Photosensitive transfer material, method for manufacturing resin pattern, method for manufacturing conductive pattern, and touch sensor

Abstract

The present invention provides a photosensitive transfer material and its application, wherein the photosensitive transfer material sequentially comprises a temporary support and a photosensitive resin layer, wherein the number of particles having a diameter of Y μm or greater in the temporary support is 15 particles / cm2, when the limiting resolution of the photosensitive resin layer is defined as X μm and the reference diameter of the particles is defined as Y μm expressed by the formula (1): Y=0.75×X. 2 the following.

Description

Technical Field

[0001] The present invention relates to a photosensitive transfer material, a method for manufacturing a resin pattern, a method for manufacturing a conductive pattern, and a touch sensor Background Art

[0002] In a display device having a touch panel such as an electrostatic capacitive input device (e.g., an organic electroluminescent (EL) display device and a liquid crystal display device), the touch panel includes a conductive pattern. The conductive pattern is used, for example, as a sensor, edge wiring, or lead wiring of a visual recognition unit. In the method for manufacturing patterns such as conductive patterns and resin patterns, for example, a method comprising the following steps is widely used: a step of providing a photosensitive resin layer and a temporary support on a substrate using a photosensitive transfer material; a step of exposing the photosensitive resin layer to a pattern via the temporary support; and a step of developing the exposed photosensitive resin layer.

[0003] In order to avoid a decrease in resolution due to impurities contained in a temporary support, Japanese Patent Application Laid-Open No. 2019-101405 discloses a photosensitive resin laminate roll in which the number of fine particles having a diameter of 2 μm or more is limited. Summary of the Invention

[0004] Technical issues to be solved by the invention

[0005] As the conductive pattern becomes higher in definition, in other words, as the required resolution increases, defects in the conductive pattern (particularly, pores) caused by impurities (e.g., coarse particles) contained in the temporary support become more apparent. Impurities contained in the temporary support hinder the exposure of the photosensitive resin layer and cause defects in the resin pattern (e.g., pores). For example, in the etching process for forming the conductive pattern, if a resin pattern containing pores is used as a protective film, pores will be generated in the conductive pattern. Therefore, it is required to reduce the pores generated in the resin pattern.

[0006] An object of one embodiment of the present invention is to provide a photosensitive transfer material having a resin pattern formed thereon that suppresses the generation of voids.

[0007] Another embodiment of the present invention aims to provide a method for manufacturing a resin pattern that suppresses the generation of voids.

[0008] Another embodiment of the present invention aims to provide a method for manufacturing a conductive pattern that suppresses the generation of voids.

[0009] Another embodiment of the present invention aims to provide a touch sensor including a conductive pattern that suppresses the generation of voids.

[0010] Means for solving technical problems

[0011] The present invention includes the following aspects.

[0012] <1> A photosensitive transfer material comprising a temporary support and a photosensitive resin layer in this order, wherein the limiting resolution of the photosensitive resin layer is defined as X μm, and when the reference diameter of the particles is defined as Y μm expressed by the formula (1): Y=0.75×X, the number of particles having a diameter of Y μm or more in the temporary support is 15 particles / cm 2 the following.

[0013] <2> according to <1> The photosensitive transfer material, wherein

[0014] The number of particles having a diameter of 10.5 μm or more in the temporary support is 1.0 particle / cm 2 the following.

[0015] <3> according to <1> or <2> The photosensitive transfer material, wherein

[0016] The temporary support has a thickness of 16 μm or less.

[0017] <4> according to <1> to <3> The photosensitive transfer material according to any one of the preceding claims, wherein

[0018] The photosensitive resin layer has a thickness of 5 μm or less.

[0019] <5> A photosensitive transfer material comprises a temporary support and a photosensitive resin layer in sequence.

[0020] The temporary support is a polyester film composed of two or more layers, and at least one surface layer does not contain a filler.

[0021] <6> according to <5> The photosensitive transfer material, wherein

[0022] The surface layer on the photosensitive resin layer side of the temporary support does not contain a filler.

[0023] <7> according to <5> or <6> The photosensitive transfer material, wherein

[0024] When the limiting resolution of the photosensitive resin layer is defined as X μm and the reference diameter of the particles is defined as Y μm represented by the formula (1): Y=0.75×X, the number of particles having a diameter of Y μm or more in the temporary support is 15 particles / cm 2 the following.

[0025] <8> according to <5> to <7> The photosensitive transfer material according to any one of the preceding claims, wherein

[0026] The arithmetic mean roughness Ra of the surface of the temporary support on the side opposite to the photosensitive resin layer is 1 nm to 50 nm.

[0027] <9> according to <5> to <8> The photosensitive transfer material according to any one of the preceding claims, wherein

[0028] The surface layer has a phase separation structure.

[0029] <10> according to <5> to <9> The photosensitive transfer material according to any one of the preceding claims, wherein

[0030] The surface layer contains a polyester resin having an alicyclic structure.

[0031] <11> according to <10> The photosensitive transfer material, wherein

[0032] The above-mentioned alicyclic structure is a cyclohexane ring.

[0033] <12> according to <10> or <11> The photosensitive transfer material, wherein

[0034] The surface layer contains copolymerized polyethylene terephthalate containing isophthalic acid as a copolymer component.

[0035] <13> A method for manufacturing a resin pattern, the method using <1> to <12> The photosensitive transfer material according to any one of the preceding claims, wherein the method for manufacturing the resin pattern comprises:

[0036] The process of preparing the substrate;

[0037] The process of bringing the photosensitive transfer material into contact with the substrate, and sequentially disposing a photosensitive resin layer and a temporary support on the substrate;

[0038] a step of exposing the photosensitive resin layer to a pattern; and

[0039] A step of developing the exposed photosensitive resin layer to form a resin pattern.

[0040] <14> according to <13> The method for manufacturing the resin pattern, wherein:

[0041] The line width of the resin pattern is 10 μm or less.

[0042] <15> A method for manufacturing a conductive pattern, the method using <1> to <12> The photosensitive transfer material according to any one of the preceding claims, wherein the method for manufacturing the conductive pattern comprises:

[0043] A step of preparing a substrate including a conductive layer;

[0044] The process of bringing the photosensitive transfer material into contact with the substrate, and sequentially disposing a photosensitive resin layer and a temporary support on the substrate;

[0045] a step of exposing the photosensitive resin layer to a pattern;

[0046] a step of developing the exposed photosensitive resin layer to form a resin pattern; and

[0047] a step of etching the conductive layer not covered by the resin pattern to form a conductive pattern.

[0048] <16> A touch sensor comprising <15> The conductive pattern is obtained by the conductive pattern manufacturing method.

[0049] Effects of the Invention

[0050] According to one embodiment of the present invention, a photosensitive transfer material is provided in which a resin pattern is formed that suppresses the generation of voids.

[0051] According to another embodiment of the present invention, a method for manufacturing a resin pattern that suppresses the generation of voids is provided.

[0052] According to another embodiment of the present invention, a method for manufacturing a conductive pattern that suppresses the generation of voids is provided.

[0053] According to another embodiment of the present invention, a touch sensor including a conductive pattern that suppresses generation of air voids is provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 It is a schematic side view showing the layer structure of the photosensitive transfer material according to the present invention.

[0055] Figure 2 It is a schematic side view showing another layer structure of the photosensitive transfer material according to the present invention.

[0056] Figure 3 It is a schematic side view showing another layer structure of the photosensitive transfer material according to the present invention. DETAILED DESCRIPTION

[0057] The following describes the embodiments of the present invention in detail. The present invention is not limited to the following embodiments. The following embodiments can be modified as appropriate within the scope of the purpose of the present invention.

[0058] When describing the embodiments of the present invention with reference to the accompanying drawings, descriptions of components and symbols that are repeated in the drawings may be omitted. Components denoted by the same symbols in the drawings are identical components. Dimensional ratios in the drawings do not necessarily represent actual dimensional ratios.

[0059] In the present invention, the numerical range represented by "to" represents a range including the numerical values before and after "to" as the lower limit and the upper limit, respectively. In the numerical ranges described in stages in the present invention, the upper limit or lower limit described in any numerical range can be replaced by the upper limit or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present invention, the upper limit or lower limit described in any numerical range can be replaced by the values shown in the Examples.

[0060] In the present invention, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0061] In the present invention, "mass %" and "weight %" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0062] In the present invention, when a plurality of substances corresponding to a certain component are present in a composition, the amount of the component in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified.

[0063] In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

[0064] In the present invention, ordinal numbers (eg, "first" and "second") are terms used to distinguish a plurality of components, and do not limit the number of components or the superiority or inferiority of components.

[0065] In the present invention, groups (atomic groups) not mentioning substitution and unsubstituted groups include groups with substitution and groups without substitution. For example, the term "alkyl" includes alkyl groups with substitution (substituted alkyl groups) and alkyl groups without substitution (unsubstituted alkyl groups).

[0066] In the present invention, chemical structural formulas may be represented by simplified structural formulas in which hydrogen atoms are omitted.

[0067] In the present invention, "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0068] In the present invention, "(meth)acrylate" means acrylate or methacrylate.

[0069] In the present invention, "(meth)acryloyl" means acryloyl or methacryloyl.

[0070] In the present invention, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light and extreme ultraviolet light (EUV (Extreme Ultraviolet Lithography) light) represented by excimer lasers, and active light (active energy rays) such as X-rays.

[0071] In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are molecular weights calculated using a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL (Tosoh Corporation), TSKgel G4000HxL (Tosoh Corporation), and TSKgel G2000HxL (Tosoh Corporation) columns, with the compounds in tetrahydrofuran (THF) detected by a differential refractometer and polystyrene as a standard substance.

[0072] In the present invention, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

[0073] In the present invention, the "solid content" refers to a component obtained by excluding the solvent from the total content of an object.

[0074] <Photosensitive transfer material>

[0075] The photosensitive transfer material according to the first embodiment of the present invention comprises a temporary support and a photosensitive resin layer in this order, wherein the limiting resolution of the photosensitive resin layer is defined as X μm, the reference diameter of the particles is defined as Y μm represented by the formula (1): Y = 0.75 × X, and the number of particles having a diameter of Y μm or more in the temporary support is 15 particles / cm 2 the following.

[0076] According to the first embodiment described above, there is provided a photosensitive transfer material having a resin pattern formed thereon that suppresses the generation of voids.

[0077] The estimated reasons for the above-mentioned effects are explained below. As mentioned above, the coarse particles contained in the temporary support hinder the exposure of the photosensitive resin layer and produce pores in the resin pattern. For example, in the technology disclosed in Japanese Patent Gazette No. 2019-101405, the number of particles with a diameter of 2 μm or more is limited to avoid the decrease in resolution caused by impurities contained in the temporary support. However, the size of the particles that cause exposure obstruction varies according to the required resolution. As the required resolution becomes smaller, the tiny particles allowed in the previous technology can also hinder the exposure of the photosensitive resin layer. Therefore, the inventors of the present invention have paid attention to the relationship between the size and number of particles contained in the temporary support relative to the resolution of the photosensitive resin layer. Based on the verification related to the relationship between the resolution of the photosensitive resin layer and the size of the particles that cause exposure obstruction, the inventors of the present invention know that particles with a diameter of Y (Y = 0.75 × X) μm or more relative to the limiting resolution (X) of the photosensitive resin layer lead to an increase in the rate of occurrence of exposure obstructions. In the photosensitive transfer material according to the first embodiment of the present invention, the number of particles having a diameter of Y μm or more in the temporary support is adjusted to 15 particles / cm based on the reference diameter (Y) of the particles derived from the limiting resolution (X) of the photosensitive resin layer. 2 The occurrence rate of exposure failure can be reduced by this. Therefore, according to the photosensitive transfer material according to the first embodiment of the present invention, there is provided a photosensitive transfer material having a resin pattern formed thereon that suppresses the occurrence of voids.

[0078] The photosensitive transfer material involved in the second embodiment of the present invention includes a temporary support body and a photosensitive resin layer in sequence, wherein the above-mentioned temporary support body is a polyester film composed of two or more layers, and at least one surface layer (i.e., at least one of the layers configured as the outermost layer on the first surface side and the outermost layer on the second surface side) does not contain filler.

[0079] According to the second embodiment described above, a photosensitive transfer material having a resin pattern formed thereon that suppresses the generation of voids can also be provided.

[0080] In the present invention, when the term "photosensitive transfer material according to the present invention" or "photosensitive transfer material" is simply referred to as "the photosensitive transfer material" unless otherwise specified, it is considered that both the first embodiment and the second embodiment are described.

[0081] Temporary support structure

[0082] The photosensitive transfer material involved in the present invention includes a temporary support. In the photosensitive transfer material, the temporary support at least supports the photosensitive resin layer. In the photosensitive transfer material, the temporary support is a component that can be peeled off from an adjacent layer (for example, a photosensitive resin layer). Hereinafter, in the photosensitive transfer material, the main surface of the temporary support facing the photosensitive resin layer is referred to as the second surface, and the main surface on the side opposite to the second surface of the temporary support is referred to as the first surface.

[0083] <Temporary Support in Photosensitive Transfer Material According to First Embodiment of the Present Invention>

[0084] Hereinafter, a temporary support (hereinafter also referred to as a temporary support (1)) in the photosensitive transfer material according to the first embodiment of the present invention will be described.

[0085] In the photosensitive transfer material according to the first embodiment of the present invention, when the limiting resolution of the photosensitive resin layer is defined as X μm and the reference diameter of the particles is defined as Y μm represented by the formula (1): Y = 0.75 × X, the number of particles having a diameter of Y μm or more in the temporary support (hereinafter sometimes referred to as "the number of specific particles (A)") is 15 particles / cm 2 The number of specific particles (A) in the temporary support (1) is 15 particles / cm 2 From the viewpoint of reducing pores, the number of specific particles (A) is preferably 14 particles / cm 2 Below, more preferably 12 / cm 2 Below, especially preferably 9 / cm 2 In addition, the number of specific particles (A) is preferably 7 particles / cm 2 Below, more preferably 6 / cm 2 Below, especially preferably 5 / cm 2 There is no lower limit on the number of specific particles (A). For example, the number of specific particles (A) can be 0 / cm 2 The number of specific particles (A) can be 0 / cm 2 or more than 0 / cm 2. As a method for reducing the number of specific particles (A), for example, reducing the amount of particles added to the temporary support (1) and suppressing the precipitation or crystallization of additives during the manufacture of the temporary support (1) can be cited. Furthermore, from the viewpoint of reducing impurities (including restricted particles in the present invention), it is preferred to use high-purity raw materials to manufacture the temporary support (1) or reduce impurities such as particles attached to the device used when manufacturing the temporary support (1). Furthermore, from the viewpoint of reducing the number of impurities per unit area (including restricted particles in the present invention), it is preferred to reduce the thickness of the temporary support (1). For example, in a method for manufacturing a temporary support (1) using an extrusion molding method, the number of specific particles (A) contained in the temporary support (1) can be adjusted by adjusting the pore size of the filter used to filter the melt and the number of times the melt is filtered.

[0086] The limiting resolution (X) of the photosensitive resin layer is described below. In the present invention, the limiting resolution of the photosensitive resin layer is defined as Xμm. The term "μm" used in relation to Xμm is a unit of length, i.e., micrometer. The limiting resolution (X) of the photosensitive resin layer is preferably 15μm or less, more preferably 10μm or less, and particularly preferably 7μm or less. There is no restriction on the lower limit of the limiting resolution (X) of the photosensitive resin layer. The lower limit of the limiting resolution (X) of the photosensitive resin layer may be, for example, 0.5μm, 1μm or 2μm. The limiting resolution (X) of the photosensitive resin layer is adjusted according to, for example, the composition of the photosensitive resin layer, the thickness of the photosensitive resin layer, and the distance between the mask and the substrate during exposure. The limiting resolution (X) of the photosensitive resin layer is determined by the following method. (1) The photosensitive transfer material is brought into contact with a polyethylene terephthalate (PET) film having a thickness of 100μm, and the photosensitive resin layer and the temporary support are sequentially arranged on the PET film. That is, by laminating the PET film and the photosensitive transfer material, a laminated body comprising at least a PET film, a photosensitive resin layer and a temporary support in sequence is obtained. In the laminated body, the structure of the layer arranged on the PET film varies according to the layer structure of the photosensitive transfer material. (2) Using an autoclave device, the obtained laminated body is pressurized and defoamed for 30 minutes under the conditions of 0.6 MPa and 60°C. (3) Using an ultra-high pressure mercury lamp, the photosensitive resin layer is exposed through a line and space pattern mask (the duty ratio is 1:1, and the line width changes stepwise from 1 μm to 20 μm at intervals of 1 μm) without peeling off the temporary support. (4) After peeling off the temporary support, development is performed. For development, a 1.0 mass % sodium carbonate aqueous solution at 25°C is used and spray development is performed for 30 seconds. By developing the photosensitive resin layer, a resin pattern is formed. The exposure amount (unit: mJ / cm 2) and simultaneously perform the above series of steps (1) to (4) until a resin pattern having a minimum line width corresponding to the pattern of the mask (hereinafter referred to as the "reference pattern" in this section) is obtained. If necessary, a mask having a line width of less than 1 μm can be used. The minimum line width of the reference pattern is used as the limiting resolution (X) of the photosensitive resin layer.

[0087] The following describes the reference diameter (Y) of particles. In the present invention, the reference diameter of particles is defined as Y μm, expressed by the formula (1): Y = 0.75 × X. The term "X" used in formula (1) represents the limiting resolution (X) of the photosensitive resin layer. The unit of X is micrometers. The term "μm" used in relation to Y μm represents a unit of length, i.e., micrometers.

[0088] In the present invention, the number of specific particles (A) is measured by the following method: 10 random areas (size of each area: 10 mm x 10 mm, total area: 1000 mm) on the surface of the temporary support are visually observed using an optical microscope. 2 ). Measure the number of particles with a diameter of Y μm or more contained in each area. "Diameter" is the maximum value of a straight line connecting two points on the contour line of the particle when viewed from above. Based on the total value of the number of particles measured in the 10 areas, calculate the diameter of each 1 cm of the measurement area. 2 The number of particles (particles / cm 2 ). The obtained value is adopted as the number of specific particles (A).

[0089] From the viewpoint of reducing pores, the number of particles having a diameter of 10.5 μm or more in the temporary support (1) (hereinafter sometimes referred to as "the number of specific particles (B)") is preferably 1.0 particle / cm 2 Below, more preferably 0.5 pieces / cm 2 Below, especially preferably 0.2 pieces / cm 2 There is no lower limit on the number of specific particles (B). For example, the number of specific particles (B) can be 0 / cm 2 The number of specific particles (B) can be 0 / cm 2 or more than 0 / cm 2 The number of specific particles (B) is measured by a method according to the method for measuring the number of specific particles (A). The number of specific particles (B) is adjusted by a method according to the method for adjusting the number of specific particles (A).

[0090] The particles in the temporary support (1) (including specific particles (A) and specific particles CB. The same shall apply to this paragraph hereinafter.) may be particulate compounds added when the temporary support (1) is produced. The particles in the temporary support (1) may be particles generated by polycondensation, elongation, or precipitation or crystallization during the cooling process of the additive added when the temporary support is produced.

[0091] Examples of particulate compounds include inorganic particles and organic particles. Examples of inorganic particles include particles comprising inorganic oxides. Examples of inorganic oxides include silica, titanium oxide, zirconium oxide, magnesium oxide, and aluminum oxide. Examples of organic particles include particles comprising polymers. Examples of polymers include acrylic resins, polyesters, polyurethanes, polycarbonates, polyolefins, and polystyrene.

[0092] Examples of additives added when preparing the temporary support (1) include a reaction catalyst for polycondensation, a coloring inhibitor, and a film-forming property-imparting agent.

[0093] Examples of the reaction catalyst used for the polycondensation include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and phosphorus compounds. Furthermore, antimony compounds, germanium compounds, or titanium compounds are preferably used as polymerization catalysts in any fractionation prior to completion of the polyester production process.

[0094] Examples of coloration inhibitors include phosphate compounds. Examples of phosphate compounds include pentavalent phosphates that do not have an aromatic ring as a substituent. Examples of pentavalent phosphates that do not have an aromatic ring as a substituent include phosphates that have a lower alkyl group having 2 or less carbon atoms as a substituent [(RO)3-P=O, R=alkyl group having 1 or 2 carbon atoms]. Examples of compounds represented by "(RO)3-P=O" include trimethyl phosphate and triethyl phosphate.

[0095] As film-forming agents, for example, alkali metal and alkaline earth metal compounds can be mentioned. In addition, in the manufacture of temporary supports or the manufacture of polyester used as the raw material of temporary supports, magnesium compounds are particularly preferably used. By including a magnesium compound in the polyester, the electrostatic applicability of the polyester is improved. In this case, it is easy to color, but by using it in combination with a coloring inhibitor, coloring can be suppressed to obtain excellent color tone and heat resistance. As magnesium compounds, for example, magnesium salts can be mentioned. As magnesium salts, for example, magnesium oxide, magnesium hydroxide, magnesium alcohol, magnesium acetate and magnesium carbonate can be mentioned. Among them, from the viewpoint of solubility in ethylene glycol, magnesium acetate is most preferably used.

[0096] The shape of the particles is not limited. Examples of the shape of the particles in plan view include circular, elliptical, polygonal, and irregular shapes.

[0097] The particles may be transparent particles, translucent particles, or colored particles such as black.

[0098] The temporary support (1) is preferably light-transmitting. In the present invention, "light-transmitting" means that the transmittance at the wavelength used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of the temporary support (1) at the wavelength used for pattern exposure (more preferably a wavelength of 365 nm) is preferably 60% or more, more preferably 70% or more. The transmittance is the ratio of the intensity of light passing through the object (outgoing light) to the intensity of light (incident light) perpendicular to the main surface of the object. The transmittance is measured using a known spectrometer (for example, "MCPD Series", OTSUKAELECTRON ICS Co., LTD).

[0099] The thickness of the temporary support (1) is not limited. From the perspective of the strength of the support, the flexibility required for bonding with the substrate, and the light transmittance required during exposure, the thickness of the temporary support (1) can be determined according to the material. From the perspective of ease of operation and versatility, the thickness of the temporary support (1) is preferably 100 μm or less, more preferably 50 μm or less, further preferably 20 μm or less, and particularly preferably 16 μm or less. From the perspective of ease of operation and versatility, the thickness of the temporary support (1) is preferably 5 μm or more, more preferably 10 μm or more. In addition, as the thickness of the temporary support (1) becomes thinner, the volume of the temporary support decreases, thereby reducing the absolute amount of particles contained in the temporary support per unit area.

[0100] The thickness of the temporary support is measured by the following method. Using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), observe a cross section along the thickness direction of the temporary support (a direction perpendicular to the main surface of the temporary support). The thickness of the temporary support is measured at 10 locations based on the observed image, and the measured values are arithmetic averaged. The obtained value is adopted as the thickness of the temporary support.

