Light-shielding material, LED array and electronic device

Abstract

To provide a photosensitive transfer material capable of obtaining an excellent rectangular pattern.SOLUTION: There are provided: a photosensitive transfer material including a temporary support and a transfer layer including a photosensitive layer, where the photosensitive layer has infrared curable properties, and a transmittance of the photosensitive layer to light having a wavelength of 830 nm is 0.1% or more; a light-shielding material including a resin layer including a first surface, a second surface opposite to the first surface, and through-holes extending from the first surface to the second surface, where a transmittance of the resin layer to light having a wavelength of 830 nm is 0.1% or more; and an LED array and an electronic device comprising the light-shielding material.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a photosensitive transfer material, a light-shielding material, an LED array, and an electronic device.

Background Art

[0002] Light Emitting Diodes (LEDs) have seen an explosive increase in demand due to their low power consumption and environmental friendliness, and are widely applied in lighting devices, backlights for liquid crystal display devices, and display devices.

[0003] Also, as a conventional transfer film, the one described in Patent Document 1 is known. Patent Document 1 describes a transfer film having a photosensitive layer containing a temporary support, a binder having a weight average molecular weight of 4000 to 25000, a polymerization initiator exceeding 0% by mass and less than 9% by mass based on the total solid content of the composition, a polymerizable monomer, and a pigment, wherein the polymerizable monomer contains a bifunctional polymerizable monomer (excluding nonaethylene glycol diacrylate), the ratio of the mass of the bifunctional polymerizable monomer to the total mass of the polymerizable monomer is 50% by mass or more, and the pigment is a black pigment.

[0004] Furthermore, as a conventional negative-type image recording material, the one described in Patent Document 2 is known. Patent Document 2 describes a heat-mode compatible negative-type image recording material containing (A) a cationic polymethine dye having a chromophore with an oxidation potential of 0.45 V (vs. SCE) or less and being infrared-absorbing and having a positive charge, (B) an onium salt as a thermal radical generator, and (C) a radically polymerizable compound, which can be recorded by irradiation with infrared rays.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] When a plurality of optical elements such as mini-LEDs and micro-LEDs are densely arranged on a substrate, a light-shielding layer is formed to suppress color mixing caused by the light. The light-shielding layer is patterned on the hole along the shape of the light-emitting body of the optical element. Conventionally, it has been manufactured by coating such as inkjet, spin coating, and slit coating using black ink. However, due to uneven film thickness of the black ink layer, there has been room for improvement in appearance due to density unevenness. From the viewpoint of film thickness uniformity, it is also known to form a light-shielding layer by dry-filmizing black ink and transferring it (Patent Document 1). However, there has been room for improvement in light leakage from the hole end when an optical element such as an LED emits light for any light-shielding material. As a result of various studies, the inventor has found that the above light leakage is related to the rectangularity of the pattern of the light-shielding layer.

[0007] An object to be solved by one embodiment of the present invention is to provide a photosensitive transfer material capable of obtaining a pattern excellent in rectangularity. Another object to be solved by one embodiment of the present invention is to provide a light-shielding material having a pattern excellent in rectangularity. Another object to be solved by another embodiment of the present invention is to provide an LED array and an electronic device including the above light-shielding material. [Means for Solving the Problems]

[0008] Means for solving the above problems include the following aspects. <1> A photosensitive transfer material having a temporary support and a transfer layer containing a photosensitive layer, wherein the photosensitive layer has infrared curability and a transmittance of the photosensitive layer to light with a wavelength of 830 nm is 0.1% or more. Photosensitive transfer material. <2> The photosensitive transfer material according to <1>, wherein the optical density of the photosensitive layer with respect to light having a wavelength of 550 nm is 3.0 or more. <3> The photosensitive transfer material according to <1> or <2>, wherein the photosensitive layer contains a colorant. <4> The photosensitive transfer material according to <3>, wherein the colorant contains an organic pigment. <5> The photosensitive transfer material according to any one of <1> to <4>, wherein the photosensitive layer contains an infrared absorber and a polymerization initiator. <6> The photosensitive transfer material according to <5>, wherein the infrared absorber is an infrared absorbing dye. <7> The photosensitive transfer material according to <5> or <6>, wherein the infrared absorber is a polymethine dye. <8> The photosensitive transfer material according to any one of <5> to <7>, wherein the oxidation potential of the infrared absorber is 0.45 V (vs. SCE) or less. <9> The photosensitive transfer material according to any one of <5> to <8>, wherein the polymerization initiator is an onium salt compound. <10> The photosensitive transfer material according to <9>, wherein the onium salt compound is at least one compound selected from the group consisting of a sulfonium salt compound and an iodonium salt compound. <11> The photosensitive transfer material according to any one of <5> to <10>, wherein the photosensitive layer further contains a polymerizable compound. <12> The photosensitive transfer material according to <11>, wherein the polymerizable compound contains a bifunctional polymerizable compound. <13> The photosensitive transfer material according to <12>, wherein the content of the bifunctional polymerizable compound is 50% by mass or more based on the total mass of the polymerizable compounds. <14> The photosensitive transfer material according to any one of <11> to <13>, wherein the polymerizable compound contains a monomer having a bisphenol A skeleton. <15> The photosensitive transfer material according to any one of <1> to <14>, wherein the photosensitive layer contains a polymer having a crosslinkable group. <16> The photosensitive transfer material according to any one of <1> to <15>, which is a photosensitive transfer material for an LED array. <17> A light-shielding material having a resin layer having a first surface, a second surface opposite to the first surface, and a through hole extending from the first surface to the second surface, wherein the transmittance of the resin layer to light with a wavelength of 830 nm is 0.1% or more. <18> The light-shielding material according to <17>, wherein the through hole has an inclination in the thickness direction of the resin layer, and the inclination angle formed by the side surface of the through hole and the first surface is 60° or more. <19> The light-shielding material according to <17> or <18>, wherein the average value of the size of the through hole on the first surface is 50 μm or less. <20> The light-shielding material according to any one of <17> to <19>, wherein the optical density of the resin layer with respect to light having a wavelength of 550 nm is 3.0 or more. <21> The light-shielding material according to any one of <17> to <20>, which is a light-shielding material for an LED array. <22> An electronic device including the light-shielding material according to any one of <17> to <20>. <23> An LED array including the light-shielding material according to <21>. <24> An electronic device including the LED array according to <23>.

Advantages of the Invention

[0009] According to one embodiment of the present invention, a photosensitive transfer material capable of obtaining a pattern excellent in rectangularity can be provided. According to another embodiment of the present invention, a light-shielding material having a pattern excellent in rectangularity can be provided. Further, according to another embodiment of the present invention, an LED array and an electronic device including the light-shielding material can be provided.

Brief Description of the Drawings

[0010]

Figure 1

Embodiments for Carrying Out the Invention

[0011] The following describes the content of the present disclosure. Although the description will be made with reference to the accompanying drawings, reference numerals may be omitted in some cases. In addition, in this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In addition, in this specification, "(meth)acryl" represents both or either of acrylic and methacrylic, "(meth)acrylate" represents both or either of acrylate and methacrylate, and "(meth)acryloyl" represents both or either of acryloyl and methacryloyl. Furthermore, in this specification, the amount of each component in the composition means the total amount of the plurality of substances corresponding to each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. In this specification, the term "step" includes not only an independent step but also a case where it cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved. In the notation of a group (atomic group) in this specification, a notation without indicating substitution or non-substitution includes both those having no substituent and those having a substituent. For example, the term "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, examples of the light used for exposure generally include actinic rays (active energy rays) such as the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In addition, the chemical structural formula in this specification may be described as a simplified structural formula omitting hydrogen atoms. In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous. In addition, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In addition, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in the present disclosure are molecular weights converted using a gel permeation chromatography (GPC) analyzer with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are product names manufactured by Tosoh Corporation), detected by a differential refractometer using solvent THF (tetrahydrofuran), and polystyrene as a standard substance. In this specification, "total solid content" refers to the total mass of the components obtained by removing the solvent from the total composition of the composition. Also, "solid content" refers to the components excluding the solvent as described above, and may be solid or liquid at 25°C, for example.

[0012] (Photosensitive transfer material) The photosensitive transfer material according to the present disclosure has a temporary support and a transfer layer containing a photosensitive layer, the photosensitive layer has infrared curability, and the transmittance of the photosensitive layer to light with a wavelength of 830 nm is 0.1% or more. The photosensitive transfer material according to the present disclosure can be suitably used as a photosensitive transfer material for an LED array.

[0013] Conventionally, light-shielding materials, particularly those used for LED arrays and the like, have poor light transmittance, and it is considered that exposure light does not reach deep into the resist, and the curability, particularly the effect in the deep part, is not sufficient. Therefore, there are often problems with the rectangularity of patterns such as through-holes. Since the photosensitive layer of the photosensitive transfer material according to the present disclosure has infrared curability and the transmittance of the photosensitive layer to light with a wavelength of 830 nm is 0.1% or more, it has appropriate transmittance to light with a wavelength of 830 nm, so the curability is improved. Also, compared with exposure with short-wavelength light such as a high-pressure mercury lamp, since the wavelength of the light is long, light refraction is suppressed, and it is considered that the pattern is exposed more faithfully. Therefore, it is estimated that the rectangularity of the obtained pattern is excellent.

[0014] <Transmittance to light with a wavelength of 830 nm> The photosensitive transfer material according to the present disclosure has a transmittance of the photosensitive layer with respect to light having a wavelength of 830 nm of 0.1% or more, and from the viewpoints of blackening property (suppression of reflection due to external reflected light, for example, suppression of reflection of fluorescent lamps), patterning property (particularly, linearity and suppression of development residues), and rectangularity of the obtained pattern, it is preferably 0.15% or more and 30% or less, and more preferably 0.20% or more and 20% or less.

[0015] <Optical density at a wavelength of 550 nm of light> The photosensitive transfer material according to the present disclosure preferably has an optical density of the photosensitive layer at a wavelength of 550 nm of light of 1.5 or more, more preferably 2.5 or more, still more preferably 3.0 or more, and particularly preferably 3.0 or more and 5.0 or less, from the viewpoints of blackening property, patterning property, and rectangularity of the obtained pattern.

[0016] In the present disclosure, the transmittance at each of the above wavelengths is measured using a spectrophotometer (UV-1800, manufactured by Shimadzu Corporation). In the present disclosure, the optical density is measured using a transmission densitometer (BMT-1, manufactured by Sakata Inx Corporation).

[0017] The photosensitive transfer material according to the present disclosure has a temporary support and a transfer layer containing a photosensitive layer. Examples of the transfer layer include, in addition to the photosensitive layer, a thermoplastic resin layer, a water-soluble resin layer, and a functional layer. The photosensitive layer preferably contains a pigment, and more preferably contains an organic pigment, from the viewpoints of blackening property, patterning property, and rectangularity of the obtained pattern. Further, the photosensitive layer preferably contains an infrared absorber and a polymerization initiator, preferably contains a colorant, a polymerizable compound, an infrared absorber, and a polymerization initiator, and more preferably contains a colorant, an alkali-soluble resin, a polymerizable compound, an infrared absorber, and a polymerization initiator, from the viewpoints of pattern formability, blackening property, patterning property, and rectangularity of the obtained pattern. The photosensitive transfer material may have the temporary support and the photosensitive layer directly laminated without any intervening layers, or may be laminated via other layers. Further, other layers may be laminated on the surface of the photosensitive layer opposite to the surface facing the temporary support. Examples of the other layers other than the temporary support and the photosensitive layer include a thermoplastic resin layer, a water-soluble resin layer, a functional layer, and a protective film.

[0018] An example of the embodiment of the photosensitive transfer material according to the present disclosure is shown below, but is not limited thereto. (1) "Temporary support / Photosensitive layer / Protective film" (2) "Temporary support / Thermoplastic resin layer / Photosensitive layer / Protective film" (3) "Temporary support / Functional layer / Photosensitive layer / Protective film" (4) "Temporary support / Thermoplastic resin layer / Functional layer / Photosensitive layer / Protective film" In each of the above configurations, the photosensitive layer is preferably a negative-type photosensitive layer.

[0019] In the case of a configuration in which the photosensitive transfer material further has other layers on the side opposite to the temporary support side of the photosensitive layer, the total thickness of the other layers arranged on the side opposite to the temporary support side of the photosensitive layer is preferably 0.1% to 30% with respect to the layer thickness of the photosensitive layer, and more preferably 0.1% to 20%.

[0020] Hereinafter, the photosensitive transfer material will be described with an example. The photosensitive transfer material 20 shown in FIG. 1 has, in this order, a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, a functional layer 15, and a photosensitive layer 17, and a protective film 19. Note that the photosensitive transfer material 20 shown in FIG. 1 is in a form in which the protective film 19 is arranged, but the protective film 19 may not be arranged. Further, the photosensitive transfer material 20 shown in FIG. 1 is in a form in which the thermoplastic resin layer 13 and the functional layer 15 are arranged, but the thermoplastic resin layer 13 and the functional layer 15 may not be arranged. Hereinafter, each element constituting the photosensitive transfer material will be described.

[0021] [Temporary support] The photosensitive transfer material used in the present disclosure has a temporary support. The temporary support supports a photosensitive layer or a laminate including a photosensitive layer, and is a peelable support.

[0022] From the viewpoint that the photosensitive layer can be exposed through the temporary support when the photosensitive layer is pattern-exposed, the temporary support preferably has light transmittance. In this specification, "having light transmittance" means that the transmittance of light having a wavelength used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive layer, the transmittance of light having a wavelength (more preferably a wavelength of 365 nm) used for pattern exposure is preferably 60% or more, and more preferably 70% or more, for the temporary support. Note that the transmittance of a layer included in the photosensitive transfer material is the ratio of the intensity of the transmitted light that has passed through the layer to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and is measured using the MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0023] Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper, and a resin film is preferable from the viewpoints of strength, flexibility, and light transmittance. Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.

[0024] The thickness (layer thickness) of the temporary support is not particularly limited, and may be selected according to the material from the viewpoints of the strength as a support, the flexibility required for bonding to a substrate for forming circuit wiring, and the light transmittance required in the first exposure step. The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 35 μm, and particularly preferably in the range of 10 μm to 20 μm from the viewpoints of ease of handling and versatility. Also, from the viewpoints of resolution and linearity in the case of exposure through the temporary support, the thickness of the temporary support is preferably 50 μm or less, and more preferably 25 μm or less.

[0025] Also, the film used as the temporary support preferably has no deformations such as wrinkles, scratches, defects, etc. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, defects, precipitates, etc. contained in the temporary support is preferably small. The number of fine particles, foreign substances, and defects with a diameter of 1 μm or more is preferably 2 50 pieces / 10 mm or less, 2 more preferably 10 pieces / 10 mm or less, 2 still more preferably 3 pieces / 10 mm or less, 2 and particularly preferably 0 pieces / 10 mm.

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

[0027] 〔Photosensitive layer〕 The photosensitive transfer material according to the present disclosure has an infrared curable photosensitive layer. The photosensitive layer has infrared curability, that is, it is a layer that can be cured by infrared rays of at least a part of the wavelengths in the infrared wavelength range (wavelength exceeding 780 nm and not exceeding 1 mm, preferably wavelength exceeding 780 nm and not exceeding 1,200 nm). Specifically, it is a layer that can be cured by exposure using an IR-LD (wavelength 830 nm) or a YAG laser (wavelength 1,064 nm). Generally, since infrared light has low irradiation energy, it is preferable to perform exposure using a high-output laser. The photosensitive layer is preferably a negative photosensitive layer in which the solubility of the exposed portion in the developer decreases upon exposure, and the unexposed portion is removed by development. Hereinafter, each component will be described in order.

