phenyl)propane [FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.], and 2,2-bis(4-(methacryloxypentadecethoxy)phenyl)propane [BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.], 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane [BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.] and ethoxylated (10) bisphenol A diacrylate [NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.].

[0331] As the ethylenically unsaturated compound B1, it is preferred that the compound represented by the following formula (Bis) is contained from the viewpoints of line width change with standing time, line width change with development temperature, and sensitivity.

[0332] [Chemical formula 1]

[0333]

[0334] In the 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 represents an integer of 2 to 40, n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 represents an integer of 0 to 30, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. When the arrangement of the repeating units of -(A-0)- and -(B-0)- is block, either -(A-0)- or -(B-0)- may be on the bisphenol structure side.

[0335] In one embodiment, n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 12. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0.

[0336] When the photosensitive resin layer contains the ethylenically unsaturated compound B1, the photosensitive resin layer may contain only one type of the ethylenically unsaturated compound B1, or may contain two or more types of the ethylenically unsaturated compound B1.

[0337] From the viewpoint of better resolution, 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, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge melting (the phenomenon in which the components in the photosensitive resin layer ooze out from the end of the photosensitive transfer material), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0338] The photosensitive resin layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1.

[0339] The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds.

[0340] Examples of ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 include compounds having one ethylenically unsaturated group in one molecule (so-called monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds having no aromatic ring, and trifunctional or higher ethylenically unsaturated compounds.

[0341] Examples of the monofunctional ethylenically unsaturated compound 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.

[0342] Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0343] Examples of the alkylene glycol di(meth)acrylate 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.

[0344] As a polyalkylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate are mentioned, for example.

[0345] As urethane di(meth)acrylate, propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate are mentioned, for example.

[0346] Examples of commercially available products of urethane di(meth)acrylate include 8UX-015A [manufactured by TAISEIFINE CHEMICAL CO, LTD.], UA-32P [manufactured by Shin-Nakamura Chemical Co., Ltd.], and UA-1100H [manufactured by Shin-Nakamura Chemical Co., Ltd.].

[0347] Examples of the trifunctional or higher ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, and alkylene oxide-modified products thereof.

[0348] “(Tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0349] In one 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 compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and further preferably 1.5:1 to 3:1.

[0350] Furthermore, in one embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0351] Examples of the alkylene oxide-modified products of 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-9300-1C L 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 LTD.], ethoxylated glyceryl triacrylates [e.g., Shin-Nakamura Chemical Co., Ltd.], ARONIX (registered trademark) T0-2349 [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.].

[0352] Furthermore, examples of ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 include ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.

[0353] From the viewpoint of curability and resolution, the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth)acrylic compound, and more preferably contains a (meth)acrylate compound.

[0354] From the viewpoint of curability, resolution and linearity, the ethylenically unsaturated compound in the photosensitive resin layer more preferably includes a (meth)acrylic compound, and the content of the acryloxy compound is 60% by mass or less relative to the total mass of the (meth)acrylic compound contained in the photosensitive resin layer.

[0355] The molecular weight of the ethylenically unsaturated compound including the ethylenically unsaturated compound B1 [when having a distribution, the weight average molecular weight (Mw)] is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0356] When the photosensitive resin layer contains a polymerizable compound, the photosensitive resin layer may contain only one type of polymerizable compound or may contain two or more types of polymerizable compounds.

[0357] 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% to 70% by mass, more preferably 20% to 60% by mass, and further preferably 20% to 50% by mass, relative to the total mass of the photosensitive resin layer.

[0358] In the case where the photosensitive resin layer includes a polymer and a polymerizable compound, from the viewpoint of unevenness followability, 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 further preferably 0.8 or more. Furthermore, the ratio of the total mass of the polymerizable compound (preferably an ethylenically unsaturated compound) to the total mass of the polymer (preferably an alkali-soluble resin) in the photosensitive resin layer is preferably 1.6 or less, more preferably 1.4 or less, and further preferably 1.2 or less.

[0359] (Polymerization initiator)

[0360] The photosensitive resin layer preferably contains a polymerization initiator.

[0361] The type of the polymerization initiator is selected according to the form of the polymerization reaction.

[0362] 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.

[0363] The photosensitive resin layer preferably contains a photopolymerization initiator.

[0364] The photopolymerization initiator is a compound that receives activating light such as ultraviolet rays, visible rays, and X-rays to initiate polymerization of a polymerizable compound.

[0365] The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0366] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0367] 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.

[0368] From the viewpoint of photosensitivity, visual recognition of the exposed part and the non-exposed part, and resolution, the photosensitive resin layer preferably contains at least one selected from 2,4,5-triarylimidazole dimers and derivatives thereof as a photoradical polymerization initiator. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different.

[0369] Examples of the 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.

[0370] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783 can be used.

[0371] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate [DBE, CAS No. 10287-53-3], benzoin methyl ether, (p,p′-dimethoxybenzyl) anisyl ester, and benzophenone.

[0372] Examples of commercially available photoradical polymerization initiators include 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 names: Omnirad 379EG, 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-one [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-hydroxycyclohexylphenyl ketone [trade name: Omnirad 184, manufactured by IGM Resins BV] BV], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: Omnirad 651, manufactured by IGM Resins BV], 2,4,6-trimethylbenzoyl-diphenylphosphine oxide [trade name: Omnirad TPO H, manufactured by IGM Resins BV], bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide [trade name: Omnirad 819, manufactured by IGM Resins BV], oxime ester-based photopolymerization initiator [trade name: Lunar 6, manufactured by DKSH Holding Ltd.], 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole [trade name: B-CIM, manufactured by Hampford], 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer [trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.〔Trade name: TR-PBG-326, manufactured by Changzhou Tronly New ElectronicMaterials CO., LTD.〕, TAZ-110〔Trade name: Midori Kagaku Co., Ltd.〕, TAZ-111〔Trade name: Midori Kagaku Co., Ltd.〕, Co., Ltd.] and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(o-benzoyl oxime) [trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.].

[0373] A photocationic polymerization initiator (so-called photoacid generator) is a compound that generates acid by receiving activating light. As a photocationic polymerization initiator, a compound that generates acid by induction with activating light having a wavelength of 300 nm or more, preferably 300 to 450 nm, is preferred, but its chemical structure is not particularly limited. In addition, a photocationic polymerization initiator that does not directly sense activating light having a wavelength of 300 nm or more can be preferably used in combination with a sensitizer if it is a compound that generates acid by induction with activating light having a wavelength of 300 nm or more.

[0374] The photocationic polymerization initiator is preferably one that generates an acid with a pKa of 4 or less, more preferably one that generates an acid with a pKa of 3 or less, and particularly preferably one that generates an acid with a pKa of 2 or less. The lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.

[0375] Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.

[0376] 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. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can be used.

[0377] As nonionic photocationic polymerization initiators, for example, trichloromethyl-s-triazine compounds, diazomethane compounds, imidosulfonate compounds and oximesulfonate compounds can be cited. As trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds, the compounds described in paragraphs 0083 to 0088 of Japanese Patent Publication No. 2011-221494 can be used. And, as oximesulfonate compounds, the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 can be used.

[0378] When the photosensitive resin layer contains a polymerization initiator, the photosensitive resin layer may contain only one type of polymerization initiator or may contain two or more types of polymerization initiators.

[0379] 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 further preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. In addition, for example, 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, relative to the total mass of the photosensitive layer.

[0380] (pigment)

[0381] From the viewpoint of the visual recognition of the exposed and non-exposed parts, the visual recognition of the pattern after development, and the resolution, the photosensitive resin layer preferably contains a pigment, and more preferably contains a pigment having a maximum absorption wavelength of 450 nm or more at a wavelength range of 400 nm to 780 nm during color development and a maximum absorption wavelength that changes by acid, alkali, or free radicals (also referred to as "pigment N"). Although the detailed mechanism is unclear, if the photosensitive resin layer contains pigment N, the adhesion with the adjacent layer (for example, the intermediate layer) is improved, thereby achieving better resolution.

[0382] In the present invention, "the maximum absorption wavelength of a pigment changes due to acid, alkali or free radicals" may refer to any one of a method in which a pigment in a colored state is decolorized by acid, alkali or free radicals, a method in which a pigment in a decolorized state is colored by acid, alkali or free radicals, and a method in which a pigment in a colored state is changed into a colored state of another hue.

[0383] Specifically, pigment N can be the compound that develops color by exposure from the bleached state change, and can also be the compound that decolorizes by exposure from the bleached state change.In the case, can be to produce acid, alkali or free radical in photosensitive layer by exposure and play a role, thereby the pigment that the state of developing color or decolorization changes, can also be the pigment that the state (such as pH) in the photosensitive resin layer changes by acid, alkali or free radical, thereby the state of developing color or decolorization changes.And, pigment N can be not via exposure, directly accept acid, alkali or free radical as stimulation and the pigment that the state of developing color or decolorization changes.

[0384] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes by an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes by a radical.

[0385] From the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion, the photosensitive resin layer preferably contains both a dye N whose maximum absorption wavelength changes due to radicals and a photoradical polymerization initiator.

[0386] Furthermore, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by acid, alkali, or radicals.

[0387] As an example of the color development mechanism of the pigment N in the present invention, the following method can be cited: a photoradical polymerization initiator, a photocationic polymerization initiator (so-called photoacid generator) or a photobase generator is added to the photosensitive resin layer, and after exposure, a radical-reactive pigment, an acid-reactive pigment or a base-reactive pigment (for example, a colorless pigment) is colored by the free radicals, acid or base generated by the photoradical polymerization initiator, the photocationic polymerization initiator or the photobase generator.