[0101] The layer structure of the temporary support (1) is not limited. The temporary support (1) can be a temporary support having a single-layer structure or a temporary support having a multi-layer structure. The layer structure of the temporary support (1) is described below. However, the layer structure of the temporary support (1) is not limited to the layer structure shown below.

[0102] Examples of the temporary support (1) having a single-layer structure include a glass substrate, a resin film, and paper. From the perspectives of strength, flexibility, and light transmittance, a resin film is preferred. Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among the above, a PET film is preferred, and a biaxially stretched PET film is more preferred. Examples of a method for producing the resin film include extrusion molding.

[0103] Examples of the temporary support (1) having a multilayer structure include a temporary support comprising a substrate and a particle-containing layer. The temporary support (1) having a multilayer structure may include a layer other than the particle-containing layer (for example, an adhesive layer).

[0104] From the viewpoint of transportability, the temporary support (1) preferably includes, in sequence, a particle-containing layer (hereinafter sometimes referred to as "the first particle-containing layer") configured as the outermost layer of the temporary support and a substrate in the stacking direction from the temporary support toward the photosensitive resin layer. In other words, the temporary support (1) preferably includes, in sequence, a substrate and a particle-containing layer (the first particle-containing layer) configured as the outermost layer on the first surface side of the temporary support. The surface containing the first particle layer includes the first surface of the temporary support (1).

[0105] From the perspective of ensuring transportability during the manufacture of the temporary support, the temporary support (1) may include, in order from the temporary support toward the stacking direction of the photosensitive resin layer, a base material and a particle-containing layer (hereinafter sometimes referred to as "the second particle-containing layer") configured as the outermost layer of the temporary support. In other words, the temporary support (1) may include, in order, a base material and a particle-containing layer (the second particle-containing layer) configured as the outermost layer on the second surface side of the temporary support. The surface containing the second particle layer includes the second surface of the temporary support (1).

[0106] The temporary support (1) may include a plurality of particle-containing layers. For example, the temporary support (1) may include a first particle-containing layer, a substrate, and a second particle-containing layer in this order in the stacking direction from the temporary support toward the photosensitive resin layer.

[0107] Examples of the substrate include glass substrates, resin films, and paper. The substrate is preferably a resin film, more preferably a polyethylene terephthalate (PET) film, and particularly preferably a biaxially stretched PET film. Examples of the resin film include the resin films already described. Examples of methods for producing the resin film include extrusion molding.

[0108] As particles in the particle-containing layer, for example, inorganic particles and organic particles can be mentioned. As inorganic particles, for example, particles containing inorganic oxides can be mentioned. As inorganic oxides, for example, silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia) and aluminum oxide (alumina) can be mentioned. As organic particles, for example, particles containing polymers can be mentioned. As polymers, for example, acrylic resins, polyesters, polyurethanes, polycarbonates, polyolefins and polystyrenes can be mentioned. From the viewpoint of the friction resistance of the particles, the particles are preferably inorganic particles, more preferably particles containing inorganic oxides, further preferably particles containing at least one selected from silicon oxide, titanium oxide, zirconium oxide, magnesium oxide and aluminum oxide, and particularly preferably particles containing silicon oxide.

[0109] From the viewpoint of reducing pores, the average particle size of the particles in the particle-containing layer is preferably 2 μm or less, more preferably 1 μm or less. Furthermore, from the viewpoint of transparency (haze), the average particle size of the particles in the particle-containing layer is preferably 300 nm or less, more preferably 100 nm or less, and particularly preferably 80 nm or less. From the viewpoint of transportability, the average particle size of the particles in the particle-containing layer is preferably 5 nm or more, more preferably 20 nm or more, and particularly preferably 40 nm or more. In the present invention, the average particle size of the particles in the particle-containing layer is measured by the following method. Using a transmission electron microscope (TEM), the particle size of 10 particles is measured. Here, "particle size" is the maximum value of a straight line connecting two points on the contour line of the particle. The arithmetic average of the measured values is adopted as the average particle size of the particles.

[0110] The shape of the particles in the particle-containing layer is not limited, and examples of the shape of the particles in plan view include circular, elliptical, polygonal, and irregular shapes.

[0111] The particle-containing layer may contain a binder. Examples of the binder include polymers. Examples of the polymer include acrylic resins, polyurethanes, polyolefins, styrene-butadiene polymers, polyesters, polyvinyl chloride, and polyvinylidene chloride.

[0112] The thickness of the particle-containing layer is not limited. From the viewpoint of easily forming protrusions by adding particles, the thickness of the particle-containing layer (excluding particles exposed on the surface of the particle-containing layer. The same applies in this paragraph below) is preferably 3 μm or less, more preferably 2 μm or less. Furthermore, from the viewpoint of uniformly present particles, the thickness of the particle-containing layer is preferably 5 nm or more, more preferably 20 nm or more. The thickness of the particle-containing layer is measured by a method according to the method for measuring the thickness of the temporary support.

[0113] The manufacturing method of the particle-containing layer is not limited. The particle-containing layer is formed, for example, by applying a particle-containing layer-forming composition to a substrate and drying the applied particle-containing layer-forming composition as needed. The particle-containing layer-forming composition is a raw material for forming the particle-containing layer. In the above method, the particle-containing layer-forming composition can be applied to an unstretched film, a uniaxially stretched film, or a biaxially stretched film. The unstretched film or uniaxially stretched film coated with the particle-containing layer-forming composition can be further stretched. The particle-containing layer can be formed together with the substrate, for example, by coextrusion.

[0114] The film used as the temporary support (1) is preferably free from deformations (such as wrinkles), scratches and defects.

[0115] From the viewpoint of pattern formation during pattern exposure via the temporary support and the transparency of the temporary support, it is preferred that the number of particles, impurities, defects and precipitates contained in the temporary support (1) is small. The number of particles, impurities and defects with a diameter of 2 μm or more is preferably 50 / 10 mm. 2 Less than 10 pieces / 10mm, more preferably 10 pieces / 10mm 2 Below, more preferably 3 / 10mm 2 Below, particularly preferably 0 / 10mm 2 .

[0116] Preferred embodiments of the temporary support (1) are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Application Laid-Open No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Application Laid-Open 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 Laid-Open No. 2019-101405. The contents of these publications are incorporated herein by reference.

[0117] Examples of the temporary support (1) include a biaxially stretched polyethylene terephthalate film having a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 μm.

[0118] <Temporary Support in Photosensitive Transfer Material According to Second Embodiment of the Present Invention>

[0119] Hereinafter, a temporary support (hereinafter also referred to as a temporary support (2)) in the photosensitive transfer material according to the second embodiment of the present invention will be described.

[0120] In the photosensitive transfer material according to the second embodiment of the present invention, the temporary support is a polyester film composed of two or more layers, and at least one surface layer may not contain a filler.

[0121] Here, the "filler" in the present invention refers to an inorganic material added to fill gaps between polyester resins in the surface layer, and has a particle size of 2.0 μm or more.

[0122] Examples of the filler, that is, the inorganic material, include the inorganic materials already described (preferably inorganic oxides).

[0123] The presence and amount of fillers are confirmed by the method described below, but in the particle measurement method described above, the fillers may be measured as part of the particles.

[0124] "The surface layer does not contain fillers" means that the average number of fillers present when observing the surface layer at 5,000x magnification at 10 viewing angles using a scanning electron microscope (SEM) and a transmission electron microscope (TEM) is 0.5 per mm. 2 That is, when confirmed by the above method, as long as the average number of fillers is 0.5 / mm 2 Hereinafter, it is considered that "the surface layer does not contain filler".

[0125] The above-mentioned observation method will be further described in detail.

[0126] The polyester resin is removed from the polyester film serving as the surface layer of the temporary support by a plasma low-temperature ashing process, leaving the filler as an inorganic material and exposing it. Regarding the treatment conditions, conditions are selected such that the polyester resin is ashed but the filler is not severely damaged. The treated sample is observed at a magnification of 5000 times using a scanning electron microscope (SEM, such as the Hitachi, Ltd. S-4000 model). The particle image is read into an image analyzer (NIRECO CORPORATION LUZEX_AP) to confirm the presence of filler and the number of particles.

[0127] When the filler is significantly damaged by the plasma low-temperature ashing method, the presence and amount of filler are confirmed by observing the cross section of the temporary support at 5000 times magnification using a transmission electron microscope (TEM, such as Hitachi, Ltd. H-600).

[0128] When observed by SEM and TEM at 5,000x magnification, the average number of fillers present was 0.5 per mm at 10 viewing angles. 2 Hereinafter, it is determined that the surface layer of the observation object does not contain particles.

[0129] When the temporary support (2) is a polyester film composed of two layers, one of the two layers becomes the surface layer on the first surface side (i.e., the layer arranged as the outermost layer on the first surface side), and the other layer becomes the surface layer on the second surface side (i.e., the layer arranged as the outermost layer on the second surface side). When the temporary support (2) is a polyester film composed of three or more layers, it is composed of the surface layer on the first surface side (i.e., the layer arranged as the outermost layer on the first surface side), the surface layer on the second surface side (i.e., the layer arranged as the outermost layer on the second surface side), and one or more intermediate layers sandwiched between these two surface layers.

[0130] The temporary support (2) is a temporary support in which at least one of the two surface layers does not contain a filler.

[0131] Furthermore, from the viewpoint of reducing pores, it is preferred that the surface layer on the photosensitive resin layer side (ie, the surface layer on the second surface side) of the temporary support (2) does not contain a filler.

[0132] From the viewpoint of reducing pores, when the limiting resolution of the photosensitive resin layer is defined as X μm and the reference diameter of the particles is defined as Y μm represented by the formula (1): Y = 0.75 × X, the number of particles having a diameter of Y μm or more in the temporary support (2) is preferably 15 particles / cm 2 Below, more preferably 12 / cm 2 Below, more preferably 9 / cm 2 Below, especially preferably 7 / cm 2 The lower limit of the number of particles having a diameter of Y μm or more in the temporary support (2) is not limited and can be 0 particles / cm 2 or more than 0 / cm 2 .

[0133] From the viewpoint of transportability, the arithmetic mean roughness Ra of the surface of the temporary support ( 2 ) opposite to the photosensitive resin layer (ie, the first surface) is preferably 1 nm to 50 nm, more preferably 1 nm to 40 nm.

[0134] The arithmetic mean roughness Ra of the surface opposite to the photosensitive resin layer (i.e., the first surface) of the temporary support (2) is measured by a method according to JIS B 0601: 1994. Specifically, it can be measured by the same method as the arithmetic mean roughness Ra of the surface of the protective film described below.

[0135] The polyester film composed of two or more layers constituting the temporary support (2) may be a film in which the resin constituting the film is mainly composed of a polyester resin. Furthermore, "the resin constituting the film is mainly composed of a polyester resin" means that at least 70 mol % or more of the resin constituting the film is a polyester resin.

[0136] The polyester resin constituting the polyester film is obtained by polymerization of monomers composed of dicarboxylic acids, diols, and ester-forming derivatives thereof. Specific examples of the polyester resin constituting the film include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyhexamethylene terephthalate, polyhexamethylene naphthalate, and copolymers thereof. Polyethylene terephthalate is particularly preferred.

[0137] As the dicarboxylic acid component (including dicarboxylic acid and its ester-forming derivative) which is a monomer for obtaining the polyester resin, an aromatic dicarboxylic acid is preferably used.

[0138] Examples of the aromatic dicarboxylic acid include terephthalic acid, 2,6-naphthalene dicarboxylic acid, and isophthalic acid, and terephthalic acid is particularly preferred.

[0139] The dicarboxylic acid component may be used alone or in combination of two or more. For example, two or more aromatic dicarboxylic acids may be used in combination, or an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid may be used in combination.

[0140] Examples of the diol component (including diols and ester-forming derivatives thereof) that is a monomer for obtaining polyester include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and neopentyl glycol. Among them, ethylene glycol is preferred.

[0141] The diol component may be used alone or in combination of two or more.

[0142] The polyester resin constituting the polyester film can be produced by conventionally known methods. For example, methods include a method of producing the polyester film by directly esterifying a dicarboxylic acid component with a diol component, then heating the reaction product under reduced pressure to remove the remaining diol component while carrying out polycondensation, and methods of producing the polyester film by using a dialkyl ester of a dicarboxylic acid as the dicarboxylic acid component, carrying out an ester exchange reaction with the diol component, and then carrying out polycondensation in the same manner as described above. Furthermore, conventionally known alkali metals, alkaline earth metals, manganese, cobalt, zinc, antimony, germanium, titanium compounds, and the like can also be used as reaction catalysts, as needed.

[0143] The intrinsic viscosity of the polyester resin constituting the polyester film is preferably 0.5 dl / g to 0.8 dl / g, more preferably 0.55 dl / g to 0.70 dl / g.

[0144] The temporary support (2) preferably has a surface layer without particles and has a phase separation structure. That is, the surface layer preferably does not contain particles and has a phase separation structure (specifically, it can be a sea-island structure). The surface layer forms surface unevenness derived from the phase separation structure by having a phase separation structure (for example, a sea-island structure) without particles. Specifically, a film having a surface layer with a phase separation structure, for example, is subjected to biaxial stretching to produce an easily stretched region and a difficultly stretched region derived from the phase separation structure, and the uneven stretching can form minute surface unevenness.

[0145] In order to form a phase-separated structure in the surface layer as described above, the surface layer preferably contains a polyester resin having an alicyclic structure. That is, the surface layer forms a phase-separated structure (e.g., an island-in-the-sea structure) by containing a main polyester resin (e.g., a polyester resin having an aromatic ring structure) and a polyester resin having an alicyclic structure having a different compatibility with the main polyester resin.

[0146] The alicyclic structure in the polyester resin having an alicyclic structure is preferably a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring, with a cyclohexane ring being particularly preferred. The polyester resin having an alicyclic structure is obtained, for example, by polycondensing dimethyl terephthalate as a dicarboxylic acid component and 1,3-cyclopropanediol, 1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanedimethanol, etc., in the presence of 200 ppm of butyltin tris(2-ethylhexanoate).

[0147] The content of the polyester resin having an alicyclic structure is preferably 3 to 10% by mass relative to the total mass of the surface layer from the viewpoints of the formation of surface irregularities and the occurrence of coating defects of the photosensitive resin layer-forming composition.

[0148] The temporary support (2) preferably contains a polyester resin having an alicyclic structure and a copolymerized polyethylene terephthalate containing isophthalic acid as a copolymer component in the surface layer.

[0149] Here, a copolymerized polyethylene terephthalate containing isophthalic acid as a copolymer component refers to a polyester resin in which ethylene glycol is the largest diol component, terephthalic acid is the largest dicarboxylic acid component, and isophthalic acid is contained as a dicarboxylic acid component. The copolymerization ratio of isophthalic acid relative to the total dicarboxylic acid component is preferably within the range of 0.1 to 49 mol%, more preferably 0.5 to 40 mol%. The inclusion of a copolymerized polyethylene terephthalate containing isophthalic acid as a copolymer component in the surface layer is preferred in terms of film-forming properties and, due to its different stretchability from polyester resins having an alicyclic structure, is preferred in terms of facilitating the formation of surface irregularities.

[0150] The content of the copolymerized polyethylene terephthalate containing isophthalic acid as a copolymer component is not particularly limited, but is preferably 10% by mass to 20% by mass based on the total mass constituting the surface layer.

[0151] From the viewpoint of reducing pores, the thickness of the surface layer is preferably 0.5 μm to 2.5 μm, more preferably 0.6 μm to 2.0 μm.

[0152] From the viewpoint of reducing pores, the thickness of the temporary support (2) is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the temporary support is, for example, 5 μm or more.

[0153] (Layer Structure)

[0154] In the temporary support (2), examples of the layer structure of the polyester film composed of two layers include layer A (surface layer) / layer B (surface layer), and examples of the layer structure of the polyester film composed of three layers include layer A / layer B (intermediate layer) / layer A, and layer A / layer B (intermediate layer) / layer C (surface layer). Examples of the polyester film composed of four or more layers include films having an intermediate layer having a laminated structure.

[0155] In addition, when the above-mentioned layer A is a surface layer that does not contain particles, the B layer (surface layer), the B layer (intermediate layer) and the C layer (surface layer) can be polyester films respectively. Within the scope of not damaging the purpose of the present invention, particles can be contained, but it can also be set as a layer (polyester film) that does not contain particles in the same way as the A layer. When the above-mentioned layer B (surface layer), the B layer (intermediate layer) or the C layer (surface layer) is a layer containing particles, the particles contained can be organic particles or inorganic particles. Examples of organic particles include particles of polyimide resins, olefins or modified olefin resins, cross-linked polystyrene resins, silicone resins, etc. Examples of inorganic particles include particles of silicon oxide, calcium carbonate, agglomerated aluminum oxide, aluminum silicate, mica, clay, talc, barium sulfate, etc.

[0156] The particles are preferably those whose surfaces have been modified with a surfactant or the like to improve their compatibility with the polyester resin. Furthermore, particles having a nearly spherical shape and a small difference in refractive index with the polyester resin are preferred. Examples include colloidal silica and organic particles, with silicone resin particles and cross-linked polystyrene resin particles being particularly preferred. Cross-linked polystyrene resin particles composed of styrene-divinylbenzene copolymers prepared by emulsion polymerization preferably have a nearly spherical shape and a uniform particle size distribution, enabling uniform protrusion formation.

[0157] The preferred form of the temporary support (2) is as follows: a polyester film consisting of three or more layers, the two surface layers do not contain particles and contain a polyester resin with an alicyclic structure, the thickness is 0.5 μm to 2.5 μm, and the arithmetic mean roughness Ra of the first surface is 1 nm to 50 nm or less.

[0158] Next, a method for manufacturing the temporary support body (2) will be described.

[0159] The polyester film composed of two or more layers as a temporary support (2) can be manufactured using a melt film-forming method based on a coextrusion method. In the case of obtaining a layer (polyester film) containing particles, for example, there is a method of dispersing the particles in ethylene glycol as a diol component to prepare a slurry, for example, after high-precision filtration of coarse particles, adding the ethylene glycol slurry in any grade before the completion of polyester polymerization. Here, when adding particles, for example, the hydrosol or alcohol sol obtained during the synthesis of the particles can be added directly without drying. In addition, a method of containing particles in the polyester film can be used in which the aqueous slurry of the particles is mixed with polyester particles and then supplied to a vent-type twin-screw kneading extruder.

[0160] Particles containing particles and particles not containing particles prepared for each layer are used. After mixing the particles containing particles and particles not containing particles as needed, they are supplied to a known melt lamination extruder. As the extruder, a single-axis or double-axis extruder can be used. In addition, in order to omit the drying process of the particles, a vent-type extruder provided with a vacuum line in the extruder can also be used. In addition, in the formation of the B layer with the largest extrusion volume, a so-called tandem extruder can also be used, in which each extruder shares the function of melting the particles and the function of maintaining the molten particles at a constant temperature.

[0161] The melt extruded by the extruder is filtered through a filter. The filter can be, for example, a high-precision filter that collects more than 95% of impurities with a diameter of 5 μm or more. Then, it is extruded into a sheet from a slit-shaped slot die, and an unstretched film is produced after cooling and solidification on a casting roller. That is, multiple extruders, multi-layer manifolds or hinge blocks (for example, hinge blocks with rectangular confluences) are stacked, and a thin sheet is extruded from the die, and cooled on a casting roller to produce an unstretched film. In this case, it is preferred to provide a static mixer or a gear pump in the flow path of the melt.

[0162] The temporary support (2) is preferably a biaxially stretched film.

[0163] The stretching method may be simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential stretching, the stretching temperature during the initial longitudinal stretching is preferably 90°C to 130°C, more preferably 100°C to 125°C, from the perspective of suppressing film breakage and thermal damage. Furthermore, from the perspective of preventing uneven stretching and scratches, stretching is preferably performed in two or more stages.

[0164] From the perspective of suppressing uneven stretching and preventing film breakage, the stretch ratio is preferably 3 to 4.5 times (preferably 3.5 to 4.3 times) in the longitudinal direction and 3.2 to 5 times (preferably 4.0 to 4.6 times) in the width direction. After stretching, from the perspective of obtaining specific requirements such as the desired thermal shrinkage rate, heat setting is preferably performed at 200°C to 230°C (preferably 210°C to 230°C) for 0.5 to 20 seconds (preferably 1 to 15 seconds). In addition, after heat setting, it is preferably subjected to a relaxation treatment of 0.1% to 7.0% in the longitudinal and / or width directions.

[0165] Hereinafter, unless otherwise specified, both the temporary support (1) and the temporary support (2) will be described simply as "temporary support".

[0166] Photosensitive resin layer

[0167] The photosensitive transfer material of the present invention comprises a photosensitive resin layer. The photosensitive resin layer is preferably a negative-working photosensitive resin layer, wherein the solubility of the exposed portion in a developer is reduced by exposure, and the unexposed portion is removed by development. However, the photosensitive resin layer is not limited to a negative-working photosensitive resin layer. The photosensitive resin layer may be a positive-working photosensitive resin layer, wherein the solubility of the exposed portion in a developer is increased by exposure, and the exposed portion is removed by development.

[0168] The photosensitive resin layer preferably contains polymer A, polymerizable compound B, and a photopolymerization initiator. The photosensitive resin layer preferably contains 10% to 90% by mass of polymer A, 5% to 70% by mass of polymerizable compound B, and 0.01% to 20% by mass of photopolymerization initiator, based on the total solids content of the photosensitive resin layer. The components of the photosensitive resin layer are described below.

[0169] (Polymer A)

[0170] As polymer A, for example, acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide, polyester, polyamide resin, epoxy resin, polyacetal, polyhydroxystyrene, polyimide resin, polybenzoxazole, polysiloxane, polyethyleneimine, polyallylamine and polyalkylene glycol can be mentioned.Polymer A is preferably an alkali-soluble polymer compound.Alkali-soluble polymer compounds include polymer compounds that are easily soluble in alkaline substances.In the present invention, "alkali solubility" refers to the property that the solubility in an aqueous solution (100g) of 1% by mass of sodium carbonate at 22°C is 0.1g or more.

[0171] From the perspective of achieving better resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the acid value of polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and particularly preferably less than 190 mgKOH / g. The lower limit of the acid value of polymer A is not limited. From the perspective of better developability, the acid value of 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. The acid value of polymer A can be adjusted by utilizing the type of structural units constituting polymer A and the content of structural units containing acid groups.

[0172] In the present invention, "acid value" refers to the mass (mg) of potassium hydroxide required to neutralize 1 g of a sample. The unit of acid value is mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

[0173] The weight average molecular weight of polymer A is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably set to 500,000 or less. The weight average molecular weight of polymer A is more preferably 100,000 or less, further preferably 80,000 or less, and particularly preferably 70,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed agglomerates and the properties of the unexposed film (for example, edge melting and chipping properties), the weight average molecular weight is preferably set to 5,000 or more. The weight average molecular weight of polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. Edge melting refers to the degree to which the photosensitive resin layer in the photosensitive transfer material wound into a roll easily protrudes from the end surface of the roll. Chipping refers to the degree to which the chips easily fly when the unexposed film is cut with a dicing machine. For example, if the generated chips are transferred to the mask used during exposure, it will become a cause of defective products. 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. In the present invention, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight). In the present invention, the weight average molecular weight and the number average molecular weight are values measured using gel permeation chromatography.