[0028] <Colorant> From the viewpoints of blackening property, patterning property, and rectangularity of the obtained pattern, the photosensitive layer preferably contains a colorant, and more preferably contains a pigment. Further, the colorant is preferably a colorant different from the infrared absorber described later. There is no particular limitation on the colorant, and known pigments and known dyes can be used. The pigment can be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and colored pigments other than black and white. Among them, from the viewpoints of blackening property, patterning property, and rectangularity of the obtained pattern, it is preferable to contain at least one pigment selected from the group consisting of red pigments, blue pigments, and green pigments, more preferably to contain red pigments and blue pigments, and particularly preferably to contain red organic pigments and blue organic pigments.

[0029] Examples of the organic pigment include phthalocyanine pigment, dioxazine pigment, quinacridone pigment, anthraquinone pigment, perylene pigment, azo pigment, diketopyrrolopyrrole pigment, pyrrolopyrrole pigment, isoindoline pigment, quinophthalone pigment, triarylmethane pigment, xanthene pigment, methine pigment, quinoline pigment, and the like.

[0030] Examples of the red pigment include, for example, C.I.Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294, 295, 296, 297, etc.

[0031] Examples of the blue pigment include, for example, C.I.Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc.

[0032] Examples of the green pigment include Color Index Pigment Green 7, 10, 36, 37, 58, 59, etc. Further, as other green pigments, a zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule may be further contained. Specific examples of such zinc phthalocyanine halogenated pigments include the compounds described in International Publication No. 2015 / 118720.

[0033] When the red pigment and the blue pigment are used in combination, the mass ratio of the content of the red pigment to the content of the blue pigment in the photosensitive layer is preferably from 3:1 to 1:3, more preferably from 2:1 to 1:2, and particularly preferably from 1.5:1 to 1:1.5, from the viewpoints of blackening property, patterning property, and rectangularity of the resulting pattern.

[0034] From the perspective of dispersion stability, the average primary particle size of the pigment is preferably from 0.005 μm to 1 μm, more preferably from 0.01 μm to 0.5 μm, and particularly preferably from 0.01 μm to 0.2 μm.

[0035] Incidentally, the average primary particle size of the pigment can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, the transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. Measure the maximum length (Dmax: the maximum length between two points on the contour of the particle image) and the maximum length perpendicular length (DV-max: the shortest length connecting perpendicularly between two straight lines when the image is sandwiched by two straight lines parallel to the maximum length) of the particle image obtained using the transmission electron microscope, and take the geometric mean value (Dmax × DV-max)1 / 2 as the particle size. Measure the particle sizes of 100 particles by this method, and take the arithmetic mean value as the average particle size, which is the average primary particle size of the pigment.

[0036] From the viewpoints of blackening property, patterning property, and the rectangularity of the obtained pattern, the content of the colorant is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 60% by mass, and particularly preferably 15% by mass to 50% by mass with respect to the total mass of the photosensitive layer.

[0037] Incidentally, when the photosensitive layer contains a pigment and the photosensitive layer is formed of a photosensitive resin composition, the pigment is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion liquid. The dispersion liquid may be prepared by adding a mixture obtained by previously mixing a pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent. For example, a commercially available dispersant can be used. The vehicle refers to the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion liquid, is liquid, and includes a binder component that holds the pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0038] There are no particular restrictions on the disperser, and examples thereof include known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Further, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For the disperser and fine pulverization, reference can be made to the descriptions in "Encyclopedia of Pigments" (written by Kunizo Asakura, first edition, Asakura Shoten, 2000, pages 438 and 310).

[0039] <Infrared absorber> From the viewpoints of blackening property, patterning property, and rectangularity of the resulting pattern, the photosensitive layer preferably contains an infrared absorber. There are no particular restrictions on the infrared absorber, and examples thereof include pigments and dyes. As the dyes used as infrared absorbers, commercially available dyes and known dyes described in documents such as "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, examples include azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium pigments, pyrylium salts, metal thiolate complexes, and the like. Among them, from the viewpoints of blackening property, patterning property, and rectangularity of the resulting pattern, it is preferably an infrared absorbing dye, more preferably a polymethine pigment, and particularly preferably a cyanine pigment.

[0040] From the viewpoints of blackening property, patterning property, and rectangularity of the resulting pattern, the oxidation potential of the infrared absorber is preferably 0.45 V or less (vs SCE), more preferably 0.40 V or less (vs SCE), and still more preferably 0.35 V or less (vs SCE). Also, although there is no specific lower limit for the oxidation potential of the infrared absorber, from the viewpoint of stability when used in combination with a polymerization initiator, it is preferably 0.10 V (vs SCE) or more, and more preferably 0.15 V (vs SCE) or more.

[0041] As such an infrared absorber, in order to reduce the oxidation potential, those having an electron-donating substituent in the chromophore of the infrared absorber are preferred. Preferred electron-donating substituents include substituents with a Hammett σ para value of -0.10 or less. Suitable substituents with a σ para value of -0.10 or less include alkyl groups such as methyl group, ethyl group, propyl group (σ para value is about -0.12 to -0.20), hydroxy group (σ para value is -0.37), alkoxy groups such as methoxy group, ethoxy group, propyloxy group, butoxy group (σ para value is about -0.24 to -0.45), aryloxy groups such as phenoxy group, toluoyloxy group (σ para value is about -0.32), (substituted) amino groups such as amino group, methylamino group, ethylamino group, butylamino group, dimethylamino group, diethylamino group, phenylamino group, diphenylamino group (σ para value is -0.50 to -0.35). Alkoxy groups and (substituted) amino groups with a large electron-donating property are particularly preferred.

[0042] Also, from the viewpoint of expanding the conjugated system of the chromophore and reducing the oxidation potential, substituents having an aromatic group linked by a heteroatom are also mentioned as preferred substituents. Examples of the heteroatom linking the aromatic group include nitrogen, oxygen, phosphorus, sulfur, selenium, etc. Particularly preferred heteroatom is sulfur. Examples of the linked aromatic group include hydrocarbon aromatic groups such as phenyl group, naphthyl group, anthranyl group, and heterocyclic groups such as furyl group, thienyl group, pyrazolyl group, triazolyl group, indolyl group, benzothiazolyl group. Heterocyclic groups are particularly preferred. These aromatic groups may have substituents. Preferred substituents include substituents with a Hammett σ para value of -0.10 or less.

[0043] As the chromophore of the infrared absorber, polymethine dyes such as cyanine dyes are preferred from the viewpoints of absorption wavelength suitability, solubility, stability, potential characteristics, etc. Among them, cyanine dyes are preferred, and heptamethine cyanine dyes having an indolenine skeleton, a benzoindolenine skeleton, a benzothiazole skeleton, a benzoxazole skeleton, or a benzoselenazole skeleton are particularly preferred from the viewpoints of absorption wavelength suitability and potential suitability. Further, these polymethine dyes are preferably cationic dyes in which the chromophore has a positive charge. Among the dyes having the chromophore as described above, preferred examples include compounds represented by the following formula (D1) or formula (D2).

[0044]

Chemical formula

[0045] In formula (D1), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (number of carbon atoms), and R 1 and R 2 may be bonded to each other to form a ring structure, and the ring to be formed is preferably a 5-membered ring or a 6-membered ring. Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring which may have a substituent. Preferred aromatic hydrocarbon rings include a benzene ring and a naphthalene ring. Further, preferred substituents include a hydrocarbon group having 12 or fewer carbon atoms, a halogen atom, an alkoxy group having 12 or fewer carbon atoms, and the like. Y 1 and Y 2 each independently represents a sulfur atom or a dialkylmethylene group having 12 or fewer carbon atoms. R 3 and R 4 each independently represents a hydrocarbon group having 20 or fewer carbon atoms which may have a substituent. Preferred substituents include an alkoxy group having 12 or fewer carbon atoms, a carboxy group, a sulfo group, and the like. R 5 ~R 8Each independently represents a hydrogen atom or a hydrocarbon group having 12 or fewer carbon atoms. From the viewpoint of availability of raw materials, it is preferably a hydrogen atom. R 9 and R 10 each independently represents an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a hydrogen atom, or R 9 and R 10 may be bonded to each other to form a ring having the following structure.

[0046]

Chemical formula

[0047] Among them, an aromatic hydrocarbon group such as a phenyl group is preferable. Also, X - represents a counter anion. However, when any of R 1 to R 8 is substituted with a sulfo group, X - is not necessary. Preferred X - is a halide ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, or sulfonate ion from the viewpoint of storage stability of the coating solution, and particularly preferably a perchlorate ion, hexafluorophosphate ion, or arylsulfonate ion.

[0048]

Chemical formula

[0049] In formula (D2), R 1 to R 8 , Ar 1 , Ar 2 , Y 1 and Y 2 are respectively synonymous with R 1 to R 8 , Ar 1 , Ar 2 , Y 1 and Y 2 in the above formula (D1). Ar3 represents a monocyclic or polycyclic heterocyclic group having at least one atom selected from nitrogen atom, oxygen atom and sulfur atom, and is preferably a heterocyclic group selected from the group consisting of thiazole-based, benzothiazole-based, naphthothiazole-based, thianaphtheno-7’,6’,4,5-thiazole-based, oxazole-based, benzoxazole-based, naphthoxazole-based, selenazole-based, benzoselenazole-based, naphthoselenazole-based, thiazoline-based, 2-quinoline-based, 4-quinoline-based, 1-isoquinoline-based, 3-isoquinoline-based, benzimidazole-based, 3,3-dialkylbenzoindolenine-based, 2-pyridine-based, 4-pyridine-based, 3,3-dialkylbenzo[e]indole-based, tetrazole-based, triazole-based, pyrimidine-based, and thiadiazole-based, and particularly preferred heterocyclic groups include those having the following structures.

[0050]

Chemical formula

[0051] Among the dyes having a chromophore as described above, the compound represented by the formula (D1) is particularly preferred.

[0052] In the present disclosure, the oxidation potential of the infrared absorber refers to a value measured by potentiometry using a hydrogen electrode, a glass electrode, a quinone-hydrogen electrode, etc. as an indicator electrode and a saturated calomel electrode, a silver-silver chloride electrode, etc. as a reference electrode in a polar solvent such as acetonitrile or methanol, and converted to a value with respect to a standard calomel electrode.

[0053] In the present disclosure, specific examples (IR-4 to IR-12) of infrared absorbers that can be preferably used are listed below together with their oxidation potentials, but the present disclosure is not limited thereto. The oxidation potential measurement conditions of the following infrared absorbers are polar solvents (0.1M (=0.1mol / L) of Et 4 NClO 4In (acetonitrile (MeCN) (where Et represents an ethyl group)), the values measured using a rotating disk electrode made of Pt as the indicator electrode and a Ag / AgCl (silver-silver chloride) electrode as the reference electrode are described as those converted to the values with respect to a standard calomel electrode as the reference electrode.

[0054] [Chemical formula]

[0055] [Chemical formula]

[0056] [Chemical formula]

[0057] The infrared absorber may be used alone or in combination of two or more. From the viewpoints of blackening property, patterning property, and rectangularity of the resulting pattern, the content of the polymerizable compound in the photosensitive layer is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 10% by mass, and particularly preferably 0.1% by mass to 5% by mass with respect to the total mass of the photosensitive layer.

[0058] [Photoinitiator] The photosensitive layer preferably contains a photoinitiator. A photoinitiator is a compound that initiates the polymerization of ethylenically unsaturated compounds upon receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photoinitiator is not particularly limited, and known photoinitiators can be used. In addition, the photoinitiators in the present disclosure are assumed to include sensitizers. Examples of the photoinitiator include a photo radical polymerization initiator and a photo cationic polymerization initiator, and a photo radical polymerization initiator is preferred.

[0059] Examples of the photo radical polymerization initiator include a photo polymerization initiator having an oxime ester structure, a photo polymerization initiator having an α-aminoalkylphenone structure, a photo polymerization initiator having an α-hydroxyalkylphenone structure, a photo polymerization initiator having an acylphosphine oxide structure, a photo polymerization initiator having an N-phenylglycine structure, and a biimidazole compound.

[0060] From the viewpoints of blackening property, patterning property, and rectangularity of the obtained pattern, the polymerization initiator is preferably an onium salt compound. From the viewpoints of blackening property, patterning property, and rectangularity of the obtained pattern, the onium salt compound is preferably at least one compound selected from the group consisting of a sulfonium salt compound and an iodonium salt compound, and more preferably an iodonium salt compound.

[0061] Examples of the onium salt compound include a diazonium salt compound, an iodonium salt compound, a sulfonium salt compound, an ammonium salt compound, a pyridinium salt compound, and the like. In the present disclosure, these onium salt compounds are presumed to function as ionic radical polymerization initiators rather than acid generators. The onium salt compound preferably used is an onium salt compound represented by the following formulas (III) to (V).

[0062] [Chemical formula]

[0063] In formula (III), Ar 11 and Ar 12 each independently represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred substituents when this aryl group has a substituent are preferably a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Z 11-represents a counter ion selected from the group consisting of halide ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, and sulfonate ions, and is preferably perchlorate ions, hexafluorophosphate ions, or arylsulfonate ions.

[0064] In formula (IV), Ar 21 represents an aryl group having 20 or fewer carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or fewer carbon atoms, an alkoxy group having 12 or fewer carbon atoms, an aryloxy group having 12 or fewer carbon atoms, an alkylamino group having 12 or fewer carbon atoms, a dialkylamino group having 12 or fewer carbon atoms, an arylamino group having 12 or fewer carbon atoms, or a diarylamino group having 12 or fewer carbon atoms. Z 21- represents a counter ion synonymous with Z 11-

[0065] In formula (V), R 31 ~R 33 each independently represents a hydrocarbon group having 20 or fewer carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or fewer carbon atoms, an alkoxy group having 12 or fewer carbon atoms, or an aryloxy group having 12 or fewer carbon atoms. Z 31- represents a counter ion synonymous with Z 11-

[0066] In the present disclosure, specific examples of the onium salt compounds ([OI-1] to [OI-10]) represented by formula (III), the onium salt compounds ([ON-1] to [ON-5]) represented by formula (IV), and the onium salt compounds ([OS-1] to [OS-6]) represented by formula (V) that can be preferably used are given below.

[0067]

Chemical formula

[0068]

Chemical formula

[0069]

Chem.

[0070]

Chem.

[0071] Moreover, as the biimidazole compound, a hexaarylbiimidazole compound is preferably mentioned. Examples of the biimidazole compound 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.

[0072] The photosensitive layer may contain a biimidazole compound alone as a photoinitiator or may contain two or more thereof. From the viewpoints of suppressing line width variation, line width change during standing time, cross-sectional shape of the resin pattern, and sensitivity, the content of the above biimidazole compound is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% to 10% by mass, and particularly preferably 5% to 10% by mass based on the total mass of the photosensitive layer.

[0073] From the viewpoints of suppressing line width variation, line width change during standing time, cross-sectional shape of the resin pattern, and sensitivity, the photoinitiator preferably contains a benzophenone compound, and more preferably contains a dialkylaminobenzophenone compound. Examples of benzophenone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-phenylbenzophenone, isophthalophenone, 4-benzoyl-4'-methylphenyl sulfide, and the like.

[0074] The photosensitive layer may contain a benzophenone compound alone or in combination of two or more as a photoinitiator. From the viewpoints of suppressing line width variation, line width change during standing time, cross-sectional shape of the resin pattern, and sensitivity, the content of the benzophenone compound is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 2% by mass, still more preferably 0.2% by mass to 1.5% by mass, and particularly preferably 0.4% by mass to 0.8% by mass based on the total mass of the photosensitive layer. When the photoinitiator contains a biimidazole compound and a benzophenone compound, the content of the benzophenone compound is preferably less than the content of the biimidazole compound from the viewpoints of suppressing line width variation, line width change during standing time, cross-sectional shape of the resin pattern, and sensitivity.

[0075] Examples of the photo radical polymerization initiator include those described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783.