[0388] Regarding pigment N, from the viewpoint of visual recognition of the exposed portion and the non-exposed portion, the maximum absorption wavelength at the wavelength range of 400nm to 780nm during color development is preferably 550nm or more, more preferably 550nm to 700nm, and further preferably 550nm to 650nm. In addition, pigment N may have only one maximum absorption wavelength at the wavelength range of 400nm to 780nm during color development, or may have two or more. In the case where pigment N has two or more maximum absorption wavelengths at the wavelength range of 400nm to 780nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450nm or more.

[0389] The maximum absorption wavelength of pigment N is obtained as follows: in an atmospheric atmosphere, using a spectrophotometer [e.g., UV3100 manufactured by SHIMADZU CORPORATION], the transmission spectrum of a solution containing pigment N (liquid temperature: 25° C.) is measured within a wavelength range of 400 nm to 780 nm, and the wavelength at which the intensity of light becomes extremely small (i.e., the maximum absorption wavelength) is detected.

[0390] Examples of dyes that develop or fade color by exposure include colorless compounds.

[0391] Examples of the dye that is decolorized by exposure include colorless compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

[0392] Among these, the dye N is preferably a colorless compound from the viewpoint of visibility of the exposed portion and the non-exposed portion.

[0393] Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (so-called triarylmethane-based dye), a colorless compound having a spiropyran skeleton (so-called spiropyran-based dye), a colorless compound having a fluoran parent skeleton (so-called fluoran parent-based dye), a colorless compound having a diarylmethane skeleton (so-called diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (so-called rhodamine lactam-based dye), a colorless compound having an indolylphthalide skeleton (so-called indolylphthalide skeleton) and a colorless goldamine skeleton (so-called colorless goldamine-based dye).

[0394] The colorless compound is preferably a triarylmethane-based dye or a fluoran-based dye, and more preferably a colorless compound having a triphenylmethane skeleton (so-called triphenylmethane-based dye) or a fluoran-based dye.

[0395] As a colorless compound, from the viewpoint of visual recognition of the exposed part and the non-exposed part, it is preferred to have a lactone ring, a sultine ring or a sultone ring. Thus, the lactone ring, the sultine ring or the sultone ring of the colorless compound can react with the free radical generated by the photo-radical polymerization initiator or the acid generated by the photo-cationic polymerization initiator, so that the colorless compound is changed to a closed ring state and decolorized, or the colorless compound is changed to an open ring state and colored.

[0396] The colorless compound is preferably a compound having a lactone ring, a sultone ring or a sultone ring and developing color by radical or acid ring opening, and more preferably a compound having a lactone ring and developing color by radical or acid ring opening.

[0397] Specific examples of the colorless compound include p,p',p"-hexamethyltriaminotriphenylmethane (so-called colorless crystal violet), Pergascript Blue SRB (manufactured by Novartis Pharma KK), crystal violet lactone, malachite green lactone, benzoyl leuco-methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran precursor, 2-anilino-3-methyl-6-(N-ethyl-p-toluidine)fluoran precursor, 3,6-dimethoxyfluoran precursor, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran precursor, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran precursor. fluoran matrix, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran matrix, 3-(N,N-diethylamino)-6-methyl-7-sulphoaminofluoran matrix, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran matrix, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran matrix, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran matrix, 3-(N,N-diethylamino)-7-chlorofluoran matrix, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran matrix, N-diethylamino)-7-benzylaminofluoran precursor, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran precursor, 3-(N,N-dibutylamino)-6-methyl-7-sulphoaminofluoran precursor, 3-piperidinyl-6-methyl-7-anilinofluoran precursor, 3-pyrrolidinyl-6-methyl-7-anilinofluoran precursor, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3- Bis(1-n-butyl-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]xanthine-3-one.

[0398] Examples of the coloring matter N include dyes.

[0399] Examples of the dye include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metamin yellow, thymol blue, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurin 4B, d-naphthalene red, Nile blue 2B, Nile blue A, methyl violet, malachite green, para-fuchsin, Victoria pure blue-naphthalenesulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), oil powder #312 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), oil red 5B (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), oil scarlet #308 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), oil red OG (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), and oil red 5B (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.). INDUSTRIES CO.,LTD.], Oil Red RR [manufactured by ORIENT CHEMICAL INDUSTRIES CO.,LTD.], Oil Green #502 [manufactured by ORIENT CHEMICAL INDUSTRIES CO.,LTD.], SPILON RED BEH special [manufactured by Hodogaya Chemical Co.,Ltd.], m-cresol violet, cresol red, rhodamine B, rhodamine 6G, sulfonyl rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyoctadecylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0400] 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.

[0401] When the photosensitive resin layer contains a pigment, from the viewpoint of visual recognizability of the exposed portion and the non-exposed portion, visual recognizability of the pattern after development, and resolution, the content of the pigment in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0402] Furthermore, when the photosensitive resin layer contains a pigment N as a pigment, from the viewpoint of visual recognizability of the exposed portion and the non-exposed portion, visual recognizability of the pattern after development, and resolution, the content of the pigment N in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0403] The content of the dye N refers to the content of the dye when all the dyes N contained in the photosensitive resin layer are in a colored state. Hereinafter, a quantitative method of the content of the dye N will be described using a dye that develops color by radicals as an example.

[0404] Prepare two solutions in which 0.001g or 0.01g of pigment is dissolved in 100mL of methyl ethyl ketone. Add the photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF) to each solution obtained, and irradiate with 365nm light to generate free radicals and make all the pigments into a colored state. Then, under an atmospheric atmosphere, use a spectrophotometer (UV3100 manufactured by SHIMADZU CORPORATION) to measure the absorbance of each solution at a liquid temperature of 25°C and make a calibration curve. Next, 3g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the pigment, and the absorbance of the solution that makes all the pigments colored is measured by the same method as above. According to the absorbance of the solution containing the photosensitive resin layer obtained, the content of the pigment contained in the photosensitive resin layer is calculated based on the calibration curve.

[0405] (Thermal cross-linking compound)

[0406] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive resin layer preferably contains a thermally crosslinkable compound.

[0407] In the present invention, the thermally crosslinkable compound having an ethylenically unsaturated group described below is not treated as an ethylenically unsaturated compound but as a thermally crosslinkable compound.

[0408] Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound.

[0409] Among these, as the heat-crosslinkable compound, from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, a blocked isocyanate compound is preferred.

[0410] Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when the alkali-soluble resin and / or the ethylenically unsaturated compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film decreases, thereby tending to enhance the function of using the film formed by curing the photosensitive resin layer as a protective film.

[0411] The blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) by a blocking agent".

[0412] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is, for example, preferably 100°C to 160°C, and more preferably 130°C to 150°C.

[0413] The dissociation temperature of the blocked isocyanate refers to "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning calorimetry) analysis using a differential scanning calorimeter".

[0414] 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.

[0415] Examples of the end-capping agent 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-0H)- in the molecule such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc.].

[0416] As the terminal blocking agent having a dissociation temperature of 100° C. to 160° C., for example, an oxime compound is preferably contained from the viewpoint of storage stability.

[0417] For example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer target, the blocked isocyanate compound preferably has an isocyanurate structure.

[0418] The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating hexamethylene diisocyanate to thereby protect it.

[0419] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure as a blocking agent are preferred from the viewpoints that the dissociation temperature can be easily set within a preferred range and development residue can be easily reduced compared to compounds not having an oxime structure.

[0420] The blocked isocyanate compound may have a polymerizable group.

[0421] The polymerizable group is not particularly limited, and known polymerizable groups may be mentioned, and a radical polymerizable group is preferred.

[0422] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.

[0423] As the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is further preferred.

[0424] As the blocked isocyanate compound, a commercially available product can be used.

[0425] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) A0I-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E and Duranate (registered trademark) WT32-B75P, manufactured by Asahi Kasei Chemicals Corporation).

[0426] Furthermore, as the blocked isocyanate compound, compounds having the following structure can also be used.

[0427] [Chemical formula 2]

[0428]

[0429] When the photosensitive resin layer contains a thermally crosslinkable compound, the photosensitive resin layer may contain only one type of thermally crosslinkable compound or may contain two or more types of thermally crosslinkable compounds.

[0430] 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 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive resin layer.

[0431] (Other ingredients)

[0432] The photosensitive resin layer may contain components other than the components described above (also referred to as “other components”) as necessary within a range that does not impair the effects of the present invention.

[0433] Examples of other components include a polymerization inhibitor, a surfactant, a sensitizer, and various additives.

[0434] When the photosensitive resin layer contains other components, it may contain only one type of other components, or may contain two or more types.

[0435] -Inhibitors-

[0436] The photosensitive resin layer may contain a polymerization inhibitor.

[0437] The polymerization inhibitor is preferably a free radical polymerization inhibitor.

[0438] Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine.

[0439] As the radical inhibitor, phenothiazine, phenoxazine or 4-methoxyphenol is preferred. In addition, in order not to impair the sensitivity of the photosensitive resin layer, it is also preferred to use nitrosophenylhydroxylamine aluminum salt as the radical inhibitor.

[0440] When the photosensitive resin layer contains a polymerization inhibitor, only one type of polymerization inhibitor may be contained, or two or more types of polymerization inhibitor may be contained.

[0441] When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive resin layer is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and further preferably 0.02 to 2.0% by mass, based on the total mass of the photosensitive resin layer.

