Transfer film, pattern formation method, laminate, and micro LED display

Abstract

The present invention addresses a first problem of providing a transfer film that exhibits excellent pattern resolution and with which high reflectance of a pattern can be obtained. In addition, the present invention addresses a second problem of providing a pattern formation method, a laminate, and a micro LED display.　A transfer film according to the present invention includes a temporary support body and a photosensitive layer. The photosensitive layer contains a sensitive material and particles having a refractive index of 2.0 or more at a wavelength of 550 nm and having an average particle diameter of 200 nm or less, and satisfies the relationship represented by formula (A).　Formula (A): X2>X1 In formula (A), X1 represents the average reflectance for visible light of the photosensitive layer. X2 represents: the average reflectance for visible light of a processed layer obtained by subjecting the photosensitive layer to i-ray exposure at an exposure amount of 200 mJ / cm2 and heating at 200°C for 1.5 hours, the photosensitive layer having been subjected to the exposure process, if the photosensitive layer is a negative type photosensitive layer; or the average reflectance for visible light of a processed layer obtained by heating the photosensitive layer at 200°C for 1.5 hours, if the photosensitive layer is a positive type photosensitive layer.

Description

Transfer film, pattern forming method, laminate, and micro LED display

[0001] The present invention relates to a transfer film, a pattern forming method, a laminate, and a micro LED (Light Emitting Diode) display.

[0002] In recent years, micro LED display elements, which have minute LED chips mounted on an array substrate of a pixel circuit, have been developed as next-generation display elements. Micro LED display elements typically include, as components, a micro LED array substrate having a substrate, a plurality of micro LED chips arranged on the substrate, and a partition layer arranged between each LED chip for the purpose of suppressing color mixing of light between adjacent pixels.

[0003] Recently, a pattern formation method using a transfer film has been widely used because the number of steps required to obtain a predetermined pattern is small. For example, Patent Document 1 discloses a dry film that can be used to form a highly reflective insulating layer on a printed wiring board on which light-emitting elements such as LEDs are mounted, the dry film having a photosensitive layer formed from a curable resin composition of a predetermined composition containing a white colorant (for example, particles of titanium oxide, etc.).

[0004] Japanese Patent Application Laid-Open No. 2020-125403

[0005] The present inventors prepared a transfer film having a photosensitive layer containing particles (e.g., titanium oxide) with reference to Patent Document 1 and examined its performance, and found that there is room for further improvement in the resolution of the pattern. In other words, it was found that there is room for further improvement in the resolution of the pattern without reducing the reflectance of the formed pattern.

[0006] Therefore, an object of the present invention is to provide a transfer film that has excellent pattern resolution and produces a pattern with high reflectance, and also to provide a pattern formation method, a laminate, and a micro LED display.

[0007] The present inventors have found that the above problems can be solved by the following configuration.

[0008] [1] A transfer film comprising a temporary support and a photosensitive layer, wherein the photosensitive layer contains particles having a refractive index of 2.0 or more and an average particle size of 200 nm or less, and a photosensitive material, and the transfer film satisfies the relationship of the following formula (A): Formula (A) X2>X1 In formula (A), X1 represents the average reflectance of the photosensitive layer for visible light. When the photosensitive layer is a negative photosensitive layer, X2 represents the average reflectance of the photosensitive layer for visible light at an exposure dose of 200 mJ / cm2 with i-rays. ２and heating the exposed photosensitive layer at 200°C for 1.5 hours. In the case where the photosensitive layer is a positive photosensitive layer, this represents the average visible light reflectance of a treated film obtained by heating the photosensitive layer at 200°C for 1.5 hours. [2] The transfer film according to [1], which satisfies the relationship of the following formula (B): Formula (B) X2 > X1 + 30% In formula (B), X1 and X2 are defined as X1 and X2 in formula (A). [3] The transfer film according to [1] or [2], wherein the photosensitive material contains a photopolymerizable compound and a photopolymerization initiator, and the photosensitive layer contains a compound that does not have a photopolymerizable group and has a boiling point of 230 to 500°C. [4] The transfer film according to any of [1] to [3], wherein the particles are titanium oxide. [5] The transfer film according to any one of [1] to [4], wherein the particles have an average primary particle diameter of 100 nm or less. [6] The transfer film according to any one of [1] to [5], wherein the photosensitive layer further contains an alkali-soluble resin. [7] The transfer film according to any one of [1] to [6], wherein a photosensitive light-absorbing layer precursor layer is further provided between the temporary support and the photosensitive layer. [8] A pattern formation method comprising: Step 1: bonding the transfer film according to any one of [1] to [7] to a substrate so that the surface of the transfer film on the photosensitive layer side faces the substrate; Step 2: pattern-exposing the photosensitive layer; Step 3: developing the pattern-exposed photosensitive layer to form a pattern; Step 4: heat-treating the developed pattern; and Step 5: peeling off the temporary support between Step 1 and Step 2 or between Step 2 and Step 3. [9] A laminate having a pattern obtained by the pattern forming method according to [8].