[0076] Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0077] Examples of commercially available photo radical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE® OXE01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxyoxime) (trade name: IRGACURE OXE02, manufactured by BASF), IRGACURE OXE03 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.Examples include oxime ester-based photoinitiators (trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0078] A photo cationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving actinic rays. As the photo cationic polymerization initiator, a compound that is sensitive to actinic rays having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm, and generates an acid is preferred, but its chemical structure is not limited. Also, for a photo cationic polymerization initiator that is not directly sensitive to actinic rays having a wavelength of 300 nm or more, if it is a compound that is sensitive to actinic rays having a wavelength of 300 nm or more and generates an acid by being used in combination with a sensitizer, it can be preferably used in combination with the sensitizer. As the photo cationic polymerization initiator, a photo cationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photo cationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photo cationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. The lower limit value of the pKa is not particularly defined, but for example, -10.0 or more is preferred.

[0079] Examples of the photo cationic polymerization initiator include ionic photo cationic polymerization initiators and non-ionic photo cationic polymerization initiators. Examples of the ionic photo cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As the ionic photo cationic polymerization initiator, the ionic photo cationic polymerization initiator described in paragraphs 0114 to 0133 of JP 2014-85643 A may be used.

[0080] Examples of the nonionic photo cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds and imide sulfonate compounds, the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 may be used. As the oxime sulfonate compounds, the compounds described in paragraphs 0084 to 0088 of WO2018 / 179640 may be used.

[0081] The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0082] The photosensitive layer may contain a photoinitiator alone or in combination of two or more. The content of the photoinitiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive layer. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, based on the total mass of the photosensitive layer.

[0083] <Alkali-soluble resin> The photosensitive layer preferably contains an alkali-soluble resin. In the present specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more. Examples of the alkali-soluble resin include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide-epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, epoxy acrylate resins obtained by the reaction of an epoxy resin and (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of an epoxy acrylate resin and an acid anhydride.

[0084] As one of the preferred embodiments of the alkali-soluble resin, a (meth)acrylic resin can be mentioned in terms of excellent alkali developability and film-forming properties. In the present specification, the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more based on all the structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of structural units derived from a (meth)acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth)acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth)acrylic compound is 100% by mass or less based on all the structural units of the (meth)acrylic resin.

[0085] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile. Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl ester is preferred. Examples of the (meth)acrylamide include acrylamides such as diacetone acrylamide.

[0086] Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid methyl, (meth)acrylic acid ethyl, (meth)acrylic acid propyl, (meth)acrylic acid butyl, (meth)acrylic acid pentyl, (meth)acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid octyl, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid nonyl, (meth)acrylic acid decyl, (meth)acrylic acid undecyl, and (meth)acrylic acid dodecyl, etc., which are (meth)acrylic acid alkyl esters having an alkyl group with 1 to 12 carbon atoms. As the (meth)acrylic acid ester, (meth)acrylic acid alkyl esters having an alkyl group with 1 to 4 carbon atoms are preferred, and (meth)acrylic acid methyl or (meth)acrylic acid ethyl is more preferred.

[0087] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer forming the above structural unit is not particularly limited as long as it is a compound other than the (meth)acrylic compound copolymerizable with the (meth)acrylic compound. Examples 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, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0088] In addition, from the viewpoint of improving the alkali developability, the (meth)acrylic resin preferably has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Among them, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above (meth)acrylic acid.

[0089] The content of the structural unit having an acid group (preferably the structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more based on the total mass of the (meth)acrylic resin in terms of excellent developability. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.

[0090] In addition, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester. The content of the structural unit derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50% by mass to 90% by mass, more preferably 60% by mass to 90% by mass, still more preferably 65% by mass to 90% by mass, based on all the structural units of the (meth)acrylic resin.

[0091] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid alkyl ester is preferable, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid alkyl ester is more preferable. In addition, 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 preferable.

[0092] In addition, from the viewpoint of more excellent effects in the present disclosure, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate. From the viewpoint of more excellent effects in the present disclosure, the total content of the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on all the structural units of the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, preferably 80% by mass or less.

[0093] In addition, from the viewpoint of more excellent effects in the present disclosure, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and at least one selected from the group consisting of a structural unit derived from acrylic acid and a structural unit derived from an alkyl acrylate. From the viewpoint of more excellent effects in the present disclosure, the mass ratio of the total content of the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate to the total content of the structural unit derived from acrylic acid and the structural unit derived from an alkyl acrylate is preferably 60 / 40 to 80 / 20.

[0094] The (meth)acrylic resin preferably has an ester group at the terminal in terms of excellent developability of the photosensitive layer after transfer. Note that the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. The (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.

[0095] Further, from the viewpoint of developability, for example, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more. Further, from the viewpoint of easily forming a strong film by thermally crosslinking with a crosslinking component upon heating, the alkali-soluble resin is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin), and still more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth)acrylic resin). When the alkali-soluble resin is a resin having a carboxy group, for example, the three-dimensional crosslink density can be increased by adding a thermally crosslinkable compound such as a blocked isocyanate compound and performing thermal crosslinking. Further, when the carboxy group of the resin having a carboxy group is anhydrified and hydrophobized, the wet heat resistance can be improved.

[0096] The carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph 0025 of JP-A-2011-095716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.

[0097] Another preferred embodiment of the alkali-soluble resin includes a styrene-acrylic copolymer. In the present specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer. In addition, 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 still more preferably 5% by mass to 80% by mass with respect to all the structural units of the copolymer. In addition, the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass to 95% by mass with respect to all the structural units of the copolymer.

[0098] From the viewpoint of more excellent effects in the present disclosure, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure. Examples of the monomer that forms the structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth)acrylate. Among them, styrene compounds are preferable, and styrene is more preferable. In addition, from the viewpoint of more excellent effects in the present disclosure, the alkali-soluble resin more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene).

[0099]

Chemical formula

[0100] When the alkali-soluble resin has 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 still more preferably 20% by mass to 60% by mass with respect to all the structural units of the alkali-soluble resin from the viewpoint of more excellent effects in the present disclosure. In addition, 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 still more preferably 20 mol% to 60 mol% with respect to all the structural units of the alkali-soluble resin from the viewpoint of more excellent effects in the present disclosure. Furthermore, from the viewpoint of more excellent effects in the present disclosure, 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%, still more preferably 20 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol% with respect to all the structural units of the alkali-soluble resin. In the present specification, when the content of the "structural unit" is defined by a molar ratio, the above "structural unit" shall be synonymous with the "monomer unit". Further, in the present specification, the above "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0101] From the viewpoint of more excellent effects in the present disclosure, the alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure. That is, the alkali-soluble resin preferably has a structural unit having an aliphatic hydrocarbon ring structure. Among them, the alkali-soluble resin more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

[0102] 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 isophorone ring. Among them, from the viewpoint of more excellent effects in the present disclosure, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 decane ring) is more preferable. 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. Further, from the viewpoint of more excellent effects in the present disclosure, the alkali-soluble resin more preferably has a structural unit represented by the following formula (Cy), and more preferably has the structural unit represented by the above formula (S) and the structural unit represented by the following formula (Cy).

[0103] [Chemical formula]

[0104] In formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0105] R in formula (Cy) M is preferably a methyl group. R in formula (Cy) Cy is preferably a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms, from the viewpoint of more excellent effects in the present disclosure. The R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in may be a monocyclic structure or a polycyclic structure. Also, the aliphatic hydrocarbon ring structure in R of formula (Cy) Cy is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure, from the viewpoint of more excellent effects in the present disclosure. Furthermore, the aliphatic hydrocarbon ring structure in R of formula (Cy) Cy is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, and more preferably a ring in which 2 to 4 aliphatic hydrocarbon rings are fused, from the viewpoint of more excellent effects in the present disclosure. Furthermore, R in formula (Cy) CyFrom the viewpoint of more excellent effects in the present disclosure, it is preferable that the oxygen atom of -C(=O)O- in the formula (Cy) and the aliphatic hydrocarbon ring structure are directly bonded, that is, it is an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and still more preferably a dicyclopentanyl group.

[0106] The alkali-soluble resin may have one kind or two or more kinds of structural units having an aliphatic hydrocarbon ring structure. When the alkali-soluble resin has a structural unit having an aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects in the present disclosure, 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 still more preferably 20% by mass to 70% by mass with respect to all the structural units of the alkali-soluble resin. Also, from the viewpoint of more excellent effects in the present disclosure, 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 still more preferably 20 mol% to 50 mol% with respect to all the structural units of the alkali-soluble resin. Furthermore, from the viewpoint of more excellent effects in the present disclosure, 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 still more preferably 20 mol% to 50 mol% with respect to all the structural units of the alkali-soluble resin.

[0107] When the alkali-soluble resin has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects in the present disclosure, the total content of the structural unit having an aromatic ring structure and the structural unit 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 still more preferably 40% by mass to 75% by mass with respect to all the structural units of the alkali-soluble resin. In addition, from the viewpoint of more excellent effects in the present disclosure, the total content of the structural unit having an aromatic ring structure and the structural unit 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 still more preferably 40 mol% to 60 mol% with respect to all the structural units of the alkali-soluble resin. Furthermore, from the viewpoint of more excellent effects in the present disclosure, 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 still more preferably 40 mol% to 60 mol% with respect to all the structural units of the alkali-soluble resin. In addition, from the viewpoint of more excellent effects in the present disclosure, 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 shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and still more preferably satisfy the following formula (SCy-2). 0.2 ≦ nS / (nS + nCy) ≦ 0.8 Formula (SCy) 0.30 ≦ nS / (nS + nCy) ≦ 0.75 Formula (SCy-1) 0.40 ≦ nS / (nS + nCy) ≦ 0.70 Formula (SCy-2)

[0108] From the viewpoint of more excellent effects in the present disclosure, the alkali-soluble resin preferably has a structural unit having an acid group. Examples of the above acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferred. As the structural unit having the above acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0109]

Chemical formula

[0110] The alkali-soluble resin may have one type of structural unit having an acid group alone or two or more types. When the alkali-soluble resin has a structural unit having an acid group, 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 still more preferably 10% by mass to 30% by mass, based on all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present disclosure. Further, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and still more preferably 20 mol% to 40 mol%, based on all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present disclosure. Furthermore, the content of the structural unit 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 still more preferably 20 mol% to 40 mol%, based on all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present disclosure.

[0111] The alkali-soluble resin preferably has a crosslinkable group, and more preferably has a structural unit having a crosslinkable group, from the viewpoint of more excellent effects in the present disclosure. In addition, from the viewpoints of the strength, blackening property, patterning property of the obtained pattern, and the rectangularity of the obtained pattern, the photosensitive layer preferably contains a polymer having a crosslinkable group as the alkali-soluble resin, and more preferably contains a polymer having a structural unit having a crosslinkable group. The crosslinkable group is preferably a radically polymerizable group, and more preferably an ethylenically unsaturated group. When the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably has a structural unit having an ethylenically unsaturated group in the side chain. In the present specification, the "main chain" represents the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the "side chain" represents an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable. Examples of the structural unit having a crosslinkable group include, but are not limited to, those shown below.

[0112] [Chemical formula]

[0113] The alkali-soluble resin may have one kind or two or more kinds of structural units having a crosslinkable group. When the alkali-soluble resin has a structural unit having a crosslinkable group, the content of the structural unit having a crosslinkable group is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and still more preferably 20% by mass to 40% by mass, based on all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present disclosure. Also, the content of the structural unit having a crosslinkable group in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 50 mol%, based on all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present disclosure.

[0114] Examples of the means for introducing a crosslinkable group into the alkali-soluble resin include a method of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride. A preferred example of the means for introducing a crosslinkable group into the alkali-soluble resin is a means of synthesizing a polymer having a carboxy group by a polymerization reaction and then reacting glycidyl (meth) acrylate with a part of the carboxy groups of the obtained resin by a polymer reaction to introduce a (meth) acryloxy group into the polymer. By this means, an alkali-soluble resin having a (meth) acryloxy group in the side chain can be obtained. The above polymerization reaction is preferably carried out under temperature conditions of 70°C to 100°C, and more preferably under temperature conditions of 80°C to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fuji Film Wako Pure Chemical Corporation is more preferred. The above polymer reaction is preferably carried out under temperature conditions of 80°C to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0115] As the alkali-soluble resin, from the viewpoint of more excellent effects in the present disclosure, the resins shown below are preferred. Note that the content ratios (a to d) of each structural unit shown below, the weight average molecular weight Mw, etc. can be appropriately changed according to the purpose.

[0116]

Chemical formula

[0117]

Chemical formula

[0118] Further, the alkali-soluble resin may contain a polymer having a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as "polymer X"). The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but a cyclic carboxylic anhydride structure is preferred. As the ring of the cyclic carboxylic anhydride structure, a 5-membered ring to 7-membered ring is preferred, a 5-membered ring or 6-membered ring is more preferred, and a 5-membered ring is even more preferred.

[0119] The structural unit having a carboxylic anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from the compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0120] [Chemical formula]

[0121] In formula P-1, R A1a represents a substituent, and n 1a number of R A1a may be the same or different, and Z 1a represents a divalent group that forms a ring containing -C(=O)-O-C(=O)-, and n 1a represents an integer of 0 or more.

[0122] R A1a Examples of the substituent represented by include an alkyl group. Z 1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms. n 1a represents an integer of 0 or more. Z 1a When represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. n 1a When represents an integer of 2 or more, a plurality of R A1a may be the same or different. Also, a plurality of R A1a may combine with each other to form a ring, but it is preferably not combined with each other to form a ring.

[0123] As the structural unit having a carboxylic anhydride structure, a structural unit derived from an unsaturated carboxylic anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride is even more preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0124] Specific examples of the structural unit having a carboxylic anhydride structure are given below. However, the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or a CF 3 group, and Me represents a methyl group.

[0125]

Chemical formula

[0126]

Chemical formula

[0127] The structural unit having a carboxylic anhydride structure in Polymer X may be a single type or two or more types.

[0128] The total content of the structural unit having a carboxylic anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, still more preferably 10 mol% to 35 mol% with respect to all the structural units of Polymer X.

[0129] The photosensitive layer may contain only one type of Polymer X or two or more types. When the photosensitive layer contains Polymer X, from the viewpoint of more excellent effects in the present disclosure, the content of Polymer X is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, still more preferably 0.5% by mass to 20% by mass, still more preferably 1% by mass to 20% by mass with respect to the total mass of the photosensitive layer.

[0130] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 100,000, particularly preferably 20,000 to 80,000 from the viewpoint of more excellent effects in the present disclosure.

[0131] The acid value of the alkali-soluble resin is preferably from 10 mgKOH / g to 200 mgKOH / g, more preferably from 60 mgKOH / g to 200 mgKOH / g. The acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070:1992.

[0132] The photosensitive layer may contain only one kind of alkali-soluble resin or may contain two or more kinds. From the viewpoint of more excellent effects in the present disclosure, the content of the alkali-soluble resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass based on the total mass of the photosensitive layer.

[0133] <Polymerizable compound> The photosensitive layer preferably contains a polymerizable compound. In the present specification, the "polymerizable compound" means a compound that polymerizes under the action of a photopolymerization initiator described later and is a compound different from the above-described alkali-soluble resin.

[0134] As the polymerizable compound, an ethylenically unsaturated compound is preferable. As the ethylenically unsaturated group, a (meth)acryloxy group is preferable. The ethylenically unsaturated compound in the present specification is a compound other than the above-described alkali-soluble resin and preferably has a molecular weight of less than 5,000. Moreover, as a preferable aspect of the ethylenically unsaturated compound used in the second embodiment, the preferable aspect of the ethylenically unsaturated compound used in the above-described first embodiment can be mentioned.

[0135] As one of the preferable aspects of the ethylenically unsaturated compound, a compound represented by the following formula (M) (simply also referred to as "compound M") can be mentioned. Q 2 -R 1 -Q 1 Formula (M) In formula (M), Q 1 and Q 2Each independently represents a (meth)acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.