[0174] The glass transition temperature (Tg) of polymer A is preferably 30°C or higher and 135°C or lower. When the Tg of polymer A is 135°C or lower, deterioration of line width or resolution when the focus position is shifted during exposure can be suppressed. The Tg of polymer A is more preferably 130°C or lower, further preferably 120°C or lower, and particularly preferably 110°C or lower. When the Tg of polymer A is 30°C or higher, edge melting resistance can be improved. The Tg of 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.

[0175] From the viewpoint of suppressing the deterioration of line width or resolution when the focus position is shifted during exposure, polymer A preferably contains a structural unit having an aromatic hydrocarbon group. Polymer A may contain one or more structural units having an aromatic hydrocarbon group. As aromatic hydrocarbon groups, for example, substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups can be cited. The content of structural units having aromatic hydrocarbon groups in polymer A is preferably 20% by mass or more relative to the total mass of polymer A, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. There is no upper limit on the content of structural units having aromatic hydrocarbon groups in polymer A. The content of structural units having aromatic hydrocarbon groups in polymer A is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, when the photosensitive resin layer contains a plurality of polymers A, the content of structural units having aromatic hydrocarbon groups is calculated as a weight average.

[0176] The structural unit with an aromatic hydrocarbon group is introduced using a monomer with an aromatic hydrocarbon group. As the monomer with an aromatic hydrocarbon group, for example, a monomer with an aralkyl group, styrene and a styrene derivative capable of polymerization (for example, methyl styrene, vinyl toluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer) can be enumerated. Among the above, preferably a monomer with an aralkyl group or styrene. When the structural unit with an aromatic hydrocarbon group in polymer A is a structural unit derived from styrene, the content of the structural unit derived from styrene is preferably 20% by mass to 80% by mass relative to the gross mass of polymer A, more preferably 25% by mass to 70% by mass, and particularly preferably 30% by mass to 60% by mass.

[0177] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl (excluding benzyl) and substituted or unsubstituted benzyl. Preferably, it is a substituted or unsubstituted benzyl.

[0178] As a monomer which has a phenylalkyl group, phenylethyl (meth)acrylate is mentioned, for example.

[0179] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group (e.g., benzyl (meth)acrylate and benzyl (meth)acrylate chloride, etc.) and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol). Of the above, benzyl (meth)acrylate is preferred. When the structural unit having an aromatic hydrocarbon group in polymer A is a structural unit derived from benzyl (meth)acrylate, the content of the structural unit derived from benzyl (meth)acrylate is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, further preferably 70% to 90% by mass, and particularly preferably 75% to 90% by mass, relative to the total mass of polymer A.

[0180] The polymer A containing a structural unit having an aromatic hydrocarbon group preferably contains a structural unit having an aromatic hydrocarbon group and at least one selected from a structural unit derived from the first monomer and a structural unit derived from the second monomer.

[0181] The polymer A not containing a structural unit having an aromatic hydrocarbon group preferably contains a structural unit derived from the first monomer, and more preferably contains a structural unit derived from the first monomer and a structural unit derived from the second monomer.

[0182] The first monomer is a monomer having a carboxyl group in the molecule. As the first monomer, for example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride and maleic acid half ester can be mentioned. Among the above, (meth) acrylic acid is preferred. Polymer A can contain one or more structural units derived from the first monomer alone. The content of the first monomer in polymer A is preferably 5% to 50% by mass relative to the total mass of polymer A, more preferably 10% to 45% by mass, and particularly preferably 15% to 35% by mass.

[0183] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates (e.g., 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, 2-ethylhexyl (meth)acrylate), esters of vinyl alcohol (e.g., vinyl acetate), and (meth)acrylonitrile. Among the above, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred. The content of the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and particularly preferably 20% to 45% by mass, relative to the total mass of polymer A.

[0184] From the perspective of suppressing deterioration in line width and resolution due to focus shift during exposure, the polymer A preferably contains at least one selected from a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene. Preferred specific examples of the polymer A include copolymers of methacrylic acid, benzyl methacrylate, and styrene, and copolymers of methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene.

[0185] In one embodiment, polymer A is preferably a polymer containing 25% to 40% by mass of structural units having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from the first monomer, and 30% to 45% by mass of structural units derived from the second monomer. Furthermore, in another embodiment, polymer A is preferably a polymer containing 70% to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group and 10% to 25% by mass of structural units derived from the first monomer.

[0186] Polymer A may have a branched structure or an alicyclic structure in its side chain. For example, by using a monomer containing a group having a branched structure in its side chain or a monomer containing a group having an alicyclic structure in its side chain, a branched structure or an alicyclic structure can be introduced into the side chain of polymer (A). The alicyclic structure in the side chain of polymer A may be monocyclic or polycyclic.

[0187] Also, the polymer A may have a linear structure in the side chain.

[0188] Examples of monomers 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, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate are more preferred.

[0189] Specific examples of monomers containing a group having an alicyclic structure in a side chain include monomers containing a monocyclic aliphatic hydrocarbon group and monomers containing a polycyclic aliphatic hydrocarbon group. Furthermore, specific examples of monomers containing a group having an alicyclic structure in a side chain include (meth)acrylates containing an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Examples of the monomer containing a group having an alicyclic structure in the side chain include (bicyclo[2.2.1]heptyl-2-(meth)acrylate, 1-adamantyl(meth)acrylate, 2-adamantyl(meth)acrylate, 3-methyl-1-adamantyl(meth)acrylate, 3,5-dimethyl-1-adamantyl(meth)acrylate, 3-ethyladamantyl(meth)acrylate, 3-methyl-5-ethyl-1-adamantyl(meth)acrylate, 3,5,8-triethyl-1-adamantyl(meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl(meth)acrylate, 2-methyl-2-adamantyl(meth)acrylate, 2-ethyl(meth)acrylate. 1-Heptyl (meth)acrylate, 3-hydroxy-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methanoindene-5-yl (meth)acrylate, octahydro-4,7-methanoindene-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among the above, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthol (meth)acrylate, and tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, and tricyclodecane (meth)acrylate are more preferred.

[0190] The photosensitive resin layer may contain one or more polymers A. When using two or more polymers A, it is preferred to use two polymers A containing structural units having aromatic hydrocarbon groups, or to use a mixture of a polymer A containing structural units having aromatic hydrocarbon groups and a polymer A not containing structural units having aromatic hydrocarbon groups. In the latter case, the proportion of the polymer A containing structural units having aromatic hydrocarbon groups used relative to the total mass of the polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0191] The content of polymer A in the photosensitive resin layer is preferably 10% to 90% by mass, more preferably 30% to 70% by mass, and particularly preferably 40% to 60% by mass, relative to the total mass of the photosensitive resin layer. From the perspective of controlling the development time, the content of polymer A is preferably 90% by mass or less. From the perspective of improving edge melting resistance, the content of polymer A is preferably 10% by mass or more.

[0192] The synthesis of polymer A is preferably carried out as follows: an appropriate amount of a free radical polymerization initiator (e.g., benzoyl peroxide and azoisobutyronitrile) is added to a solution of monomers diluted with a solvent (e.g., acetone, methyl ethyl ketone, and isopropyl alcohol), followed by heating and stirring. Synthesis may also be performed while a portion of the mixture is dropwise added to the reaction solution. Alternatively, after the reaction is complete, a solvent is further added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as the synthesis apparatus.

[0193] (Polymerizable compound B)

[0194] The polymerizable compound B is a compound having a polymerizable group. In the present invention, 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.

[0195] The polymerizable group is not limited as long as it is a group involved in the polymerization reaction, and examples thereof include ethylenically unsaturated groups (e.g., vinyl, acryloyl, methacryloyl, styryl, and maleimide) and cationic polymerizable groups (e.g., epoxy and oxetane). The polymerizable group is preferably an ethylenically unsaturated group, more preferably an acryloyl or methacryloyl group.

[0196] In terms of achieving better photosensitivity in the photosensitive resin layer, the polymerizable compound B is preferably a compound having at least one ethylenically unsaturated group (i.e., an ethylenically unsaturated compound), and more preferably a compound having two or more ethylenically unsaturated groups per molecule (i.e., a multifunctional ethylenically unsaturated compound). Furthermore, in terms of achieving better resolution and peelability, 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 particularly preferably 2 or less. The ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group.

[0197] In terms of the better balance of the photosensitivity, resolution and stripping properties of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound having 2 or 3 ethylenically unsaturated groups in one molecule (i.e., a difunctional or trifunctional ethylenically unsaturated compound), more preferably a compound having 2 ethylenically unsaturated groups in one molecule (i.e., a difunctional ethylenically unsaturated compound). From the viewpoint of excellent stripping properties, the content of the difunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60% by mass or more relative to the total mass of the polymerizable compound B, more preferably more than 70% by mass, and particularly preferably more than 90% by mass. The upper limit of the content of the difunctional ethylenically unsaturated compound is not limited. The content of the difunctional ethylenically unsaturated compound in the photosensitive resin layer can be 100% by mass relative to the total mass of the polymerizable compound B. That is, all of the polymerizable compound B contained in the photosensitive resin layer can be difunctional ethylenically unsaturated compounds.

[0198] The photosensitive resin layer preferably contains an aromatic ring and a polymerizable compound B1 having two ethylenically unsaturated groups. The polymerizable compound B1 is a compound having two ethylenically unsaturated groups in one molecule (ie, a bifunctional ethylenically unsaturated compound) in the above-mentioned polymerizable compound B.

[0199] Examples of the aromatic ring include aromatic hydrocarbon rings (e.g., benzene rings, naphthalene rings, and anthracene rings), aromatic heterocyclic rings (e.g., thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings), and condensed rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent. The polymerizable compound B1 may have two or more aromatic rings.

[0200] From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the polymerizable compound B1 preferably has a bisphenol structure. As the bisphenol structure, for example, 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) can be cited. The bisphenol structure is preferably a bisphenol A structure. As the polymerizable compound B1 having a bisphenol structure, for example, a compound having a bisphenol structure and two ethylenically unsaturated groups (preferably (meth)acryloyl groups) bonded to both ends of the above-mentioned bisphenol structure can be cited. Each ethylenically unsaturated group may be directly bonded to the end of the bisphenol structure, or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not limited. The number of alkyleneoxy groups added to the bisphenol structure is preferably 4 to 16 per molecule, and more preferably 6 to 14. Polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162. The contents of the aforementioned publication are incorporated herein by reference.

[0201] The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane. Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodeethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxypentadecethoxy)phenyl)propane (BPE-1300, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ESTER A-BPE-10, Shin-Nakamura Chemical Co., Ltd.).

[0202] Examples of the polymerizable compound B1 include compounds represented by the following formula (I).

[0203] [Chemical Formula 1]

[0204]

[0205] In formula (I), R1 and R2 each independently represent a hydrogen atom or a methyl group, A represents C2H4, B represents C3H6, n1 and n3 each independently represent an integer of 1 to 39, n1+n3 is an integer of 2 to 40, n2 and n4 each independently represent an integer of 0 to 29, n2+n4 is an integer of 0 to 30, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. In the case of a block, -(AO)- may be a bisphenyl side, and -(BO)- may be a bisphenyl side. n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12. 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.

[0206] The photosensitive resin layer may contain one or two or more polymerizable compounds B1.

[0207] From the perspective of achieving better resolution, the content of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but from the perspective of transferability and edge melting resistance, it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0208] From the perspective of achieving better resolution, the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B in the photosensitive resin layer is preferably 40% by mass or greater, more preferably 50% by mass or greater, even more preferably 55% by mass or greater, and particularly preferably 60% by mass or greater. There is no upper limit for the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B in the photosensitive resin layer. From the perspective of releasability, the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B in the photosensitive resin layer is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0209] The photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1 described above. Examples of the polymerizable compound B other than the polymerizable compound B1 include monofunctional ethylenically unsaturated compounds (i.e., compounds having one ethylenically unsaturated group in one molecule), bifunctional ethylenically unsaturated compounds having no aromatic ring (i.e., compounds having no aromatic ring and having two ethylenically unsaturated groups in one molecule), and trifunctional or higher ethylenically unsaturated compounds (i.e., compounds having three or more ethylenically unsaturated groups in one molecule).

[0210] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl butanediol, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0211] 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.

[0212] Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0213] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0214] Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available urethane di(meth)acrylates include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Co., Ltd.).

[0215] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and alkylene oxide-modified compounds thereof. Here, "(tri / tetra / penta / hexa) (meth)acrylate" encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra) (meth)acrylate" encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0216] Examples of the alkylene oxide-modified trifunctional or higher ethylenically unsaturated compound include caprolactone-modified (meth)acrylate compounds (e.g., KAYARAD DPCA-20 (Nippon Kayaku Co., Ltd.) and A-9300-1CL (Shin-Nakamura Chemical Co., Ltd.)), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 (Nippon Kayaku Co., Ltd.), ATM-35E (Shin-Nakamura Chemical Co., Ltd.), A-9300 (Shin-Nakamura Chemical Co., Ltd.), and EBECRYL 135 (DAICEL-ALLNEX LTD.)), ethoxylated glyceryl triacrylate (e.g., A-GLY-9E (Shin-Nakamura Chemical Co., Ltd.)), ARONIX TO-2349 (TOAGOSEI Co., Ltd.), ARONIX M-520 (Toagosei Co., Ltd.), and ARONIX M-510 (Toagosei Co., Ltd.).

[0217] From the perspective of resistance to processing solutions such as development, the photosensitive resin layer preferably contains the polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. The mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound (total mass of the polymerizable compound B1:total mass of the trifunctional or higher ethylenically unsaturated compound) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and particularly preferably 1.5:1 to 3:1.

[0218] As the polymerizable compound B other than the polymerizable compound B1, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

[0219] The photosensitive resin layer may contain one or more polymerizable compounds B.

[0220] The content of the polymerizable compound B in the photosensitive resin layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.

[0221] The molecular weight of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200. The molecular weight of the polymerizable compound B having a molecular weight distribution is represented by a weight average molecular weight (Mw).

[0222] From the perspectives of resolution and linearity, the ratio Mm / Mb of the content Mm of the ethylenically unsaturated compound in the photosensitive resin layer to the content Mb of the polymer A is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. From the perspectives of curability and resolution, the ethylenically unsaturated compound in the photosensitive resin layer preferably comprises a (meth)acrylic acid compound, more preferably a (meth)acrylate compound. From the perspectives of curability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive resin layer more preferably comprises a (meth)acrylic acid compound, and the content of the acrylic acid compound is 60% by mass or less relative to the total mass of the (meth)acrylic acid compound contained in the photosensitive resin layer.

[0223] (Photopolymerization initiator)

[0224] The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving active light (eg, ultraviolet light, visible light, and X-rays).

[0225] The type of photopolymerization initiator is not limited. The photopolymerization initiator involved in the present invention includes known photopolymerization initiators. Examples of the photopolymerization initiator include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0226] 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.

[0227] From the perspectives of photosensitivity, visibility of the exposed portion, visibility of the non-exposed portion, 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. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different. Examples of derivatives of the 2,4,5-triarylimidazole dimer 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.

[0228] As the photoradical polymerization initiator, for example, 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.

[0229] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, and anisil (p,p′-dimethoxybenzyl).

[0230] Examples of commercially available photoradical polymerization initiators include TAZ-110 (trade name: Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (trade name: Midori Kagaku Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE OXE01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE02, BASF), IRGACURE OXE03 (BASF), and IRGACURE OXE04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), BV), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV), and an oxime ester-based photopolymerization initiator (trade name: Lunar 6, DKSH MANAGEMENT LTD.Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (also known as 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, trade name: B-CIM, Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetoxime) (trade name: TR-PBG-326, CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.).

[0231] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid in response to active light. Preferred photocationic polymerization initiators are compounds that generate an acid in response to active light having a wavelength of 300 nm or longer (preferably a wavelength of 300 nm to 450 nm). Furthermore, photocationic polymerization initiators that are not directly sensitive to active light having a wavelength of 300 nm or longer can be preferably used in combination with a sensitizer, as long as they are compounds that generate an acid in response to active light having a wavelength of 300 nm or longer when used in combination with a sensitizer.

[0232] The photocationic polymerization initiator preferably generates an acid having a pKa of 4 or less, more preferably generates an acid having a pKa of 3 or less, and particularly preferably generates an acid having a pKa of 2 or less. The lower limit of the pKa is not particularly limited. The pKa of the acid generated by the photocationic polymerization initiator is preferably not less than -10.0.

[0233] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds (e.g., diaryliodonium salts and triarylsulfonium salts) and quaternary ammonium salts. Examples of ionic photocationic polymerization initiators include those described in paragraphs 0114 to 0133 of Japanese Patent Application Laid-Open No. 2014-85643. Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-221494. Furthermore, as the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 can be used.

[0234] The photosensitive resin layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from 2,4,5-triarylimidazole dimers and derivatives thereof.

[0235] The photosensitive resin layer may contain one or two or more photopolymerization initiators.

[0236] The content of the photopolymerization initiator in the photosensitive resin layer is preferably 0.1% by mass or greater, more preferably 0.5% by mass or greater, and particularly preferably 1.0% by mass or greater, relative to the total mass of the photosensitive resin layer. There is no upper limit to the content of the photopolymerization initiator. The content of the photopolymerization initiator in the photosensitive resin layer is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

[0237] (pigment)

[0238] From the perspectives of visibility of the exposed portion, visibility of the non-exposed portion, visibility of the pattern after development, and resolution, the photosensitive resin layer preferably contains a pigment (hereinafter sometimes referred to as "pigment N") having a maximum absorption wavelength of 450 nm or longer within the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes in response to acid, base, or free radicals. The inclusion of pigment N in the photosensitive resin layer improves adhesion to layers adjacent to the photosensitive resin layer (e.g., a temporary support) and improves resolution.

[0239] In the present invention, the term "the maximum absorption wavelength changes due to acid, alkali or free radicals" used with respect to a pigment includes (1) a method in which a pigment in a coloring state is decolorized by an acid, alkali or free radical, (2) a method in which a pigment in a decolorized state is colorized by an acid, alkali or free radical, and (3) a method in which a pigment in a coloring state changes to a coloring state of another hue. For example, the pigment N may be a compound that changes from a decolorized state by exposure to light and develops color, or a compound that changes from a coloring state by exposure to light and decolorizes. The pigment N may be a pigment that changes in coloring or decoloring state by the action of an acid, alkali or free radical generated in the photosensitive resin layer due to exposure. The pigment N may be a pigment that changes in coloring or decoloring state by the action of an acid, alkali or free radicals in the photosensitive resin layer (e.g., pH). Furthermore, the pigment N may be a pigment that changes in coloring or decoloring state by the action of an acid, alkali or free radicals without exposure.

[0240] 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.

[0241] From the perspective of visibility of the exposed area, visibility of the non-exposed area, and resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a dye whose maximum absorption wavelength changes due to free radicals. From the perspective of visibility of the exposed area, visibility of the non-exposed area, and resolution, the photosensitive resin layer preferably contains, as the dye N, a dye whose maximum absorption wavelength changes due to free radicals and a photoradical polymerization initiator.

[0242] From the viewpoints of visibility of the exposed area, visibility of the non-exposed area, and pattern visibility and resolution after development, the dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals.

[0243] As the coloring mechanism of the dye N in the present invention, for example, a method in which a radical-reactive dye, an acid-reactive dye or a base-reactive dye (for example, a colorless dye) develops color by free radicals, acids or bases generated from a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator contained in the photosensitive resin layer.

[0244] From the perspective of visibility of the exposed portion and the non-exposed portion, the maximum absorption wavelength of the pigment N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or greater, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm. The number of maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development may be one or two or more. When the number of maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development is two or more, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or greater.

[0245] The maximum absorption wavelength of Pigment N is determined by the following method. Under atmospheric conditions, the transmission spectrum of a solution containing Pigment N (liquid temperature: 25°C) is measured in the wavelength range of 400 nm to 780 nm using a spectrophotometer (e.g., UV3100, Shimadzu Corporation). The wavelength at which the light intensity reaches its minimum is detected. The wavelength at which the light intensity reaches its minimum is used as the maximum absorption wavelength.

[0246] Examples of dyes that develop or fade color by exposure include colorless dyes.

[0247] Examples of the dye that is decolorized by exposure include leuco dyes, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

[0248] From the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion, the dye N is preferably a colorless dye.

[0249] Examples of colorless dyes include colorless dyes having a triarylmethane skeleton (triarylmethane-based dyes), colorless dyes having a spiropyran skeleton (spiropyran-based dyes), colorless dyes having a fluoran skeleton (fluoran-based dyes), colorless dyes having a diarylmethane skeleton (diarylmethane-based dyes), colorless dyes having a rhodamine lactam skeleton (rhodamine lactam-based dyes), colorless dyes having an indolylphthalide skeleton (indolylphthalide-based dyes), and colorless dyes having a leucochromamine skeleton (leucochromamine-based dyes). Among the above, triarylmethane-based dyes or fluoran-based dyes are preferred, and colorless dyes having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferred.

[0250] From the viewpoint of visibility of the exposed portion and the non-exposed portion, the colorless pigment preferably has a lactone ring, a sultine ring, or a sultone ring. The lactone ring, the sultine ring, or the sultone ring in the colorless pigment reacts with the free radical generated by the photoradical polymerization initiator or the acid generated by the photocationic polymerization initiator, thereby changing the colorless pigment into a closed-loop state and decolorizing it or changing the colorless pigment into an open-loop state and developing it. The colorless pigment is preferably a compound having a lactone ring, a sultine ring, or a sultone ring and developing the color through free radical or acid ring opening, more preferably a compound having a lactone ring and developing the color through free radical or acid ring opening.

[0251] Specific examples of the colorless pigment include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (Novartis International AG), crystal violet lactone, malachite green lactone, benzoyl leuco-methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-formyldiamino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran. Fluoran, 3-(N,N-diethylamino)-6-methyl-7-phenylfluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-phenylfluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-phenylfluoran, 3-hydropyridyl-6-methyl-7-anilinofluoran, 3-pyrrolidinol-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butylamino)-6-methyl-7-phenylfluoran, phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthan-3-one.

[0252] Examples of the pigment N include dyes. Examples of the dye include brilliant green, ethyl violet, methyl green, crystal violet, Viscin red, methyl violet 2B, quinolizine red, rose bengal, formyl yellow, thimorph, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurine 4B, α-naphthyl red, naphthalene blue 2B, naphthalene blue A, methyl violet, malachite green, hydroquinone, Victoria Pure Blue-alkylnaphthalenesulfonate, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue #603 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Pink #312 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red 5B (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Scarlet #308 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red OG (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red RR (ORIENT CHEMICAL INDUSTRIES CO., LTD), Oil Green #502 (ORIENT CHEMICAL INDUSTRIES CO., LTD), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol violet, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, aureolamine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0253] The pigment N is preferably leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-alkylnaphthalene sulfonate.