[10] A micro LED display having the laminate according to [9].

[0009] According to the present invention, a transfer film having excellent pattern resolution and high reflectance of the resulting pattern can be provided. Furthermore, according to the present invention, a pattern forming method, a laminate, and a micro LED display can be provided.

[0010] It is a schematic cross-sectional view showing an example of an embodiment of the transfer film of the present invention. It is a schematic cross-sectional view showing an example of an embodiment of the transfer film of the present invention. It is a diagram (nomograph) explaining a method for measuring the boiling point of compound Y.

[0011] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in the numerical ranges described in stages in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0012] Furthermore, the term "step" in this specification does not only refer to an independent step, but also includes a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved. In this specification, unless otherwise specified, the temperature condition may be 25°C. For example, the temperature when performing each of the above steps may be 25°C, unless otherwise specified.

[0013] In this specification, "transparent" means that the average transmittance of visible light in the wavelength range of 400 to 700 nm is 80% or more, and preferably 90% or more. The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer V-570 manufactured by JASCO Corporation.

[0014] In this specification, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp, such as g-line, h-line, and i-line, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In addition, in the present invention, light means actinic rays or radiation.

[0015] In this specification, unless otherwise specified, "exposure" includes not only exposure using far ultraviolet light, extreme ultraviolet light, X-rays, EUV light, etc., as typified by mercury lamps and excimer lasers, but also exposure using particle beams such as electron beams and ion beams.

[0016] In this specification, unless otherwise specified, the refractive index value is the refractive index value for light with a wavelength of 550 nm at 25° C., and is a value measured by an ellipsometer.

[0017] In this specification, unless otherwise specified, the average reflectance of visible light refers to the average reflectance of visible light having a wavelength of 400 to 700 nm, and is a value measured using a spectrophotometer. For example, the spectrophotometer that can be used is the V-570 spectrophotometer manufactured by JASCO Corporation.

[0018] In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0019] In this specification, unless otherwise specified, the content ratio of each repeating unit in a polymer is a molar ratio.

[0020] In this specification, "(meth)acrylic acid" is a concept that encompasses both acrylic acid and methacrylic acid, "(meth)acryloyl group" is a concept that encompasses both acryloyl group and methacryloyl group, and "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate.

[0021] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more.

[0022] In this specification, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more.

[0023] In this specification, the "solid content" of a composition refers to the components that form a composition layer formed using the composition. Usually, when the composition contains a solvent (e.g., an organic solvent and water), it refers to all components excluding the solvent. Furthermore, liquid components are also considered to be solid content if they form a composition layer. However, when the photosensitive layer of the transfer film contains a solvent with a boiling point of 230 to 500°C that may be a type of compound Y described below, the solvent with a boiling point of 230 to 500°C that may be a type of compound Y described above is considered to be "solid content."

[0024] In this specification, unless otherwise specified, the thickness (film thickness) of a layer is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0025] In this specification, unless otherwise specified, the boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg).