[0442] The content of the polymerization inhibitor in the photosensitive resin layer is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound.

[0443] -Surfactant-

[0444] The photosensitive resin layer may contain a surfactant.

[0445] Examples of the surfactant include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362.

[0446] As the surfactant, a nonionic surfactant or a fluorine-based surfactant is preferred.

[0447] As the surfactant, from the viewpoint of improving environmental adaptability, a surfactant containing silicon (for example, a silicone-based surfactant) is preferred.

[0448] Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, and 25R2 [all manufactured by BASF], Tetronic (trade name) 304, 701, 704, 901, 904, and 150R1 [all manufactured by BASF], Solsperse (trade name) 20000 [all manufactured by The Lubrizol Corporation], NCW-101, NCW-1001 and NCW-1002 [manufactured by FUJIFILM Wako PureChemica Corporation], PIONIN (trade name) D-6112, D-6112-W and D-6315 [manufactured by TAKEMOTO OIL & FAT CO., LTD.], OLFINE (trade name) E1010, Surfynol (trade name) 104, 400 and 440 [manufactured by Nissin Chemical Co., Ltd.], etc.

[0449] Examples of commercially available fluorine-based surfactants include MEGAFACE (trade 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-600, F-601, F-602, F-603, F-604, F-605, F-606, F-607, F-608, F-609, F-610, F-611, F-612, F-613, F-614, F-615, F-616, F-617, F-618, F-619, F-620, F-621, F-622, F-623, F-624, F-625 -556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K and DS-21〔Above are provided by DIC Corporation], Fluor ad (trade name) 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 Inc.], PolyFox (trade name) PF636, PF656, PF6320, PF6520 and PF7002 [all manufactured by OMNOVA Solutions Inc.] and Ftergent (trade name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M and 245F [all manufactured by NEOS COMPANY LIMITED], etc.

[0450] As a fluorine-based surfactant, an acrylic compound can also be preferably used. The acrylic compound has a molecular structure having a functional group containing a fluorine atom, and if heat is applied, the functional group containing the fluorine atom is partially cut off and the fluorine atom is volatilized. As such a fluorine-based surfactant, for example, MEGAFACE (trade name) DS series manufactured by DIC Corporation can be cited [The Chemical Daily Co., Ltd. (February 22, 2016), NIKKEIBUSINE SSDAILY (February 23, 2016)], specifically, MEGAFACE (registered trademark) DS-21 can be cited.

[0451] 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.

[0452] As the fluorine-based surfactant, a blocked polymer can also be used.

[0453] As the fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which contains a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and / or propyleneoxy groups).

[0454] As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. As such a fluorine-based surfactant, for example, MEGAFACE (trade name) RS-101, RS-102, RS-718K and RS-72-K (the above are manufactured by DIC Corporation) can be cited.

[0455] As the fluorine-based surfactant, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental suitability, a substitute material for perfluorooctanoic acid (PFOA) or perfluorooctane sulfonic acid (PFOS) is preferred as the fluorine-based surfactant.

[0456] Examples of the surfactant containing silicon include silicone-based surfactants.

[0457] Examples of the silicone-based surfactant include linear polymers containing a siloxane bond and modified siloxane polymers having an organic group introduced into a side chain or a terminal.

[0458] Specific examples of the silicone surfactant include DOWSIL (trade name) 8032ADDITION, TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA and TORAY SILICONE SH8400 (all manufactured by Dow Corning Toray Co., Ltd.], X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 [manufactured by Shin-Etsu Chemical Co., Ltd.], F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 [manufactured by Mom entive Performance Materials Inc.] and BYK307, BYK323 and BYK330 [all manufactured by BYK-Chemie Corporation].

[0459] When the photosensitive resin layer contains a surfactant, only one type of surfactant may be contained, or two or more types may be contained.

[0460] 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 to 10% by mass, more preferably 0.01 to 3% by mass, based on the total mass of the photosensitive resin layer.

[0461] -Sensitizer-

[0462] The photosensitive resin layer may contain a sensitizer.

[0463] The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used.

[0464] Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthones, 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.

[0465] When the photosensitive resin layer contains a sensitizer, only one type of sensitizer may be contained, or two or more types of sensitizer may be contained.

[0466] 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.

[0467] From the viewpoint of improving sensitivity to light sources and improving curing speed based on the balance between polymerization speed and chain transfer, the content of the sensitizer in the photosensitive resin layer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive resin layer.

[0468] - Various additives -

[0469] The photosensitive resin layer may contain known additives as necessary.

[0470] Examples of the additive include plasticizers, heterocyclic compounds, benzotriazole compounds, carboxybenzotriazole compounds, pyridine compounds (eg, isonicotinamide), purine bases (eg, adenine), and solvents.

[0471] When the photosensitive resin layer contains an additive, only one type of additive may be contained, or two or more types of additives may be contained.

[0472] Examples of the benzotriazole compound 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.

[0473] 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, commercially available products such as CBT-1 (trade name, manufactured by JOHOKU CHEMICAL CO., LTD.) can also be used as the carboxybenzotriazole compound.

[0474] When the photosensitive resin layer contains a benzotriazole compound and / or a carboxybenzotriazole compound, the total content of the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin layer is not particularly limited, but is preferably 0.01% 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.

[0475] From the viewpoint of providing storage stability to the photosensitive resin layer, the total content of the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin layer is preferably set to 0.01% by mass or more relative to the total mass of the photosensitive resin layer. On the other hand, from the viewpoint of maintaining sensitivity and suppressing fading of the dye, the total content of the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin layer is preferably set to 3% by mass or less relative to the total mass of the photosensitive resin layer.

[0476] The photosensitive resin layer may contain at least one selected from a plasticizer and a heterocyclic compound.

[0477] Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International Publication No. 2018 / 179640.

[0478] The photosensitive resin layer may contain a solvent.

[0479] When the photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

[0480] Furthermore, the photosensitive resin layer may 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 precipitation inhibitors.

[0481] Additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents of this publication are incorporated into this specification.

[0482] (Impurities, etc.)

[0483] The photosensitive resin layer may contain a predetermined amount of impurities.

[0484] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof.

[0485] Among these, halide ions, sodium ions, and potassium ions are easily mixed as impurities, and therefore, the contents thereof are preferably set to be as follows.

[0486] The content of impurities in the photosensitive resin layer is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less relative to the total mass of the photosensitive resin layer. In addition, the content of impurities in the photosensitive resin layer may be, for example, 1 mass ppb or more, or 0.1 mass ppm or more relative to the total mass of the photosensitive resin layer.

[0487] As methods for setting the impurity content within the above range, for example, there can be mentioned: a method of selecting a raw material with a small impurity content as a raw material of a composition for forming a photosensitive resin layer (so-called photosensitive resin composition); a method of preventing impurities from being mixed when forming the photosensitive resin layer; and a method of removing impurities by washing. By this method, the impurity content can be set within the above range.

[0488] The impurities can be quantified by a known method such as TCP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

[0489] 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 as low as possible.

[0490] 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 further preferably 4 mass ppm or less relative to the total mass of the photosensitive resin layer. In addition, 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 relative to the total mass of the photosensitive resin layer.

[0491] The content of the above-mentioned compound can be suppressed by the same method as the content of the above-mentioned metal impurities.

[0492] Furthermore, the above compounds can be quantified by known measurement methods.

[0493] From the viewpoint of improving reliability and lamination properties, the content of water 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.

[0494] (Residual Monomer)

[0495] The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the above-mentioned alkali-soluble resin.

[0496] From the viewpoint of pattern formation and reliability, the content of residual monomers in the photosensitive resin layer is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, and further preferably 500 mass ppm or less relative to the total mass of the alkali-soluble resin. In addition, the content of residual monomers in the photosensitive resin layer may be, for example, 1 mass ppm or more, or 10 mass ppm or more relative to the total mass of the alkali-soluble resin.

[0497] From the viewpoint of pattern formation and reliability, the content of residual monomers in the photosensitive resin layer is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and further preferably 100 mass ppm or less relative to the total mass of the photosensitive resin layer. In addition, the content of residual monomers 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.

[0498] The residual amount of monomers when synthesizing an alkali-soluble resin by polymer reaction is also preferably set to 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 set to the above amount.

[0499] The amount of the residual monomers can be measured by a known method such as liquid chromatography and gas chromatography.

[0500] (pigment)

[0501] The photosensitive resin layer may be a colored layer containing a pigment.

[0502] The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and color pigments other than black and white.

[0503] When forming a black-based pattern, it is preferable to select a black pigment as the pigment.

[0504] As the black pigment, a known black pigment (for example, an organic pigment or an inorganic pigment) can be appropriately selected within a range not impairing the effects of the present invention.

[0505] As the black pigment, from the viewpoint of optical density, for example, preferably, carbon black, titanium oxide, titanium carbide, iron oxide, and graphite are used.

[0506] Among these, carbon black is particularly preferred as the black pigment.

[0507] As the carbon black, from the viewpoint of surface resistance, carbon black at least a part of the surface of which is coated with a resin is preferred.

[0508] From the viewpoint of dispersion stability, the particle diameter of the black pigment is preferably 0.001 μm to 0.1 μm, and more preferably 0.01 μm to 0.08 μm in terms of number average particle diameter.

[0509] The particle size refers to the diameter of a circle obtained by calculating the area of ​​the pigment particles based on a photographic image of the pigment particles taken with an electron microscope and taking into account a circle with the same area as the area of ​​the pigment particles. The number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 particle sizes calculated.