[0254] The photosensitive resin layer may contain one or more dyes N.

[0255] From the viewpoint of visibility of the exposed portion, visibility of the non-exposed portion, pattern visibility after development and resolution, the content of pigment N is preferably 0.1% by mass or more relative to the total mass of the photosensitive resin layer, 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. The content of pigment N refers to the content of pigment N when all the pigments N contained in the photosensitive resin layer are in a color-developed state. Below, the quantitative method of the pigment is described by taking the pigment developed by free radicals as an example. A solution in which a pigment (0.001g) is dissolved in methyl ethyl ketone (100mL) and a solution in which 0.01g is dissolved in methyl ethyl ketone (100mL) are prepared. A photoradical polymerization initiator (Irgacure OXE01, BASF JAPAN LTD.) is added to each solution and then irradiated with 365nm light to generate free radicals, so that all pigments become a color-developed state. The absorbance of each solution at 25°C was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions to create a calibration curve. Next, the absorbance of a solution in which the pigment was fully colored was measured using the same method as above, except that the photosensitive resin layer (3 g) was dissolved in methyl ethyl ketone instead of the pigment. The amount of pigment contained in the photosensitive resin layer was calculated from the absorbance of the solution containing the photosensitive resin layer based on the calibration curve.

[0256] (Surfactant)

[0257] From the perspective of thickness uniformity, the photosensitive resin layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. The surfactant is preferably a nonionic surfactant. The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant.

[0258] Examples of commercially available fluorine-based surfactants include Megaface (e.g., F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-564, F-565, F-566, F-567, F-568, F-569, F-570, F-571, F-572, F-573, F-574, F-575, F-576, F-577, F-578, F-579, F-580, F-581, F-582, F-583, F-584, F-585, F-586, F-587, F-588, F-589, F-590, F-591, F-592, F-593, F-594, F-595, F-596, F-597, F-598, F-599, F-600, F-601, F-602, F-603, F-604, F-605, F-606, F-607, F-608, F-609, F-609, F-601, 1. F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-578-2, MFS-579, MFS-586, MFS-587, MFS-6 28. MFS-631, MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K and DS-21, DIC Corporation), Fluorad (e.g., FC430, FC431, FC171, Sumitomo 3M Limited), Surflon (e.g., S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40, AGC Inc.), PolyFox (e.g., PF636, PF656, PF6320, and PF6520, PF7002, OMNOVA Solutions Inc.), Ftergent (e.g., 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 and 683, Neos Corporation), U-120E (Uni-chem Co., Ltd.).

[0259] As fluorine-based surfactants, acrylic compounds having a molecular structure containing a functional group containing a fluorine atom and in which the functional group containing a fluorine atom is partially cleaved when heat is applied, thereby volatilizing the fluorine atom can also be used. Examples of such fluorine-based surfactants include the Megaface DS series from DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industry News (February 23, 2016), for example, Megaface DS-21).

[0260] As the fluorine-based surfactant, a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound can also be used.

[0261] As the fluorine-based surfactant, a block polymer can also be used.

[0262] As the fluorine-based surfactant, a fluorine-containing polymer compound comprising a structural unit derived from a (meth)acrylate compound containing a fluorine atom and a structural unit derived from a (meth)acrylate compound containing two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy or propyleneoxy groups) can also be used.

[0263] As the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in the side chain can also be used. As commercially available products of the above-mentioned fluorine-based surfactant, for example, Megaface (for example, RS-101, RS-102, RS-718K and RS-72-K, DIC CORPORATION) can be cited.

[0264] From the viewpoint of improving environmental suitability, the fluorine-based surfactant is preferably a surfactant derived from an alternative material of a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS).

[0265] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates (eg, glycerin ethoxylate) and propoxylates (eg, glycerin propoxylate) thereof. Examples of the nonionic surfactants include 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 (e.g., L10, L31, L61, L62, 10R5, 17R2, and 25R2, HYDROPALAT WE 3323, BASF), Tetronic (e.g., 304, 701, 704, 901, 904, and 150R1, BASF), Solsperse 20000 (The Lubrizol Corporation), NCW-101 (FUJIFILM Wako Pure Chemical Corporation), NCW-1001 (FUJIFILM Wako Pure Chemical Corporation), NCW-1002 (FUJIFILM Wako Pure Chemical Corporation), PIONIN (e.g., D-1105, D-6112, D-6112-W, and D-6315, Takemoto Oil & Fat Co., Ltd.), OLFINE E1010 (Nissin Chemical Co., Ltd.), and Surfynol (e.g., 104, 400, and 440, Nissin Chemical Co., Ltd.).

[0266] Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having an organic group introduced into a side chain or a terminal.

[0267] Examples of the surfactant include DOWSIL 8032 ADDITIVE, Toray SILICONE DC3PA, Toray SILICONE SH7PA, Toray SILICONE DC11PA, Toray SILICONE SH21PA, Toray SILICONE SH28PA, Toray SILICONE SH29PA, Toray SILICONE SH30PA, and Toray SILICONE SH8400 (Dow Corning Toray Co., Ltd.).

[0268] Examples of the surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation).

[0269] Examples of the surfactant include 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 (Shin-Etsu Chemical Co., Ltd.).

[0270] Examples of the surfactant include F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (Momentive Performance Materials Inc.).

[0271] Examples of the surfactant include BYK307, BYK323, and BYK330 (BYK Co., Ltd.).

[0272] Examples of the surfactant include BYK300, BYK306, BYK310, BYK320, BYK325, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK Co., Ltd.).

[0273] The photosensitive resin layer may contain one or more surfactants.

[0274] The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, relative to the total mass of the photosensitive resin layer.

[0275] (additive)

[0276] In addition to the above-mentioned components, the photosensitive resin layer may contain known additives as needed. Examples of additives include thermally crosslinkable compounds, free radical inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, plasticizers, heterocyclic compounds, and solvents. The photosensitive resin layer may contain one or more additives.

[0277] From the perspective 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. In addition, in this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.

[0278] Examples of the heat-crosslinkable compound include methylol compounds and blocked isocyanate compounds, of which blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.

[0279] The blocked isocyanate compound reacts with hydroxyl groups and carboxyl groups. Therefore, for example, when the polymer A 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 the film formed by curing the photosensitive resin layer when used as a protective film.

[0280] 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.

[0281] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C.

[0282] 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."

[0283] 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.

[0284] Examples of the end-capping agent having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (such as dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, which have a structure represented by -C(=N-OH)- in the molecule).

[0285] Among these, as a 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.

[0286] For example, from the viewpoints of improving the brittleness of the film and enhancing the adhesion to the transfer target, the blocked isocyanate compound preferably has an isocyanurate structure.

[0287] The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating hexamethylene diisocyanate to protect it.

[0288] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred from the viewpoint that the dissociation temperature can be more easily set within a preferred range and development residue can be easily reduced compared to compounds not having an oxime structure.

[0289] The blocked isocyanate compound may have a polymerizable group.

[0290] The polymerizable group is not particularly limited, and a known polymerizable group can be used. A radical polymerizable group is preferred.

[0291] 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.

[0292] Among these, as the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is further preferred.

[0293] As the blocked isocyanate compound, a commercially available product can be used.

[0294] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0295] Furthermore, as the blocked isocyanate compound, compounds having the following structures can also be used.

[0296] [Chemical Formula 2]

[0297]

[0298] The heat-crosslinkable compound may be used alone or in combination of two or more.

[0299] When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer.

[0300] Examples of free radical inhibitors include the thermal inhibitors described in paragraph 0018 of Japanese Patent Gazette No. 4502784. Preferred free radical inhibitors include phenothiazine, phenoxazine, or 4-methoxyphenol. Examples of free radical inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine. To minimize the sensitivity of the photosensitive resin layer, nitrosophenylhydroxylamine aluminum salt is preferably used as the free radical inhibitor.

[0301] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0302] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminovinylcarboxybenzotriazole. Examples of commercially available carboxybenzotriazoles include CBT-1 (JOHOKU CHEMICAL CO., LTD.).

[0303] The total content of the radical inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass, relative to the total mass of the photosensitive resin layer. From the perspective of imparting storage stability to the photosensitive resin layer, the total content of these additives is preferably 0.01% by mass or greater. On the other hand, from the perspective of maintaining sensitivity and suppressing dye discoloration, the total content of these additives is preferably 3% by mass or less.

[0304] There is no limitation on the type of sensitizer. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0305] 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 case where the photosensitive resin layer contains a sensitizer is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0306] Examples of the plasticizer and heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0307] Examples of the solvent include the solvents described in the following section “Method for Forming a Photosensitive Resin Layer.” For example, when a photosensitive resin layer is formed using a photosensitive resin layer-forming composition containing a solvent, the solvent may remain in the photosensitive resin layer.

[0308] The photosensitive resin layer may further contain at least one selected from metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors.

[0309] Additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-85643, the contents of which are incorporated herein by reference.

[0310] (Impurities)

[0311] The photosensitive resin layer may contain impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Halide ions, sodium ions, and potassium ions are easily incorporated as impurities, so the content of halide ions, sodium ions, and potassium ions is preferably within the following ranges.

[0312] The content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and particularly preferably 2 ppm or less relative to the total mass of the photosensitive resin layer. The content of impurities in the photosensitive resin layer may be 1 ppb or more or 0.1 ppm or more relative to the total mass of the photosensitive resin layer. Methods for setting the content of impurities within the above range include selecting raw materials with a low impurity content, preventing the mixing of impurities when forming the photosensitive resin layer, and removing them by washing. Impurities are quantified by, for example, known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0313] The photosensitive resin layer preferably contains a low content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these compounds in the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and particularly preferably 4 ppm or less, relative to the total mass of the photosensitive resin layer. The content of these compounds in the photosensitive resin layer may be 10 ppb or more or 100 ppb or more relative to the total mass of the photosensitive resin layer. The content of these compounds is adjusted by the same method as that for adjusting the content of the impurities. Furthermore, the compounds are quantified by a known assay method.

[0314] From the viewpoint of improving reliability and lamination properties, the water content in the photosensitive resin layer is preferably 0.01 to 1.0 mass %, more preferably 0.05 to 0.5 mass %, relative to the total mass of the photosensitive resin layer.

[0315] (Residual monomers)

[0316] The photosensitive resin layer may contain residual monomers, for example, residual monomers corresponding to the structural units of the polymer A described above.

[0317] From the viewpoint of pattern formation and reliability, the residual monomer content is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the polymer A. The lower limit of the residual monomer content is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, relative to the total mass of the polymer A.

[0318] From the perspective of pattern formation and reliability, the content of residual monomers corresponding to the structural units of polymer A is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm or less, relative to the total mass of the photosensitive resin layer. The lower limit of the content of residual monomers corresponding to the structural units of polymer A is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, relative to the total mass of the photosensitive resin layer.

[0319] The residual monomer content of the monomers when synthesizing polymer A by polymer reaction is also preferably within the above range. For example, when synthesizing polymer A by reacting glycidyl acrylate with a carboxylic acid side chain, the glycidyl acrylate content is preferably within the above range.

[0320] The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0321] (thickness)

[0322] The thickness of the photosensitive resin layer is not limited. The thickness of the photosensitive resin layer is determined, for example, within the range of 0.1 μm to 100 μm. From the viewpoint of developability and resolution, the thickness of the photosensitive resin layer is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. In addition, the thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5 μm or less. From the viewpoint of resistance to processing liquids such as developer, the thickness of the photosensitive resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and particularly preferably 0.5 μm or more. In addition, the thickness of the photosensitive resin layer is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 5 μm. Furthermore, the thickness of the photosensitive resin layer is preferably 0.5 μm to 5 μm, and particularly preferably 0.5 μm to 4 μm. The thickness of the photosensitive resin layer is measured by a method according to the method for measuring the thickness of the temporary support.

[0323] (Transmittance)

[0324] From the perspective of achieving superior adhesion, the transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or greater, more preferably 30% or greater, and particularly preferably 50% or greater. There is no upper limit to the transmittance of the photosensitive resin layer at a wavelength of 365 nm. The transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 99.9% or less.

[0325] (Method for Forming Photosensitive Resin Layer)

[0326] The method for forming the photosensitive resin layer is not limited as long as it is a method that can form a layer containing the above-mentioned components. The photosensitive resin layer is formed, for example, by preparing a photosensitive resin layer-forming composition, applying the photosensitive resin layer-forming composition to a temporary support, and drying the applied photosensitive resin layer-forming composition.

[0327] Examples of the photosensitive resin layer-forming composition include compositions containing polymer A, polymerizable compound B, and a photopolymerization initiator. The photosensitive resin layer-forming composition preferably contains a solvent to adjust its viscosity and facilitate formation of the photosensitive resin layer.

[0328] The solvent is not limited as long as it can dissolve or disperse the components of the photosensitive resin layer. 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), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

[0329] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0330] Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0331] Examples of the solvent include 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. The contents of these publications are incorporated herein by reference.

[0332] The composition for forming a photosensitive resin layer may contain one or more solvents. The composition for forming a photosensitive resin layer preferably contains at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, more preferably contains at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one solvent selected from a ketone solvent and a cyclic ether solvent, and particularly preferably contains at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.

[0333] The content of the solvent in the photosensitive resin layer-forming composition is preferably 50 to 1,900 parts by mass, and 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.

[0334] The method for preparing the photosensitive resin layer-forming composition is not limited. The photosensitive resin layer-forming composition can be prepared, for example, by preliminarily preparing a solution of each component dissolved in a solvent and mixing the resulting solution in predetermined proportions. Prior to forming the photosensitive resin layer, the photosensitive resin layer-forming composition is preferably filtered using a filter with a pore size of 0.2 μm to 30 μm.

[0335] Examples of a method for applying the photosensitive resin layer-forming composition include slit coating, spin coating, curtain coating, and inkjet coating.

[0336] Thermoplastic resin layer

[0337] The photosensitive transfer material involved in the present invention may contain a thermoplastic resin layer. When the photosensitive transfer material includes a thermoplastic resin layer, the followability of the photosensitive transfer material to the substrate is improved during the bonding of the photosensitive transfer material and the substrate, and the mixing of bubbles between the photosensitive transfer material and the substrate is suppressed. In addition, when the photosensitive transfer material includes a thermoplastic resin layer, the adhesion between the layers is improved. The photosensitive transfer material involved in the present invention preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Regarding the thermoplastic resin layer, it is described, for example, in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-85643. The contents of the above-mentioned publication are incorporated into this specification by reference.

[0338] (Alkali-soluble resin)

[0339] The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin. Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0340] From the perspective of developability and adhesion to adjacent layers, the alkali-soluble resin is preferably an acrylic resin. Here, the acrylic resin refers to a resin containing at least one selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylates, and structural units derived from (meth)acrylic acid amides. From the perspective of developability and adhesion to adjacent layers, the alkali-soluble resin is particularly preferably an acrylic resin containing structural units derived from (meth)acrylic acid.

[0341] The total content of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylate, and the structural units derived from (meth)acrylic acid amide is preferably 50% by mass or more relative to the total mass of the acrylic resin. The total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylate is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, relative to the total mass of the acrylic resin.

[0342] The alkali-soluble resin preferably contains an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group. The acid group is preferably a carboxyl group.

[0343] From the perspective of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or greater, more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or greater. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

[0344] Examples of the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more include the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraph 0025 of JP-A-2011-95716, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs 0033 to 0052 of JP-A-2010-237589, and the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the binder polymer described in paragraphs 0053 to 0068 of JP-A-2016-224162.

[0345] The content of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

[0346] The alkali-soluble resin may contain a reactive group. Examples of the reactive group include ethylenically unsaturated groups, condensation-polymerizable groups (e.g., hydroxyl groups and carboxyl groups), and addition-polymerizable groups (e.g., epoxy groups and (blocked) isocyanate groups).

[0347] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.

[0348] The thermoplastic resin layer may contain one or two or more alkali-soluble resins.

[0349] From the viewpoint of developability and adhesion with adjacent layers, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, further preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass, relative to the total mass of the thermoplastic resin layer.

[0350] (pigment)

[0351] The thermoplastic resin layer preferably includes a pigment (hereinafter sometimes referred to as "pigment B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm when developing color and a maximum absorption wavelength that changes due to acid, base, or free radicals. Preferred embodiments of pigment B are the same as those of pigment N except for the following matters.

[0352] From the viewpoint of visibility of the exposed area, visibility of the non-exposed area, and resolution, the dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with acid.

[0353] The thermoplastic resin layer may contain one or more dyes B.

[0354] From the viewpoint of visibility of the exposure portion and the visibility of the non-exposure portion, the content of pigment B is preferably 0.2% by mass or more relative to the total mass of the thermoplastic resin layer, more preferably 0.2% by mass to 6% by mass, further preferably 0.2% by mass to 5% by mass, and especially preferably 0.25% by mass to 3.0% by mass. Here, the content of pigment B refers to the content of the pigment when all the pigments B contained in the thermoplastic resin layer become a color-developing state. Below, the quantitative method of the pigment is described with the pigment developed by free radicals as an example. A solution obtained by dissolving pigment B (0.001g) in methyl ethyl ketone (100mL) and a solution obtained by dissolving pigment B (0.01g) in methyl ethyl ketone (100mL) were prepared. A photoradical polymerization initiator (Irgacure OXE01, BASF JAPAN LTD.) was added to each solution, and then, irradiated with 365nm light to generate free radicals, so that all pigments become a color-developing state. The absorbance of each solution at 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric conditions to create a calibration curve. Next, the absorbance of the solution in which the pigment was fully colored was measured using the same method as above, except that the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone instead of the pigment. The amount of pigment contained in the thermoplastic resin layer was calculated from the absorbance of the solution containing the thermoplastic resin layer based on the calibration curve.

[0355] From the viewpoint of visibility of the exposed area, visibility of the non-exposed area, and resolution, the thermoplastic resin layer preferably contains a dye whose maximum absorption wavelength changes due to acid as dye B and a compound that generates acid by light. The compound that generates acid by light will be described later.

[0356] (compounds that generate acids, bases, or free radicals by light)

[0357] The thermoplastic resin layer may contain a compound that generates an acid, base, or free radical by light (hereinafter sometimes referred to as "compound C"). Compound C is preferably a compound that generates an acid, base, or free radical by receiving active light (e.g., ultraviolet light and visible light). Examples of compound C include photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Of the above, photoacid generators are preferred.

[0358] From the perspective of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the photocationic polymerization initiators described in the above "photosensitive resin layer." Preferred embodiments of the photoacid generator are the same as those described in the above "photosensitive resin layer," except for the following. From the perspective of sensitivity and resolution, the photoacid generator preferably includes at least one selected from an onium salt compound and an oxime sulfonate compound. From the perspective of sensitivity, resolution, and adhesion, the photoacid generator preferably includes an oxime sulfonate compound. Specific examples of preferred photoacid generators are shown below.

[0359] [Chemical Formula 3]

[0360]

[0361] The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamine, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylthiobenzoyl 4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0362] The thermoplastic resin layer may contain a photoradical polymerization initiator (photoradical polymerization initiator). Examples of the photoradical polymerization initiator include the photoradical polymerization initiators described in the above-mentioned "photosensitive resin layer". Preferred embodiments of the photoradical polymerization initiator are the same as those described in the above-mentioned "photosensitive resin layer".

[0363] The thermoplastic resin layer may contain one or more compounds C.

[0364] From the viewpoint of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, the content of compound C in the thermoplastic resin layer is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0365] (Plasticizer)

[0366] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0367] The molecular weight of the plasticizer (the weight average molecular weight (Mw) when the plasticizer has a molecular weight distribution) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

[0368] Examples of plasticizers include compounds that are compatible with alkali-soluble resins and impart plasticity. From the perspective of imparting plasticity, the plasticizer is preferably a compound containing an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethoxy structure or a polypropyleneoxy structure.

[0369] From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution and adhesion to adjacent layers, it is more preferred that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. As the (meth)acrylate compound used as the plasticizer, for example, the (meth)acrylate compound described in the above-mentioned "polymerizable compound B" can be cited. In the case where the thermoplastic resin layer is in contact with the photosensitive resin layer in the photosensitive transfer material, the thermoplastic resin layer and the photosensitive resin layer preferably contain the same (meth)acrylate compound. By containing the same (meth)acrylate compound in the thermoplastic resin layer and the photosensitive resin layer, the diffusion of components between the layers is suppressed and the storage stability is improved.

[0370] From the viewpoint of adhesion with adjacent layers, the (meth)acrylate compound used as a plasticizer preferably does not polymerize even in the exposed portion after exposure.

[0371] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule.

[0372] The (meth)acrylate compound used as the plasticizer is also preferably a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group.

[0373] The thermoplastic resin layer may contain one or more plasticizers.

[0374] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the content of the plasticizer in the thermoplastic resin layer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0375] (Surfactant)

[0376] From the perspective of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include those described in the section "Photosensitive resin layer." Preferred embodiments of the surfactant are the same as those described in the section "Photosensitive resin layer."

[0377] The thermoplastic resin layer may contain one or more surfactants.

[0378] The content of the surfactant in the thermoplastic resin layer is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, relative to the total mass of the thermoplastic resin layer.

[0379] (Sensitizer)

[0380] The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include those described in the section "photosensitive resin layer."

[0381] The thermoplastic resin layer may contain one or more sensitizers.

[0382] From the viewpoint of improving sensitivity to light sources and visibility of exposed and non-exposed areas, the content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the thermoplastic resin layer.

[0383] (additive)

[0384] The thermoplastic resin layer may contain known additives in addition to the above-mentioned components as needed.

[0385] (thickness)

[0386] The thickness of the thermoplastic resin layer is not limited. From the perspective of adhesion with adjacent layers, the thickness of the thermoplastic resin layer is preferably 1 μm or greater, more preferably 2 μm or greater. From the perspective of developability and resolution, the thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The thickness of the thermoplastic resin layer is measured using a method similar to the method for measuring the thickness of a temporary support.

[0387] (Method for Forming Thermoplastic Resin Layer)

[0388] The method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. The thermoplastic resin layer is formed, for example, by preparing a thermoplastic resin layer-forming composition, applying the thermoplastic resin layer-forming composition to an object (e.g., a photosensitive resin layer), and drying the applied thermoplastic resin layer-forming composition.

[0389] In order to adjust the viscosity of the thermoplastic resin layer-forming composition and facilitate the formation of the thermoplastic resin layer, the thermoplastic resin layer-forming composition preferably contains a solvent. The solvent is not limited as long as it can dissolve or disperse the components of the thermoplastic resin layer. Examples of the solvent include the solvents described in the above section "Photosensitive resin layer." Preferred embodiments of the solvent are the same as those described in the above section "Photosensitive resin layer."