[0026] [Transfer film] The transfer film of the present invention is a transfer film comprising a temporary support and a photosensitive layer, wherein the photosensitive layer comprises particles (hereinafter also referred to as "specific particles") having a refractive index of 2.0 or more and an average particle diameter of 200 nm or less, and a photosensitive material, and the transfer film satisfies the relationship of the following formula (A): Formula (A) X2>X1 In formula (A), X1 represents the average reflectance of the photosensitive layer for visible light. When the photosensitive layer is a negative photosensitive layer, X2 represents the average reflectance of the photosensitive layer for visible light at an exposure dose of 200 mJ / cm2 of i-rays. ２ and heating the exposed photosensitive layer at 200°C for 1.5 hours. In the case where the photosensitive layer is a positive photosensitive layer, the average reflectance of the exposed photosensitive layer is expressed as the average reflectance of the exposed photosensitive layer at 200°C for 1.5 hours.

[0027] When the photosensitive layer of the transfer film having the above configuration is transferred to a transfer target and then subjected to an exposure treatment and a predetermined heating treatment (e.g., heating treatment at 200°C for 1.5 hours), its average reflectance of visible light increases compared to before the exposure treatment. In other words, the photosensitive layer of the transfer film having the above configuration has a low average reflectance of visible light when transferred to a transfer target and subjected to an exposure treatment, while when subjected to a predetermined heating treatment after the exposure treatment (e.g., after the exposure treatment and before or after the development treatment), the average reflectance of visible light increases. The above characteristics of the transfer film of the present invention are derived from the behavior of the specific particles contained in the photosensitive layer. When the photosensitive layer is subjected to an exposure treatment, the specific particles are dispersed relatively uniformly within the layer, suppressing the formation of aggregates, resulting in a relatively low average reflectance of visible light. Therefore, when forming a pattern using the transfer film of the present invention, the exposure light easily penetrates deep into the photosensitive layer during the exposure process of the photosensitive layer transferred to the transfer substrate, making it easier to form a fine pattern (i.e., high pattern resolution). On the other hand, it is presumed that performing a predetermined heat treatment promotes aggregation of specific particles, increasing the average visible light reflectance of the pattern, which becomes higher than the average visible light reflectance of the photosensitive layer before the predetermined heat treatment. The pattern obtained by performing a predetermined heat treatment after the exposure treatment has a high average visible light reflectance, and when used, for example, as a partition layer in a micro LED display element, it can exhibit good reflective function and improve the brightness during white display (when the light source is on).

[0028] One example of a method for controlling particle aggregation by subjecting the photosensitive layer to the predetermined heat treatment is to incorporate a component (such as compound Y, described below) that can be volatilized by the predetermined heat treatment into the material forming the photosensitive layer. The component suppresses aggregation by improving the compatibility between the specific particles and the photosensitive material in the photosensitive layer during exposure treatment, and is volatilized from the layer when the predetermined heat treatment is applied, which is thought to facilitate the formation of an aggregate structure by the specific particles in the layer.

[0029] Hereinafter, the transfer film of the present invention may be said to have "better effects of the present invention" when it has better pattern resolution and / or when the pattern formed by the transfer film of the present invention has a higher average visible light reflectance.

[0030] The configuration of the transfer film of the present invention will be described in more detail below with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a transfer film. The transfer film 1 shown in FIG. 1 has, in this order, a temporary support 10, a photosensitive layer 12, and a protective film 14. The photosensitive layer 12 contains specific particles and a photosensitive material and is a layer that satisfies the relationship of formula (A) above. The photosensitive layer 12 may be either a positive-type photosensitive layer or a negative-type photosensitive layer, but is preferably a negative-type photosensitive layer. The pattern formed by transferring the photosensitive layer 12 of the transfer film 1 to a transfer target has a high average reflectance of visible light. For example, when applied as a partition layer of a micro LED display element, it can highly reflect light from a light source and improve the brightness during white display (when the light source is on). Note that while the transfer film 1 shown in FIG. 1 has a protective film 14, the protective film 14 need not be provided.