[0510] As the white pigment, the white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Laid-Open No. 2005-007765 can be used. Specifically, as the inorganic pigment in the white pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate is preferred, titanium oxide or zinc oxide is more preferred, titanium oxide is further preferred, rutile or anatase titanium oxide is particularly preferred, and rutile titanium oxide is most preferred.

[0511] 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, thereby suppressing the catalytic activity of titanium oxide and improving heat resistance and delustering properties.

[0512] As the surface treatment of titanium oxide, from the viewpoint of reducing the thickness of the photosensitive layer after heating, at least one of an aluminum oxide treatment and a zirconium oxide treatment is preferred, and both an aluminum oxide treatment and a zirconium oxide treatment are particularly preferred.

[0513] When the photosensitive resin layer is a colored layer, it is preferred that the photosensitive resin layer further contains a color pigment other than the black pigment and the white pigment from the viewpoint of transferability.

[0514] When the photosensitive resin layer contains a color pigment, the particle size of the color pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the viewpoint of better dispersibility.

[0515] As color pigments, for example, Victoria Pure Blue B0 (Color Index C Color Index) (also referred to as "CI") 42595), gold amine (CI41000), fat black HB C CI26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR C CI Pigment Yellow 83), Permanent Magenta FBB (CI Pigment Red 146), Master Yeast Red ESB (CI Pigment Violet 19), Permanent Gem FBH C CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Blue 15), Monolight Fast Black BC 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:i, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64 and CI Pigment Violet 23.

[0516] Among these, CI Pigment Red 177 is preferred as the color pigment.

[0517] In the case where 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 % and less than 40 mass %, more preferably in the range of more than 3 mass % and less than 35 mass %, further preferably in the range of more than 5 mass % and less than 35 mass %, and particularly preferably in the range of more than 10 mass % and less than 35 mass %, relative to the total mass of the photosensitive resin layer.

[0518] When the photosensitive resin layer contains pigments other than black pigment (i.e., white pigment and color pigment), the content of pigments other than black pigment in the photosensitive resin layer is preferably 30% by mass or less, more preferably 1% by mass to 20% by mass, and further preferably 3% by mass to 15% by mass, relative to the content of black pigment.

[0519] 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.

[0520] The dispersion liquid can be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent or a vehicle liquid and dispersing it with a disperser.

[0521] Regarding the pigment dispersant, it is sufficient to select it according to the pigment and the solvent, for example, a commercially available dispersant can be used. In addition, the vehicle liquid refers to the medium part that disperses the pigment when making a pigment dispersion liquid, which is in liquid form and contains a binder component that keeps the black pigment in a dispersed state and a solvent component (i.e., an organic solvent) that dissolves and dilutes the binder component.

[0522] The disperser is not particularly limited, and examples thereof include known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. After dispersion by a disperser, fine pulverization may be performed using frictional force due to mechanical grinding.

[0523] Regarding dispersers and fine grinding, reference can be made to the records in "Dictionary of Pigments" (written by Kunizo Asakura, first edition, Asakura Bookstore, 2000, pages 438 and 310).

[0524] <<Thickness of Photosensitive Resin Layer>>

[0525] From the viewpoint of developability and resolution, the thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 10 μm or less, further 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.

[0526] The thickness of the photosensitive resin layer refers to an average thickness calculated by arithmetic average of thicknesses at five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0527] For example, when the transfer layer is a photosensitive resin layer, an intermediate layer and a thermoplastic resin layer, from the viewpoint of resolution and concave-convex tracking performance, 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 further preferably 20% to 30%.

[0528] <<Light Transmittance>>

[0529] From the viewpoint of better 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 further 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 99.9% or less, for example.

[0530] <Method for Forming Photosensitive Resin Layer>

[0531] The method for forming the photosensitive resin layer is not limited as long as the target photosensitive resin layer can be obtained.

[0532] As a method for forming a photosensitive resin layer, for example, the following method can be cited: preparing a photosensitive resin layer-forming composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, etc., applying the prepared photosensitive resin layer-forming composition to an intermediate layer or a protective film, and drying the applied photosensitive resin layer-forming composition.

[0533] The photosensitive resin layer-forming composition preferably contains a solvent from the viewpoint of easily forming a photosensitive resin layer by adjusting the viscosity.

[0534] 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 thereof.

[0535] The solvent is preferably a solvent containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, more preferably a mixed solvent containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from ketone solvents and cyclic ether solvents, and further preferably a mixed solvent containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, at least one selected from ketone solvents and cyclic ether solvents, and at least one selected from alcohol solvents.

[0536] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether [e.g., 1-methoxy-2-propanol (MFG)], propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0537] Specific examples of the alkylene glycol ether acetate solvent are as described above, and therefore description thereof is omitted here.

[0538] 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 Japanese Patent Application Laid-Open No. 2018-177889 can be used, and these contents are incorporated into this specification.

[0539] When the photosensitive resin layer-forming composition contains a solvent, the composition may contain only one type of solvent or two or more types of solvent.

[0540] When the photosensitive resin layer forming composition contains a solvent, the content of the solvent when the photosensitive resin layer forming composition is applied is preferably 50 to 1900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin layer forming composition.

[0541] The method for preparing the photosensitive resin layer-forming composition is not particularly limited, and examples thereof include a method of preparing a solution obtained by dissolving each component in the above-mentioned solvent in advance and mixing the obtained solution at a predetermined ratio to prepare the photosensitive resin layer-forming composition.

[0542] The photosensitive resin layer-forming composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the photosensitive resin layer.

[0543] The method for applying the photosensitive resin layer-forming composition is not particularly limited, and the composition may be applied by a known method.

[0544] Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0545] As a method for drying the applied photosensitive resin layer-forming composition, heating drying and reduced-pressure drying are preferred.

[0546] Examples of the drying method include natural drying, heat drying, and reduced-pressure drying.

[0547] For drying, the above-mentioned methods can be applied alone or in combination of two or more.

[0548] The drying temperature is preferably 70° C. or higher, more preferably 80° C. or higher.

[0549] The upper limit of the drying temperature is not particularly limited, but is, for example, preferably 180° C. or lower, and more preferably 150° C. or lower.

[0550] The applied photosensitive resin layer-forming composition may be dried while continuously changing the temperature.

[0551] The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The upper limit of the drying time is not particularly limited, but is, for example, preferably 600 seconds or shorter, and more preferably 300 seconds or shorter.

[0552] <Protective film>

[0553] The photosensitive transfer material according to the present invention preferably has a protective film.

[0554] Examples of the material constituting the protective film include resin films and paper.

[0555] From the viewpoint of strength and flexibility, the protective film is preferably a resin film.

[0556] Examples of the protective film include polyolefin films (eg, polypropylene films and polyethylene films), polyester films (eg, polyethylene terephthalate films), polycarbonate films, cellulose triacetate films, and polystyrene films.

[0557] The protective film is preferably a polypropylene film, a polyethylene film or a polyethylene terephthalate film.

[0558] The thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, further preferably 5 μm to 40 μm, and particularly preferably 15 μm to 30 μm.

[0559] The thickness of the protective film refers to an average thickness calculated by arithmetic average of thicknesses at five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0560] From the viewpoint of better resolution, the arithmetic mean roughness Ra value of the surface on the photosensitive resin layer side of the protective film (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 further preferably 0.05 μm or less. The lower limit of the arithmetic mean roughness Ra value of the surface of the protective film is not particularly limited, but is preferably 0.001 μm or more, for example.

[0561] The arithmetic mean roughness Ra value of the surface of the protective film is measured by the following method.

[0562] The surface of the protective film was measured using a three-dimensional optical profiler (New View 7300, manufactured by Zygo Corporation) to obtain the surface profile of the protective film. As the measurement / analysis software, Microscope Application of MetroPro ver8.3.2 was used. Next, the Surface Map screen was displayed using the above analysis software, and histogram data was obtained in the Surface Map screen. Based on the obtained histogram data, the arithmetic mean roughness Ra of the surface of the protective film was calculated.

[0563] <Other layers>

[0564] The photosensitive transfer material according to the present invention may have other layers.

[0565] As other layers, for example, a refractive index adjustment layer (so-called contrast enhancement layer) can be cited. Contrast enhancement layers are described in paragraph 0134 of International Publication No. 2018 / 179640.

[0566] In addition, other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents of these publications are incorporated into this specification.

[0567] <Method for producing photosensitive transfer material>

[0568] The method for producing the photosensitive transfer material according to the present invention is not particularly limited.

[0569] The photosensitive transfer material according to the present invention can be produced by a known method.

[0570] The photosensitive transfer material involved in the present invention is preferably manufactured by the following method: a method (hereinafter also referred to as "manufacturing method A") comprising the step of forming a thermoplastic resin layer, an intermediate layer and a photosensitive resin layer containing a copolyester resin on a temporary support by coating and drying (hereinafter also referred to as "step A1"); or a method (hereinafter also referred to as "manufacturing method B") comprising the step of forming a photosensitive resin layer, an intermediate layer and a thermoplastic resin layer containing a copolyester resin on a protective film by coating and drying and the step of bonding a temporary support to the above-mentioned thermoplastic resin layer by heat lamination (hereinafter also referred to as "step B2").

[0571] According to the manufacturing method A and the manufacturing method B, the photosensitive transfer material according to the present invention can be manufactured more simply.

[0572] Hereinafter, the manufacturing method A and the manufacturing method B will be described, but the description of the same matters as those described in the section of the photosensitive transfer material according to the present invention will be omitted.