[0390] The thermoplastic resin layer-forming composition may contain one or more solvents.

[0391] The content of the solvent in the thermoplastic resin layer-forming composition is preferably 50 to 1,900 parts by mass, and 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.

[0392] The thermoplastic resin layer-forming composition is prepared, for example, by a method according to the method for preparing the photosensitive resin layer-forming composition. The thermoplastic resin layer-forming composition is applied, for example, by a method according to the method for applying the photosensitive resin layer-forming composition.

[0393] The Middle Layer

[0394] The photosensitive transfer material of the present invention preferably contains an intermediate layer between the photosensitive resin layer and the thermoplastic resin layer. By containing an intermediate layer in the photosensitive transfer material, it is possible to suppress the mixing of components generated between layers during the formation of the photosensitive transfer material or the storage of the photosensitive transfer material. From the viewpoint of suppressing the mixing of components generated between layers during the development and formation of the photosensitive transfer material or the storage of the photosensitive transfer material, the intermediate layer is preferably a water-soluble layer. In the present invention, "water-soluble" refers to the property of having a solubility of 0.1 g or more in water (100 g) with a pH of 7.0 and a liquid temperature of 22°C.

[0395] Examples of intermediate layers include the oxygen barrier layer described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-72724. These layers are preferred for improving sensitivity during exposure, reducing the time load on the exposure machine, and increasing productivity. The oxygen barrier layer preferably exhibits low oxygen permeability and is dispersible or soluble in water or an alkaline aqueous solution (1% by mass sodium carbonate aqueous solution, liquid temperature: 22°C).

[0396] The intermediate layer preferably contains a resin. Examples of the resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins. The resin may be a homopolymer or a copolymer. The resin is preferably a water-soluble resin.

[0397] From the viewpoint of suppressing mixing of components between the layers during formation of the oxygen barrier and the photosensitive transfer material or storage of the photosensitive transfer material, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinyl pyrrolidone.

[0398] From the viewpoint of suppressing mixing of components between layers, the resin contained in the intermediate layer is preferably a resin different from the polymer A contained in the photosensitive resin layer and a resin different from the thermoplastic resin (eg, alkali-soluble resin) contained in the thermoplastic resin layer.

[0399] The intermediate layer may contain one or more resins.

[0400] From the viewpoint of suppressing mixing of components generated between the layers during the formation of the oxygen barrier and photosensitive transfer material or the storage of the photosensitive transfer material, the content of the resin in the intermediate layer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass relative to the total mass of the intermediate layer.

[0401] The intermediate layer may contain additives such as surfactants as needed. Examples of surfactants include those described in the section "Photosensitive resin layer." Preferred embodiments of the surfactants are the same as those described in the section "Photosensitive resin layer."

[0402] The thickness of the intermediate layer is not limited. The thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. If the thickness of the intermediate layer is within the above range, oxygen barrier properties will not be reduced, mixing of components between layers during the formation or storage of the photosensitive transfer material can be suppressed, and an increase in the time required to remove the intermediate layer during the development process can be suppressed. The thickness of the intermediate layer is measured using the same method as for measuring the thickness of a temporary support.

[0403] The method for forming the intermediate layer is not limited. The intermediate layer is formed, for example, by preparing an intermediate layer-forming composition containing a resin and any additives, applying the intermediate layer-forming composition to the surface of the thermoplastic resin layer or the photosensitive resin layer, and drying the applied intermediate layer-forming composition.

[0404] In order to adjust the viscosity of the intermediate layer-forming composition and facilitate the formation of the intermediate layer, the intermediate layer-forming composition preferably contains a solvent. The solvent is not limited as long as it can dissolve or disperse the resin. 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. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

[0405] Protective Film

[0406] The photosensitive transfer material of the present invention preferably includes a protective film. The photosensitive transfer material of the present invention preferably includes a temporary support, a photosensitive resin layer, and a protective film in this order. The protective film is preferably the outermost layer of the photosensitive transfer material.

[0407] Examples of protective films include resin films and paper. Resin films are preferred from the perspectives of strength and flexibility. Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, triacetylcellulose films, polystyrene films, and polycarbonate films. Among these, polyethylene films, polypropylene films, and polyethylene terephthalate films are preferred.

[0408] The thickness of the protective film is not limited. The thickness of the protective film is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm. The thickness of the protective film is measured by the method for measuring the thickness of the temporary support.

[0409] From the perspective of achieving better resolution, the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the protective film (hereinafter sometimes referred to as the "surface of the protective film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. By having the arithmetic mean roughness Ra of the surface of the protective film within the above range, it is believed that the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern is improved. The lower limit of the arithmetic mean roughness Ra of the protective film is preferably 0.001 μm or more.

[0410] The arithmetic mean roughness Ra of the surface of the protective film is measured by the following method. Using a three-dimensional optical analyzer (New View7300, Zygo Company), the surface profile of the protective film is obtained under the following conditions. As the measurement and analysis software, the Microscope Application of MetroPro ver8.3.2 is used. Then, the Surface Map screen is displayed using the above-mentioned analysis software, and the histogram numbers are obtained in the Surface Map screen. The arithmetic mean roughness Ra is calculated from the obtained histogram numbers. In the measurement of the arithmetic mean roughness Ra of the surface of the protective film contained in the photosensitive transfer material, the protective film is peeled off from the photosensitive transfer material, and the arithmetic mean roughness Ra of the surface of the displayed protective film is measured.

[0411] 《Relationship between temporary support, photosensitive resin layer and protective film》

[0412] The photosensitive transfer material involved in the present invention is preferably as follows:

[0413] The elongation at break of a cured film formed by curing the photosensitive resin layer at 120° C. is 15% or more, and the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive resin layer side is 50 nm or less.

[0414] The arithmetic mean roughness Ra of the surface of the protective film on the photosensitive resin layer side is 150 nm or less.

[0415] Furthermore, the photosensitive transfer material according to the present invention preferably satisfies the following formula (R1).

[0416] X×Y≤1,500: Formula (R1)

[0417] In the formula (R1), X represents the elongation at break of a cured film obtained by curing the photosensitive resin layer at 120° C. (%), and Y represents the arithmetic mean roughness Ra (nm) of the surface of the temporary support on the photosensitive resin layer side.

[0418] More preferably, X×Y is 750 or less.

[0419] The elongation at break at 120° C. is preferably at least twice as large as the elongation at break at 23° C. of a cured film obtained by curing the photosensitive resin layer.

[0420] Using an ultra-high pressure mercury lamp at 120 mJ / cm 2 A photosensitive resin layer with a thickness of 20 μm was exposed and cured, and then a high-pressure mercury lamp was used to irradiate the layer at 400 mJ / cm 2 The cured film was further exposed and heated at 145° C. for 30 minutes, and the elongation at break was measured by a tensile test.

[0421] Furthermore, the photosensitive transfer material according to the present invention preferably satisfies the following formula (R2).

[0422] Y≤Z: Formula (R2)

[0423] In the above formula (R2), Y represents the arithmetic mean roughness Ra value (nm) of the surface of the temporary support on the photosensitive resin layer side, and Z represents the arithmetic mean roughness Ra value (nm) of the surface of the protective film on the photosensitive resin layer side.

[0424] Other Layers

[0425] The photosensitive transfer material of the present invention may contain layers other than the above-mentioned layers (hereinafter referred to as "other layers" in this paragraph). Examples of other layers include contrast enhancement layers (also referred to as refractive index adjustment layers). Contrast enhancement layers are described in paragraph 0134 of International Publication No. 2018 / 179640. Other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of these publications are incorporated into this specification by reference.

[0426] 《Method for producing photosensitive transfer material》

[0427] The method for producing the photosensitive transfer material of the present invention is not limited. The photosensitive transfer material can be produced, for example, by the above-mentioned method for forming each layer. Figure 1 and Figure 2 A method for producing a photosensitive transfer material will be described. Figure 1 It is a schematic diagram showing the structure of the photosensitive transfer material according to the present invention. Figure 2 It is a schematic diagram showing the structure of a photosensitive transfer material according to another embodiment of the present invention. Figure 3 It is a schematic diagram showing the structure of a photosensitive transfer material according to another embodiment of the present invention.

[0428] Figure 1The photosensitive transfer material 100 shown contains a temporary support 10, a photosensitive resin layer 20 and a protective film 30 in this order. The photosensitive transfer material 100 is manufactured, for example, by the following method. A temporary support 10 having a second surface 10b is prepared on the first surface 10a and the side opposite to the first surface 10a. A photosensitive resin layer-forming composition is applied to the second surface 10b of the temporary support 10, and the applied photosensitive resin layer-forming composition is dried to form a photosensitive resin layer 20. A protective film 30 is arranged on the photosensitive resin layer 20. The photosensitive transfer material 100 manufactured by the above method is wound up, thereby making and storing a roll-shaped photosensitive transfer material 100. The roll-shaped photosensitive transfer material 100 is used for bonding to a substrate, for example, by a roll-to-roll method.

[0429] Figure 2 The photosensitive transfer material 110 shown includes a temporary support 11, a photosensitive resin layer 20, and a protective film 30 in this order. The temporary support 11 includes a particle-containing layer 11-1 and a substrate 11-2 in this order in the stacking direction from the temporary support 11 toward the photosensitive resin layer 20. In the temporary support 11, the particle-containing layer 11-1 is arranged as the outermost layer on the first surface 11a side of the temporary support 11. In the temporary support 11, the substrate 11-2 is arranged as the outermost layer on the second surface 11b side of the temporary support 11. The photosensitive transfer material 110 is manufactured by the same method as the above-mentioned method for manufacturing the photosensitive transfer material 100, except that the temporary support 11 is prepared, for example, instead of the temporary support 10.

[0430] Figure 3 The photosensitive transfer material 120 shown includes, in order, a temporary support 10, a thermoplastic resin layer 40, an intermediate layer 50, a photosensitive resin layer 20, and a protective film 30. For example, a method for producing the photosensitive transfer material 120 may be exemplified by forming, in order, the thermoplastic resin layer 40, the intermediate layer 50, the photosensitive resin layer 20, and the protective film 30 on the second surface 10b of the temporary support according to the above-described method.

[0431] The method for producing the photosensitive transfer material according to the present invention is not limited to the above-described method. For example, the photosensitive transfer material can be produced by forming each layer on a protective film instead of a temporary support.

[0432] 《Applications of Photosensitive Transfer Materials》

[0433] The photosensitive transfer material involved in the present invention is preferably used for various applications required for precision micro-machining based on photolithography. For example, after the photosensitive resin layer is patterned, the photosensitive resin layer or its cured product can be used as a coating for etching or electroforming mainly by electroplating. The cured product obtained by patterning can be used as a permanent film. The cured product obtained by patterning can be used as a wiring protective film having an interlayer insulating film, a wiring protective film or a refractive index matching layer. The photosensitive transfer material involved in the present invention is preferably used for a method for forming wiring in a semiconductor package, a printed circuit board or a sensor substrate. The photosensitive transfer material involved in the present invention is preferably used for a method for forming a conductive film such as a touch panel, an electromagnetic shielding material and a thin film heater. The photosensitive transfer material involved in the present invention is preferably used for a method for forming a structure in a liquid crystal sealing material, a micromachine and a microelectronic area.

[0434] The photosensitive transfer material according to the present invention can be used as a photosensitive transfer material for a wiring protection film, for example. Examples of layer structures of photosensitive transfer materials preferably used as a photosensitive transfer material for a wiring protection film include the following (1) and (2).

[0435] (1) Temporary support / photosensitive resin layer / refractive index adjustment layer / protective film

[0436] (2) Temporary support / photosensitive resin layer / protective film

[0437] Hereinafter, the constituent elements of a photosensitive transfer material preferably used as a wiring protective film will be described. However, the constituent elements of a photosensitive transfer material preferably used as a wiring protective film are not limited to the constituent elements described below.

[0438] (Temporary support)

[0439] Examples of the temporary support include those described in the above section "Temporary Support." Preferred embodiments of the temporary support are the same as those described in the above section "Temporary Support."

[0440] (Protective film)

[0441] Examples of the protective film include the protective films described in the above section "Protective film." Preferred embodiments of the protective film are the same as those described in the above section "Protective film."

[0442] (Photosensitive resin layer)

[0443] -Alkali soluble resin-

[0444] The photosensitive resin layer preferably contains an alkali-soluble resin.

[0445] Examples of the alkali-soluble resin include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkanol resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by reacting an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting an epoxy acrylate resin with an acid anhydride.

[0446] As one of the preferred aspects of the alkali-soluble resin, a (meth)acrylic resin is mentioned because it is excellent in alkali developability and thin film formability.

[0447] In this specification, a (meth)acrylic resin refers to a resin having structural units derived from a (meth)acrylic compound. The content of the structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to all structural units in the (meth)acrylic resin.

[0448] The (meth)acrylic resin may be composed solely of structural units derived from a (meth)acrylic compound, or may contain structural units derived from a polymerizable monomer other than a (meth)acrylic compound. Specifically, the upper limit of the content of structural units derived from a (meth)acrylic compound is 100% by mass or less relative to all structural units in the (meth)acrylic resin.

[0449] Examples of the (meth)acrylic acid compound include (meth)acrylic acid, (meth)acrylate, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile.

[0450] Examples of the (meth)acrylate include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred.

[0451] Examples of (meth)acrylamide include acrylamides such as diacetone acrylamide.

[0452] Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

[0453] As the (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.

[0454] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound.

[0455] The polymerizable monomer forming the above-mentioned structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic acid compound copolymerizable with the (meth)acrylic acid compound. Examples thereof include styrene compounds which may have a substituent at the α position or on the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene; vinyl alcohol esters such as acrylonitrile and vinyl n-butyl ether; maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid.

[0456] These polymerizable monomers may be used alone or in combination of two or more.

[0457] Furthermore, from the viewpoint of further improving alkali developability, the (meth)acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfone group, a phosphoric acid group, and a phosphonic acid group.

[0458] Among these, the (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably contains a structural unit derived from the above-mentioned (meth)acrylic acid.

[0459] In terms of excellent developability, the content of structural units having an acid group (preferably structural units derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin. The upper limit is not particularly limited, but in terms of excellent alkali resistance, it is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0460] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth)acrylate.

[0461] The content of the structural unit derived from the alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and further preferably 65 to 90% by mass, based on all the structural units of the (meth)acrylic resin.

[0462] The (meth)acrylic resin preferably contains both a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate. More preferably, the (meth)acrylic resin contains only a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate.

[0463] Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

[0464] Furthermore, from the viewpoint of resolution, the (meth)acrylic resin preferably has at least one selected from structural units derived from methacrylic acid and structural units derived from alkyl methacrylates, and preferably has both structural units derived from methacrylic acid and structural units derived from alkyl methacrylates.

[0465] From the perspective of resolution, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, and more preferably 60% by mass or more, relative to all structural units in the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, and preferably 80% by mass or less.

[0466] Furthermore, from the viewpoint of resolution, the (meth)acrylic resin preferably has at least one selected from structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and at least one selected from structural units derived from acrylic acid and structural units derived from acrylate alkyl esters.

[0467] From the viewpoint of resolution, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is preferably 60 / 40 to 80 / 20 in terms of mass ratio relative to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.

[0468] The (meth)acrylic resin preferably has an ester group at the terminal, from the viewpoint of excellent developability of the photosensitive resin layer after transfer.

[0469] The terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used for synthesis. A (meth)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0470] Furthermore, from the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, for example.

[0471] Furthermore, from the viewpoint of easily forming a strong film by thermal cross-linking with the cross-linking component by heating, the alkali-soluble resin is more preferably, for example, a resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing resin), and further preferably a (meth) acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing (meth) acrylic resin).

[0472] If the alkali-soluble resin is a carboxyl resin, the three-dimensional crosslinking density can be increased by thermal crosslinking, for example, by adding a thermally crosslinkable compound such as a blocked isocyanate compound. Furthermore, if the carboxyl groups of the carboxyl resin are dehydrated and hydrophobized, moist heat resistance can be improved.

[0473] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above-mentioned acid value conditions are satisfied, and can be appropriately selected from known (meth)acrylic resins.

[0474] For example, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or higher among the polymers described in paragraph 0025 of JP-A-2011-095716 and carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or higher among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589 can be preferably used.

[0475] Another preferred embodiment of the alkali-soluble resin is a styrene-acrylic acid copolymer. In this specification, a styrene-acrylic acid copolymer refers to a resin having structural units derived from a styrene compound and structural units derived from a (meth)acrylic acid compound, wherein the total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic acid compound is preferably 30% by mass or more, and more preferably 50% by mass or more, relative to all structural units of the copolymer.

[0476] The content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5% by mass to 80% by mass, based on all the structural units of the copolymer.

[0477] The content of the structural unit derived from the (meth)acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% to 95% by mass, based on all the structural units of the copolymer.

[0478] From the viewpoint of the moisture permeability and strength of the obtained cured film, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

[0479] Examples of the monomer forming the structural unit having an aromatic ring structure include styrene compounds such as styrene, t-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth)acrylate.

[0480] Among them, styrene compounds are preferred, and styrene is more preferred.

[0481] Furthermore, from the viewpoint of the moisture permeability and strength of the obtained cured film, the alkali-soluble resin more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene).

[0482] [Chemical Formula 4]

[0483]

[0484] When the alkali-soluble resin contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and even more preferably 20% by mass to 60% by mass based on all the structural units of the alkali-soluble resin, from the viewpoint of moisture permeability and strength of the obtained cured film.

[0485] Furthermore, from the viewpoint of moisture permeability and strength of the obtained cured film, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 60 mol%, relative to all structural units of the alkali-soluble resin.

[0486] Furthermore, from the viewpoint of the moisture permeability and strength of the obtained cured film, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, further preferably 20 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, relative to all the structural units of the alkali-soluble resin.

[0487] In this specification, when the content of a "structural unit" is specified by molar ratio, the "structural unit" and the "monomer unit" have the same meaning. Furthermore, in this specification, the "monomer unit" may be modified after polymerization through a polymer reaction or the like. This also applies hereinafter.

[0488] From the perspectives of suppressing development residue, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure. That is, the alkali-soluble resin preferably contains a structural unit having an aliphatic hydrocarbon ring structure. Among these, the alkali-soluble resin more preferably has a ring structure comprising two or more condensed aliphatic hydrocarbon rings.

[0489] Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborane ring.

[0490] Among them, from the viewpoints of development residue suppression, strength of the obtained cured film, and adhesion of the obtained uncured film, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2，6 ]decane ring).

[0491] Examples of the monomer that forms the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0492] Furthermore, from the viewpoints of development residue suppression, the strength of the obtained cured film, and the adhesion of the obtained uncured film, the alkali-soluble resin more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above-mentioned formula (S) and a structural unit represented by the following formula (Cy).

[0493] [Chemical Formula 5]

[0494]

[0495] R in formula (Cy) M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0496] R in formula (Cy) M Preferred is methyl.

[0497] From the viewpoint of development residue suppression, strength of the obtained cured film, and adhesion of the obtained uncured film, R in formula (Cy) CyIt is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

[0498] R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in may be a monocyclic structure or a polycyclic structure.

[0499] Furthermore, from the viewpoints of development residue suppression, strength of the obtained cured film, and adhesion of the obtained uncured film, R in formula (Cy) is preferably Cy The aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isoborane ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, further preferably a tetrahydrodicyclopentadiene ring structure.

[0500] Furthermore, from the viewpoints of development residue suppression, strength of the obtained cured film, and adhesion of the obtained uncured film, R in formula (Cy) is preferably Cy The aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring in which 2 to 4 aliphatic hydrocarbon rings are condensed.

[0501] Furthermore, from the viewpoints of development residue suppression, strength of the obtained cured film, and adhesion of the obtained uncured film, R in the formula (Cy) is preferably Cy The group in which the oxygen atom of -C(=O)O- in formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group is preferred, a cyclohexyl group or a dicyclopentyl group is more preferred, and a dicyclopentyl group is further preferred.

[0502] The alkali-soluble resin may contain one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may contain two or more types.

[0503] When the alkali-soluble resin contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and even more preferably 20% by mass to 70% by mass relative to all the structural units in the alkali-soluble resin, from the viewpoints of development residue suppression, strength of the obtained cured film, and adhesion of the obtained uncured film.

[0504] Furthermore, from the viewpoints of development residue suppression, strength of the obtained cured film, and adhesion of the obtained uncured film, the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 50 mol%, relative to all the structural units of the alkali-soluble resin.

[0505] Furthermore, from the viewpoint of suppressing development residue, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and further preferably 20 mol% to 50 mol%, relative to all the structural units of the alkali-soluble resin.

[0506] In the case where the alkali-soluble resin contains structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and further preferably 40% by mass to 75% by mass relative to all the structural units of the alkali-soluble resin, from the viewpoint of development residue suppression, strength of the obtained cured film, and adhesion of the obtained uncured film.

[0507] Furthermore, from the viewpoints of suppressing development residue, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and even more preferably 40 mol% to 60 mol%, relative to all the structural units of the alkali-soluble resin.

[0508] Furthermore, from the viewpoints of the development residue suppression property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and even more preferably 40 mol% to 60 mol% relative to all the structural units of the alkali-soluble resin.

[0509] Furthermore, from the viewpoints of development residue suppression, the strength of the obtained cured film, and the adhesion of the obtained uncured film, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the alkali-soluble resin preferably satisfy the relationship represented by the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2).

[0510] 0.2≤nS / (nS+nCy)≤0.8: Formula (SCy)

[0511] 0.30≤nS / (nS+nCy)≤0.75: Formula (SCy-1)

[0512] 0.40≤nS / (nS+nCy)≤0.70: Formula (SCy-2)

[0513] From the viewpoint of developability and adhesion to the substrate, the alkali-soluble resin preferably contains a structural unit having an acid group.

[0514] Examples of the acid group include a carboxyl group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxyl group is preferred.

[0515] As the structural unit having the acid group, a structural unit derived from (meth)acrylic acid as shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0516] [Chemical Formula 6]

[0517]

[0518] The alkali-soluble resin may contain one type of structural unit having an acid group alone, or may contain two or more types.

[0519] When the alkali-soluble resin contains a structural unit having an acid group, from the viewpoint of developability and adhesion to the substrate, the content of the structural unit having an acid group is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and further preferably 10% by mass to 30% by mass relative to all the structural units of the alkali-soluble resin.

[0520] Furthermore, from the viewpoint of developability and adhesion to the substrate, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 mol% to 70 mol% relative to all the structural units of the alkali-soluble resin, more preferably 10 mol% to 50 mol%, and further preferably 20 mol% to 40 mol%.

[0521] Furthermore, from the viewpoint of developability and adhesion to the substrate, the content of the structural units derived from (meth)acrylic acid in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and even more preferably 20 mol% to 40 mol%, relative to all the structural units of the alkali-soluble resin.