[0136] In formula (M), Q 1 and Q 2 are preferably the same group from the viewpoint of ease of synthesis. 1 and Q 2 are preferably the same group. Also, in formula (M), Q 1 and Q 2 are preferably acryloyloxy groups from the viewpoint of reactivity. As R 1 in formula (M), from the viewpoint of more excellent effects in the present disclosure, an alkylene group, an alkyleneoxyalkylene group (-L 1 -O-L 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferable, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is still more preferable, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferable. The above hydrocarbon group only needs to have a chain structure at least partially, and there is no particular limitation on the part other than the above chain structure. For example, it may be any of a branched chain, a cyclic structure, or a linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, and combinations thereof. A group obtained by combining an alkylene group or two or more alkylene groups with one or more arylene groups is preferable, an alkylene group is more preferable, and a linear alkylene group is still more preferable. Incidentally, each L 1 independently represents an alkylene group, and an ethylene group, a propylene group, or a butylene group is preferable, and an ethylene group or a 1,2-propylene group is more preferable. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

[0137] Also, Q 1 and Q 2The number of atoms in the shortest linking chain connecting them is preferably from 3 to 50, more preferably from 4 to 40, still more preferably from 6 to 20, and particularly preferably from 8 to 12, in terms of the more excellent effects in the present disclosure. In the present specification, "Q 1 and Q 2 the number of atoms in the shortest linking chain connecting them" means the shortest number of atoms connecting from the atom in R 1 connected to Q 1 to the atom in R 2 connected to Q 1 is.

[0138] 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 - heptanediol di(meth)acrylate, 1,8 - octanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, 1,4 - cyclohexanediol di(meth)acrylate, tricyclodecane dimethanol 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. The above ester monomers can also be used as a mixture. Among the above compounds, from the viewpoint of more excellent effects in the present disclosure, it is preferably at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; more preferably at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, and 1,10 - decanediol di(meth)acrylate; and still more preferably at least one compound selected from the group consisting of 1,9 - nonanediol di(meth)acrylate and 1,10 - decanediol di(meth)acrylate.

[0139] Further, as one of the preferred embodiments of the ethylenically unsaturated compound, a polyfunctional ethylenically unsaturated compound having two or more functional groups is exemplified. In the present specification, the "polyfunctional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0140] There is no particular limitation on the bifunctional ethylenically unsaturated compound, and it can be appropriately selected from known compounds. Examples of the bifunctional ethylenically unsaturated compound other than the above compound M include tricyclodecane dimethanol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate.

[0141] Examples of commercially available difunctional 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.).

[0142] There is no particular limitation on the ethylenically unsaturated compounds having three or more functional groups, and they can be appropriately selected from known compounds. Examples of the ethylenically unsaturated compounds having three or more functional groups 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 glycerin tri(meth)acrylate skeleton.

[0143] Here, “(tri / tetra / penta / hexa)(meth)acrylate” is a concept encompassing tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra)(meth)acrylate” is a concept encompassing tri(meth)acrylate and tetra(meth)acrylate.

[0144] Examples of ethylenically unsaturated compounds include caprolactone-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., etc.), and ethoxylated glycerol triacrylate (such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0145] Examples of ethylenically unsaturated compounds also include urethane (meth)acrylate compounds. Examples of urethane (meth)acrylate include urethane di(meth)acrylate, such as propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. In addition, examples of urethane (meth)acrylate also include urethane (meth)acrylate having a functionality of 3 or more. The lower limit of the number of functional groups is more preferably 6 or more, and even more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of urethane (meth)acrylate having a functionality of 3 or more 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.), etc.

[0146] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group. Examples of the acid group include a phosphoric acid group, a sulfo group, and a carboxy group. Among these, as the acid group, a carboxy group is preferred. Examples of the ethylenically unsaturated compound having an acid group include 3- to 4-functional ethylenically unsaturated compounds having an acid group [compounds obtained by introducing a carboxy group into a pentaerythritol tri- and tetraacrylate (PETA) skeleton (acid value: 80 mgKOH / g to 120 mgKOH / g)], 5- to 6-functional ethylenically unsaturated compounds having an acid group [compounds obtained by introducing a carboxy group into a dipentaerythritol penta- and hexaacrylate (DPHA) skeleton (acid value: 25 mgKOH / g to 70 mgKOH / g)], and the like. These ethylenically unsaturated compounds having 3 or more functional groups with an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group as needed.

[0147] As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of a bifunctional or higher-functional ethylenically unsaturated compound having a carboxy group and its carboxylic acid anhydride is preferable. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher-functional ethylenically unsaturated compound having a carboxy group and its carboxylic acid anhydride, the developability and film strength are further enhanced. The bifunctional or higher-functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of the bifunctional or higher-functional ethylenically unsaturated compound having a carboxy 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.).

[0148] 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 No. 2004-239942 is preferable, and the content described in this publication is incorporated herein.

[0149] Examples of the ethylenically unsaturated compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and alkyl (meth)acrylates. These may be used alone or in combination of two or more.

[0150] Examples of the compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate in which the number of ethylene oxide groups is 2 to 14; polypropylene glycol di(meth)acrylate in which the number of propylene oxide groups is 2 to 14; polyethylene polypropylene glycol di(meth)acrylate in which the number of ethylene oxide groups is 2 to 14 and the number of propylene oxide groups is 2 to 14; trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable.

[0151] Examples of ethylenically unsaturated compounds include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), ethoxylated glycerol triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

[0152] As the ethylenically unsaturated compound, those containing an ester bond are particularly preferable in terms of excellent developability of the photosensitive layer after transcription. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable in terms of excellent effects in the present disclosure, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable. From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group with 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure. Examples of the ethylenically unsaturated compound having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0153] 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). As the ethylenically unsaturated compound, an ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferable, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecane dimethanol di(meth)acrylate is even more preferable. As the aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects in the present disclosure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure is preferable.

[0154] -Ethylenically unsaturated compound B1- The photosensitive layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-described ethylenically unsaturated compounds.

[0155] In the photosensitive layer, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the polymerizable compound is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more from the viewpoint of more excellent resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is preferably 99% by mass or less, and more preferably 95% by mass or less.

[0156] Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring, aromatic heterocyclic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring, and condensed rings thereof. An aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable. The above aromatic ring may have a substituent. The ethylenically unsaturated compound B1 may have only one aromatic ring or two or more aromatic rings.

[0157] Since the ethylenically unsaturated compound B1 suppresses the swelling of the photosensitive layer by the developer and improves the resolution, it preferably has a bisphenol structure. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). The bisphenol A structure is preferred.

[0158] Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferred, and an ethyleneoxy group is more preferred. The number of added alkyleneoxy groups to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 is more preferred. The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the content described in this publication is incorporated herein.

[0159] As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0160] From the viewpoints of the change in line width during the standing time, the change in line width with the development temperature, and sensitivity, the ethylenically unsaturated compound B1 preferably contains a compound represented by the following formula (Bis).

[0161] [Chemical formula]

[0162] In formula (Bis), R 1 and R 2 each independently represent a hydrogen atom or a methyl group, A is C 2 H 4 and B is C 3 H 6 n 1 and n 3 each independently represent an integer from 1 to 39, and n 1 + n 3 is an integer from 2 to 40, n 2 and n 4 each independently represent an integer from 0 to 29, and n 2 + n 4is an integer from 0 to 30, and the repeating unit sequences of -(A-O)- and -(B-O)- may be random or block. In the case of a block, either -(A-O)- or -(B-O)- may be on the bisphenol structure side. In one embodiment, n 1 +n 2 +n 3 +n 4 is preferably an integer from 2 to 20, more preferably an integer from 2 to 16, and even more preferably an integer from 4 to 12. Also, n 2 +n 4 is preferably an integer from 0 to 10, more preferably an integer from 0 to 4, even more preferably an integer from 0 to 2, and particularly preferably 0.

[0163] Among them, the polymerizable compound preferably contains a monomer having a bisphenol A skeleton, and more preferably contains a bifunctional monomer having a bisphenol A skeleton, from the viewpoints of darkening property, patterning property, and rectangularity of the resulting pattern.

[0164] The ethylenically unsaturated compound B1 may be used alone or in combination of two or more. The content of the ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoints of transferability and edge fusion (the phenomenon that components in the photosensitive layer ooze out from the edge of the photosensitive transfer material).

[0165] The molecular weight of the ethylenically unsaturated compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, even more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200. Among the ethylenically unsaturated compounds contained in the photosensitive layer, the proportion of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, based on the content of all the ethylenically unsaturated compounds contained in the photosensitive layer.

[0166] As one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains an ethylenically unsaturated compound having two or more functional groups, more preferably contains an ethylenically unsaturated compound having three or more functional groups, and still more preferably contains an ethylenically unsaturated compound having three or four functional groups.

[0167] Also, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble resin having a structural unit having an aliphatic hydrocarbon ring.

[0168] Also, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0169] Also, as one of the preferred embodiments of the photosensitive layer, the photosensitive 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.

[0170] Also, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and an ethylenically unsaturated compound having three or more functional groups (preferably a (meth)acrylate compound having three or more functional groups).

[0171] From the viewpoints of blackening property and rectangularity of the obtained pattern, the polymerizable compound preferably contains a bifunctional polymerizable compound. In addition, from the viewpoints of blackening property and rectangularity of the resulting pattern, the content of the bifunctional polymerizable compound is preferably 50% by mass or more, more preferably 50% by mass or more and 100% by mass or less, and particularly preferably 50% by mass or more and 90% by mass or less based on the total mass of the polymerizable compounds.

[0172] In addition, as one of the preferred embodiments of the photosensitive layer, from the viewpoint of rust prevention, the photosensitive layer preferably contains Compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure. In addition, as one of the preferred embodiments of the photosensitive layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the photosensitive layer preferably contains Compound M and an ethylenically unsaturated compound having an acid group. More preferably, it contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group. Even more preferably, it contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having three or more functional groups, and an ethylenically unsaturated compound having an acid group. Particularly preferably, it contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having three or more functional groups, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound. Also, as one of the preferred embodiments of the photosensitive layer, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0173] The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the ethylenically unsaturated compound having two or more functional groups in the above ethylenically unsaturated compound is preferably 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass, based on the total content of all the ethylenically unsaturated compounds contained in the photosensitive layer.

[0174] From the viewpoints of blackening property, rectangularity of the obtained pattern, resolution, and peelability of the cover film of the transfer film, the value of the ratio Mm / Mb of the content Mm of the polymerizable compound to the content Mb of the alkali-soluble resin in the photosensitive layer is preferably less than 1.0, more preferably less than 0.8, still more preferably 0.05 or more and 0.75 or less, and particularly preferably 0.10 or more and 0.50 or less. Also, from the viewpoints of curability and resolution, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth)acrylic compound. Furthermore, from the viewpoints of curability, resolution, and linearity, the polymerizable compound in the photosensitive layer preferably contains a (meth)acrylic compound, and the content of the acrylic compound relative to the total mass of the (meth)acrylic compound contained in the photosensitive layer is more preferably 60% by mass or less.

[0175] The polymerizable compound may be used alone or in combination of two or more. From the viewpoints of blackening property, rectangularity of the obtained pattern, resolution, and peelability of the cover film of the transfer film, the content of the polymerizable compound in the photosensitive layer is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, based on the total mass of the photosensitive layer.

[0176] <Heterocyclic compound> The photosensitive layer may contain a heterocyclic compound. The heterocyclic ring of the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of the heteroatom of 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.

[0177] Examples of the heterocyclic compound include an imidazole compound, a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound. Among them, as the heterocyclic compound, from the viewpoints of blackening property and rectangularity of the obtained pattern, at least one compound selected from the group consisting of an imidazole compound, a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound, and a benzoxazole compound is preferable, at least one compound selected from the group consisting of an imidazole compound, a triazole compound, and a tetrazole compound is more preferable, and a triazole compound is particularly preferable.

[0178] Preferable specific examples of the heterocyclic compound are shown below. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5-triphenylimidazole, and the like.

[0179] Examples of the triazole compound and the benzotriazole compound include the following compounds.

[0180]

Chemical formula

[0181]

Chemical formula

[0182] Examples of the tetrazole compound include the following compounds.

[0183]

Chemical formula

[0184]

Chemical formula

[0185] Examples of the thiadiazole compound include the following compounds.

[0186]

Chemical formula

[0187] Examples of the triazine compound include the following compounds.

[0188]

Chemical formula

[0189] Examples of the rhodanine compound include the following compounds.

[0190]

Chemical formula

[0191] Examples of the thiazole compound include the following compounds.

[0192]

Chemical formula

[0193] Examples of the benzothiazole compound include the following compounds.

[0194]

Chemical formula

[0195] Examples of the benzimidazole compound include the following compounds.

[0196]

Chemical formula

[0197] [Chemistry]

[0198] Examples of the benzoxazole compound include the following compounds.

[0199] [Chemistry]

[0200] The heterocyclic compound may be used alone or in combination of two or more. When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, more preferably 0.02% by mass to 10.0% by mass, still more preferably 0.05% by mass to 8.0% by mass, and particularly preferably 0.10% by mass to 5.0% by mass with respect to the total mass of the photosensitive layer.

[0201] <Aliphatic thiol compound> The photosensitive layer may contain an aliphatic thiol compound. When the photosensitive layer contains an aliphatic thiol compound, the en-thiol reaction between the aliphatic thiol compound and the ethylenically unsaturated compound suppresses the curing shrinkage of the formed film and relaxes the stress.

[0202] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, an aliphatic thiol compound having two or more functional groups) is preferable. Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is more preferable from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure). In this specification, the "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0203] As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and still more preferably 150 to 1,000.

[0204] As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, from the viewpoint of the adhesion of the formed pattern, 2 to 10 functional groups are preferable, 2 to 8 functional groups are more preferable, and 2 to 6 functional groups are still more preferable.

[0205] 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-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(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 di(mercaptoethyl)ether.

[0206] Among the above, as the polyfunctional aliphatic thiol compound, at least one compound selected from the group consisting of 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 is preferable.

[0207] 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.

[0208] The photosensitive layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds. When the photosensitive layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% to 50% by mass, still more preferably 5% to 30% by mass, and particularly preferably 8% to 20% by mass based on the total mass of the photosensitive layer.

[0209] <Thermocrosslinkable compound> From the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, the photosensitive layer preferably contains a thermocrosslinkable compound. In this specification, the thermocrosslinkable compound having an ethylenically unsaturated group described later is treated as a thermocrosslinkable compound and not as an ethylenically unsaturated compound. Examples of the thermocrosslinkable compound include a methylol compound and a blocked isocyanate compound. Among them, from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, the blocked isocyanate compound is preferable. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when an alkali-soluble resin and / or an ethylenically unsaturated compound or the like has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the function when the film obtained by curing the photosensitive layer is used as a protective film tends to be enhanced. Note that the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected with a blocking agent (so-called masked)".

[0210] 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. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter". As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

[0211] Examples of the blocking agent having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and compounds having a structure represented by -C(=N-OH)- in the molecule such as cyclohexanone oxime). Among these, as the blocking agent having a dissociation temperature of 100°C to 160°C, for example, from the viewpoint of storage stability, it is preferable to contain an oxime compound.

[0212] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoints of improving the brittleness of the film and enhancing the adhesion to the transfer target. The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferable from the viewpoints that it is easier to make the dissociation temperature in a preferable range than a compound having no oxime structure and that it is easier to reduce the development residue.

[0213] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, with a radically polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as glycidyl group. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0214] Commercially available products can be used as the blocked isocyanate compound. Examples of commercially available products of the blocked isocyanate compound include Karens (registered trademark) AOI-BM, Karens (registered trademark) MOI-BM, Karens (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), and block-type Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). In addition, a compound having the following structure can also be used as the blocked isocyanate compound.

[0215] [Chemical formula]

[0216] The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive 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 layer.