[0573] (Manufacturing method A)

[0574] The production method A is a method for producing a photosensitive transfer material including the step (ie, step A1) of sequentially forming a thermoplastic resin layer including a copolyester resin, an intermediate layer, and a photosensitive resin layer on a temporary support by coating and drying.

[0575] The manufacturing method A may include steps other than step A1.

[0576] As a process other than step A1, for example, there is mentioned a process of bonding a protective film to the photosensitive resin layer formed in step A1 by heat lamination (hereinafter also referred to as "step A2").

[0577] -Process A1-

[0578] Step A1 is a step of sequentially forming a thermoplastic resin layer including a copolyester resin, an intermediate layer, and a photosensitive resin layer on a temporary support by coating and drying.

[0579] 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 the intermediate layer are respectively described in the above-mentioned "method for forming a thermoplastic resin layer", "method for forming an intermediate layer", and "method for forming a photosensitive resin layer".

[0580] -Process A2-

[0581] Step A2 is a step of bonding a protective film to the photosensitive resin layer formed in step A1 by heat lamination.

[0582] The mechanism of heat lamination is not particularly limited, and a known laminator can be used.

[0583] The laminator is preferably a device that includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0584] The temperature of heat lamination is not particularly limited, but is, for example, preferably 20°C to 100°C, and more preferably 25°C to 60°C.

[0585] (Manufacturing method B)

[0586] Manufacturing method B is a method for manufacturing a photosensitive transfer material, which includes the following steps: forming a photosensitive resin layer, an intermediate layer and a thermoplastic resin layer containing a copolymerized polyester resin in sequence on a protective film by coating and drying (i.e., step B1); and bonding a temporary support body to the above-mentioned thermoplastic resin layer by thermal lamination (i.e., step B2).

[0587] The manufacturing method B may include steps other than step B1 and step B2.

[0588] -Process B1-

[0589] Step B1 is a step of sequentially forming a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer containing a copolymerized polyester resin on a protective film by coating and drying.

[0590] The method of forming a photosensitive resin layer on a protective film, the method of forming an intermediate layer on a photosensitive resin layer, and the method of forming a thermoplastic resin layer on an intermediate layer are respectively described in the above-mentioned “method of forming a photosensitive resin layer”, “method of forming an intermediate layer”, and “method of forming a thermoplastic resin layer”.

[0591] -Process B2-

[0592] Step B2 is a step of bonding the temporary support to the thermoplastic resin layer formed in step B1 by heat lamination.

[0593] The mechanism of heat lamination is not particularly limited, and a known laminator can be used.

[0594] The laminator is preferably a device that includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0595] The temperature of heat lamination is not particularly limited, but is, for example, preferably 20°C to 100°C, and more preferably 25°C to 60°C.

[0596] The photosensitive transfer material produced in the above manner can be wound up to prepare and store a roll-shaped photosensitive transfer material. The roll-shaped photosensitive transfer material can be provided in its original form in the step of laminating with a substrate in a roll-to-roll method.

[0597] [Method for producing a substrate with a pattern]

[0598] The method for manufacturing a substrate with a pattern involved in the present invention (hereinafter, also referred to as the "manufacturing method involved in the present invention") includes, in sequence: a step of bonding a photosensitive transfer material and a substrate in a manner such that the transfer layer side of the photosensitive transfer material involved in the present invention is in contact with the substrate (hereinafter, also referred to as the "bonding step"); a step of removing a temporary support from the bonded body by peeling between the thermoplastic resin layer and the intermediate layer (hereinafter, also referred to as the "temporary support removal step"); a step of pattern-exposing a transfer layer including an intermediate layer and a photosensitive resin layer via an exposure mask (hereinafter, also referred to as the "exposure step"); and a step of developing the transfer layer exposed to the pattern to form a pattern (hereinafter, also referred to as the "development step").

[0599] The method for producing a patterned substrate according to the present invention uses the photosensitive transfer material according to the present invention, and therefore can form a high-resolution resist pattern.

[0600] The production method according to the present invention 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.

[0601] As other steps, for example, there are a protective film removing step and a pressurizing step.

[0602] <Protective film removal process>

[0603] When the photosensitive transfer material according to the present invention has a protective film, the production method according to the present invention preferably includes a step of removing the protective film from the photosensitive transfer material before the laminating step (so-called protective film removing step).

[0604] The photosensitive transfer material according to the present invention is as described above, and therefore its description is omitted here.

[0605] The method for removing the protective film from the photosensitive transfer material according to the present invention is not particularly limited, and a known method can be applied.

[0606] <Laminating process>

[0607] The manufacturing method according to the present invention includes a step (ie, a laminating 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 invention is in contact with the substrate.

[0608] When the photosensitive transfer material and the substrate are bonded together, the transfer layer in contact with the substrate becomes a layer (eg, photosensitive resin layer) in contact with the protective film, for example, when the photosensitive transfer material according to the present invention has a protective film.

[0609] According to the laminating step, a laminated body of the photosensitive transfer material and the substrate can be obtained.

[0610] A known method can be applied to the bonding of the photosensitive transfer material and the substrate.

[0611] In the laminating step, the photosensitive transfer material and the substrate are preferably brought into pressure contact with each other.

[0612] For example, it is preferable to overlap the transfer layer side of the photosensitive transfer material and the substrate, and apply pressure and heat using a mechanism such as a roller to pressure-bond the photosensitive transfer material and the substrate.

[0613] In the method of pressure-bonding the substrate and the photosensitive transfer material, a known lamination method can be applied.

[0614] Examples of the lamination method include a method using a known laminator such as a vacuum laminator and an automatic cutting laminator.

[0615] The lamination temperature is not particularly limited, but is preferably 70°C to 130°C, for example.

[0616] The substrate is not particularly limited, and a known substrate can be used.

[0617] 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 required.

[0618] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

[0619] A preferred embodiment of the substrate is described, for example, in paragraph 0140 of International Publication No. 2018 / 155193, and the content is incorporated into this specification.

[0620] Examples of the base material constituting the substrate include metals (eg, Invar, which is an iron-nickel alloy), glass, silicon, and films.

[0621] The base material constituting the substrate may be transparent.

[0622] Examples of the transparent glass substrate include tempered glass represented by Gorilla Glass manufactured by Corning Incorporated Co., Ltd. Also, materials described in Japanese Patent Application Laid-Open Nos. 2010-86684, 2010-152809, and 2010-257492 can be used as the transparent glass substrate.

[0623] When a film substrate is used as the substrate, it is preferred to use a film substrate with small optical strain and / or high transparency. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0624] In the case of roll-to-roll production, the substrate is preferably a film substrate.

[0625] Examples of the metal layer included in the substrate include conductive layers used in general circuit wiring and touch panel wiring.

[0626] From the viewpoint of conductivity and thin line formability, the conductive layer is preferably at least one layer selected from 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.

[0627] The substrate may have a single metal layer or may have two or more metal layers.

[0628] When there are two or more metal layers, it is preferable that the metal layers are made of different materials.

[0629] Examples of the material of the metal layer include metals and conductive metal oxides.

[0630] Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0631] As the conductive metal oxide, for example, ITO (IndiumTinOxide: indium tin oxide), IZO (IndiumZincOxide: indium zinc oxide) and SiO 2 can be cited.

[0632] In one embodiment, the substrate may be a metal substrate.

[0633] The photosensitive transfer material of the present invention can suppress the generation of lamination bubbles by the thermoplastic resin layer during heat lamination, and can remove the thermoplastic resin layer together with the temporary support during pattern exposure, thereby shortening the exposure gap. Therefore, the photosensitive transfer material of the present invention can be particularly preferably used for fine processing of a metal substrate for a vapor deposition mask having fine concavo-convex surfaces.

[0634] The metal substrate has a first surface and a second surface located opposite to the first surface.

[0635] The structure of the metal substrate can be a single-layer structure or a multi-layer structure.

[0636] Examples of the metal element contained in the metal substrate include Cu, Ni, Fe, Cr, Mn, and Co.

[0637] 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 further preferably contains Cu.

[0638] The metal substrate may contain elements other than the metal element. Examples of elements other than the metal element include B, C, N, O, P, S, and Cl.

[0639] As an example of a preferred metal substrate, a copper substrate can be mentioned.

[0640] A part or the whole of the metal substrate may be an alloy.

[0641] Examples of the alloy include nickel-cobalt (Ni—Co) alloys and iron-nickel (Fe—Ni) alloys.

[0642] In one embodiment, the metal substrate preferably includes an iron-nickel (Fe—Ni) alloy.

[0643] The roughness Rmax of the first surface of the metal substrate may be 0.5 μm to 5.0 μm. The roughness Rmax of the second surface of the metal layer may be 0.5 μm to 5.0 μm.

[0644] 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.

[0645] The thickness of the metal layer refers to an average thickness calculated by arithmetic average of thicknesses at five locations measured by cross-sectional observation using a scanning electron microscope (SEM).

[0646] <Pressure Process>

[0647] The production method according to the present invention preferably includes a step of pressurizing the laminate of the photosensitive transfer material and the substrate (so-called pressurizing step).

[0648] By pressurizing the laminated body, the adhesion between the transfer layer and the substrate is improved, and the ability of the transfer layer to follow the irregularities of the substrate surface is improved.

[0649] The pressed laminated body has a substrate, a transfer layer, and a temporary support in this order.

[0650] As a method of pressurizing the bonded body, for example, a method of subjecting the bonded body to autoclave treatment can be mentioned. As an example of the autoclave treatment conditions, the conditions of pressure 0.45 MPa, temperature 50° C., and treatment time 1 hour can be mentioned.