[0031] FIG. 2 is a cross-sectional schematic diagram showing another example of an embodiment of the transfer film of the present invention. The transfer film 2 shown in FIG. 2 has a temporary support 10, a photosensitive light-absorbing layer precursor layer 22, a photosensitive layer 12, and a protective film 14, in this order. That is, the transfer film 2 further has a photosensitive light-absorbing layer precursor layer 22 between the temporary support 10 and the photosensitive layer 12 of the transfer film 10. The photosensitive light-absorbing layer precursor layer 22 is a layer that exhibits photosensitivity and may be either a positive-type photosensitive layer or a negative-type photosensitive layer, but is preferably a negative-type photosensitive layer. A pattern formed by transferring the photosensitive layer 12 and the photosensitive light-absorbing layer precursor layer 22 of the transfer film 2 to a transfer target has a high average reflectance of visible light in the layer derived from the photosensitive layer 12, and can absorb light in the light-absorbing layer derived from the photosensitive light-absorbing layer precursor layer 22, which is formed on the surface opposite the transfer target side of the pattern. Therefore, for example, when a pattern formed using the transfer film 2 is applied as a partition layer of a micro LED display element, when the micro LED display element displays white (when the light source is on), the resin layer portion derived from the photosensitive layer 12 can highly reflect light from the light source, thereby improving brightness. Also, when the micro LED display element displays black (when the light source is off), reflection of external light is suppressed by the light absorption layer of the partition layer, resulting in excellent black density.

[0032] Hereinafter, each element constituting the transfer film of the present invention will be described.

[0033] [Temporary Support] The transfer film of the present invention has a temporary support. The temporary support is a member that supports a composition layer disposed on a temporary support such as a photosensitive layer, and is ultimately removed by a peeling treatment.

[0034] The temporary support may have a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. The temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat. Examples of the film include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. Among these, polyethylene terephthalate film is preferred as the temporary support. Furthermore, it is preferable that the film used as the temporary support is free from deformation such as wrinkles and scratches.

[0035] The temporary support preferably has high transparency in order to enable pattern exposure through the temporary support, and the transmittance at 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. Preferred values ​​of transmittance include, for example, 87%, 92%, and 98%. In terms of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the temporary support has a small haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. In terms of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support should be 50 / 10 mm. ２ Preferably, 10 pieces / 10 mm or less ２ More preferably, 3 pieces / 10 mm or less ２ More preferably, 0 pieces / 10 mm or less ２ is particularly preferred.

[0036] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, even more preferably 5 to 50 μm, and most preferably 5 to 25 μm.

[0037] Furthermore, the surface of the temporary support that comes into contact with the composition layer may be surface-modified by UV (ultraviolet) irradiation, corona discharge, plasma, or the like, for the purpose of improving adhesion between the temporary support and a composition layer such as a photosensitive layer formed on the temporary support.

[0038] When the surface modification of the temporary support is carried out by UV irradiation, the exposure dose is 10 to 2000 mJ / cm ２ is preferably 50 to 1000 mJ / cm ２ Examples of light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs), all of which emit light in the 150 to 450 nm wavelength band. There are no particular limitations on the lamp output or illuminance, as long as the light irradiation amount is within this range.

[0039] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm.

[0040] The temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning used films, etc., and chipping them, and then using these as materials to form films. Specific examples of recycled products include the Ecouse series from Toray Industries, Inc. Preferred forms of the temporary support are described, for example, in paragraphs

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

[0057] of WO 2012 / 081680 A, and paragraphs

[0029] to

[0040] of WO 2018 / 179370 A, the contents of which are incorporated herein by reference.

[0041] To improve handling properties, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4300, Cosmoshine A4160, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0042] [Photosensitive Layer] The transfer film of the present invention includes a photosensitive layer. The photosensitive layer includes specific particles and a photosensitive material, and satisfies the relationship of the following formula (A). The photosensitive layer may be either a positive-type photosensitive layer or a negative-type photosensitive layer, but is preferably a negative-type photosensitive layer.

[0043] Formula (A) X2>X1 In formula (A), X1 represents the average reflectance of the photosensitive layer for visible light. When the photosensitive layer is a negative photosensitive layer, X2 represents the average reflectance of the photosensitive layer for visible light at an exposure dose of 200 mJ / cm 2 of i-line. ２ and heating the exposed photosensitive layer at 200°C for 1.5 hours. In the case where the photosensitive layer is a positive photosensitive layer, the average reflectance of the exposed photosensitive layer is expressed as the average reflectance of the exposed photosensitive layer at 200°C for 1.5 hours.