[0217] [Surfactant] The photosensitive layer may contain a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of the surfactant include the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0218] As the surfactant, a fluorosurfactant or a silicone surfactant is preferred. Examples of commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation); Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc.); PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by NEOS Co., Ltd.), and the like.

[0219] In addition, it is also preferable to use 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 as the fluorosurfactant. A block polymer can also be used as the fluorosurfactant. As the fluorosurfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably an ethyleneoxy group or a propyleneoxy group) can also be preferably used. A fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorosurfactant. Examples thereof include Megafac (trade name) RS-101, RS-102, RS-718K, RS-72-K (the above are manufactured by DIC Corporation), etc.

[0220] Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (the above are manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (the above are manufactured by BASF), Solsperse (trade name) 20000 (the above are manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (the above are manufactured by Fujifilm Wako Pure Chemical Corporation), Pyonin (trade name) D-6112, D-6112-W, D-6315 (the above are manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfynol 104, 400, 440 (the above are manufactured by Nissin Chemical Industry Co., Ltd.), and the like. In recent years, compounds having a linear perfluoroalkyl group with 7 or more carbon atoms have raised concerns about environmental compatibility. Therefore, the use of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) has been restricted. For this reason, it is preferable to use a surfactant using alternative materials for PFOA and PFOS.

[0221] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains or terminals. Specific examples of silicone surfactants include DOWSIL (trade name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as 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, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie GmbH), etc.

[0222] The surfactant may be used alone or in combination of two or more. When the photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, more preferably 0.01% by mass to 1.0% by mass, and still more preferably 0.05% by mass to 0.80% by mass with respect to the total mass of the photosensitive layer.

[0223] <Polymerization inhibitor> The photosensitive layer may contain a polymerization inhibitor. A polymerization inhibitor refers to a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0224] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; hindered phenol compounds such as bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)], 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among them, in terms of more excellent effects in the present disclosure, as the polymerization inhibitor, at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or its salt, and a hindered phenol compound is preferable, and phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylene bis(oxyethylene)], 2,4-bis〔(laurylthio)methyl〕-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), and N-nitrosophenylhydroxylamine aluminum salt are more preferable.

[0225] The polymerization inhibitor may be used alone or in combination of two or more. When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01 to 5.0% by mass, and still more preferably 0.04% by mass to 3.0% by mass based on the total mass of the photosensitive layer.

[0226] <Hydrogen donating compound> The photosensitive layer may contain a hydrogen donating compound. The hydrogen donating compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing the polymerization inhibition of ethylenically unsaturated compounds by oxygen. Examples of the hydrogen donating compound include amines and amino acid compounds.

[0227] Examples of the amines include compounds described in "Journal of Polymer Society", Vol. 10, p. 3173 (1972) by M.R. Sander et al., Japanese Patent Publication No. 44-020189, Japanese Unexamined Patent Application Publication No. 51-082102, Japanese Unexamined Patent Application Publication No. 52-134692, Japanese Unexamined Patent Application Publication No. 59-138205, Japanese Unexamined Patent Application Publication No. 60-084305, Japanese Unexamined Patent Application Publication No. 62-018537, Japanese Unexamined Patent Application Publication No. 64-033104, and Research Disclosure No. 33825. More specifically, examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among them, at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferable as the amines in terms of more excellent effects in the present disclosure.

[0228] Examples of the amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, N-phenylglycine is preferable as the amino acid compound in terms of more excellent effects in the present disclosure.

[0229] Examples of the hydrogen-donating compounds also include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithiane) described in Japanese Unexamined Patent Application Publication No. 6-308727.

[0230] The hydrogen-donating compounds may be used alone or in combination of two or more. When the photosensitive 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 still more preferably 0.03% by mass to 5.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer.

[0231] <Other components> The photosensitive layer may contain components other than the above-described components (hereinafter also referred to as "other components"). Examples of the other components include antioxidants and particles (e.g., metal oxide particles). Further, as the other components, other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706 are also included.

[0232] -Antioxidant- Examples of the antioxidant include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (alias: phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, para-aminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among them, as the antioxidant, 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable.

[0233] When the photosensitive 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 still more preferably 0.01% by mass or more, based on the total mass of the photosensitive layer. The upper limit is not particularly limited, but preferably 1% by mass or less.

[0234] -Particles- The particles are particles other than the above-described pigments, and metal oxide particles are preferable. The metals in the metal oxide particles include metalloids such as B, Si, Ge, As, Sb, and Te. From the viewpoint of, for example, the transparency of the cured film, the average primary particle diameter of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and calculating the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0235] When the photosensitive layer contains particles, it may contain only one kind of particles having different metal species, sizes, etc., or may contain two or more kinds. The photosensitive layer either does not contain particles, or when the photosensitive layer contains particles, the content of the particles is preferably more than 0% by mass and 35% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably more than 0% by mass and 5% by mass or less, even more preferably more than 0% by mass and 1% by mass or less, and particularly preferably does not contain particles, based on the total mass of the photosensitive layer.

[0236] <Impurities, etc.> The photosensitive layer may contain a predetermined amount of impurities. Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and their ions. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so it is preferable to have the following content.

[0237] The content of the impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less, by mass. The content of the impurities can be 1 ppb or more, and may be 0.1 ppm or more, by mass.

[0238] As methods for making the impurities fall within the above ranges, examples include selecting raw materials for the composition that have a low impurity content, preventing the mixing of impurities during the production of the photosensitive layer, and washing to remove them. By such methods, the amount of impurities can be made to fall within the above ranges.

[0239] Impurities can be quantified by known methods such as, for example, inductively coupled plasma (ICP) optical emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0240] In the photosensitive layer, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably low. As the content of these compounds relative to the total mass of the photosensitive layer, on a mass basis, 100 ppm or less is preferable, 20 ppm or less is more preferable, and 4 ppm or less is even more preferable. The lower limit can be 10 ppb or more, and can be 100 ppb or more, on a mass basis, relative to the total mass of the photosensitive layer. The content of these compounds can be suppressed by the same methods as the above-mentioned metal impurities. Also, they can be quantified by known measurement methods.

[0241] From the viewpoint of improving reliability and laminatability, the water content in the photosensitive layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass.

[0242] <Residual monomer> The photosensitive layer may contain residual monomers corresponding to each structural unit of the above-described alkali-soluble resin. The content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and still more preferably 500 ppm by mass or less with respect to the total mass of the alkali-soluble resin from the viewpoints of patterning property and reliability. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. The residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and still more preferably 100 ppm by mass or less with respect to the total mass of the photosensitive layer from the viewpoints of patterning property and reliability. The lower limit is not particularly limited, but is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0243] The amount of the residual monomer in the synthesis of the alkali-soluble resin by the polymer reaction is also preferably in the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable to set the content of glycidyl acrylate in the above range. The amount of the residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0244] <Layer thickness of the photosensitive layer> The layer thickness of the photosensitive layer is not particularly limited, but is often 30 μm or less. From the viewpoint of more excellent effects in the present disclosure, it is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. As the lower limit, from the viewpoint of excellent strength of the film obtained by curing the photosensitive layer, it is preferably 0.60 μm or more, and more preferably 1.5 μm or more. The thickness of the photosensitive layer can be calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM), for example.

[0245] <Forming method> The forming method of the photosensitive layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. As a method for forming a photosensitive layer, for example, a method is provided in which a photosensitive resin composition containing a pigment, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a solvent, and the like is prepared, the photosensitive resin composition is applied to the surface of a temporary support or the like, and the coating film of the photosensitive resin composition is dried.

[0246] Examples of the photosensitive resin composition used for forming the photosensitive layer include compositions containing a pigment, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, the above optional components, and a solvent. The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive layer.

[0247] - Solvent - The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse a pigment, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and the above optional components, and known solvents can be used. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these. When producing a photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, a functional layer, and a photosensitive layer, the photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among them, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least two kinds of ketone solvents is even more preferable.

[0248] 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. 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. As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of JP-A-2018-177889 may be used, and the contents thereof are incorporated herein.

[0249] The photosensitive resin composition may contain a single solvent or two or more solvents. When applying the photosensitive resin composition, the content of the solvent is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition.

[0250] The method for preparing the photosensitive resin composition is not particularly limited. For example, there is a method of preparing a solution in which each component is dissolved in the above solvent in advance, and then mixing the obtained solutions at a predetermined ratio to prepare the photosensitive resin composition. Before forming the photosensitive layer, the photosensitive resin composition is preferably filtered using a filter with a pore size of 0.2 μm to 30 μm.

[0251] The coating method of the photosensitive resin composition is not particularly limited, and it may be coated by a known method. Examples of the coating method include printing method, spraying method, roll coating method, bar coating method, curtain coating method, spin coating method, and die coating method (i.e., slit coating method). Also, the photosensitive layer may be formed by applying the photosensitive resin composition onto a protective film described later and drying it.

[0252] As the drying method of the coating film of the photosensitive resin composition, heat drying and vacuum drying are preferred. As the drying temperature, 80°C or higher is preferred, and 90°C or higher is more preferred. Also, as the upper limit value, 130°C or lower is preferred, and 120°C or lower is more preferred. It is also possible to dry by continuously changing the temperature. Also, as the drying time, 20 seconds or longer is preferred, 40 seconds or longer is more preferred, and 60 seconds or longer is even more preferred. Also, although the upper limit value is not particularly limited, 600 seconds or shorter is preferred, and 300 seconds or shorter is more preferred.

[0253] 〔Thermoplastic resin layer〕 The photosensitive transfer material may include a thermoplastic resin layer. The photosensitive transfer material preferably includes a thermoplastic resin layer between the temporary support and the photosensitive layer. By providing a thermoplastic resin layer between the temporary support and the photosensitive layer of the photosensitive transfer material, the followability to the substrate is improved, the mixing of air bubbles between the substrate and the photosensitive transfer material is suppressed, and the adhesion to an adjacent layer (for example, the temporary support) is improved.

[0254] <Alkali-soluble resin> 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 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 glycols.

[0255] From the viewpoints of developability and adhesion to an adjacent layer, an acrylic resin is preferred as the alkali-soluble resin. Here, the acrylic resin means a resin having at least one structural unit selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylate ester, and a structural unit derived from (meth)acrylamide. As the acrylic resin, the total content of the structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylate ester, and the structural unit derived from (meth)acrylamide is preferably 50% by mass or more based on the total mass of the acrylic resin. Among them, the total content of the structural unit derived from (meth)acrylic acid and the structural unit derived from (meth)acrylate ester is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, based on the total mass of the acrylic resin.

[0256] Also, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferred. From the viewpoint of developability, an alkali-soluble resin having an acid value of 60 mgKOH / g or more is more preferred as the alkali-soluble resin, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is even more preferred. The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

[0257] The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins and used. For example, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the alkali-soluble resins described in paragraphs 0053 to 0068 of JP-A-2016-224162 can be mentioned. The copolymerization ratio of the structural unit having a carboxy group in the above carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 12% by mass to 30% by mass with respect to the total mass of the acrylic resin. As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoints of developability and adhesion to an adjacent layer.

[0258] The alkali-soluble resin may have a crosslinkable group. The crosslinkable group may be any addition-polymerizable group, and examples thereof include ethylenically unsaturated groups; polycondensable groups such as hydroxy groups and carboxy groups; and polyaddition-reactive groups such as epoxy groups and (block) isocyanate groups.

[0259] 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 still more preferably 20,000 to 50,000.

[0260] The thermoplastic resin layer may contain one kind of the alkali-soluble resin alone, or may contain two or more kinds thereof. From the viewpoints of developability and adhesion to an adjacent layer, 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, still more preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer.

[0261] <Dye> The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") having a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development of 450 nm or more, and the maximum absorption wavelength of which is changed by an acid, a base, or a radical.

[0262] From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid. From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength is changed by an acid as dye B and a compound that generates an acid by light described later.

[0263] In this specification, that a dye "has a maximum absorption wavelength changed by an acid, a base, or a radical" may mean any of a mode in which a dye in a colored state is decolorized by an acid, a base, or a radical, a mode in which a dye in a decolorized state is colored by an acid, a base, or a radical, and a mode in which a dye in a colored state is changed to a colored state of another hue. Specifically, dye B may be a compound that changes from a decolorized state to a colored state by exposure, or a compound that changes from a colored state to a decolorized state by exposure. In this case, it may also be a dye whose colored or decolorized state changes by the generation and action of an acid, a base, or a radical in the photosensitive layer by exposure, or a dye whose colored or decolorized state changes by the change of the state (for example, pH) in the photosensitive layer by an acid, a base, or a radical. Further, it may also be a dye whose colored or decolorized state changes by directly receiving an acid, a base, or a radical as a stimulus without passing through exposure.

[0264] Among them, from the viewpoints of visibility and resolution of the exposed portion and the unexposed portion, the dye B is preferably a dye whose maximum absorption wavelength changes due to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes due to a radical. From the viewpoints of visibility and resolution of the exposed portion and the unexposed portion, the photosensitive layer preferably contains both a dye whose maximum absorption wavelength changes due to a radical as the dye B and a photo radical polymerization initiator. Also, from the viewpoint of visibility of the exposed portion and the unexposed portion, the dye B is preferably a dye that develops color due to an acid, a base, or a radical.

[0265] As an example of the color development mechanism of the dye B in the present disclosure, a photo radical polymerization initiator, a photo cationic polymerization initiator (photo acid generator), or a photo base generator is added to the photosensitive layer, and after exposure, radicals, acids, or bases generated from the photo radical polymerization initiator, the photo cationic polymerization initiator, or the photo base generator cause a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (for example, a leuco dye) to develop color.

[0266] From the viewpoint of visibility of the exposed portion and the unexposed portion, the maximum absorption wavelength of the dye B in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or more, more preferably 550 nm to 700 nm, and still more preferably 550 nm to 650 nm. Also, the dye B may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or may have two or more. When the dye B has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0267] The maximum absorption wavelength of the dye B is obtained by measuring the transmission spectrum of a solution (liquid temperature 25 °C) containing the dye B in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) under an air atmosphere and detecting the wavelength at which the light intensity becomes minimum (maximum absorption wavelength).

[0268] Examples of the dye that develops or fades in color upon exposure include leuco compounds. Examples of the dye that fades in color upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye B, a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.

[0269] Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropyran dye), a leuco compound having a fluoran skeleton (fluoran dye), a leuco compound having a diarylmethane skeleton (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indolyl phthalide skeleton (indolyl phthalide dye), and a leuco compound having a leuco auramine skeleton (leuco auramine dye). Among them, a triarylmethane dye or a fluoran dye is preferable, and a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluoran dye is more preferable.

[0270] As the leuco compound, it is preferable to have a lactone ring, a sultine ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion. Thereby, the lactone ring, the sultine ring, or the sultone ring of the leuco compound can be reacted with a radical generated from a photo radical polymerization initiator or an acid generated from a photo cationic polymerization initiator to change the leuco compound to a closed-ring state to fade in color, or change the leuco compound to an open-ring state to develop color. As the leuco compound, a compound having a lactone ring, a sultine ring, or a sultone ring and in which the lactone ring, the sultine ring, or the sultone ring is opened by a radical or an acid to develop color is preferable, and a compound having a lactone ring and in which the lactone ring is opened by a radical or an acid to develop color is more preferable.

[0271] Examples of the pigment B include the following dyes and leuco compounds. Specific examples of the dyes among the pigment B include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinoline red, rose bengal, metanil yellow, thymol sulfophthalein, xylenol blue, methyl orange, para methyl red, congo red, benzopurpurin 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, para fuchsine, victoria pure blue - naphthalene sulfonate, victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by Orient Chemical Industries, Ltd.), oil pink #312 (manufactured by Orient Chemical Industries, Ltd.), oil red 5B (manufactured by Orient Chemical Industries, Ltd.), oil scarlet #308 (manufactured by Orient Chemical Industries, Ltd.), oil red OG (manufactured by Orient Chemical Industries, Ltd.), oil red RR (manufactured by Orient Chemical Industries, Ltd.), oil green #502 (manufactured by Orient Chemical Industries, Ltd.), spiron red BEH special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0272] Specific examples of the leuco compound among the coloring matters B include p,p’,p”-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chloro-fluorane, 3-(N,N-diethylamino)-6-methoxy-7-amino-fluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chloro-fluorane, 3-(N,N-diethylamino)-7-benzylamino-fluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-xanthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3’,6’-bis(diphenylamino)spiroisobenzofuran-1(3H),9’-[9H]xanthen-3-one.