[0522] From the viewpoint of curability and the strength of the obtained cured film, the alkali-soluble resin preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

[0523] As the reactive group, a radical polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. When the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

[0524] In this specification, a "main chain" refers to the relatively longest bond chain in the molecule of a polymer compound constituting a resin, and a "side chain" refers to an atomic group branching from the main chain.

[0525] As the ethylenically unsaturated group, an allyl group or a (meth)acryloyloxy group is more preferable.

[0526] Examples of the structural unit having a reactive group include the following structural units, but the present invention is not limited to these.

[0527] [Chemical Formula 7]

[0528]

[0529] The alkali-soluble resin may contain one type of structural unit having a reactive group alone, or may contain two or more types.

[0530] When the alkali-soluble resin contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass relative to all the structural units of the alkali-soluble resin, from the viewpoint of curability and the strength of the obtained cured film.

[0531] Furthermore, from the viewpoint of curability and the strength of the obtained cured film, the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 50 mol%, relative to all the structural units of the alkali-soluble resin.

[0532] Examples of methods for introducing reactive groups into alkali-soluble resins include reacting compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic anhydride with functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfonic groups.

[0533] A preferred example of a method for introducing a reactive group into an alkali-soluble resin is a method in which a polymer having carboxyl groups is synthesized by polymerization, and then glycidyl (meth)acrylate is reacted with a portion of the carboxyl groups of the obtained resin by polymer reaction to introduce a (meth)acryloyloxy group into the polymer. This method can produce an alkali-soluble resin having a (meth)acryloyloxy group in its side chain.

[0534] The polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably at a temperature of 80°C to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo initiator, and more preferably V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. The polymer reaction is preferably carried out at a temperature of 80°C to 110°C. In the polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0535] From the viewpoint of achieving more excellent effects in the present invention, the following resins are preferred as alkali-soluble resins. The content ratios (a to d) and weight average molecular weight Mw of the following structural units can be appropriately changed depending on the intended purpose.

[0536] [Chemical Formula 8]

[0537]

[0538] In the above resins, preferably, a is 20% to 60% by mass, b is 10% to 50% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass.

[0539] [Chemical Formula 9]

[0540]

[0541] In the above resins, preferably, a is 20% to 60% by mass, b is 10% to 50% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass.

[0542] [Chemical Formula 10]

[0543]

[0544] In the above resin, preferably, a is 30% to 65% by mass, b is 1.0% to 20% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass.

[0545] [Chemical Formula 11]

[0546]

[0547] In the above resins, preferably, a is 1.0 to 20% by mass, b is 20 to 60% by mass, c is 5.0 to 25% by mass, and d is 10 to 50% by mass.

[0548] Furthermore, the alkali-soluble resin may include a polymer containing a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X").

[0549] The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure.

[0550] The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and still more preferably a 5-membered ring.

[0551] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing a divalent group formed by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group formed by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0552] [Chemical Formula 12]

[0553]

[0554] In formula P-1, R A1a represents a substituent, n 1a R A1a Can be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, n 1a Indicates an integer greater than 0.

[0555] As R A1a Examples of the substituent represented by include an alkyl group.

[0556] As Z 1a , preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further preferably an alkylene group having 2 carbon atoms.

[0557] n 1a Indicates an integer greater than 0. 1a In the case of an alkylene group having 2 to 4 carbon atoms, n 1a It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

[0558] In n 1aWhen an integer greater than 2 is represented, there are multiple R A1a Can be the same or different. Also, there are multiple R A1a They may bond to each other to form a ring, but preferably bond to each other without forming a ring.

[0559] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, further preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

[0560] Specific examples of the structural unit having a carboxylic acid anhydride structure are given below, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group or a CF3 group, and Me represents a methyl group.

[0561] [Chemical Formula 13]

[0562]

[0563] [Chemical Formula 14]

[0564]

[0565] The structural unit having a carboxylic acid anhydride structure in the polymer X may be a single type or two or more types.

[0566] The total content of the structural units having a carboxylic anhydride structure is preferably 0 mol% to 60 mol% based on all structural units of the polymer X, more preferably 5 mol% to 40 mol%, further preferably 10 mol% to 35 mol%.

[0567] The photosensitive resin layer may contain only one type of polymer X, or may contain two or more types.

[0568] When the photosensitive resin layer contains a polymer X, from the viewpoint of resolution and developability, the content of the polymer X is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, further preferably 0.5% by mass to 20% by mass, and even more preferably 1% by mass to 20% by mass, relative to the total mass of the photosensitive resin layer.

[0569] From the viewpoint of improving resolution and developability, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0570] The acid value of the alkali-soluble resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, further preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 60 mgKOH / g to 110 mgKOH / g.

[0571] The acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070:1992.

[0572] From the viewpoint of developability, the dispersion degree (weight average molecular weight / number average molecular weight) of the alkali-soluble resin 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.

[0573] The photosensitive resin layer may contain only one type of alkali-soluble resin, or may contain two or more types.

[0574] From the viewpoint of photosensitivity, resolution, and developability, the content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass relative to the total mass of the photosensitive resin layer.

[0575] -Polymerizable compound-

[0576] The photosensitive resin layer may contain a polymerizable compound.

[0577] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radical polymerizable groups and cation polymerizable groups, and radical polymerizable groups are preferred.

[0578] The polymerizable compound preferably contains a polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound").

[0579] As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferred.

[0580] In addition, the ethylenically unsaturated compound in this specification is a compound other than the above-mentioned binder polymer, and preferably has a molecular weight of less than 5,000.

[0581] Preferred embodiments of the ethylenically unsaturated compound are the same as the preferred embodiments of the ethylenically unsaturated compound described in the section "Photosensitive resin layer" above.

[0582] One preferred embodiment of the ethylenically unsaturated compound includes a compound represented by the following formula (M) (also simply referred to as "compound M").

[0583] Q 2 -R 1-Q 1 :Formula (M)

[0584] Q in formula (M) 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 It represents a divalent linking group having a chain structure.

[0585] Q in formula (M) 1 and Q 2 From the perspective of ease of synthesis, Q 1 and Q 2 The same groups are preferred.

[0586] Furthermore, from the viewpoint of reactivity, Q in formula (M) 1 and Q 2 An acryloyloxy group is preferred.

[0587] As R in formula (M) 1 From the viewpoint of development residue suppression, rust resistance, and bending resistance of the obtained cured film, alkylene, alkyleneoxyalkylene (-L 1 -OL 1 -) or polyalkyleneoxyalkylene (-(L 1 -O) P -L 1 -), more preferably a hydrocarbon group or polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, further preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

[0588] The above-mentioned hydrocarbon group only needs to have a chain structure in at least a part. There is no particular limitation on the part other than the above-mentioned chain structure. For example, it can be any one of a branched, cyclic or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, and a combination thereof. Preferably, it is an alkylene group or a group composed of two or more alkylene groups and one or more arylene groups. More preferably, it is an alkylene group, and even more preferably, a linear alkylene group.

[0589] In addition, the above L 1 Each independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group or a 1,2-propylene group.

[0590] p represents an integer of 2 or greater, and is preferably an integer of 2-10.

[0591] Furthermore, from the viewpoints of development residue suppression, rust prevention, and bending resistance of the obtained cured film, the linker Q in the compound M is preferably 1 With Q 2The number of atoms in the shortest connecting chain between the two groups is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

[0592] In this manual, "Connecting Q 1 With Q 2 The number of atoms in the shortest chain between 1 R 1 Atoms in Q 2 R 1 The shortest number of atoms connected to the atoms in the string.

[0593] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-pentanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. These ester monomers may also be used as a mixture.

[0594] Among the above compounds, from the viewpoints of development residue suppression, rust prevention, and flex resistance of the obtained cured film, at least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred. At least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred. Even more preferred is at least one compound selected from 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

[0595] Furthermore, as one preferred embodiment of the ethylenically unsaturated compound, a bifunctional or higher functional ethylenically unsaturated compound can be mentioned.

[0596] In this specification, a "bifunctional or higher-functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0597] As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred.

[0598] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0599] The bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.

[0600] Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0601] Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK ESTER A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK ESTER DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK ESTER A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK ESTER A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0602] The trifunctional or higher-functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.

[0603] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerol tri(meth)acrylate skeleton.

[0604] Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth)acrylate compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified compounds of (meth)acrylate compounds (e.g., KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd. and ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEXL T.), and ethoxylated glyceryl triacrylate (e.g., NK ESTER A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0605] Examples of the ethylenically unsaturated compound include urethane (meth)acrylate compounds.

[0606] Examples of the urethane (meth)acrylate include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylate and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylate.

[0607] Furthermore, examples of urethane (meth)acrylates include trifunctional or higher urethane (meth)acrylates. The lower limit of the number of functional groups is more preferably hexafunctional or higher, and even more preferably octafunctional or higher. The upper limit of the number of functional groups is preferably 20 or lower. Examples of trifunctional or higher-functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0608] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group.

[0609] Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

[0610] Among these, as the acid group, a carboxyl group is preferred.

[0611] Examples of the ethylenically unsaturated compound having an acid group include trifunctional to tetrafunctional ethylenically unsaturated compounds having an acid group [ethylenically unsaturated compounds having a carboxyl group introduced into the skeleton of pentaerythritol tri- and tetraacrylate (PETA) (acid value: 80 mgKOH / g to 120 mgKOH / g)], and pentafunctional to hexafunctional ethylenically unsaturated compounds having an acid group [ethylenically unsaturated compounds having a carboxyl group introduced into the skeleton of dipentaerythritol penta- and hexaacrylate (DPHA) [acid value: 25 mgKOH / g to 70 mgKOH / g)].

[0612] These trifunctional or higher-functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, as needed.

[0613] As the ethylenically unsaturated compound having an acid group, at least one selected from bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof is preferred.

[0614] When the ethylenically unsaturated compound having an acid group is at least one selected from bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof, the developability and the film strength are further improved.

[0615] The bifunctional or higher functional ethylenically unsaturated compound having a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0616] Examples of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0617] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 is preferred, and the contents described in the publication are incorporated into the present specification.

[0618] Examples of the ethylenically unsaturated compound include compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, compounds obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, and alkyl (meth)acrylates.

[0619] These can be used alone or in combination of two or more.

[0620] Examples of compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyol include bisphenol A (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, and 2,2-bis(4((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; and polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0621] Among them, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0622] Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-iCL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX Ltd., etc.), and ethoxylated glyceryl triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0623] As the ethylenically unsaturated compound, an ethylenically unsaturated compound containing an ester bond is preferred also from the viewpoint of excellent developability.

[0624] The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule. However, from the viewpoint of excellent curability and developability, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0625] From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure.

[0626] Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0627] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).

[0628] As the above-mentioned ethylenically unsaturated compound, an ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from a tricyclodecane structure and a tricyclodecene structure) is preferred, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed is more preferred, and tricyclodecane dimethanol di(meth)acrylate is further preferred.

[0629] The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborane structure from the viewpoint of the moisture permeability and flex resistance of the obtained cured film and the adhesiveness of the obtained uncured film.

[0630] The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0631] The proportion of the ethylenically unsaturated compounds having a molecular weight of 300 or less in the ethylenically unsaturated compounds contained in the photosensitive resin layer is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the content of all ethylenically unsaturated compounds contained in the photosensitive resin layer.

[0632] As one preferred embodiment of the photosensitive resin layer, the photosensitive resin layer preferably contains a difunctional or higher-functional ethylenically unsaturated compound, more preferably a trifunctional or higher-functional ethylenically unsaturated compound, and even more preferably a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0633] Furthermore, as one preferred embodiment of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble resin containing a structural unit having an aliphatic hydrocarbon ring.

[0634] Furthermore, as one of the preferred forms of the photosensitive resin layer, the photosensitive resin layer preferably comprises a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a multifunctional ethylenically unsaturated compound having a carboxylic acid group, and further preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a succinic acid modified form of dipentaerythritol pentaacrylate.

[0635] Furthermore, as one of the preferred forms of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0636] Furthermore, as one of the preferred aspects of the photosensitive resin layer, from the viewpoint of development residue suppression and rust resistance, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound).

[0637] The mass ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the trifunctional or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.

[0638] The content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass, based on the total amount of all ethylenically unsaturated compounds.

[0639] The content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 40% by mass, based on the total mass of the photosensitive resin layer.

[0640] Furthermore, as one of the preferred aspects of the photosensitive resin layer, the photosensitive resin layer preferably contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention.

[0641] Furthermore, as one of the preferred aspects of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue inhibition and rust resistance, the photosensitive resin layer preferably comprises compound M and an ethylenically unsaturated compound having an acid group, more preferably comprises compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an ethylenically unsaturated compound having an acid group, further preferably comprises compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound and an ethylenically unsaturated compound having an acid group, and particularly preferably comprises compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group and a carbamate (meth)acrylate compound.

[0642] Furthermore, as one of the preferred aspects of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue suppression and rust resistance, the photosensitive resin layer preferably comprises 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, further preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group and a urethane acrylate compound.

[0643] The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0644] The content of the difunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass relative to the total content of all ethylenically unsaturated compounds contained in the photosensitive resin layer.

[0645] The ethylenically unsaturated compound may be used alone or in combination of two or more.

[0646] The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, further preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass, based on the total mass of the photosensitive resin layer.

[0647] -Polymerization initiator-

[0648] The photosensitive resin layer may contain a polymerization initiator.

[0649] As the polymerization initiator, a photopolymerization initiator is preferred.

[0650] Preferred embodiments of the photopolymerization initiator are the same as those described in the section of the "photosensitive resin layer".

[0651] The polymerization initiator may be used alone or in combination of two or more.

[0652] The content of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. Furthermore, the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

[0653] -Heterocyclic compounds-

[0654] The photosensitive resin layer may contain a heterocyclic compound.

[0655] The heterocyclic ring of the heterocyclic compound may be either a monocyclic ring or a polycyclic ring.

[0656] Examples of the heteroatom possessed by the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0657] Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

[0658] Among the above, the heterocyclic compound is preferably at least one compound selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds and benzoxazole compounds, and more preferably at least one compound selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzoxazole compounds.

[0659] Preferred specific examples of the heterocyclic compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0660] [Chemical Formula 15]

[0661]

[0662] [Chemical Formula 16]

[0663]

[0664] Examples of the tetrazole compound include the following compounds.

[0665] [Chemical Formula 17]

[0666]

[0667] [Chemical Formula 18]

[0668]

[0669] Examples of the thiadiazole compound include the following compounds.

[0670] [Chemical Formula 19]

[0671]

[0672] Examples of the triazine compound include the following compounds.

[0673] [Chemical Formula 20]

[0674]

[0675] Examples of the rhodanine compound include the following compounds.

[0676] [Chemical Formula 21]

[0677]

[0678] Examples of the thiazole compound include the following compounds.

[0679] [Chemical Formula 22]

[0680]

[0681] Examples of the benzothiazole compound include the following compounds.

[0682] [Chemical Formula 23]

[0683]

[0684] Examples of the benzimidazole compound include the following compounds.

[0685] [Chemical Formula 24]

[0686]

[0687] [Chemical Formula 25]

[0688]

[0689] Examples of the benzoxazole compound include the following compounds.

[0690] [Chemical Formula 26]

[0691]

[0692] The heterocyclic compound may be used alone or in combination of two or more.

[0693] When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, more preferably 0.10% by mass to 10.0% by mass, further preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass, relative to the total mass of the photosensitive resin layer.

[0694] -Aliphatic thiol compounds-

[0695] The photosensitive resin layer may contain an aliphatic thiol compound.

[0696] When the photosensitive resin layer contains an aliphatic thiol compound, the aliphatic thiol compound and the ethylenically unsaturated compound undergo an ene-thiol reaction, whereby the curing shrinkage of the formed film is suppressed and stress is relaxed.

[0697] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (ie, a bifunctional or higher-functional aliphatic thiol compound).

[0698] Among the above, as the aliphatic thiol compound, from the viewpoint of the adhesion of the formed pattern (particularly the adhesion after exposure), a polyfunctional aliphatic thiol compound is more preferred.

[0699] In this specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0700] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of not less than 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0701] The number of functional groups of the polyfunctional aliphatic thiol compound is preferably difunctional to decafunctional, more preferably difunctional to octafunctional, and even more preferably difunctional to hexafunctional, from the viewpoint of adhesion of the formed pattern.

[0702] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, and trimethylolpropane tris(3-mercaptobutyrate). (3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid and bis(mercaptoethyl) ether.

[0703] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0704] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0705] The photosensitive resin layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds.

[0706] When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, further preferably 5% by mass to 30% by mass, and particularly preferably 8% by mass to 20% by mass, relative to the total mass of the photosensitive resin layer.

[0707] -Thermal cross-linking compound-

[0708] 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.

[0709] Examples of the thermally crosslinkable compound include the thermally crosslinkable compounds described in the section "photosensitive resin layer" above.

[0710] The heat-crosslinkable compound may be used alone or in combination of two or more.

[0711] When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer.

[0712] -Surfactants-

[0713] The photosensitive resin layer may contain a surfactant.

[0714] Examples of the surfactant include the surfactants described in the section of the above-mentioned "photosensitive resin layer".

[0715] The surfactant may be used alone or in combination of two or more.

[0716] When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.01 to 1.0 mass %, and further preferably 0.05 to 0.80 mass % relative to the total mass of the photosensitive resin layer.

[0717] -Free radical inhibitor-

[0718] The photosensitive resin layer may contain a radical polymerization inhibitor.

[0719] Examples of the radical polymerization inhibitor include the radical polymerization inhibitors described in the section "photosensitive resin layer" above.

[0720] The radical polymerization inhibitor may be used alone or in combination of two or more.

[0721] When the photosensitive resin layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass, relative to the total mass of the photosensitive resin layer. When the content is 0.01% by mass or greater, the storage stability of the photosensitive resin layer is further improved. On the other hand, when the content is 3% by mass or less, the sensitivity is maintained and the discoloration of the dye is suppressed.

[0722] -Hydrogen-donating compounds-

[0723] The photosensitive resin layer may contain a hydrogen-donating compound.

[0724] The hydrogen-donating compound has the functions of further increasing the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

[0725] Examples of the hydrogen-donating compound include amines and amino acid compounds.

[0726] Examples of the amines include compounds described in "Journal of Polymer Society" by MR Sander et al., Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Laid-Open No. 51-082102, Japanese Patent Application Laid-Open No. 52-134692, Japanese Patent Application Laid-Open No. 59-138205, Japanese Patent Application Laid-Open No. 60-084305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, and Research Disclosure No. 33825. More specific examples include 4,4′-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0727] Among them, from the viewpoints of sensitivity, curing speed, and curing properties, the amine is preferably at least one selected from 4,4′-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0728] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0729] Among them, N-phenylglycine is preferred as the amino acid compound from the viewpoints of sensitivity, curing speed, and curing properties.

[0730] Examples of hydrogen-donating compounds include organometallic compounds (tributyltin acetate, etc.) described in JP-B 48-042965, hydrogen donors described in JP-B 55-034414, and sulfur compounds (trithiane, etc.) described in JP-A 6-308727.

[0731] The hydrogen-donating compound may be used alone or in combination of two or more.

[0732] When the photosensitive resin layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and further preferably 0.03% by mass to 5.0% by mass relative to the total mass of the photosensitive resin layer, from the viewpoint of improving the curing rate by balancing the polymerization growth rate and chain transfer.

[0733] -Impurities-

[0734] The photosensitive resin layer may contain a predetermined amount of impurities.

[0735] Examples of the impurities include those described in the above section "photosensitive resin layer".

[0736] -Residual monomers-

[0737] The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the polymer A described above.

[0738] Examples of the residual monomers corresponding to the structural units of the polymer A in the photosensitive resin layer include the residual monomers corresponding to the structural units of the polymer A described in the section "photosensitive resin layer".

[0739] -Other ingredients-

[0740] The photosensitive resin layer may contain components other than the components already described (hereinafter also referred to as "other components"). Examples of other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Examples of other components include the additives described in paragraphs 0058 to 0071 of Japanese Patent Application Laid-Open No. 2000-310706.

[0741] As the particles, metal oxide particles are preferred.

[0742] The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0743] For example, from the viewpoint of transparency of the cured film, the average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm.

[0744] 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.

[0745] When the photosensitive resin layer contains particles, the photosensitive resin layer may contain only one type of particles having different metal types, sizes, etc., or may contain two or more types.

[0746] It is preferred that the photosensitive resin layer does not contain particles, or when the photosensitive resin layer contains particles, the content of the particles is greater than 0 mass % and less than 35 mass % relative to the total mass of the photosensitive resin layer. It is more preferred that the photosensitive resin layer does not contain particles, or the content of the particles is greater than 0 mass % and less than 10 mass % relative to the total mass of the photosensitive resin layer. It is further preferred that the photosensitive resin layer does not contain particles, or the content of the particles is greater than 0 mass % and less than 5 mass % relative to the total mass of the photosensitive resin layer. It is further preferred that the photosensitive resin layer does not contain particles, or the content of the particles is greater than 0 mass % and less than 1 mass % relative to the total mass of the photosensitive resin layer. It is particularly preferred that the photosensitive resin layer does not contain particles.

[0747] The photosensitive resin layer may contain a colorant (a pigment, a dye, etc.), but preferably contains substantially no colorant, for example, from the viewpoint of transparency.

[0748] When the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1 mass %, more preferably less than 0.1 mass %, relative to the total mass of the photosensitive resin layer.

[0749] Examples of the antioxidant include 3-pyrazolidinones such as 1-phenyl-3-pyrazolidinone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidinone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

[0750] Among them, from the viewpoint of storage stability and curability, as the antioxidant, 3-pyrazolidinones are preferred, and 1-phenyl-3-pyrazolidinone is more preferred.

[0751] When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 1% by mass or less.

[0752] -Thickness of the photosensitive resin layer-

[0753] The thickness (layer thickness) of the photosensitive resin layer is not particularly limited, but from the perspective of developability and resolution, it is preferably 30 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, particularly preferably 10 μm or less, and most preferably 5.0 μm or less. As a lower limit, from the perspective of excellent strength of the film obtained by curing the photosensitive resin layer, it is preferably 0.60 μm or more, more preferably 1.5 μm or more.

[0754] -Refractive Index of Photosensitive Resin Layer-

[0755] The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

[0756] -Color of the photosensitive resin layer-

[0757] The photosensitive resin layer is preferably colorless. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is CIE1976 (L * , a * , b * ) color space L * The value is preferably 10 to 90, a* The value is preferably -1.0 to 1.0, b * The value is preferably -1.0 to 1.0.

[0758] Moreover, the pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) is preferably colorless.

[0759] Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is in CIE1976 (L * , a * , b * ) The L of the pattern in the color space * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably -1.0 to 1.0.