[0044] The photosensitive layer in the transfer film preferably satisfies the relationship of the following formula (B): In formula (B), X1 and X2 have the same meanings as X1 and X2 in formula (A). Formula (B) X2>X1+30%

[0045] <Procedure for Measuring X1 and X2> Hereinafter, an example of a procedure for measuring the average visible light reflectance (X1) of the photosensitive layer and the average visible light reflectance (X2) of the photosensitive layer after a predetermined treatment will be described.

[0046] (Procedure for measuring X1) <<Preparation of Laminate Sample (Test Piece)>> A laminate sample is prepared by contacting the surface of the transfer film opposite to the temporary support side with a glass substrate, transferring (laminating) the transfer film to the glass substrate, and then peeling off the temporary support. If the transfer film has a protective film, the protective film is peeled off and the transfer film is transferred to the glass substrate. An example of the configuration of the laminate sample obtained in this manner is a configuration having a glass substrate and a photosensitive layer disposed on the glass substrate.

[0047] The transfer can be carried out using a commercially available device (for example, a known laminator such as a vacuum laminator or an auto-cut laminator). The temperature when transferring the transfer film onto the glass substrate is not particularly limited, but is preferably, for example, 80 to 150°C, and more preferably 90 to 120°C. Furthermore, when transferring the transfer film onto the glass substrate, it is preferably carried out by roll-to-roll transfer, and the conveying speed at that time is, for example, preferably 0.5 to 5 m / min, and more preferably 1.5 to 3 m / min. Furthermore, the glass substrate is not particularly limited, but for example, soda glass, alkali-free glass, quartz glass, etc. can be used.

[0048] Using the laminate sample described above, the average visible light reflectance of the photosensitive layer (average reflectance of visible light with a wavelength of 400 to 700 nm) is measured. The method for measuring the average visible light reflectance is as described above. The upper limit of the average visible light reflectance of the photosensitive layer represented by X1 is preferably 70% or less, more preferably 50% or less, even more preferably 30% or less, and particularly preferably 10% or less. The lower limit of the average visible light reflectance of the photosensitive layer represented by X1 may be 0% or more, and may be, for example, 0.01% or more or 0.1% or more.

[0049] (Procedure for measuring X2) <<Preparation of Laminate Sample (Test Piece)>> The surface of the transfer film opposite to the temporary support side is brought into contact with a glass substrate, and the transfer film is transferred (laminated) onto the glass substrate to prepare a laminate sample. If the transfer film has a protective film, the protective film is peeled off and the transfer film is transferred onto the glass substrate. After transfer, the temporary support may or may not be peeled off, but it is preferable that it is not peeled off. An example of the configuration of the laminate sample obtained in this manner is a configuration having a glass substrate, a photosensitive layer, and a temporary support in this order.

[0050] <<Measurement Procedure for X2 When the Photosensitive Layer is a Negative-Working Photosensitive Layer>> When the photosensitive layer is a negative-working photosensitive layer, the photosensitive layer of the above-described laminate sample is exposed to i-line light at an exposure dose of 200 mJ / cm. ２ After the exposure treatment, the exposed photosensitive layer is further subjected to a heat treatment at 200°C for 1.5 hours. The average reflectance of visible light (average reflectance of visible light with a wavelength of 400 to 700 nm) is measured using the thus obtained treated laminate sample (treated film). The specific procedure is as follows.

[0051] The exposure device is not particularly limited as long as it can irradiate ultraviolet rays, but for example, a proximity type exposure device having an ultra-high pressure mercury lamp (Hitachi High-Tech Electronics Engineering Co., Ltd.) is preferably used. The exposure treatment is preferably carried out via a temporary support, and i-rays are irradiated at 200 mJ / cm2 onto the photosensitive layer in the laminate sample via the temporary support. ２ It is preferable to carry out the exposure treatment by irradiating the entire surface with an exposure amount of 1000 ppm or more. When the exposure treatment is carried out via a temporary support, the temporary support is peeled off from the laminate sample after the exposure treatment after the exposure treatment and before the heat treatment.