[0273] Dye B is preferably a dye whose maximum absorption wavelength changes due to radicals from the viewpoints of visibility of the exposed and unexposed portions, pattern visibility after development, and resolution, and more preferably a dye that develops color due to radicals. As the dye B, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue - naphthalene sulfonate is preferable.

[0274] Dye B may be used alone or in combination of two or more. From the viewpoint of visibility of the exposed and unexposed portions, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, still more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass with respect to the total mass of the thermoplastic resin layer.

[0275] Here, the content of dye B means the content of the dye when all the dye B contained in the thermoplastic resin layer is in a colored state. Below, taking the dye that develops color due to radicals as an example, the method for quantifying the content of dye B will be described. Prepare a solution by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone. To each of the obtained solutions, add a photo - radical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd.), and generate radicals by irradiating with light of 365 nm to make all the dyes in a colored state. Then, in an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25 °C and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are colored in the same manner as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. Calculate the amount of the dye contained in the thermoplastic resin layer based on the calibration curve from the absorbance of the solution containing the thermoplastic resin layer obtained.

[0276] <Compound that generates an acid, a base, or a radical by light> The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical upon exposure to light (simply referred to as "Compound C"). As Compound C, a compound that generates an acid, a base, or a radical upon exposure to actinic rays such as ultraviolet rays and visible light is preferable. As Compound C, known photoacid generators, photobase generators, and photo radical polymerization initiators (photo radical generators) can be used. Among them, photoacid generators are preferable.

[0277] - Photoacid generator - From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the photo cationic polymerization initiators that the above-described photosensitive layer may contain, and the preferred embodiments are the same except for the points described later.

[0278] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoints of sensitivity, resolution, and adhesion, it is more preferable to contain an oxime sulfonate compound. In addition, as the photoacid generator, a photoacid generator having the following structure is also preferable.

[0279]

Chemical formula

[0280] - Photo radical polymerization initiator - The thermoplastic resin layer may contain a photo radical polymerization initiator (photo radical polymerization initiator). Examples of the photo radical polymerization initiator include the photo radical polymerization initiators that the above-described photosensitive layer may contain, and the preferred embodiments are the same.

[0281] - Photobase generator - The thermoplastic resin layer may contain a photobase generator. The photo base generator is not particularly limited as long as it is a known photo base generator. For example, 2-nitrobenzyl cyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamine, O-carbamoyl oxime, {[(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-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethyl borate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine can be mentioned.

[0282] The thermoplastic resin layer may contain Compound C alone or in combination of two or more. From the viewpoints of visibility and resolution of the exposed portion and the unexposed portion, the content of Compound C is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, based on the total mass of the thermoplastic resin layer.

[0283] <Plasticizer> From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the thermoplastic resin layer preferably contains a plasticizer. The plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin. The molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. However, from the perspective of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and a polyalkylene glycol compound is more preferable. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0284] Also, from the perspectives of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the perspectives of compatibility, resolution, and adhesion to an adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described as the ethylenically unsaturated compounds contained in the photosensitive layer described above. In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive layer are directly contacted and laminated, it is preferable that both the thermoplastic resin layer and the photosensitive layer contain the same (meth)acrylate compound. This is because when the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound, component diffusion between the layers is suppressed and storage stability is improved.

[0285] When the thermoplastic resin layer contains a (meth)acrylate compound as the plasticizer, from the perspective of adhesion to an adjacent layer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure. Also, from the perspectives of resolution, adhesion to an adjacent layer, and developability, the (meth)acrylate compound used as the plasticizer is preferably a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule. Furthermore, as the (meth)acrylate compound used as the plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferable.

[0286] The thermoplastic resin layer may contain a plasticizer alone or in combination of two or more kinds. From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass based on the total mass of the thermoplastic resin layer.

[0287] <Surfactant> From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants that the above-described photosensitive layer may contain, and preferred embodiments are the same.

[0288] The thermoplastic resin layer may contain a surfactant alone or in combination of two or more kinds. 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 based on the total mass of the thermoplastic resin layer.

[0289] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that the above-described photosensitive layer may contain.

[0290] The thermoplastic resin layer may contain a sensitizer alone or in combination of two or more kinds. The content of the sensitizer can be appropriately selected according to the purpose. From the viewpoints of improving the sensitivity to the light source and the visibility of the exposed portion and the non-exposed portion, the range of 0.01% by mass to 5% by mass is preferable, and the range of 0.05% by mass to 1% by mass is more preferable based on the total mass of the thermoplastic resin layer.

[0291] <Additives, etc.> The thermoplastic resin layer may contain known additives as necessary in addition to the above components. Regarding the thermoplastic resin layer, it is described in paragraphs 0189 to 0193 of JP-A-2014-85643, and the content described in this publication is incorporated herein.

[0292] <Physical properties, etc.> The layer thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion to an adjacent layer, 1 μm or more is preferable, and 2 μm or more is more preferable. The upper limit is not particularly limited, but from the viewpoints of developability and resolution, 20 μm or less is preferable, 10 μm or less is more preferable, and 5 μm or less is still more preferable.

[0293] <Forming method> The forming method of the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. Examples of the forming method of the thermoplastic resin layer include preparing a thermoplastic resin composition containing the above components and a solvent, applying the thermoplastic resin composition onto the surface of a temporary support or the like, and drying the coating film of the thermoplastic resin composition. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

[0294] - Solvent - The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above components contained in the thermoplastic resin layer. Examples of the solvent contained in the thermoplastic resin composition include the solvents that the above-described photosensitive resin composition may contain, and the preferred embodiments are the same.

[0295] The solvent contained in the thermoplastic resin composition may be a single species or two or more species. When applying the thermoplastic resin composition, the content of the solvent is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition.

[0296] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the preparation method of the photosensitive resin composition and the formation method of the photosensitive layer described above. For example, a solution in which each component contained in the thermoplastic resin layer is dissolved in the above solvent is prepared in advance, and the obtained solutions are mixed at a predetermined ratio to prepare a thermoplastic resin composition. The obtained thermoplastic resin composition is applied to the surface of a temporary support, and the coating film of the thermoplastic resin composition is dried to form a thermoplastic resin layer. Alternatively, after forming a photosensitive layer and a water-soluble resin layer on the protective film described later, a thermoplastic resin layer may be formed on the surface of the water-soluble resin layer.

[0297] [Water-soluble resin layer] The photosensitive transfer material preferably includes a water-soluble resin layer between the thermoplastic resin layer and the photosensitive layer. By providing the water-soluble resin layer, mixing of components during application of multiple layers and during storage after application can be suppressed. The water-soluble resin layer is preferably a water-soluble layer from the viewpoints of developability and suppression of mixing of components during application of multiple layers and during storage after application. In this specification, "water-soluble" means that the solubility in 100 g of water at pH 7.0 with a liquid temperature of 22°C is 0.1 g or more.

[0298] Examples of the water-soluble resin layer include an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-72724. When the water-soluble resin layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and productivity is improved, which is preferable. The oxygen barrier layer used as the water-soluble resin layer may be appropriately selected from known layers described in the above publications and the like. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22°C) is preferable.

[0299] The water-soluble resin layer preferably contains a resin. Examples of the resin contained in the water-soluble resin layer include resins such as polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. As the resin contained in the water-soluble resin layer, a water-soluble resin is preferred. Also, from the viewpoint of suppressing the mixing of components between multiple layers, the resin contained in the water-soluble resin layer is preferably a resin that is different from both the polymer A contained in the photosensitive layer and the thermoplastic resin (e.g., an alkali-soluble resin) contained in the thermoplastic resin layer.

[0300] The water-soluble resin layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinyl pyrrolidone, from the viewpoints of oxygen barrier properties and suppressing the mixing of components during the application of multiple layers and during storage after application.

[0301] The water-soluble resin layer may contain one of the above resins alone or two or more of them. The content of the resin in the water-soluble resin layer is not particularly limited, but from the viewpoints of oxygen barrier properties and suppressing the mixing of components during the application of multiple layers and during storage after application, 50% by mass to 100% by mass is preferred, 70% by mass to 100% by mass is more preferred, 80% by mass to 100% by mass is still more preferred, and 90% by mass to 100% by mass is particularly preferred, based on the total mass of the water-soluble resin layer. Also, the water-soluble resin layer may contain additives such as surfactants as necessary.

[0302] The layer thickness of the water-soluble resin layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. When the thickness of the water-soluble resin layer is within the above range, the oxygen barrier properties are not reduced, the mixing of components during the application of multiple layers and during storage after application can be suppressed, and an increase in the removal time of the water-soluble resin layer during development can be suppressed.

[0303] The method for forming the water-soluble resin layer is not particularly limited. For example, a water-soluble resin layer composition containing the above resin and optional additives is prepared, applied to the surface of the thermoplastic resin layer or the photosensitive layer, and the coating film of the water-soluble resin layer composition is dried to form the water-soluble resin layer. The water-soluble resin layer composition preferably contains a solvent in order to adjust the viscosity of the water-soluble resin layer composition and facilitate the formation of the water-soluble resin layer.

[0304] The solvent contained in the water-soluble resin layer composition is not particularly limited as long as it can dissolve or disperse the above resin. At least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred.

[0305] 〔Functional layer〕 The photosensitive transfer material may be provided with a functional layer between the temporary support or the thermoplastic resin layer and the photosensitive layer. Examples of the functional layer include an oxygen barrier film having an oxygen barrier function described in paragraph 0027 of Japanese Patent No. 4502784. The oxygen barrier film preferably exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among them, an oxygen barrier film containing a combination of polyvinyl alcohol and polyvinylpyrrolidone is preferred. The dry thickness of the functional layer is preferably 0.2 μm to 5 μm, more preferably 0.5 μm to 3 μm, and still more preferably 1 μm to 2.5 μm.

[0306] 〔Protective film〕 The photosensitive transfer material preferably includes a protective film in contact with the surface of the photosensitive layer that does not face the temporary support.

[0307] Examples of materials constituting the protective film include resin films and paper, and resin films are preferred from the viewpoints of strength and flexibility. Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, triacetyl cellulose films, polystyrene films, and polycarbonate films. Among them, polyethylene films, polypropylene films, or polyethylene terephthalate films are preferred.

[0308] The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, and more preferably 10 to 50 μm. In addition, the arithmetic mean roughness Ra value of the surface of the protective film (hereinafter also simply referred to as "the surface of the protective film") that contacts the photosensitive layer is preferably 0.3 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less from the viewpoint of excellent resolution. It is considered that when the Ra value of the surface of the protective film is within the above range, the uniformity of the layer thickness of the photosensitive layer and the formed resin pattern is improved. The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 0.001 μm or more.

[0309] The Ra value of the surface of the protective film is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), measure the surface of the protective film under the following conditions to obtain the surface profile of the optical film. As the measurement / analysis software, use the Microscope Application of MetroPro ver8.3.2. Next, display the Surface Map screen with the above analysis software, and obtain histogram data in the Surface Map screen. Calculate the arithmetic mean roughness from the obtained histogram data to obtain the Ra value of the surface of the protective film. When the protective film is adhered to the photosensitive transfer material, the protective film may be peeled off from the photosensitive transfer material, and the Ra value of the surface on the peeled side may be measured.

[0310] The method of laminating the protective film to the photosensitive layer or the like is not particularly limited, and known methods can be mentioned. Examples of the apparatus for laminating the protective film to the photosensitive layer or the like include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0311] The photosensitive transfer material may include layers other than the above-described layers (hereinafter also referred to as "other layers"). Examples of the other layers include a contrast enhancement layer. The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018 / 179640. The 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 herein.

[0312] From the viewpoint of further exerting the effects in the present disclosure, the total thickness of the layers other than the temporary support and the protective film in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less. From the viewpoint of further exerting the effects in the present disclosure, the total thickness of the photosensitive layer, the water-soluble resin layer, and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[0313] The photosensitive transfer material according to the present disclosure can be suitably used for various applications that require precision microfabrication by photolithography. After patterning the photosensitive layer, the photosensitive layer may be etched using it as a coating film, or electroforming mainly based on electroplating may be performed. Further, the cured film obtained by patterning may be used as a permanent film, and for example, it may be used as an interlayer insulating film, a wiring protection film, a wiring protection film having an index matching layer, or the like. In addition, the photosensitive transfer material according to the present disclosure can be suitably used for various wiring formation applications of semiconductor packages, printed circuit boards, and sensor boards, conductive films such as LED arrays, touch panels, electromagnetic shielding materials, and film heaters, liquid crystal sealing materials, and the formation of structures in the fields of micromachines and microelectronics.

[0314] 〔Manufacturing method of photosensitive transfer material〕 The manufacturing method of the photosensitive transfer material used in the present disclosure is not particularly limited, and known manufacturing methods, for example, known methods for forming each layer can be used. Hereinafter, with reference to FIG. 1, the manufacturing method of the photosensitive transfer material according to the present disclosure will be described. However, the photosensitive transfer material according to the present disclosure is not limited to those having the configuration shown in FIG. 1. FIG. 1 is a schematic cross-sectional view showing an example of the layer structure in an embodiment of the photosensitive transfer material according to the present disclosure. The photosensitive transfer material 20 shown in FIG. 1 has a structure in which a temporary support 11, a thermoplastic resin layer 13, a functional layer 15, a photosensitive layer 17, and a protective film 19 are laminated in this order.

[0315] Examples of the manufacturing method of the photosensitive transfer material 20 include a step of forming the thermoplastic resin layer 13 by applying a thermoplastic resin composition on the surface of the temporary support 11 and then drying the coating film of the thermoplastic resin composition, and a step of forming the functional layer 15 by applying a functional layer forming composition on the surface of the thermoplastic resin layer 13 and then drying the coating film of the functional layer forming composition. And a step of forming the photosensitive layer 17 by applying a photosensitive resin composition on the surface of the functional layer 15 and then drying the coating film of the photosensitive resin composition. In the above manufacturing method, it is preferable to use a thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a composition for forming a functional layer containing at least one selected from the group consisting of water and a water-miscible organic solvent, and a photosensitive resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Thereby, the application of the composition for forming a functional layer to the surface of the thermoplastic resin layer 13 and / or the mixing of the components contained in the thermoplastic resin layer 13 and the components contained in the functional layer 15 during the storage period of the laminate having the coating film of the composition for forming a functional layer can be suppressed, and further, the application of the photosensitive resin composition to the surface of the functional layer 15 and / or the mixing of the components contained in the functional layer 15 and the components contained in the photosensitive layer 17 during the storage period of the laminate having the coating film of the photosensitive resin composition can be suppressed.

[0316] A photosensitive transfer material 20 is manufactured by pressing a protective film 19 onto the photosensitive layer 17 of the laminate manufactured by the above manufacturing method. As a method for manufacturing the photosensitive transfer material used in the present disclosure, it is preferable to manufacture a photosensitive transfer material 20 including a temporary support 11, a thermoplastic resin layer 13, a functional layer 15, a photosensitive layer 17, and a protective film 19 by including a step of providing a protective film 19 so as to be in contact with the second surface of the photosensitive layer 17. After manufacturing the photosensitive transfer material 20 by the above manufacturing method, the photosensitive transfer material 20 may be wound up to produce and store a photosensitive transfer material in a roll form. The photosensitive transfer material in a roll form can be provided in the same form in the step of bonding to a substrate by a roll-to-roll method described later.