[0651] <Temporary Support Removal Step>

[0652] The production method according to the present invention includes a step of removing the temporary support from the bonded body by peeling between the thermoplastic resin layer and the intermediate layer (ie, a temporary support removal step).

[0653] If the temporary support is removed before the exposure process, the exposure gap becomes shorter, so it is easy to obtain a high-resolution resist pattern. In addition, the blur of the optical image tends to be reduced, and the mask fidelity and line width uniformity of the obtained resist pattern can be further improved.

[0654] Furthermore, if the temporary support is removed before the exposure step, the influence of pinholes from the temporary support can be eliminated, so that a defect-free resist pattern tends to be obtained.

[0655] The method for removing the temporary support is not particularly limited.

[0656] In the production method according to the present invention, the photosensitive transfer material according to the present invention described above is used as the photosensitive transfer material. Therefore, the thermoplastic resin layer and the intermediate layer are peeled off well, and the temporary support is removed from the laminate together with the thermoplastic resin layer.

[0657] <Exposure Process>

[0658] The manufacturing method according to the present invention includes a step of pattern-exposing the transfer layer including the intermediate layer and the photosensitive resin layer through a mask (ie, an exposure step).

[0659] “Pattern exposure” refers to exposure in a patterned form, that is, exposure in a form with exposed areas and non-exposed areas. The positional relationship between the exposed area and the non-exposed area in pattern exposure is not particularly limited and can be appropriately adjusted, for example, depending on the shape of the target pattern.

[0660] According to the exposure step, an exposed portion and a non-exposed portion are formed in the photosensitive resin layer.

[0661] For example, when the photosensitive resin layer is a negative type, the exposed portion of the photosensitive resin layer on the substrate under the pattern exposure is cured and finally becomes a cured film. On the other hand, the non-exposed portion of the photosensitive resin layer on the substrate under the pattern exposure is not cured, and is dissolved and removed by the developer in the development step described later. The non-exposed portion can form an opening of the cured film after the development step.

[0662] The light for pattern exposure is preferably irradiated onto the transfer layer in a direction from the transfer layer toward the substrate.

[0663] As a light source for pattern exposure, any light having a wavelength region (for example, 365 nm or 405 nm) capable of irradiating the photosensitive resin layer can be appropriately selected and used.

[0664] The dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The “dominant wavelength” refers to the wavelength with the highest intensity.

[0665] Examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0666] The exposure dose is preferably 5 mJ / cm 2 ~200mJ / cm 2 , more preferably 10 mJ / cm 2 ~200mJ / cm 2 .

[0667] Since the exposure step is performed after the temporary support removal step, the exposure gap is reduced by removing the temporary support, and a pattern more faithful to the mask can be obtained.

[0668] In the exposure step, the transfer layer may be pattern-exposed with the mask in contact with the transfer layer or with the mask not in contact with the transfer layer but close to the transfer layer. The "transfer layer" mentioned here includes the intermediate layer and the photosensitive resin layer.

[0669] In the temporary support removal step, the temporary support is removed by peeling between the thermoplastic resin layer and the intermediate layer, so that the mask is in contact with the intermediate layer instead of the photosensitive resin layer. Therefore, even when the transfer layer is pattern-exposed with the mask in contact with the transfer layer, the transportability is not easily reduced due to the adhesion of the mask to the photosensitive resin layer, and stable production can be performed.

[0670] The exposure can be performed, for example, in any environment of atmospheric air, reduced pressure, or vacuum.

[0671] Examples of the exposure method include a contact exposure method, a proximity exposure method, and a projection exposure method.

[0672] Among these, the contact exposure method is preferable as the exposure method.

[0673] The contact exposure method is a method of performing exposure by bringing a mask into contact with the surface of an exposure object.

[0674] Regarding the contact exposure method, a relatively cheap exposure machine is used, the productivity is high, and high resolution can be obtained. In the contact exposure method, the shorter the distance from the mask to the photosensitive resin layer, that is, the exposure gap, the less blurring of the image, and a high-resolution image that is faithful to the mask can be obtained. In the manufacturing method of the present invention, since the exposure process is performed after the temporary support body removal process, the exposure gap becomes shorter by removing the temporary support body. Therefore, it tends to be easy to obtain a high-resolution image that is faithful to the mask.

[0675] Examples of the mask include a chrome mask, a latex mask, and a film mask.

[0676] <Development Process>

[0677] The manufacturing method according to the present invention includes a step of developing the pattern-exposed transfer layer to form a pattern (development step).

[0678] The pattern is formed by developing the transfer layer exposed in a pattern.

[0679] The pattern is formed by removing the exposed portion or the non-exposed portion of the transfer layer.

[0680] When the photosensitive resin layer included in the transfer layer is a negative type, the non-exposed portion of the transfer layer is removed, and a resin pattern is formed from the exposed portion of the transfer layer.

[0681] Development can be performed using a developer.

[0682] As the developer, an alkaline aqueous solution is preferred.

[0683] Examples of the basic compound contained in the aqueous alkali 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).

[0684] The pH of the alkaline aqueous solution at 25°C is preferably 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12.

[0685] The content of the basic compound in the aqueous alkaline solution is preferably 0.1% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, relative to the total mass of the aqueous alkaline solution.

[0686] As a developer preferably used in the present invention, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 is mentioned, for example.

[0687] Examples of the developing method include spin immersion developing, shower developing, shower and spin developing, and immersion developing. Shower developing is a developing method in which a developing solution is sprayed onto an object by showering.

[0688] As a development method preferably used in the present invention, the development method described in paragraph 0195 of International Publication No. 2015 / 093271 is mentioned, for example.

[0689] It is preferred that the developer and residue remaining after the development step are removed.

[0690] Examples of a method for removing the developer and residue include a spray treatment and an Air Knife treatment.

[0691] In the shower treatment, liquid such as water or a cleaning agent is sprayed toward the object by showering. Residues can also be removed using a brush.

[0692] Example

[0693] Below, the present invention is further described in detail using examples. The materials, usage amounts, ratios, processing contents and processing steps shown in the following examples, as long as they do not depart from the purpose of the present invention, can be appropriately changed. Therefore, the scope of the present invention should not be interpreted in a limited manner by the examples shown below.

[0694] In addition, "%" is based on mass unless otherwise specified.

[0695] In the following examples, the weight average molecular weight of a resin is a weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC).

[0696] [Manufacturing of photosensitive transfer material]

[0697] <Example 1>

[0698] 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 manufactured by the following steps.

[0699] Composition A containing the components listed in the "thermoplastic resin layer" column of Table 1 was prepared. 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 listed in Table 1.

[0700] A composition B containing the components listed in the "intermediate layer" column of Table 1 was prepared. Composition B was applied on 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 listed in Table 1.

[0701] Composition C containing the components listed in the "Photosensitive resin layer" column of Table 1 was prepared. Composition C was applied on 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 listed in Table 1.

[0702] Finally, a protective film [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 photosensitive resin layer by heat lamination.

[0703] Through the above, the photosensitive transfer material of Example 1 was obtained.

[0704] <Example 2 to Example 4>

[0705] Except having made the composition of composition A, composition B, and composition C into the composition described in Table 1, the same operation as in Example 1 was carried out to obtain each photosensitive transfer material of Example 2 to Example 4.

[0706] <Example 5>

[0707] The 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 manufactured by the following steps.

[0708] Composition C containing the components listed in the column "Photosensitive resin layer" of Table 1 was prepared. Composition C was applied on a protective film [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 photosensitive resin layer. The thickness of the photosensitive resin layer is as listed in Table 1.

[0709] Composition B containing the components listed in the "Intermediate Layer" column of Table 1 was prepared. Composition B was applied on 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 listed in Table 1.

[0710] Composition A containing the components listed in the "Thermoplastic resin layer" column of Table 1 was prepared. Composition A was applied on 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 listed in Table 1.

[0711] Finally, a temporary support [trade name: Lumirror (registered trademark) 16KS40, thickness: 16 μm, biaxially stretched PET film, manufactured by TORAY INDUSTRIES, INC.] was bonded to the exposed surface of the thermoplastic resin layer by heat lamination.

[0712] Through the above, the photosensitive transfer material of Example 5 was obtained.

[0713] <Comparative Example 1, Comparative Example 2 and Comparative Example 4>

[0714] Except having used the compositions of Composition A, Composition B, and Composition C as described in Table 2, the same operation as in Example 1 was carried out to obtain photosensitive transfer materials of Comparative Examples 1, 2, and 4.

[0715] <Comparative Example 3>

[0716] The 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 procedures.

[0717] Composition B containing the components listed in the "Intermediate Layer" column of Table 2 was prepared. Composition B was applied onto a temporary support [Model: 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 listed in Table 2.

[0718] Composition C containing the components listed in the "Photosensitive resin layer" column of Table 2 was prepared. Composition C was applied on 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 listed in Table 2.

[0719] Finally, a protective film [Model: 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 heat lamination.

[0720] Through the above, the photosensitive transfer material of Comparative Example 3 was obtained.

[0721] [Table 1]

[0722]

[0723] [Table 2]

[0724]

[0725] In Tables 1 and 2, "-" in the composition column means that the corresponding component was not used.

[0726] In Tables 1 and 2, "forward order" in the coating order column refers to a method of coating composition A, composition B and composition C in sequence on a temporary support (wherein, for Comparative Example 3, it refers to a method of coating composition B and composition C in sequence on a temporary support), and "reverse order" refers to a method of coating composition C, composition B and composition A in sequence on a protective film.