[0052] After the exposure treatment, the laminate sample is heated for 1.5 hours at 200° C. Examples of the heating method include methods using a heating device such as a convection oven, an IR heater, or a hot plate, and among these, heat treatment in a convection oven is preferred.

[0053] <<Measurement Procedure for X2 When the Photosensitive Layer is a Positive-Working Photosensitive Layer>> When the photosensitive layer is a positive-working photosensitive layer, the photosensitive layer of the above-mentioned laminate sample is subjected to a heat treatment at 200°C for 1.5 hours, and the average reflectance of visible light (average reflectance of visible light with a wavelength of 400 to 700 nm) is measured using the resulting treated laminate sample (treated film). The specific procedure is as follows.

[0054] The temporary support of the laminate sample is peeled off from the laminate sample before the heat treatment. Then, the laminate sample from which the temporary support has been peeled off is heated at 200° C. for 1.5 hours. Examples of the heating method include a method using a heating device such as a convection oven, an IR heater, or a hot plate, and among these, heat treatment in a convection oven is preferred.

[0055] Using the laminate sample (treated film) after the predetermined treatment described above, the average visible light reflectance (average reflectance of visible light with a wavelength of 400 to 700 nm) of the photosensitive layer that has undergone the predetermined treatment is measured. The method for measuring the average visible light reflectance is as described above. The lower limit of the average visible light reflectance of the photosensitive layer represented by X2 is preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, and particularly preferably 70% or more. The upper limit of the average visible light reflectance of the photosensitive layer represented by X2 may be 100% or less, and may be, for example, 99% or less or 98% or less.

[0056] The difference (X2-X1) between the average visible light reflectance of the photosensitive layer represented by X2 and the average visible light reflectance of the photosensitive layer represented by X1 is preferably more than 30%, more preferably 40% or more, and even more preferably 50% or more. The upper limit is not particularly limited, but is preferably, for example, 80% or less.

[0057] Various materials contained in the photosensitive layer will be described below. <<Specific Particles>> The photosensitive layer contains particles (specific particles) having a refractive index of 2.0 or more and an average particle size of 200 nm or less.

[0058] The upper limit of the average particle diameter of the specific particles is 200 nm or less, preferably 100 nm or less, more preferably 60 nm or less, and even more preferably 40 nm or less. The lower limit is preferably 5 nm or more, more preferably 10 nm or more, since this increases the average reflectance of visible light of the pattern formed by the transfer film. The average particle diameter of the specific particles is measured by the following method. The transfer film is cut in a direction normal to the surface of the photosensitive layer, and the photosensitive layer region on the cut surface is observed with a transmission electron microscope (TEM), and the major axes of 30 particles selected within the observation field are measured. The average (arithmetic mean) of the major axes of the 30 measured particles is taken as the average particle diameter of the specific particles. The major axis refers to the length of the longest line segment connecting any two points on the contour line of the particle in the observed image. Furthermore, when particles in the observed image form an aggregate by aggregation, the aggregated particles as a whole are regarded as a single particle, and the longest line segment among the line segments connecting any two points on the outline of the aggregate is measured. As the transmission electron microscope, for example, an HT-7700 manufactured by Hitachi High-Technologies Corporation can be used. Furthermore, the magnification during observation is preferably, for example, 500,000 times.

[0059] The upper limit of the average primary particle diameter of the specific particles is preferably 200 nm or less, more preferably 100 nm or less, even more preferably 60 nm or less, and still more preferably 40 nm or less, in terms of better effects of the present invention. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more.

[0060] The average primary particle diameter of the specific particles is measured by the following method. The transfer film is cut in the direction normal to the surface of the photosensitive layer, and the photosensitive layer region of the cut surface is observed with a transmission electron microscope (TEM), and the major axes of 30 randomly selected non-aggregated specific particles (primary particles) within the observation field are measured. The average (arithmetic mean) of the major axes of the measured 30 particles is taken as the average particle diameter of the specific particles. The definition of major axis is as described above.