[0760] -Moisture Permeability of Photosensitive Resin Layer-

[0761] From the viewpoint of rust prevention, the moisture permeability of the pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) at a layer thickness of 40 μm is preferably 500 g / (m 2 ·24hr) or less, more preferably 300g / (m 2 ·24hr) or less, more preferably 100g / (m 2 ·24hr) or less.

[0762] In addition, in the cured film obtained by curing the photosensitive resin layer, the i-ray was used at an exposure dose of 300 mJ / cm 2 After the photosensitive resin layer was exposed, post-baking was performed at 145° C. for 30 minutes, and the moisture permeability was measured.

[0763] (Refractive Index Adjustment Layer)

[0764] The photosensitive transfer material preferably has a refractive index adjusting layer.

[0765] As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjusting layer include alkali-soluble resins, ethylenically unsaturated compounds, metal salts, and particles.

[0766] The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin.

[0767] Examples of the alkali-soluble resin and the ethylenically unsaturated compound include the alkali-soluble resin and the ethylenically unsaturated compound described in the section of the above-mentioned "photosensitive resin layer".

[0768] Examples of the particles include metal oxide particles and metal particles.

[0769] The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0770] For example, from the viewpoint of transparency of the cured film, the average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm.

[0771] 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.

[0772] Specifically, the metal oxide particles are preferably at least one selected from zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), silicon dioxide particles (SiO 2 particles), and composite particles thereof.

[0773] Among these, as the metal oxide particles, for example, from the viewpoint of easy adjustment of the refractive index, at least one selected from zirconium oxide particles and titanium oxide particles is more preferable.

[0774] Commercially available metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (NanoUse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconia particles (NanoUse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0775] The particles may be used alone or in combination of two or more.

[0776] The content of the particles in the refractive index adjusting layer is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and further preferably 40 to 85 mass %, relative to the total mass of the refractive index adjusting layer.

[0777] When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 40 to 85 mass % relative to the total mass of the refractive index adjusting layer.

[0778] The refractive index of the refractive index adjusting layer is preferably higher than the refractive index of the photosensitive resin layer.

[0779] The refractive index of the refractive index adjusting layer is preferably 1.50 or higher, more preferably 1.55 or higher, further preferably 1.60 or higher, and particularly preferably 1.65 or higher. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or lower, more preferably 1.85 or lower, and particularly preferably 1.78 or lower.

[0780] The thickness of the refractive index adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm.

[0781] The refractive index adjusting layer is formed, for example, using a refractive index adjusting layer. The composition for forming the refractive index adjusting layer preferably contains the various components and solvents described above for forming the refractive index adjusting layer. Furthermore, in the composition for forming the refractive index adjusting layer, the preferred range of the content of each component relative to the total solids content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjusting layer described above.

[0782] The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, but 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.

[0783] Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred.

[0784] The solvent may be used alone or in combination of two or more.

[0785] The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

[0786] The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0787] (Relationship between Temporary Support, Photosensitive Resin Layer, and Protective Film)

[0788] In the photosensitive transfer material preferably used as the photosensitive transfer material for a wiring protective film, it is also preferable that the above-mentioned relationship among the temporary support, the photosensitive resin layer, and the protective film is satisfied.

[0789] <Method for Manufacturing Resin Pattern>

[0790] The method for manufacturing a resin pattern according to one embodiment of the present invention is a method for manufacturing a resin pattern using the photosensitive transfer material according to the present invention. According to one embodiment of the present invention, a method for manufacturing a resin pattern that suppresses the generation of pores is provided. The method for manufacturing a resin pattern according to one embodiment of the present invention preferably includes: a process of preparing a substrate (hereinafter sometimes referred to as a "preparation process"); a process of contacting a photosensitive transfer material with the above-mentioned substrate, and sequentially arranging a photosensitive resin layer and a temporary support body on the above-mentioned substrate (hereinafter sometimes referred to as a "lamination process"); a process of pattern-exposing the above-mentioned photosensitive resin layer (hereinafter sometimes referred to as an "exposure process"); and a process of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter sometimes referred to as a "development process").

[0791] Preparation Process

[0792] In the preparation step, a substrate is prepared. The type of substrate is not limited. The substrate is preferably a substrate comprising a conductive layer. Furthermore, the substrate is preferably a substrate comprising a base material and a conductive layer on the base material, and more preferably a substrate comprising a base material and a conductive layer in contact with the base material. The conductive layer may be disposed on a single side of the base material. The conductive layer may be disposed on both sides of the base material. The substrate may include layers other than the conductive layer.

[0793] Examples of the substrate include glass, silicon, and resin films. The substrate is preferably transparent. In the present invention, "transparent" means a transmittance of 80% or greater at a wavelength of 400 nm to 700 nm. The refractive index of the substrate is preferably 1.50 to 1.52.

[0794] Examples of transparent glass include tempered glass represented by Gorilla Glass from Corning Incorporated Co., Ltd. As transparent glass, materials described in Japanese Patent Application Laid-Open Nos. 2010-86684, 2010-152809, and 2010-257492 may also be used.

[0795] The resin film is preferably a resin film having small optical distortion or high transparency. Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0796] In the method for producing a resin pattern using a roll-to-roll method, the base material is preferably a resin film.

[0797] The conductive layer may be, for example, a conductive layer used in general circuit wiring or touch panel wiring. The conductive layer is preferably an electrode pattern corresponding to a sensor in a visible portion of a capacitive touch panel or wiring in a peripheral lead portion.

[0798] From the viewpoint of conductivity and thin line formability, the conductive layer is preferably at least one 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 particularly preferably a copper layer or a silver layer.

[0799] Components of the conductive layer include metals and conductive metal oxides. Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2. In the present invention, "conductivity" means a volume resistivity of less than 1×10 6 The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Ωcm.

[0800] When a resin pattern is produced using a substrate including a plurality of conductive layers, it is preferred that at least one of the plurality of conductive layers contain a conductive metal oxide.

[0801] The substrate may include one or more conductive layers. When the substrate includes two or more conductive layers, the substrate preferably includes two or more conductive layers formed of different materials.

[0802] Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of International Publication No. 2018 / 155193, the contents of which are incorporated into this specification by reference.

[0803] As a substrate containing a conductive layer, a substrate having at least one of a transparent electrode and a circuitous wiring is preferred. The substrate described above can be preferably used as a touch panel substrate. The transparent electrode can preferably function as a touch panel electrode. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide) and metal fine wires such as a metal mesh and metal nanowires. Examples of the metal fine wires include fine wires of silver, copper, etc. Among them, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0804] The material of the bypass wiring is preferably metal. Examples of metals used as the material of the bypass wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metal elements. The material of the bypass wiring is preferably copper, molybdenum, aluminum, or titanium, with copper being particularly preferred.

[0805] Laminating process

[0806] In the laminating step, a photosensitive transfer material is brought into contact with a substrate, and a photosensitive resin layer and a temporary support are sequentially arranged on the substrate.

[0807] The photosensitive transfer material is as described in the above section "Photosensitive transfer material." Preferred embodiments of the photosensitive transfer material used in the laminating step are the same as those described in the above section "Photosensitive transfer material."

[0808] In the laminating process, the photosensitive resin layer and the temporary support disposed on the substrate are the photosensitive resin layer and the temporary support contained in the photosensitive transfer material, respectively. That is, the layer structure of the laminate obtained by the laminating process changes according to the layer structure of the photosensitive transfer material. For example, in the laminating process, if a photosensitive transfer material containing a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in sequence is brought into contact with the substrate, the photosensitive resin layer, the intermediate layer, the thermoplastic resin layer, and the temporary support are sequentially disposed on the substrate. In the case where the photosensitive transfer material contains a protective film, the protective film is removed from the photosensitive transfer material and the photosensitive transfer material is brought into contact with the substrate.

[0809] In the laminating step, the photosensitive transfer material is preferably brought into contact with the substrate and pressure-bonded to the substrate. For example, the photosensitive transfer material is preferably brought into contact with the substrate and pressure-bonded to the substrate and the substrate and the photosensitive transfer material by applying pressure and heat using a device such as a roller.

[0810] In the method of contacting the photosensitive transfer material with the substrate (including the method of press-bonding the photosensitive transfer material to the substrate), for example, a known transfer method or a known lamination method is used. In the method of contacting the photosensitive transfer material with the substrate, for example, a laminator, a vacuum laminator, or an automatic cutting laminator is used, which can further improve productivity.

[0811] Exposure Process

[0812] In the exposure step, the photosensitive resin layer is subjected to pattern exposure. The arrangement and size of the pattern in the pattern exposure are not limited. At least a portion of the pattern (preferably a portion corresponding to the electrode pattern or lead wiring of the touch panel) preferably includes fine lines having a width of 20 μm or less, and more preferably includes fine lines having a width of 10 μm or less.

[0813] Examples of the light source in the exposure step include a light source that irradiates light having a wavelength capable of exposing the photosensitive resin layer (e.g., 365 nm or 405 nm). Examples of the light source include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

[0814] The exposure dose is preferably 5 mJ / cm 2 ~300mJ / cm 2 , more preferably 10 mJ / cm 2 ~200mJ / cm 2 .

[0815] In the exposure step, the temporary support may be peeled off before pattern exposure of the photosensitive resin layer. In the exposure step, the temporary support may be peeled off before pattern exposure of the photosensitive resin layer via the temporary support.

[0816] In an exposure method using a photomask, when a temporary support is peeled off before pattern exposure, the photomask may be brought into contact with the photosensitive resin layer to expose the photosensitive resin layer, or the photomask may be brought close to the photosensitive resin layer without bringing the photomask into contact with the photosensitive resin layer to expose the photosensitive resin layer. In an exposure method using a photomask, when the photosensitive resin layer is exposed via a temporary support, the photomask may be brought into contact with the temporary support to expose the photosensitive resin layer, or the photomask may be brought close to the temporary support without bringing the photomask into contact with the temporary support to expose the photosensitive resin layer. In order to prevent contamination of the photomask caused by contact between the photosensitive resin layer and the photomask and to avoid the influence on exposure caused by impurities attached to the photomask, it is preferred to perform pattern exposure on the photosensitive resin layer via a temporary support.

[0817] There is no limitation on the exposure method. Examples of the exposure method include contact exposure and non-contact exposure. Examples of the contact exposure method include a method of exposing a photosensitive resin layer to a pattern using a photomask. Examples of the non-contact exposure method include a proximity exposure method, a projection exposure method using a lens system or a reflector system, and a direct exposure method using an exposure laser. In the projection exposure method using a lens system or a reflector system, an exposure machine having an appropriate numerical aperture (NA) of a lens can be used depending on the required resolution and depth of focus. In the direct exposure method, the drawing can be performed directly on the photosensitive layer, or reduced projection exposure can be performed on the photosensitive layer via a lens. The exposure can be performed in the atmosphere, under reduced pressure, or under vacuum. The exposure can be performed by inserting a liquid such as water between the light source and the photosensitive resin layer.

[0818] Development Process

[0819] In the development step, the exposed photosensitive resin layer is developed to form a resin pattern. If the photosensitive resin layer is a negative-working photosensitive resin layer, the unexposed portions of the photosensitive resin layer are removed, and the exposed portions of the photosensitive resin layer form a resin pattern. If the photosensitive resin layer is a positive-working photosensitive resin layer, the exposed portions of the photosensitive resin layer are removed, and the unexposed portions of the photosensitive resin layer form a resin pattern. Furthermore, in the lamination step, the thermoplastic resin layer and intermediate layer disposed on the substrate are removed along with the removed photosensitive resin layer. The thermoplastic resin layer and intermediate layer can be removed by dissolving or dispersing them in a developer.

[0820] Development is performed, for example, using a developer. The developer is not limited as long as it is a developer for the photosensitive resin layer to be removed. As the developer, a known developer is used. As the developer, for example, the developer described in Japanese Patent Application Laid-Open No. 5-72724 can be cited. The developer is preferably an alkaline aqueous solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain a water-soluble organic solvent and / or a surfactant. As the developer, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 is also preferred.

[0821] The liquid temperature of the developer is not limited, but is preferably 20°C to 40°C.

[0822] There are no limitations on the development method. Examples of the development method include puddle development, shower development, shower and spin development, or immersion development. Shower development involves spraying a developer onto the exposed photosensitive resin layer to remove the target photosensitive resin layer.

[0823] After the development step, it is preferred to remove development residues by spraying a cleaning agent and wiping with a brush.

[0824] The line width of the resin pattern obtained by the above-mentioned process is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less. There is no limit to the lower limit of the line width of the resin pattern. The line width of the resin pattern can be, for example, 1 μm or more. The line width of the resin pattern is measured by the following method. The resin pattern is observed using a scanning electron microscope (SEM), and the line width of 30 parts in the resin pattern is measured. The arithmetic average of the measured values is used as the line width of the resin pattern.

[0825] The resin pattern obtained through the above-mentioned steps can be used as a permanent film or a protective film for etching.

[0826] Roll-to-roll method

[0827] The method for manufacturing a resin pattern is preferably performed by a roll-to-roll method. The roll-to-roll method refers to a method that includes using a substrate that is wound and unwound, including a step of unwinding a substrate or a laminate containing the substrate before any step included in the method for manufacturing a resin pattern (sometimes referred to as an "unwinding step") and a step of winding up a substrate or a laminate containing the substrate after any step (hereinafter sometimes referred to as a "winding step"), and performing at least one step (preferably all steps) while carrying the substrate or the laminate containing the substrate. As the unwinding method in the unwinding step and the winding method in the winding step, for example, a known method suitable for the roll-to-roll method is used.

[0828] <Method for Manufacturing Conductive Pattern>

[0829] The method for manufacturing a conductive pattern according to one embodiment of the present invention is a method for manufacturing a conductive pattern using the photosensitive transfer material according to the present invention. According to one embodiment of the present invention, a method for manufacturing a conductive pattern that suppresses the generation of pores is provided. The method for manufacturing a conductive pattern according to one embodiment of the present invention preferably includes: a process of preparing a substrate containing a conductive layer (hereinafter sometimes referred to as a "preparation process"); a process of contacting a photosensitive transfer material with the above-mentioned substrate, and sequentially arranging a photosensitive resin layer and a temporary support body on the above-mentioned substrate (hereinafter sometimes referred to as a "lamination process"); a process of pattern-exposing the above-mentioned photosensitive resin layer (hereinafter sometimes referred to as an "exposure process"); a process of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter sometimes referred to as a "development process"); and a process of etching the above-mentioned conductive layer not covered by the above-mentioned resin pattern to form a conductive pattern (hereinafter sometimes referred to as an "etching process").

[0830] Preparation Process

[0831] In the preparation step, a substrate including a conductive layer is prepared. The substrate including a conductive layer is as described above in the section "Method for Producing a Resin Pattern." Preferred embodiments of the substrate including a conductive layer are the same as those described above in the section "Method for Producing a Resin Pattern."

[0832] Laminating process

[0833] In the laminating step, a photosensitive transfer material is brought into contact with a substrate, and a photosensitive resin layer and a temporary support are sequentially disposed on the substrate. The laminating step is as described above in the section "Method for Producing a Resin Pattern." Preferred embodiments of the laminating step are the same as those described in the section "Method for Producing a Resin Pattern."

[0834] Exposure Process

[0835] In the exposure step, the photosensitive resin layer is pattern-exposed. The exposure step is as described above in the "Method for Producing a Resin Pattern." Preferred embodiments of the exposure step are the same as those described above in the "Method for Producing a Resin Pattern."

[0836] Development Process

[0837] In the development step, the exposed photosensitive resin layer is developed to form a resin pattern. The development step is as described above in the section "Method for Producing a Resin Pattern." Preferred embodiments of the development step are the same as those described above in the section "Method for Producing a Resin Pattern."

[0838] Etching Process

[0839] In the etching process, the conductive layer not covered by the resin pattern is etched to form a conductive pattern. During the etching process, the resin pattern acts as a protective film for the conductive layer. In the etching process, the conductive layer not covered by the resin pattern is removed by etching, and the conductive pattern is formed in the conductive layer covered by the resin pattern.

[0840] As the etching method, for example, a known method is used. Examples of the etching method include the method described in paragraphs 0209 to 0210 of Japanese Patent Application Laid-Open No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese Patent Application Laid-Open No. 2010-152155, wet etching by immersion in an etching solution, and dry etching (for example, plasma etching).

[0841] Regarding the etching solution used in the wet etching method, an acidic or alkaline etching solution can be appropriately selected according to the etching object. Examples of acidic etching solutions include aqueous solutions containing at least one acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of acidic etching solutions include aqueous solutions containing the above-mentioned acidic components and at least one salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component can also be a component composed of a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions containing at least one alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide). Examples of alkaline etching solutions include aqueous solutions containing the above-mentioned alkaline components and salts (e.g., potassium permanganate). The alkaline component can also be a component composed of a combination of multiple alkaline components.

[0842] Removal Process

[0843] The method for manufacturing a conductive pattern according to one embodiment of the present invention preferably includes a step of removing a remaining resin pattern after the etching step.

[0844] Examples of methods for removing the resin pattern include chemical treatment. A preferred method is to use a removal solution. Examples of methods for removing the resin pattern using a removal solution include immersing the substrate having the resin pattern in a stirring removal solution at a temperature of 30°C to 80°C (preferably 50°C to 80°C) for 1 to 30 minutes.

[0845] Examples of the removal liquid include those containing an inorganic or organic base component and at least one selected from water, dimethyl sulfoxide, and N-methylpyrrolidone. Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0846] The remaining resin pattern can be removed by a known method such as spraying, showering, or spin-on immersion.

[0847] Other Processes

[0848] The method for producing a conductive pattern according to one embodiment of the present invention may include other steps in addition to the above-described steps. Examples of these other steps include the following. Furthermore, the exposure step, development step, and other steps applicable to the method for producing a conductive pattern according to one embodiment of the present invention are described in paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-23696. The contents of the aforementioned publication are incorporated herein by reference.

[0849] (Process for reducing visible light reflectivity)

[0850] The method for manufacturing a conductive pattern according to one embodiment of the present invention may include a step of performing a treatment to reduce the visible light reflectivity of a portion or all of the multiple conductive layers of the substrate. As a treatment to reduce the visible light reflectivity, for example, an oxidation treatment can be cited. For example, when the conductive layer contains copper, the copper is oxidized to form copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectivity of the conductive layer. The treatment to reduce the visible light reflectivity is described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of Japanese Patent Application Publication No. 2013-206315. The contents described in these publications are incorporated into this specification by reference.

[0851] (Step of Forming an Insulating Film and Step of Forming a New Conductive Layer on the Surface of the Insulating Film)

[0852] The method for manufacturing a conductive pattern according to one embodiment of the present invention also preferably includes a step of forming an insulating film on the surface of the conductive pattern and a step of forming a new conductive layer on the surface of the insulating film. Through the above-mentioned steps, a second electrode pattern insulated from the first electrode pattern can be formed. As a method for forming an insulating film, for example, a method of forming a known permanent film can be cited. An insulating film having a desired pattern can also be formed by photolithography using a photosensitive material having insulating properties. As a method for forming a new conductive layer on the surface of an insulating film, for example, a method of forming a new conductive layer having a desired pattern by photolithography using a photosensitive material having conductive properties can be cited.

[0853] In the method for producing a conductive pattern according to one embodiment of the present invention, it is also preferred to use a substrate having multiple conductive layers on both sides of the substrate to form circuits sequentially or simultaneously on the conductive layers formed on both sides of the substrate. According to the above method, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface of the substrate. Such a conductive pattern can be used, for example, as circuit wiring for a touch panel. Such a conductive pattern is preferably formed using a roll-to-roll process.

[0854] Roll-to-roll method

[0855] The method for producing a conductive pattern according to one embodiment of the present invention is preferably performed by a roll-to-roll method. The roll-to-roll method is as described in the above section "Method for producing a resin pattern."

[0856] The Purpose of Circuit Wiring

[0857] The conductive pattern obtained by the method for manufacturing a conductive pattern according to one embodiment of the present invention is suitable for use in various devices. Devices including the conductive pattern include, for example, input devices, preferably touch panels, and more preferably capacitive touch panels. The input device can be used in display devices such as organic EL displays and liquid crystal displays. Furthermore, the conductive pattern obtained by the method for manufacturing a conductive pattern according to one embodiment of the present invention is preferably suitable for use in touch sensors.

[0858] <Touch Sensor>

[0859] A touch sensor according to one embodiment of the present invention includes a conductive pattern obtained by a method for manufacturing a conductive pattern according to one embodiment of the present invention. The components of the touch sensor according to one embodiment of the present invention are not limited except that they include a conductive pattern obtained by a method for manufacturing a conductive pattern according to one embodiment of the present invention. The conductive pattern is used, for example, as a transparent electrode or frame wiring of a touch sensor. The shape and size of the conductive pattern are determined, for example, according to the intended touch sensor. As patterns of a photomask for manufacturing a conductive pattern, for example, pattern A and pattern B described in Japanese Patent Application Publication No. 2019-204070 can be cited. As components other than the conductive pattern, for example, components contained in a known touch sensor can be utilized. Regarding the touch sensor, for example, it is described in Japanese Patent Application Publication No. 6486341 and Japanese Patent Application Publication No. 2016-155978. These publications are incorporated into this specification by reference. The known method for manufacturing a touch sensor is referred to in order to form the components of the touch sensor other than the conductive pattern.

[0860] The touch sensor is suitable for various input devices, for example. As an input device, a touch panel can be mentioned, for example.

[0861] Examples of detection methods for touch panels include a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among these, the capacitance method is preferred.

[0862] Examples of touch panel types include an in-cell type (e.g., the structure described in FIG. 5, FIG. 6, FIG. 7, and FIG. 8 of Japanese Unexamined Patent Publication No. 2012-517051), a so-called out-cell type (e.g., the structure described in FIG. 19 of Japanese Unexamined Patent Publication No. 2013-168125, and the structure described in FIG. 2012-89102). Figure 1 5 ), OGS (OneGlass Solution: single glass solution) type, TOL (Touch-on-Lens: lens touch) type (for example, Japanese Patent Application Laid-Open No. 2013-54727 Figure 2), various plug-in types (so-called GG, G1·G2, GFF, GF2, GF1 and G1F), and other structures (for example, the structure described in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871).

[0863] Example

[0864] Hereinafter, the present invention will be described in detail with reference to the examples. However, the present invention is not limited to the following examples. The contents of the examples shown below (e.g., materials, usage amounts, ratios, processing contents, and processing steps) can be appropriately changed within the scope of the purpose of the present invention.

[0865] <Preparation of Particle-Containing Layer-Forming Composition 1>

[0866] The mixture obtained by mixing the following components was filtered using a 6 μm filter (F20, Mahle Filter Systems Japan Corp.) and degassed using a 2×6 Radial Flow Super Phobic (Polypore Co., Ltd.).