[0317] The photosensitive transfer material according to the present disclosure can be suitably used for manufacturing a light-shielding material for an LED array.

[0318] (Light-shielding material) The light-shielding material according to the present disclosure has a resin layer having a first surface, a second surface opposite to the first surface, and a through-hole extending from the first surface to the second surface, and the transmittance of the resin layer to light with a wavelength of 830 nm is 0.1% or more. The light-shielding material according to the present disclosure can be suitably used as a light-shielding material for an LED array.

[0319] 〔Base material〕 The light-shielding material according to the present disclosure has a base material. As the base material used for the light-shielding material according to the present disclosure, a known base material or a known substrate may be used. Examples of the base material include glass, silicon, and film. The base material is preferably transparent. As used herein, "transparent" means that the transmittance of light with a wavelength of 400 nm to 700 nm is 80% or more. In addition, the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

[0320] Examples of the transparent glass substrate include tempered glass represented by Corning's Gorilla Glass. In addition, as the transparent glass substrate, the materials used in JP-A Nos. 2010-86684, 2010-152809, and 2010-257492 can be used.

[0321] When using a film as the base material, it is preferable to use a film with small optical distortion and / or high transparency. Examples of the material of such a film include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, polyimide, and cycloolefin polymer.

[0322] When manufacturing by a roll-to-roll method, a film is preferable as the base material.

[0323] When using a substrate, as the base material, a substrate having a conductive layer is preferable, and it is more preferable to have a conductive layer on the surface of the substrate. The substrate may have any layer other than the conductive layer as required. Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

[0324] Examples of the conductive layer of the substrate include a conductive layer such as circuit wiring. From the viewpoints of conductivity and fine wire formation, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and still more preferably a copper layer or a silver layer. The substrate may have a single conductive layer or two or more conductive layers. When having two or more conductive layers, it is preferable to have conductive layers of different materials.

[0325] Examples of the material of the conductive layer include a metal and a conductive metal oxide. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 and the like. In this specification, "conductive" means that the volume resistivity is less than 1×10 6 Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Ωcm.

[0326] When manufacturing a light-shielding material using a substrate having a plurality of conductive layers, it is preferable that at least one of the plurality of conductive layers contains a conductive metal oxide.

[0327] The substrate having a conductive layer may have a transparent electrode. The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a fine metal wire such as a metal mesh and silver nanowire. Examples of the fine metal wire include fine wires of silver, copper, etc. Among them, silver conductive materials such as silver mesh and silver nanowire are preferred.

[0328] 〔Resin layer〕 The light-shielding material according to the present disclosure has a resin layer on the above substrate. The resin layer in the light-shielding material according to the present disclosure is preferably a layer formed by curing the photosensitive layer in the photosensitive transfer material according to the present disclosure. Further, the resin layer preferably has a pattern shape of a desired shape.

[0329] The preferred embodiments of the respective components of the resin layer are the same as the preferred embodiments of the respective components of the photosensitive layer in the photosensitive transfer material according to the present disclosure, except as described later and except for components whose chemical structure changes before and after curing. The content of the resin contained in the resin layer is preferably 30% by mass to 90% by mass, more preferably 40% by mass to 80% by mass, and particularly preferably 55% by mass to 80% by mass with respect to the total mass of the resin layer from the viewpoints of blackening property and strength.

[0330] <Transmittance of light with a wavelength of 830 nm> In the light-shielding material according to the present disclosure, the transmittance of the resin layer to light with a wavelength of 830 nm is 0.1% or more, and preferably 0.15% or more and 30% or less, more preferably 0.20% or more and 20% or less from the viewpoints of blackening property and rectangularity of the pattern.

[0331] <Optical density of light with a wavelength of 550 nm> For the light-shielding material according to the present disclosure, the optical density of the resin layer at a wavelength of 550 nm of light is preferably 1.5 or more, more preferably 2.5 or more, still more preferably 3.0 or more, and particularly preferably 3.0 or more and 5.0 or less from the viewpoints of blackening property and rectangularity of the pattern.

[0332] The resin layer has a first surface, a second surface opposite to the first surface, and a through-hole extending from the first surface to the second surface. The shape of the through-hole is not particularly limited, and examples thereof include a columnar shape, a polygonal columnar shape, an elliptical columnar shape, a frustum of a cone shape, an inverted frustum of a cone shape, a frustum of a polygonal pyramid shape, an inverted frustum of a polygonal pyramid shape, an elliptical frustum of a cone shape, an inverted elliptical frustum of a cone shape, etc. Also, the cross-sectional shape in a plane perpendicular to the thickness direction of the resin layer may be an irregular shape. Further, the inclination angle formed by the side surface of the through-hole and the substrate surface is preferably 60° or more, more preferably 70° or more and 110° or less, and particularly preferably 80° or more and 100° or less from the viewpoint of the rectangularity of the obtained pattern. The average value of the size of the through-hole on the surface in contact with the substrate is preferably 100 μm, more preferably 60 μm or less, still more preferably 50 μm or less, and particularly preferably 1 μm or more and 50 μm or less from the viewpoints of the rectangularity of the obtained pattern, the luminance of the LED, and the luminous efficiency of the LED.

[0333] The layer thickness of the resin layer is not particularly limited, but is often 30 μm or less. From the viewpoint of more excellent effects in the present disclosure, 20 μm or less is preferable, 15 μm or less is more preferable, and 10 μm or less is particularly preferable. As the lower limit, 0.60 μm or more is preferable, and 1.5 μm or more is more preferable from the viewpoint of excellent strength. The thickness of the resin layer, the inclination angle, and the average value of the size of the through-hole can be calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM), for example.

[0334] <Method for manufacturing a light-shielding material> The manufacturing method of the light-shielding material according to the present disclosure is not particularly limited, but it is preferably a manufacturing method of forming a resin layer on a substrate using the photosensitive transfer material according to the present disclosure. As the manufacturing method of the light-shielding material, in the photosensitive transfer material according to the present disclosure, a step of bringing the outermost layer on the side having the photosensitive layer into contact with the substrate and bonding them (hereinafter also referred to as the "bonding step"), a step of pattern-exposing the photosensitive layer (hereinafter also referred to as the "exposure step"), and a step of developing the exposed photosensitive layer to form a resin layer (hereinafter also referred to as the "development step") are preferably included in this order. Further, from the viewpoint of more exerting the effects in the present disclosure, the manufacturing method of the light-shielding material according to the present disclosure preferably includes a hole pattern (through hole) in at least a part of the resin layer, and more preferably includes a hole pattern (through hole) having a maximum diameter of 100 μm or less in at least a part of the resin pattern.

[0335] - Bonding step - The manufacturing method of the light-shielding material preferably includes the bonding step. In the bonding step, it is preferable to bring the substrate (when a conductive layer is provided on the surface of the substrate, the conductive layer) into contact with the outermost layer on the side having the photosensitive layer with respect to the temporary support in the photosensitive transfer material, and press-bond the photosensitive transfer material and the substrate. In the above aspect, the adhesion between the outermost layer on the side having the photosensitive layer with respect to the temporary support in the photosensitive transfer material and the substrate is improved.

[0336] When the photosensitive transfer material includes a protective film, the protective film may be removed from the surface of the photosensitive layer and then bonded. Further, in the bonding step, when the photosensitive transfer material further includes a layer other than the protective film (for example, a high refractive index layer and / or a low refractive index layer) on the surface on the side not facing the temporary support of the photosensitive layer, the surface on the side not having the temporary support of the photosensitive layer and the substrate are bonded via that layer.

[0337] The method of laminating the base material and the photosensitive transfer material is not particularly limited, and known transfer methods and laminating methods can be used. The bonding of the photosensitive transfer material to the base material is preferably carried out by overlapping the outermost layer on the photosensitive layer side with respect to the temporary support in the photosensitive transfer material and the base material, and applying pressure and heat using means such as a roll. For bonding, known laminators such as laminators, vacuum laminators, and auto-cut laminators that can enhance productivity can be used. The laminating temperature is not particularly limited, but for example, it is preferably 70°C to 130°C.

[0338] The manufacturing method of the light-shielding material including the bonding step is preferably carried out by a roll-to-roll method. Hereinafter, the roll-to-roll method will be described. The roll-to-roll method means using a substrate that can be wound and unwound as a substrate, and before any step included in the method for manufacturing a resin pattern or the method for manufacturing a circuit wiring, a step of unwinding the substrate or a structure including the substrate (also referred to as the "unwinding step"), and after any step, a step of winding up the substrate or a structure including the substrate (also referred to as the "winding-up step"), and including a method of performing at least any step (preferably all steps, or all steps other than the heating step) while transporting the substrate or a structure including the substrate. The unwinding method in the unwinding step and the winding method in the winding-up step are not particularly limited, and known methods can be used in the manufacturing method to which the roll-to-roll method is applied.

[0339] -Exposure step- The manufacturing method of the light-shielding material preferably includes a step of pattern-exposing the photosensitive layer (exposure step) after the above bonding step. Here, "pattern exposure" refers to a form of exposure in a pattern shape, that is, exposure in a form where an exposed portion and a non-exposed portion exist. The positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited and is adjusted as appropriate.

[0340] The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited. For example, to improve the display quality of a display device (such as a touch panel) provided with an input device having circuit wiring manufactured by a circuit wiring manufacturing method, and to reduce the area occupied by the extraction wiring, at least a part of the pattern (preferably the electrode pattern of the touch panel and / or the part of the extraction wiring) preferably includes a thin line with a width of 20 μm or less, and more preferably includes a thin line with a width of 10 μm or less.

[0341] <Exposure process> The method for producing the light-shielding material according to the present disclosure preferably includes an exposure step of imagewise exposing the photosensitive transfer material transferred to the base material according to the present disclosure to form an exposed portion and an unexposed portion. The photosensitive transfer material according to the present disclosure is preferably exposed imagewise by laser exposure through a transparent original image having a line image, a halftone image, etc. or by laser beam scanning using digital data. The wavelength of the light source is preferably 750 nm to 1,400 nm. As the light source with a wavelength of 750 nm to 1,400 nm, a solid laser and a semiconductor laser that emit infrared rays are suitable. Regarding the infrared laser, the output is preferably 100 mW or more, the exposure time per pixel is preferably within 20 microseconds, and the irradiation energy amount is preferably 10 mJ / cm2 to 300 mJ / cm2. Also, it is preferable to use a multi-beam laser device to shorten the exposure time. The exposure mechanism may be any of an inner drum method, an outer drum method, a flat bed method, etc.

[0342] In the exposure process, after peeling the temporary support from the photosensitive layer, pattern exposure may be performed, or before peeling the temporary support, pattern exposure may be performed through the temporary support and then the temporary support may be peeled off. When the mask is peeled off before exposure, it may be exposed in contact with the photosensitive layer or exposed in proximity without contact. When exposing without peeling the temporary support, the mask may be exposed in contact with the temporary support or exposed in proximity without contact. In order to prevent mask contamination due to contact between the photosensitive layer and the mask and avoid the influence on exposure caused by foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling the temporary support. In addition, in the case of contact exposure, the contact exposure method can be appropriately selected and used; in the case of non-contact exposure, the proximity exposure method, the projection exposure method using a lens system or a mirror system, or the direct exposure method using an exposure laser or the like can be appropriately selected and used. In the case of projection exposure using a lens system or a mirror system, an exposure machine having an appropriate numerical aperture (NA) of the lens can be used according to the required resolution and depth of focus. In the case of the direct exposure method, drawing may be directly performed on the photosensitive layer, or reduced projection exposure may be performed on the photosensitive layer through a lens. In addition, exposure may be performed not only in the atmosphere but also under reduced pressure or in a vacuum, or exposure may be performed with a liquid such as water interposed between the light source and the photosensitive layer.

[0343] -Peeling Process- The method for manufacturing the light-shielding material may include a peeling process of peeling the temporary support between the bonding process and the exposure process, or between the exposure process and the development process. The method for peeling the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.

[0344] -Development Process- The method for manufacturing the light-shielding material preferably includes a process (development process) of developing the exposed photosensitive layer to form a resin layer after the above exposure process. When the photosensitive transfer material has a thermoplastic resin and a functional layer or a water-soluble resin layer, in the development process, the thermoplastic resin layer and the functional layer or the water-soluble resin layer in the non-exposed area are also removed together with the photosensitive layer in the non-exposed area. Further, in the development process, the thermoplastic resin layer and the functional layer or the water-soluble resin layer in the exposed area may also be removed in a form dissolved or dispersed in the developer.

[0345] The development of the exposed photosensitive layer in the development process can be performed using a developer. The developer is not particularly limited as long as it can remove the non-image part (non-exposed part) of the photosensitive layer. For example, known developers such as the developer described in JP-A-5-72724 can be used. As the developer, an alkaline aqueous solution-based developer containing a compound with pKa = 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L (liter) is preferred. The developer may contain a water-soluble organic solvent and / or a surfactant. Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). As the developer, the developer described in paragraph 0194 of WO 2015 / 093271 is also preferably mentioned. Preferred development methods include, for example, the development method described in paragraph 0195 of WO 2015 / 093271.

[0346] The development method is not particularly limited and may be any of paddle development, shower development, shower and spin development, and dip development. Shower development is a development process in which the developer is sprayed onto the photosensitive layer after exposure by a shower to remove the non-exposed area. After the development process, it is preferable to spray a cleaning agent by a shower and rub it with a brush to remove the development residue. The liquid temperature of the developer is not particularly limited, but preferably 20°C to 40°C.

[0347] -Protective film peeling step- When the photosensitive transfer material has a protective film, the method for manufacturing the light-shielding material preferably includes a step of peeling the protective film from the photosensitive transfer material. The method for peeling the protective film is not limited, and known methods can be applied.

[0348] -Post-exposure step and post-baking step- The method for manufacturing the light-shielding material may have a step of exposing (post-exposure step) and / or a step of heating (post-baking step) the resin layer obtained by the above-described development step. When both the post-exposure step and the post-baking step are included, it is preferable to perform post-baking after post-exposure.

[0349] -Other steps- The method for manufacturing the light-shielding material may include any step (other steps) other than the steps described above. For example, the following steps may be mentioned, but are not limited to these steps. In addition, examples of the exposure step, development step, and other steps applicable to the method for manufacturing circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696. Furthermore, examples of other steps include, but are not limited to, a step of reducing the visible light reflectance described in paragraph 0172 of WO 2019 / 022089, a step of forming a new conductive layer on an insulating film described in paragraph 0172 of WO 2019 / 022089, and the like.

[0350] -Step of reducing visible light reflectance- The method for manufacturing the light-shielding material may include a step of performing a treatment for reducing the visible light reflectance of some or all of the plurality of conductive layers of the substrate. As a process for reducing the visible light reflectance, an oxidation process can be mentioned. When the substrate has a conductive layer containing copper, the copper can be oxidized to form copper oxide, and by blackening the conductive layer, the visible light reflectance of the conductive layer can be reduced. Regarding the process for reducing the visible light reflectance, it is described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315, and the contents described in these publications are incorporated herein.

[0351] - A step of forming an insulating film, and a step of forming a new conductive layer on the surface of the insulating film - The method for manufacturing the light-shielding material preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and examples include known methods for forming a permanent film. Also, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0352] The method for manufacturing the light-shielding material preferably uses a substrate having a plurality of conductive layers on both surfaces of the substrate, and circuit formation is sequentially or simultaneously performed on the conductive layers formed on both surfaces of the substrate. With such a configuration, a circuit wiring in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface can be formed. Also, it is preferable to form such a circuit wiring in a roll-to-roll manner from both sides of the substrate.