[0727] In the case of "positive order", after the thermoplastic resin layer, the intermediate layer and the photosensitive resin layer are sequentially formed on the temporary support by coating and drying, the protective film is attached to the photosensitive resin layer by thermal lamination. In the case of "reverse order", after the photosensitive resin layer, the intermediate layer and the thermoplastic resin layer are sequentially formed on the protective film by coating and drying, the temporary support is attached to the photosensitive resin layer by thermal lamination.

[0728] The abbreviations shown in Tables 1 and 2 have the following meanings, respectively.

[0729] "BYRON BX-1001": Amorphous copolyester resin manufactured by TOYOBO CO., LTD., Tg: -18°C, Mn: 28000, hydroxyl value: 8KOHmg / g, acid value: less than 2KOHmg / g

[0730] "BYRON GK-800": Amorphous copolyester resin manufactured by TOYOBO CO., LTD., Tg: 50°C, Mn: 27000, hydroxyl value: 7 KOHmg / g, acid value: less than 2 KOHmg / g

[0731] "BYRON 802": Amorphous copolyester resin manufactured by TOYOBO CO., LTD., Tg: 60°C, Mn: 3000, hydroxyl value: 37 KOHmg / g, acid value: less than 1 KOHmg / g

[0732] “Polymer 1”: benzyl methacrylate (BzMA) / methacrylic acid (MAA) / acrylic acid (AA) = 78 / 14.5 / 7.5 (mass ratio), Mw: 14,000, solid content: 40% by mass

[0733] "EVAFLEX EV45X": Ethylene-vinyl acetate copolymer resin manufactured by DOW-MITSUIPOLYCHEMICALS CO., LTD.

[0734] "A-DCP": NK Ester A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate

[0735] "8UX-015A": 8UX-015A manufactured by TAISEI FINE CHEMICAL CO., LTD., UV curing urethane acrylate

[0736] "TO-2349": ARONIX TO-2349 manufactured by TOAGOSEI CO., LTD.

[0737] "CBT-1": CBT-1 manufactured by JOHOKU CHEMICAL CO., LTD., carboxybenzotriazole

[0738] “F-552”: MEGAFACE F-552 manufactured by DIC Corporation, fluorine-based surfactant, solid content: 30% by mass (methyl ethyl ketone solution)

[0739] “EXP-S-315”: EXP-S-315 manufactured by DIC Corporation, silicone-based surfactant, solid content: 30% by mass (methyl ethyl ketone solution)

[0740] "MMPGAc": 1-methoxy-2-propyl acetate

[0741] "MEK": Methyl Ethyl Ketone

[0742] "MFG": 1-methoxy-2-propanol

[0743] "PVA": PVA 205 manufactured by KURARAY CO., LTD., polyvinyl alcohol

[0744] "PVP": K-30 manufactured by NIPPON SHOKUBAI CO., LTD., polyvinyl pyrrolidone

[0745] "HPMC": METOLOSE 60SH-03 manufactured by Shin-Etsu Chemical Co., Ltd., hydroxypropyl methylcellulose

[0746] "SNOWTEX OYL": Colloidal silica manufactured by Nissan Chemical Corporation, a substance in which silica particles are dispersed in water

[0747] "F-444": MEGAFACE F-444 manufactured by DIC Corporation, a fluorine-based surfactant

[0748] "EXP-S-506": EXP-S-506 manufactured by DIC Corporation, silicone-based surfactant

[0749] "MeOH": methanol

[0750] “M / B”: Ratio of the total mass of the polymerizable compound to the total mass of the polymer

[0751] "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

[0752] "BPE-500": NK Ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd., 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane

[0753] "ARONIX M-270": ARONIX M-270 manufactured by TOAGOSEI CO., LTD., polypropylene glycol diacrylate

[0754] "B-CIM": 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole manufactured by Hampford

[0755] "EAB-F": 4,4'-bis(diethylamino)benzophenone obtained from Sanyo Trading Co., Ltd.

[0756] "Phenidone 1% MEK solution": a methyl ethyl ketone solution containing 1% by mass of phenidone

[0757] "Compound A": N-phenylcarbamoylmethyl-N-carboxymethylaniline manufactured by FUJIFILM Wako Pure Chemical Corporation

[0758] "LCV": Colorless crystal violet manufactured by Tokyo Chemical Industry Co., Ltd., a pigment that develops color due to free radicals

[0759] [evaluate]

[0760] Using each of the photosensitive transfer materials of Examples 1 to 5 and Comparative Examples 1 to 4, the following evaluations were performed.

[0761] 1. Peelability between thermoplastic resin layer and intermediate layer

[0762] 1-1. Production of evaluation laminate

[0763] (1) Examples 1 to 5, and Comparative Examples 1, 2, and 4

[0764] An Invar alloy substrate was prepared as a metal substrate. The surface roughness Rmax of the Invar alloy substrate was 0.80 μm. The average thickness of the Invar alloy substrate was 50 μm.

[0765] The photosensitive transfer material was cut into a size of 30 mm × 100 mm, and the protective film was peeled off. The photosensitive transfer material and the Invar alloy substrate were laminated using a roll laminator at a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called laminating speed) of 4 m / min. A photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support were sequentially arranged on the surface of the Invar alloy substrate. In the above manner, a laminate for evaluation was obtained.

[0766] (2) Comparative Example 3

[0767] An Invar alloy substrate was prepared as a metal substrate. The surface roughness Rmax of the Invar alloy substrate was 0.80 μm. The average thickness of the Invar alloy substrate was 50 μm.

[0768] The photosensitive transfer material was cut into a size of 30 mm × 100 mm, and the protective film was peeled off. The photosensitive transfer material and the Invar alloy substrate were laminated using a roll laminator at a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called laminating speed) of 4 m / min. A photosensitive resin layer, an intermediate layer, and a temporary support were sequentially arranged on the surface of the Invar alloy substrate. In the above manner, a laminate for evaluation was obtained.

[0769] 1-2. Evaluation test

[0770] 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 treated laminate was attached to a glass having a thickness of 0.7 mm using a double-sided tape. For the laminate attached to the glass, a 180° peeling test of peeling off the temporary support was performed using Tensilon at a peeling speed of 300 mm / min, and the peeling force was measured. In addition, the laminate after the peeling test was observed to confirm the peeling interface. Then, the peelability between the thermoplastic resin layer and the intermediate layer was evaluated according to the following evaluation criteria.

[0771] In the following evaluation criteria, "5", "4" and "3" are practically acceptable levels, and "5" is most preferable.

[0772] -Evaluation Criteria-

[0773] 5: The thermoplastic resin layer and the intermediate layer are peeled off, and the interlayer peeling force is 25 mN / cm or less.

[0774] 4: The thermoplastic resin layer and the intermediate layer peeled off, and the interlayer peeling force was within the range of more than 25 mN / cm and not more than 50 mN / cm.

[0775] 3: The thermoplastic resin layer and the intermediate layer are peeled, and the interlayer peeling force is in the range of more than 50 mN / cm and not more than 100 mN / cm.

[0776] 2: The thermoplastic resin layer and the intermediate layer peel off, and the interlayer peeling force exceeds 100 mN / cm.

[0777] 1: Delamination between layers other than between the thermoplastic resin layer and the intermediate layer.

[0778] The results of confirming the peeling interface (in the table, marked as "peeling interface when peeling the temporary support") are shown in Table 3. In addition, "between the thermoplastic resin layer / intermediate layer" in the table means that peeling has occurred between the thermoplastic resin layer and the intermediate layer, "between the temporary support / thermoplastic resin layer" means that peeling has occurred between the temporary support and the thermoplastic resin layer, and "between the temporary support / intermediate layer" means that peeling has occurred between the temporary support and the intermediate layer.

[0779] In addition, when the thermoplastic resin layer and the intermediate layer were peeled off, the measured values ​​of the peel force [in the table, marked 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, marked as "peelability between thermoplastic resin layer / intermediate layer"] are shown in Table 3.

[0780] 2.Laminated foam

[0781] 2-1. Production of evaluation laminate

[0782] A laminate for evaluation was obtained in the same manner as in "1-1 Preparation of laminate for evaluation" in the above "1. Peelability between thermoplastic resin layer and intermediate layer".

[0783] 2-2. Evaluation test

[0784] The obtained laminate was observed using an optical microscope with a 10x objective lens to confirm whether there were bubbles (so-called lamination bubbles) remaining between the Invar alloy substrate and the photosensitive resin layer when the laminate was bonded (i.e., laminated) using a roll laminator. The observation area was set to 50,000 μm 2 When lamination bubbles were confirmed, the size and amount of lamination bubbles per unit area were measured. Then, evaluation was performed according to the following evaluation criteria.

[0785] Table 3 shows the evaluation results.

[0786] In the following evaluation criteria, "5", "4" and "3" are practically acceptable levels, and "5" is most preferred. In addition, the "long diameter" of the laminated bubble in the following evaluation criteria refers to the longest diameter of the laminated bubble.

[0787] -Evaluation Criteria-

[0788] 5: Lamination bubbles were not confirmed at all.

[0789] 4: No lamination bubbles with a major diameter exceeding 100 μm were found, but lamination bubbles with a major diameter of 100 μm or less were found at 10000 μm. 2 It is within the range of 1 or more and 5 or less.

[0790] 3: No lamination bubbles with a major diameter exceeding 100 μm were found, but lamination bubbles with a major diameter of 100 μm or less were found at 10000 μm. 2 Within the range of more than 5 and less than 50.