[0867] Acrylic polymer (AS-563A, DAICEL MIRAIZU LTD., solid content: 27.5% by mass): 167 parts by mass

[0868] Nonionic surfactant (NAROACTY CL95, Sanyo Chemical Industries, Ltd., solid content: 100% by mass): 0.7 parts by mass

[0869] Anionic surfactant (RAPISOL A-90, NOF CORPORATION, water-diluted solution with a solid content concentration of 1% by mass): 114.4 parts by mass

[0870] Carnauba wax dispersion (Cellulose 524, CHUKYO YUSHI CO., LTD., solid content: 30% by mass): 7 parts by mass

[0871] Carbodiimide compound (CARBODILITE V-02-L2, Nisshinbo Chemical Inc., diluted with water to a solid content concentration of 10% by mass): 20.9 parts by mass

[0872] Matting agent (Snowtex XL, Nissan Chemical Corporation, solid content: 40% by mass, average particle size: 50 nm): 2.8 parts by mass

[0873] Water: 690.2 parts by mass

[0874] <Manufacturing of Temporary Support 1>

[0875] The temporary support body 1 was manufactured by the following method.

[0876] (Extrusion molding)

[0877] Pellets of polyethylene terephthalate (PET) produced using a citric acid chelate organic titanium complex described in Japanese Patent No. 5575671 as a polymerization catalyst were dried to a moisture content of 50 ppm or less. The dried pellets were placed in the hopper of a 30 mm diameter single-screw kneading extruder and melted at 280°C. The melt was passed through a filter (pore size: 2 μm) and then extruded from a die onto a cooling roller at 25°C to obtain an unstretched film. In the above method, the melt was brought into close contact with the cooling roller using electrostatic application.

[0878] (Stretching and coating)

[0879] The cured unstretched film was subjected to sequential biaxial stretching by the following method, thereby forming a particle-containing layer having a thickness of 40 nm on a polyethylene terephthalate film having a thickness of 16 μm.

[0880] (a) Longitudinal stretching

[0881] The unstretched film was stretched in the longitudinal direction (conveying direction) by passing it between two pairs of nip rolls having different peripheral speeds. The conditions for longitudinal stretching are shown below.

[0882] Preheating temperature: 75℃

[0883] Stretching temperature: 90℃

[0884] ·Stretching ratio: 3.4 times

[0885] ·Stretching speed: 1,300% / second

[0886] (b) Coating

[0887] The particle-containing layer-forming composition 1 was applied to one side of the longitudinally stretched film using a bar coater so that the thickness after film formation would be 40 nm.

[0888] (c) Transverse stretching

[0889] The film coated with the particle-containing layer-forming composition 1 was stretched in the transverse direction using a tenter under the following conditions.

[0890] Preheating temperature: 110℃

[0891] Stretching temperature: 120℃

[0892] ·Stretching ratio: 4.2 times

[0893] ·Stretching speed: 50% / second

[0894] (Heat setting and heat relaxation)

[0895] The biaxially stretched film was heat-set under the following conditions after being stretched in the longitudinal direction and in the transverse direction.

[0896] Heat setting temperature: 227℃

[0897] Heat setting time: 6 seconds

[0898] After heat setting, the tenter width was reduced and the biaxially stretched film was heat relaxed under the following conditions.

[0899] Thermal relaxation temperature: 190°C

[0900] Thermal relaxation rate: 4%

[0901] (Coiling)

[0902] After heat setting and heat relaxation, the film's ends were trimmed, and the film's ends were extruded (knurled) to a width of 10 mm. The film was then wound up at a tension of 40 kg / m. The film's width was 1.5 m, and the roll length was 6,300 m. The resulting film roll served as temporary support 1.

[0903] The temporary support 1 contains a polyethylene terephthalate film (substrate) and a particle-containing layer in sequence. The haze of the temporary support 1 is 0.2%. Using a haze meter (NIPPON DENSHOKU INDUSTRIES Co., LTD., NDH2000), the haze was measured as the total light haze. The heat shrinkage based on heating at 150°C for 30 minutes is 1.0% on the MD (machine direction) side and 0.2% on the TD (the direction orthogonal to the transport direction on the surface of the film, transverse direction) side. The thickness of the particle-containing layer measured from the cross-sectional TEM photograph is 40nm. Using the HT-7700 transmission electron microscope (TEM) made by Hitachi High-Technologies Corporation, the average particle size of the particles contained in the particle-containing layer measured by the above method is 50nm.

[0904] <Manufacturing of Temporary Support 2>

[0905] A temporary support 2 was obtained by the same method as the method for producing the temporary support 1 except that the number of times the melt was passed through the filter was changed to two in the extrusion molding.

[0906] <Manufacturing of Temporary Support 3>

[0907] A temporary support 3 was obtained by the same method as the method for producing the temporary support 1 except that the pore size of the filter was changed to 3 μm during extrusion molding.

[0908] <Manufacturing of Temporary Support 4>

[0909] A temporary support 4 was obtained by the same method as the method for producing the temporary support 3 except that the number of times the melt was passed through the filter was changed to two in the extrusion molding.

[0910] <Manufacturing of Temporary Support 5>

[0911] A temporary support 5 was obtained by the same method as the method for producing the temporary support 3 except that the number of times the melt was passed through the filter was changed to three times during the extrusion molding.

[0912] <Manufacturing of Temporary Support 6>

[0913] A temporary support body 6 was obtained by the same method as the method for producing the temporary support body 4 except that the ejection amount was adjusted so that the thickness of the temporary support body would be 10 μm during extrusion molding.

[0914] <Manufacturing of Temporary Support 7>

[0915] A temporary support 7 was obtained by the same method as the method for producing the temporary support 1 except that the pore size of the filter was changed to 5 μm during extrusion molding.

[0916] <Number of particles>

[0917] Ten random areas (size of each area: 10 mm×10 mm, total area: 1000 mm) on the surface of the temporary support were visually observed using an optical microscope. 2 The number of particles with a diameter of 3 μm or more in each area was measured. The total number of particles measured in 10 areas was used to calculate the number of particles per 1 cm of the measurement area. 2 The number of particles (particles / cm 2 The measurement results are shown below.

[0918] In Table 1, the column "3 μm to" shows the number of particles with a diameter of 3 μm or more and less than 4.5 μm (particles / cm 2 ), the column "4.5 μm to" shows the number of particles with a diameter of 4.5 μm or more and less than 6 μm (particles / cm 2 ), the column "6 μm to" shows the number of particles with a diameter of 6 μm or more and less than 7.5 μm (particles / cm 2 ), the column "9 μm to" shows the number of particles with a diameter of 9 μm or more and less than 10.5 μm (particles / cm 2 ), the column "10.5 μm to" shows the number of particles with a diameter of 10.5 μm or more (particles / cm 2 ).

[0919] [Table 1]

[0920]

[0921] <Preparation of Photosensitive Resin Layer-Forming Compositions 1 to 4>

[0922] Methyl ethyl ketone (400 parts by mass), propylene glycol monomethyl ether (40 parts by mass), propylene glycol monomethyl ether acetate (200 parts by mass), methanol (20 parts by mass) and the following components were mixed to prepare photosensitive resin layer-forming compositions 1 to 4.

[0923] [Table 2]

[0924]

[0925] <Preparation of Thermoplastic Resin Layer-Forming Composition 1>

[0926] Methyl ethyl ketone (500 parts by mass), propylene glycol monomethyl ether (20 parts by mass), propylene glycol monomethyl ether acetate (200 parts by mass) and the following components were mixed to prepare a thermoplastic resin layer-forming composition 1.

[0927] [Table 3]

[0928]

[0929] The meanings of the abbreviations described in the above table are shown below.

[0930] A-2: benzyl methacrylate / methacrylic acid / acrylic acid copolymer (75% by mass / 10% by mass / 15% by mass, weight average molecular weight: 30,000, Tg: 75°C, acid value: 186 mgKOH / g)

[0931] B-1: Compound having the structure shown below (a dye that develops color when exposed to acid)

[0932] [Chemical Formula 27]

[0933]

[0934] C-1: Compound having the structure shown below (photoacid generator, synthesized according to the compound described in paragraph 0227 of JP-A-2013-47765 and the method described in paragraph 0227.)

[0935] [Chemical Formula 28]

[0936]

[0937] D-3: NK ESTER A-DCP (tricyclodecane dimethanol diacrylate, Shin-Nakamura Chemical Co., Ltd.)

[0938] D-4: 8UX-015A (multifunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.)

[0939] D-5: ARONIX TO-2349 (polyfunctional acrylate compound having a carboxyl group, TOAGOSEI CO., Ltd.)

[0940] E-1: Megaface F-552 (fluorinated surfactant, DIC Corporation)

[0941] F-1: Phenothiazine (FUJIFILM Wako Pure Chemical Corporation)

[0942] F-2: CBT-1 (carboxybenzotriazole, JOHOKU CHEMICAL CO., LTD)

[0943] <Preparation of Water-Soluble Resin Layer-Forming Composition 1>

[0944] The following components were mixed to prepare a composition 1 for forming a water-soluble resin layer.

[0945] Ion exchange water: 38.12 parts by mass

[0946] Methanol (MITSUBISHI GAS CHEMICAL COMPANY, INC.): 57.17 parts by mass

[0947] KURARAY CO., LTD. POVAL 4-88LA (polyvinyl alcohol, KURARAY CO., LTD.): 3.22 parts by mass

[0948] Polyvinylpyrrolidone K-30 (NIPPON SHOKUBAI CO., Ltd.): 1.49 parts by mass

[0949] MEGAFACE F-444 (fluorinated surfactant, DIC Corporation): 0.0035 parts

[0950] <Example 1>

[0951] Using a slit nozzle, the thermoplastic resin layer-forming composition 1 was applied to the side of the temporary support substrate (polyethylene terephthalate film) opposite the surface where the particle-containing layer would be formed. The applied thermoplastic resin layer-forming composition 1 was dried at 100°C for 120 seconds to form a thermoplastic resin layer having a thickness of 2.0 μm.

[0952] Using a slit nozzle, a water-soluble resin layer-forming composition 1 was applied onto the thermoplastic resin layer. The applied water-soluble resin layer-forming composition 1 was dried at 120°C for 120 seconds to form a water-soluble resin layer having a thickness of 1.0 μm. This water-soluble resin layer served as the intermediate layer.

[0953] The photosensitive resin layer-forming composition 2 was applied onto the water-soluble resin layer using a slit nozzle, and the applied photosensitive resin layer-forming composition 2 was dried at 100° C. for 120 seconds to form a photosensitive resin layer having a thickness of 4.0 μm.

[0954] The photosensitive transfer material obtained by the above steps contains a temporary support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive resin layer in this order. The layer structures of the thermoplastic resin layer, the water-soluble resin layer, and the photosensitive resin layer are shown in Tables 4 and 5.

[0955] <Examples 2 to 10 and Comparative Example 1>

[0956] A photosensitive transfer material was obtained by the same procedure as that described in Example 1 except that the type and layer structure of the temporary support were appropriately changed as described in Tables 4 and 5.

[0957] <Resolution>

[0958] (1) A copper layer with a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film with a thickness of 100 μm by sputtering, thereby producing a PET substrate with a copper layer. A photosensitive transfer material and a PET substrate with a copper layer were laminated by a roll-to-roll method using a vacuum laminator (MCK Co., Ltd., roll temperature: 100°C, line pressure: 1.0 MPa, line speed: 0.5 m / min). The obtained laminate contained at least a PET film, a copper layer, a photosensitive resin layer, and a temporary support in this order. (2) The obtained laminate was pressurized and defoamed for 30 minutes under the conditions of 0.6 MPa and 60°C using an autoclave apparatus. (3) The photosensitive resin layer was exposed using an ultra-high pressure mercury lamp through a line and space pattern mask (duty ratio of 1:1, line width changing stepwise by 1 μm from 1 μm to 20 μm) without peeling off the temporary support. (4) After peeling off the temporary support, development was performed. For development, a 1.0 mass % sodium carbonate aqueous solution at 25° C. was used and spray development was performed for 30 seconds. By developing the photosensitive resin layer, a resin pattern was formed. Each time the exposure amount (unit: mJ / cm 2 ) were simultaneously performed until a resin pattern having a minimum line width corresponding to the mask pattern (hereinafter referred to as the "reference pattern" in this section) was obtained. The minimum line width of the reference pattern was used as the limiting resolution (X) of the photosensitive resin layer. The evaluation results are shown in Table 5.

[0959] <Air Holes in Wiring Pattern>

[0960] A mask for forming wiring was used (the duty ratio was 1:1, and the line width was changed in stages from 1 μm to 20 μm at intervals of 1 μm. The length of the wiring pattern was 50 mm. The number of wirings was 10.). In addition, a wiring pattern (i.e., a resin pattern) was formed by the same method as described in the above-mentioned "resolution" item (i.e., a method of exposing a photosensitive resin layer with a reference exposure amount to form a resin pattern). The wiring pattern was visually observed using an optical microscope, and the pores of the wiring pattern were evaluated based on the maximum size and number of the pores and according to the following criteria. The evaluation results are shown in Table 5.

[0961] A: No air holes were observed, or air holes smaller than 1 / 4 of the wiring width were observed.

[0962] B: A void having a size exceeding 1 / 4 and not more than 1 / 2 of the wiring width was observed.

[0963] C: A void larger than 1 / 2 and less than 3 / 4 of the wiring width was observed.

[0964] D: A void larger than 3 / 4 of the wiring width was observed.

[0965] [Table 4]

[0966]

[0967] [Table 5]

[0968]

[0969] Table 5 shows that the generation of voids in the wiring patterns of Examples 1 to 10 was suppressed compared with Comparative Example 1.

[0970] <Examples 11 to 21>

[0971] (Production of Polyester A Pellets)

[0972] While distilling off water at 255°C, an esterification reaction was carried out with 86.5 parts by mass of terephthalic acid and 37.1 parts by mass of ethylene glycol. After the esterification reaction was completed, 0.02 parts by mass of trimethylphosphoric acid, 0.06 parts by mass of magnesium acetate, 0.01 parts by mass of lithium acetate, and 0.0085 parts by mass of antimony trioxide were added. The mixture was then heated to 290°C under reduced pressure. After the temperature was raised, a polycondensation reaction was carried out to obtain polyester A pellets having an intrinsic viscosity of 0.63 dl / g (referred to as polyester A in Table 6).

[0973] (Production of Polyester C Pellets)

[0974] Using terephthalic acid as the dicarboxylic acid component and CHDM (cyclohexanedimethanol) as the diol component, a polycondensation reaction was carried out in the presence of 200 ppm of butyltin tris(2-ethylhexanoate) to obtain polyester C particles having an alicyclic structure (referred to as polyester C in Table 6).

[0975] (Production of Polyester E Pellets)

[0976] When polyester A particles were produced in the same manner as described above, after the esterification reaction was completed, spherical silica having a volume average particle size of 0.2 μm, a volume shape factor f=0.51, and a volume average particle size of 0.06 μm, a volume shape factor f=0.51, and a Mohs hardness of 7 was added, respectively. Then, a polycondensation reaction was carried out to obtain two types of silica-containing polyester E particles (referred to as polyester E in Table 6) each containing 1% by mass of spherical silica relative to the mass of polyester A.

[0977] The spherical silica is monodisperse silica particles obtained by adding a mixed solution of ethanol and ethyl silicate to the mixed solution while stirring, stirring the resulting reaction solution, performing a hydrolysis reaction of the ethyl silicate and a polycondensation reaction of the hydrolysis product, and then stirring the reaction solution after the reaction.

[0978] (Production of Polyester G Pellets)

[0979] To 100 parts by mass of dimethyl terephthalate and 64 parts by mass of ethylene glycol were added 0.04 parts by mass of manganese acetate and 0.03 parts by mass of antimony trioxide as catalysts to carry out an ester exchange reaction. Then, a slurry containing agglomerated alumina was added to the reaction product, and then antimony trioxide was added to carry out a polycondensation reaction to obtain polyester G particles (referred to as polyester G in Table 6) having an intrinsic viscosity of 0.62 dl / g and containing 2% by mass of agglomerated alumina.

[0980] The slurry containing the agglomerated alumina was prepared by using delta-alumina as the agglomerated alumina, preparing a 10 mass % ethylene glycol slurry, pulverizing and dispersing it using a sand mill, and filtering it using a 3 μm filter with a collection efficiency of 95%.

[0981] (Production of Polyester Z Pellets)

[0982] When polyester A particles were produced in the same manner as described above, spherical silica (SO-C1 manufactured by Admatech Inc., particle size: 0.2 μm to 0.4 μm) was added after the esterification reaction was completed, and then a polycondensation reaction was carried out to obtain silica-containing polyester Z particles containing 1 mass% of spherical silica relative to the mass of polyester A (referred to as polyester Z in Table 6).

[0983] (Fabrication of Temporary Support Body 8)

[0984] A temporary support 8 (a single-layer polyethylene terephthalate film having a thickness of 16 μm) was produced in the same manner as in the production of the temporary support 1 except that the particle-containing layer was not formed.

[0985] The arithmetic mean roughness Ra of the first surface of the temporary support 8 was 0.2 nm.

[0986] (Fabrication of Temporary Support Body 9)

[0987] Surface irregularities were formed on the first surface of the temporary support 8 by thermal nanoimprinting (heating temperature: 130° C., pressure: 0.1 MPa), thereby producing a temporary support 9 (a single-layer polyethylene terephthalate film having a thickness of 16 μm).

[0988] The arithmetic mean roughness Ra of the first surface of the temporary support 9 is 35 nm.

[0989] (Fabrication of Temporary Supports 10 to 15)

[0990] For each layer, a mixture of raw materials prepared with the formulations shown in Table 6 was stirred in a mixer and then fed into a vented twin-screw extruder for layer A and layer B. The melt was extruded at 275°C, filtered twice through a 3μm pore size filter, and then joined and laminated using a rectangular three-layer hinge block to produce a three-layer laminate consisting of layer A / layer B / layer A. The laminate was then wound onto a casting drum with a surface temperature of 25°C using an electrostatic cast method over a cooling roll maintained at 28...

Claims

1. A photosensitive transfer material comprising a temporary support and a photosensitive resin layer in this order, When the limiting resolution of the photosensitive resin layer is defined as X μm and the reference diameter of the particles is defined as Y μm represented by the formula (1): Y=0.75×X, the number of particles having a diameter of Y μm or more in the temporary support is 15 particles / cm 2 the following, As the limiting resolution of the photosensitive resin layer, the minimum line width of the resin pattern having the minimum line width corresponding to the pattern of the mask obtained by performing the following series of steps (1) to (4) while adjusting the exposure amount each time is adopted. (1) a photosensitive transfer material is brought into contact with a polyethylene terephthalate film having a thickness of 100 μm, and a photosensitive resin layer and a temporary support are sequentially arranged on the polyethylene terephthalate film; (2) Using an autoclave apparatus, the obtained laminate was defoamed under pressure at 0.6 MPa and 60°C for 30 minutes; (3) Using an ultra-high pressure mercury lamp, without peeling off the temporary support, the photosensitive resin layer is exposed through a line and space pattern mask with a duty ratio of 1:1 and a line width that changes stepwise by 1 μm from 1 μm to 20 μm; (4) After the temporary support was peeled off, the photosensitive resin layer was developed to form a resin pattern. The development was performed by shower development using a 1.0 mass % sodium carbonate aqueous solution at 25° C. for 30 seconds.

2. The photosensitive transfer material according to claim 1, wherein The number of particles having a diameter of 10.5 μm or greater in the temporary support is 1.0 particle / cm 2 the following.

3. The photosensitive transfer material according to claim 1 or 2, wherein The temporary support has a thickness of 16 μm or less.

4. The photosensitive transfer material according to claim 1 or 2, wherein The photosensitive resin layer has a thickness of 5 μm or less.

5. A photosensitive transfer material comprising a temporary support and a photosensitive resin layer in this order, The temporary support is a polyester film composed of two or more layers, and at least one surface layer does not contain fillers. The surface layer forms a phase separation structure by containing a polyester resin having an aromatic ring structure and a polyester resin having an alicyclic structure having a different compatibility with the polyester resin having an aromatic ring structure. The arithmetic mean roughness Ra of the surface of the temporary support on the side opposite to the photosensitive resin layer side is 1 nm to 50 nm.

6. The photosensitive transfer material according to claim 5, wherein The surface layer on the photosensitive resin layer side of the temporary support does not contain a filler.

7. The photosensitive transfer material according to claim 5 or 6, wherein When the limiting resolution of the photosensitive resin layer is defined as X μm and the reference diameter of the particles is defined as Y μm represented by the formula (1): Y=0.75×X, the number of particles having a diameter of Y μm or more in the temporary support is 15 particles / cm 2 the following, As the limiting resolution of the photosensitive resin layer, the minimum line width of the resin pattern having the minimum line width corresponding to the pattern of the mask obtained by performing the following series of steps (1) to (4) while adjusting the exposure amount each time is adopted. (1) a photosensitive transfer material is brought into contact with a polyethylene terephthalate film having a thickness of 100 μm, and a photosensitive resin layer and a temporary support are sequentially arranged on the polyethylene terephthalate film; (2) Using an autoclave apparatus, the obtained laminate was defoamed under pressure at 0.6 MPa and 60°C for 30 minutes; (3) Using an ultra-high pressure mercury lamp, without peeling off the temporary support, the photosensitive resin layer is exposed through a line and space pattern mask with a duty ratio of 1:1 and a line width that changes stepwise by 1 μm from 1 μm to 20 μm; (4) After the temporary support was peeled off, the photosensitive resin layer was developed to form a resin pattern. The development was performed by shower development using a 1.0 mass % sodium carbonate aqueous solution at 25° C. for 30 seconds.

8. The photosensitive transfer material according to claim 5 or 6, wherein The alicyclic structure is a cyclohexane ring.

9. The photosensitive transfer material according to claim 5 or 6, wherein The surface layer contains copolymerized polyethylene terephthalate containing isophthalic acid as a copolymer component.

10. A method for manufacturing a resin pattern, the method using the photosensitive transfer material according to any one of claims 1 to 9, the method comprising: The process of preparing the substrate; The process of bringing the photosensitive transfer material into contact with the substrate, and sequentially disposing a photosensitive resin layer and a temporary support on the substrate; A process of exposing the photosensitive resin layer to a pattern; and A step of developing the exposed photosensitive resin layer to form a resin pattern.

11. The method for manufacturing a resin pattern according to claim 10, wherein: The line width of the resin pattern is less than 10 μm.

12. A method for manufacturing a conductive pattern, the method using the photosensitive transfer material according to any one of claims 1 to 9, the method comprising: A step of preparing a substrate including a conductive layer; The process of bringing the photosensitive transfer material into contact with the substrate, and sequentially disposing a photosensitive resin layer and a temporary support on the substrate; A process of exposing the photosensitive resin layer to a pattern; a step of developing the exposed photosensitive resin layer to form a resin pattern; and A step of etching the conductive layer not covered by the resin pattern to form a conductive pattern. 13 . A touch sensor comprising a conductive pattern obtained by the method for manufacturing a conductive pattern according to claim 12 .

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