[0353] (LED array) The LED array according to the present disclosure includes the light-shielding material according to the present disclosure. In addition, the LED array according to the present disclosure may be one in which two or more LEDs or LED elements are arranged. In the LED array according to the present disclosure, the shape of the arrangement of the LEDs or LED elements is not particularly limited, and may be an arbitrary shape arrangement as desired, such as linear, curved, cross-shaped, lattice-shaped, circular, elliptical, star-shaped, irregular-shaped, etc. The number of LEDs or LED elements in the LED array according to the present disclosure may be two or more, and can be appropriately selected as desired, for example, 10 to 1,000,000, etc. In addition, there are no particular restrictions on the size and shape of the LED array according to the present disclosure, and they can be appropriately selected as desired. Furthermore, there are no particular restrictions on the size and shape of the LEDs or LED elements in the LED array according to the present disclosure, and they can be appropriately selected as desired. The color of the LEDs or LED elements in the LED array according to the present disclosure is not particularly limited, and examples include red, blue, green, etc. It may be an LED array with only a single color, an LED array having two or more colors, or a white LED array having red, blue, and green LEDs or LED elements.

[0354] (Electronic device) The electronic device according to the present disclosure includes the LED array according to the present disclosure. The electronic device according to the present disclosure is not particularly limited, and can be used in known electronic devices using an LED array. Examples include lighting devices, exposure light sources, sensors, displays, etc.

Example

[0355] The embodiments of the present invention will be further specifically described with examples below. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0356] (Examples 1 to 27, and Comparative Example 1) <Preparation of Photosensitive Layer-Forming Composition> According to the formulations described in Table 1 below, these components were stirred and mixed to prepare photosensitive layer coating liquids 1 to 18 (photosensitive layer-forming compositions), respectively. The details of the compounds described in Table 1 and their contents are as shown below.

[0357]

Table 1

[0358] Also, the details of the compounds described in Table 1 are shown below. Red Pigment Dispersion Liquid 1: Red Pigment Dispersion Liquid 1 prepared by the following method Blue Pigment Dispersion Liquid 1: Blue Pigment Dispersion Liquid 1 prepared by the following method Green Pigment Dispersion Liquid 1: Green Pigment Dispersion Liquid 1 prepared by the following method Black Pigment Dispersion Liquid 1: IRBK-0001 (manufactured by Tokushiki Co., Ltd., containing near-infrared light-transmitting organic pigment, pigment concentration 16%, additive 5%, PGMEA solution) Black Pigment Dispersion Liquid 2: FDK-017 (manufactured by Tokyo Ink Co., Ltd., containing carbon black, pigment concentration 20%, additive 7%, PGMEA solution), primary particle size of black pigment 35 nm BPE-500: 2,2-bis(4-(methacryloxy pentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. DPHA: Dipentaerythritol hexaacrylate, KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. A-DCP: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Polymer 1: PGMEA solution of benzyl methacrylate / methacrylic acid copolymer (70 mol% / 30 mol%, Mw 12,000, acid value 113 mgKOH / g, solid content concentration 37.8%) Polymer 2: The following P-3 [OI-5]: [OI-5] described above [OS-4]: [OS-4] described above IR-8: IR-8 described above (oxidation potential 0.35 V vs. SCE) IR-786 Perchlorate: The following compound (oxidation potential 0.53 V vs. SCE) N-Phenylglycine: Manufactured by Tokyo Chemical Industry Co., Ltd. TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd. Leuco Crystal Violet: Manufactured by Tokyo Chemical Industry Co., Ltd. MMPG-Ac: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko K.K.) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) F-552: Fluorine-based surfactant, Megafac F552, manufactured by DIC Corporation

[0359]

Chemical formula

[0360] <Preparation of Red Pigment Dispersion Liquid 1> The following pigment, dispersant, dispersion aid, binder resin, and solvent were mixed. Here, 80% of the volume of the dispersion container of zirconia beads (average particle size 0.3 mm) was mixed, and then filled into a picomill dispersion container and dispersed for 6 minutes of retention time (RT) to prepare Red Pigment Dispersion Liquid 1.

[0361] - Composition of Red Pigment Dispersion Liquid 1 - · C.I. Pigment Red 254: 100 parts by mass · DisperBYK-2000 (dispersant manufactured by BYK): 33 parts by mass · Acrylic resin (copolymer of benzyl methacrylate / methacrylic acid with a molar ratio of 70 / 30, weight average molecular weight (Mw) 12,000, acid value 113 mg KOH / g, propylene glycol monomethyl ether acetate (PGMEA) solution with a solid content concentration of 40%): 125 parts by mass · PGMEA: 242 parts by mass

[0362] <Preparation of Blue Pigment Dispersion Liquid 1> The cyan pigment dispersion liquid 1 was prepared in the same manner as the red pigment dispersion liquid 1, except that C.I. Pigment Blue 15:6 was used instead of C.I. Pigment Red 254.

[0363] <Preparation of green pigment dispersion liquid 1> The green pigment dispersion liquid 1 was prepared in the same manner as the red pigment dispersion liquid 1, except that C.I. Pigment Green 58 was used instead of C.I. Pigment Red 254.

[0364] <Preparation of P-3> According to the following method, a 36.2 mass% solution of polymer P-3 as a P-3 solution was prepared. Polymer P-3 is the resin shown below and is also an alkali-soluble resin. 113.5 g of propylene glycol monomethyl ether was charged into a flask and heated to 90 °C under a nitrogen stream. A solution prepared by dissolving 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid in 30 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 27.6 g of polymerization initiator V-601 (manufactured by Fuji Film Wako Pure Chemical Corporation) in 57.7 g of propylene glycol monomethyl ether were simultaneously added dropwise over 3 hours. After completion of the dropwise addition, 2.5 g of V-601 was added three times at 1-hour intervals. Thereafter, the reaction was continued for another 3 hours. Thereafter, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. Under an air stream, the temperature of the reaction solution was raised to 100 °C, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (Blemmer G manufactured by NOF Corporation) was added dropwise thereto over 20 minutes. This was reacted at 100 °C for 7 hours to obtain a solution of polymer P-3. The solid content concentration of the obtained solution was 36.3%. Regarding polymer P-3, the weight average molecular weight in terms of standard polystyrene in GPC was 18,000, the dispersity was 2.3, and the acid value was 124 mgKOH / g. The amount of residual monomer measured using gas chromatography was less than 0.1 mass% with respect to the solid content of polymer P-3 for any monomer. The structure of polymer P-3 is shown below. The molar ratio of the repeating units in the formula was 55.1:26.5:1.6:16.8 in order from the leftmost repeating unit.

[0365]

Chemical formula

[0366] <Preparation of photosensitive transfer material 1 (Examples 1 to 23, Comparative Example 1)> On a temporary support of a polyethylene terephthalate film with a thickness of 25 μm, using a slit nozzle, a coating solution for a thermoplastic (non-photosensitive) resin layer having the following formulation H1 was applied and dried to form a thermoplastic (non-photosensitive) resin layer. Next, a coating solution for a functional layer having the following formulation P1 was applied onto the thermoplastic (non-photosensitive) resin layer and dried to obtain a functional layer. Further, the above-described composition for forming a photosensitive layer was applied onto the functional layer and dried to obtain a photosensitive layer. By the method described above, a thermoplastic (non-photosensitive) resin layer with a dry film thickness of 6.0 μm, a functional layer with a dry film thickness of 1.3 μm, and a photosensitive layer with the thickness after drying described in Table 2 were provided on the temporary support, and finally, a protective film (a 12-μm-thick polypropylene film) was pressure-bonded to the surface of the photosensitive layer. Thus, photosensitive transfer materials each having a temporary support, a thermoplastic (non-photosensitive) resin layer, a functional layer (oxygen barrier film), a photosensitive layer, and a protective film were produced.

[0367] <Fabrication of Photosensitive Transfer Material 2 (Examples 24 and 25)> On a temporary support of a polyethylene terephthalate film with a thickness of 14 μm, using a slit nozzle, the above-described composition for forming a photosensitive layer was applied onto the functional layer and dried to obtain a photosensitive layer. Finally, a protective film (a 12-μm-thick polypropylene film) was pressure-bonded to the surface of the photosensitive layer. Thus, photosensitive transfer materials each having a temporary support, a photosensitive layer containing a photosensitive resin composition, and a protective film were produced.

[0368] ~Coating Solution for Thermoplastic (Non-Photosensitive) Resin Layer: Formulation H1~ ·Methanol: 11.1 parts ·Propylene Glycol Monomethyl Ether Acetate: 6.36 parts ·Methyl Ethyl Ketone: 52.4 parts ·Copolymer of Methyl Methacrylate / 2-Ethylhexyl Acrylate / Benzyl Methacrylate / Methacrylic Acid (Copolymer Composition Ratio (Molar Ratio) = 55 / 11.7 / 4.5 / 28.8, Weight-Average Molecular Weight = 100,000, Glass Transition Temperature (Tg) ≒ 70°C): 5.83 parts · Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63 / 37, weight average molecular weight = 10,000, Tg ≒ 100 °C): 13.6 parts · 2,2-Bis[4-(methacryloxy polyethoxy)phenyl]propane (manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 parts · Fluorine-based surfactant (methyl ethyl ketone solution with a solid content of 30% by mass, manufactured by DIC Corporation, Megafac (registered trademark) F780F): 0.54 part

[0369] ~ Coating liquid for functional layer: Formulation P1 ~ · PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, degree of polymerization 550): 32.2 parts · Polyvinylpyrrolidone (manufactured by ISP Japan Co., Ltd., K-30): 14.9 parts · Distilled water: 524 parts · Methanol: 429 parts

[0370] <Measurement of optical properties> The optical density, transmittance, and reflectance were measured by the method described above.

[0371] <Evaluation of blackening property> (1) A photosensitive transfer film with the protective film peeled off was laminated on a 100-μm-thick polyethylene terephthalate (PET) film using a laminator (roll temperature: 100 °C, line pressure: 1.0 MPa, line speed: 0.5 m / min). (2) The obtained laminate was pressure-degassed for 30 minutes under the conditions of 0.6 MPa and 60 °C using an autoclave apparatus. (3) Without peeling the temporary support, the transfer substrate was fixed to a 0.3-mm-thick aluminum plate, and then the photosensitive resin layer was exposed to a square hole pattern (changing stepwise from 10 μm to 100 μm on each side at 10-μm intervals) with an exposure amount under the condition of an output of 10 W using a Trendsetter 3244VFS manufactured by Creo equipped with a water-cooled 40-W infrared semiconductor laser. (4) After peeling off the temporary support, development was carried out. Development was performed by shower development using an aqueous solution of 1.0 mass% sodium carbonate at 25°C. The development time was 1.5 times the dissolution time of the unexposed portion of the 1.0 mass% sodium carbonate aqueous solution at 25°C. By the above method, (3) and (4) were repeated until one side of the resin pattern of the photosensitive resin composition corresponding to the 50-μm square hole pattern of the mask became exactly 50 μm. (5) Then, exposure was carried out using a high-pressure mercury lamp at 400 mJ / cm 2 Further, an oven treatment was performed at 150°C for 30 minutes.

[0372] Among the resist patterns obtained above, the black appearance when visually observing the portion without square holes by reflecting the light of a three-wavelength fluorescent lamp from various directions was evaluated according to the following criteria. A: Appears black at any angle. B: There is an angle at which faint light reflection can be visually recognized around the reflected fluorescent lamp.

[0373] <Resist Shape Evaluation> - Angle with the substrate - Among the resin patterns obtained in the blackening property evaluation, the cross-sectional shape of the square hole resin pattern at a location where one side is 50 μm was observed using a scanning electron microscope (SEM). The curve constituting the inclined surface of the inclined portion was approximated to a straight line, and this straight line was defined as the inclination angle θ. The closer θ is to 90°, the better the rectangularity. A: The inclination angle is 80° or more and 100° or less. B: The inclination angle is 70° or more and less than 80°. C: The inclination angle is 60° or more and less than 70°. D: The inclination angle is less than 60°.

[0374] <Patterning Property Evaluation> - Development residue - Among the resin patterns obtained by blackening evaluation, the cross-sectional shape of the square hole of the resin pattern at a location where one side was 50 μm was observed using a scanning electron microscope (SEM), and the state of the residue near the substrate was evaluated according to the following criteria. A: No development residue was observed. B: Among 10 holes confirmed, residue was confirmed at 1 or 2 locations. C: Among 10 holes confirmed, residue was confirmed at 3 or more locations.

[0375] -Linearity- On a polyethylene terephthalate (PET) film with a thickness of 100 μm, a photosensitive transfer material and a PET substrate with a copper layer were laminated by a roll-to-roll method using a vacuum laminator (manufactured by MCK Co., Ltd., roll temperature: 110 °C, line pressure: 1.0 MPa, line speed: 0.5 m / min). The obtained laminate includes at least a PET film, a photosensitive layer, and a temporary support, in this order. The obtained laminate was pressure-defoamed for 0.5 hours under the conditions of 0.6 MPa and 60 °C using an autoclave device. Without peeling the temporary support, after fixing the transfer substrate to an aluminum plate with a thickness of 0.3 mm, exposure was performed with a variable exposure amount under the condition of an output of 9 W using a Trendsetter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser, for a line-and-space pattern (the duty ratio is 1:1, and the line width changes stepwise from 10 μm to 200 μm at 10 μm intervals) on the photosensitive resin layer. After peeling the temporary support, development was carried out. Development was performed using a 1.0 mass% aqueous sodium carbonate solution at 25 °C by shower development. The development time was 1.5 times the dissolution time of the unexposed portion of the 1.0 mass% aqueous sodium carbonate solution at 25 °C. By the above method, the exposure amount (hereinafter referred to as the "reference exposure amount") at which the line width of the resin pattern corresponding to the 100 μm line-and-space pattern becomes exactly 100 μm was determined. Next, a sample obtained by exposing the photosensitive resin layer at the reference exposure amount was observed for the resin pattern using a scanning electron microscope (SEM), and the maximum - minimum value of the line width (hereinafter referred to as the "variation value of the line width") was measured in a range of 1,000 μm in length. Based on the variation value of the line width, the linearity of the resin pattern was evaluated according to the following criteria. A: The variation value of the line width is less than 5 μm. B: The variation value of the line width is 5 μm or more and less than 15 μm. C: The variation value of the line width is 15 μm or more.

[0376] The evaluation results are summarized and shown in Table 2.

[0377]

Table 2

[0378] Note that the photosensitive transfer materials of Examples 24 and 25 are photosensitive transfer materials that do not have a thermoplastic resin layer and a functional layer as the intermediate layer.

[0379] As shown in Table 2 above, the photosensitive transfer materials of Examples 1 to 27 obtained patterns with better rectangularity compared to the photosensitive transfer material of Comparative Example 1. In addition, when the photosensitive transfer materials of Examples 1, 2, 4, 5, 7 to 27 were used, they had excellent blackening properties, and in particular, multiple images around the through - holes could be suppressed, and they could be suitably used for LED arrays.

Explanation of Reference Numerals

[0380] 11: Temporary support, 12: Transfer layer, 13: Thermoplastic resin layer, 15: Functional layer, 17: Photosensitive layer, 19: Protective film, 20: Photosensitive transfer material

Claims

1. a resin layer having a first surface, a second surface opposite to the first surface, and a through hole extending from the first surface to the second surface; The resin layer has a transmittance of 0.1% or more for light having a wavelength of 830 nm. Shading material.

2. the through hole has an inclination in a thickness direction of the resin layer, The light-shielding material according to claim 1 , wherein an inclination angle between a side surface of the through hole and the first surface is 60° or more.

3. The light-shielding material according to claim 1 or 2, wherein an average value of the size of the through holes in the first surface is 50 μm or less.

4. 4. The light-shielding material according to claim 1, wherein the optical density of the resin layer for light with a wavelength of 550 nm is 3.0 or more.

5. The light-shielding material according to any one of claims 1 to 4, which is a light-shielding material for an LED array.

6. An electronic device comprising the light shielding material according to any one of claims 1 to 5.

7. An LED array comprising the light shielding material according to any one of claims 1 to 5.

8. An electronic device comprising the LED array according to claim 7.

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