[0791] 2: Confirmed that the laminated bubble with a long diameter of more than 100μm is 2 The number of lamination bubbles is within the range of 1 or more and 5 or less, or no lamination bubbles with a major diameter exceeding 100 μm are observed, but 10000 μm or more are observed. 2 More than 50 laminated bubbles have a major diameter of 100 μm or less.

[0792] 1: Confirmed every 10000μm 2 More than 5 laminated bubbles have a major diameter exceeding 100 μm.

[0793] 3. Attachment of exposure mask

[0794] 3-1. Production of evaluation laminate

[0795] (1) Examples 1 to 5, and Comparative Examples 1, 2, and 4

[0796] An Invar alloy substrate was prepared as a metal substrate. The surface roughness Rmax of the Invar alloy substrate was 0.80 μm. The average thickness of the Invar alloy substrate was 50 μm.

[0797] The photosensitive transfer material was cut into a size of 90 mm × 90 mm, and the protective film was peeled off. The photosensitive transfer material and the Invar alloy substrate were laminated using a roll laminator at a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called laminating speed) of 4 m / min. A photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support were sequentially arranged on the surface of the Invar alloy substrate. In the above manner, a laminate for evaluation was obtained.

[0798] (2) Comparative Example 3

[0799] An Invar alloy substrate was prepared as a metal substrate. The surface roughness Rmax of the Invar alloy substrate was 0.80 μm. The average thickness of the Invar alloy substrate was 50 μm.

[0800] The photosensitive transfer material was cut into a size of 90 mm × 90 mm, and the protective film was peeled off. The photosensitive transfer material and the Invar alloy substrate were laminated using a roll laminator at a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (so-called laminating speed) of 4 m / min. A photosensitive resin layer, an intermediate layer, and a temporary support were sequentially arranged on the surface of the Invar alloy substrate. In the above manner, a laminate for evaluation was obtained.

[0801] 3-2. Evaluation test

[0802] 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 treated laminate, and the surface exposed by peeling (i.e., the exposed surface of the thermoplastic resin layer or the intermediate layer) was overlapped in contact with a glass exposure mask (specifically, a blue plate glass for full solid exposure), and a load of 1.96 N was applied to 63 mm × 63 mm for 60 seconds. After the static friction coefficient was measured in accordance with JIS K 7125: 1999, the contact surface of the exposure mask (i.e., the contact surface with the above-mentioned exposure surface) was observed. Then, the adhesion to the exposure mask was evaluated according to the following evaluation criteria.

[0803] Table 3 shows the evaluation results.

[0804] In the following evaluation criteria, "3" and "2" are practically acceptable levels, and "3" is most preferable.

[0805] -Evaluation Criteria-

[0806] 3: No contamination was observed on the exposure mask, and the static friction coefficient was 1.0 or less.

[0807] 2: No contamination was observed on the exposure mask, and the static friction coefficient exceeded 1.0.

[0808] 1: A portion of the transfer layer was transferred to the exposure mask, and contamination was observed on the exposure mask.

[0809] The "transfer layer" in the above-mentioned "3. Attachment to an exposure mask" and the following "4. Resolution" refers to the following layer.

[0810] Examples 1 to 5, and Comparative Examples 3 and 4: Photosensitive resin layer and intermediate layer

[0811] Comparative Examples 1 and 2: Photosensitive resin layer, intermediate layer, and thermoplastic resin layer

[0812] 4. Resolution 4-1. Production of evaluation laminate

[0813] In the same manner as in "3-1. Production of evaluation laminated body" in the above-mentioned "3. Attachment to exposure mask", a laminated body for evaluation was obtained.

[0814] 4-2. Evaluation test

[0815] The obtained laminate was autoclaved 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 treated laminate so that the exposure mask was in close contact with the surface exposed by peeling (i.e., the exposed surface of the thermoplastic resin layer or the intermediate layer). The exposure mask has a plurality of square shading portions. The size of each shading portion changes in units of 1 μm in the range of 1 μm in length × 1 μm in width to 20 μm in length × 20 μm in width. A high-pressure mercury lamp exposure machine (model: MAP-1200L, main wavelength: 365 nm, manufactured by Japan Science Engineering Co., Ltd.) was used to irradiate the transfer layer after the operation of peeling off the temporary support from the exposure mask side. The exposure amount was adjusted to an exposure amount in which the diameter of the resist pattern obtained after development corresponding to the 20 μm pattern of the exposure mask becomes the pattern diameter of the mask (i.e., 20 μm).

[0816] Next, a development treatment 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 set to twice the minimum development time. "Minimum development time" refers to the minimum time required for the photosensitive resin layer of the unexposed part to be completely dissolved by the development treatment. The development method was set to spray development. Specifically, first, after the minimum time required for the photosensitive resin layer of the unexposed part to be completely dissolved by spray development was calculated, the photosensitive resin layer exposed by the pattern was sprayed for twice the minimum development time. After development, AirKnife treatment was performed, and after removing the developer, pure water with a liquid temperature of 25°C was used for 30 seconds of spray treatment, and further AirKnife treatment was performed. Through the above, a laminate substrate with a resist pattern was obtained. The obtained laminate substrate with a resist pattern was observed using a scanning electron microscope (SEM), and the size of the minimum aperture that could be distinguished was confirmed. Then, the resolution was evaluated according to the following evaluation criteria.

[0817] Table 3 shows the evaluation results.

[0818] In the following evaluation criteria, "3" and "2" are practically acceptable levels, and "3" is most preferable.

[0819] -Evaluation Criteria-

[0820] 3: The minimum aperture that can be resolved is less than 3μm.

[0821] 2: The minimum aperture that can be resolved is in the range of more than 3 μm and less than 5 μm.

[0822] 1: The minimum aperture that can be resolved exceeds 5μm.

[0823] [Table 3]

[0824]

[0825] In Table 3, "-" in the column of the type of thermoplastic resin means that no thermoplastic resin was used. Also, "-" in the columns of Tg and Mn of copolyester resin means that no copolyester resin was used and there is no corresponding item.

[0826] In Table 3, the value described in the column of Tg of the copolyester resin is a value obtained by weighted average of Tg of the copolyester resin contained in the thermoplastic resin layer.

[0827] In Table 3, the value described in the column of Mn of the copolyester resin is a weighted average value of Mn of the copolyester resin contained in the thermoplastic resin layer.

[0828] In Table 3, "Unable to measure" in the column "Peel force between thermoplastic resin layer / intermediate layer" means that the peeling occurred at a position other than between the thermoplastic resin layer and the intermediate layer during the peel test and could not be measured.

[0829] From the results shown in Table 3, it was confirmed that the photosensitive transfer material according to the present invention peeled off between the thermoplastic resin layer and the intermediate layer when the temporary support was peeled off, and that the peelability between the thermoplastic resin layer and the intermediate layer was excellent.

[0830] Furthermore, it was confirmed that when the photosensitive transfer material according to the present invention is laminated on a substrate, bubbles are less likely to be entrapped between the substrate and the photosensitive resin layer.

[0831] Furthermore, it was confirmed that the intermediate layer, which is a layer in contact with the mask, is less likely to adhere to the mask when the photosensitive transfer material according to the present invention is subjected to contact exposure.

[0832] Furthermore, it was confirmed that the photosensitive transfer material according to the present invention has excellent resolution.

[0833] On the other hand, it was confirmed that when the photosensitive transfer materials of Comparative Examples 1 and 2 having a thermoplastic resin layer containing an acrylic resin were subjected to an operation of peeling off the temporary support, the thermoplastic resin layer was peeled off between the temporary support and the thermoplastic resin layer, and the thermoplastic resin layer that became the layer in contact with the mask during contact exposure was easily adhered to the mask.

[0834] When the temporary support was peeled off, the photosensitive transfer material of Comparative Example 3 without the thermoplastic resin layer peeled off between the temporary support and the intermediate layer. It was confirmed that the photosensitive transfer material of Comparative Example 3 was not easy to be entrained between the substrate and the photosensitive resin layer when laminated on the substrate.

[0835] It was confirmed that when the temporary support was peeled off in the photosensitive transfer material of Comparative Example 4 having a thermoplastic resin layer containing ethylene-vinyl acetate copolymer resin, peeling occurred between the thermoplastic resin layer and the intermediate layer, but the peelability between the thermoplastic resin layer and the intermediate layer was significantly poor compared with the photosensitive transfer material of the embodiment.

[0836] Explanation of symbols

[0837] 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 comprising a temporary support, a thermoplastic resin layer containing a copolyester resin, an intermediate layer and a photosensitive resin layer in this order.

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

3. The photosensitive transfer material according to claim 1 or 2, wherein The thermoplastic resin layer is in contact with the intermediate layer.

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

5. The photosensitive transfer material according to claim 1 or 2, wherein The copolyester resin has a number average molecular weight in the range of 3,000 to 30,000 both inclusive, and a glass transition temperature in the range of -20°C to 80°C both inclusive.

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

7. The photosensitive transfer material according to claim 1 or 2, wherein The photosensitive resin layer includes a surfactant containing silicon.

8. The photosensitive transfer material according to claim 1 or 2, wherein The thermoplastic resin layer contains a surfactant containing silicon.

9. A method for producing a photosensitive transfer material, comprising the steps of: forming a thermoplastic resin layer containing a copolyester resin, an intermediate layer, and a photosensitive resin layer in sequence on a temporary support by coating and drying.

10. A method for producing a photosensitive transfer material, comprising the following steps: By coating and drying, a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer containing a copolymerized polyester resin are sequentially formed on the protective film; and The temporary support is bonded to the thermoplastic resin layer by heat lamination.

Images