[0061] The lower limit of the refractive index of the specific particles is 2.0 or more, preferably 2.2 or more, more preferably 2.4 or more, in order to increase the average reflectance of visible light of the pattern formed by the transfer film. The upper limit of the refractive index of the specific particles is, for example, preferably 5.0 or less, more preferably 4.0 or less.

[0062] The refractive index of the specific particles is measured by the following method. The transfer film is cut in the direction normal to the surface of the photosensitive layer, and the photosensitive layer region on the cut surface is observed using a transmission electron microscope (TEM) to calculate the area ratio occupied by the specific particles within the observation field. This is performed for 30 visual fields, and the arithmetic mean of the area ratios at the 30 locations is calculated. Next, the arithmetic mean of the obtained area ratios is raised to the power of 1.5, which is the volume fraction of the specific particles in the photosensitive layer (the volume fraction of the specific particles relative to the total volume of the photosensitive layer; hereinafter also referred to as the "particle concentration"). In addition, the refractive index of a photosensitive layer that does not contain specific particles (hereinafter also referred to as the "refractive index of the matrix component (component of the photosensitive layer other than the specific particles)") is measured in advance using an ellipsometry method, and the refractive index of the specific particles (refractive index at a wavelength of 550 nm) is determined by analyzing the particle-containing photosensitive layer using the refractive index of the matrix component and the particle concentration. The refractive index of the matrix component is a refractive index (refractive index at a wavelength of 550 nm) obtained by the following method. When the matrix component is known, a film of the known matrix component (in other words, a film formed from the components of the photosensitive layer excluding specific particles) is prepared, and the refractive index of the film is measured based on ellipsometry. When the matrix component is unknown, a film component analysis of the particle-containing photosensitive layer is performed to identify the main component, and the refractive index of this main component is regarded as the refractive index of the matrix component. The refractive index of the main component can be a literature value, or, if the main component is a resin (e.g., an acrylic resin or a polyimide resin), the refractive index of a resin film prepared using the resin can be used. As the ellipsometer, a spectroscopic ellipsometer M-2000 (manufactured by Woollam) or the like can be used.

[0063] The specific particles are preferably inorganic particles. Examples of the inorganic particles include titanium oxide particles, strontium titanate particles, barium titanate particles, zinc oxide particles, magnesium oxide particles, zirconium oxide particles, aluminum oxide particles, barium sulfate particles, and zinc sulfide particles, and titanium oxide particles are more preferred. The specific particles are also preferably white particles.

[0064] The titanium oxide may be either rutile or anatase titanium oxide, with rutile titanium oxide being preferred. The shape of the titanium oxide particles is not particularly limited, and examples thereof include isotropic shapes (e.g., spherical and polyhedral shapes), anisotropic shapes (e.g., needle-like, rod-like, and plate-like shapes), and amorphous shapes.

[0065] The specific particles may be surface-treated with a surface treatment agent such as an organic compound. Examples of surface treatment agents used for the surface treatment of titanium oxide include polyols, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrated silica, alkanolamines, stearic acid, organosiloxanes, zirconium oxide, hydrogen dimethicone, silane coupling agents, and titanate coupling agents. The surface treatment may be carried out using one type of surface treatment agent alone, or two or more types of surface treatment agents in combination.

[0066] The specific particles are also preferably coated with a basic metal oxide or basic metal hydroxide, such as a metal compound containing magnesium, zirconium, cerium, strontium, antimony, barium, or calcium.

[0067] Commercially available products can be used as the specific particles. Commercially available products may be used as they are, or may be classified before use. Examples of commercially available titanium oxide particles include Typepaque MPT-136 and TTO-51, both of which are products of Ishihara Sangyo Kaisha, Ltd.

[0068] The content of the specific particles in the photosensitive layer is preferably 3 to 50% by mass, more preferably 7 to 30% by mass, and even more preferably 10 to 20% by mass, based on the total mass of the photosensitive layer. In the photosensitive layer, the specific particles may be used alone or in combination of two or more types.

[0069] <<Photosensitive Material>> The photosensitive layer contains a photosensitive material. By including the photosensitive material, the photosensitive layer can form a pattern by exposure after being transferred to a transfer target. The photosensitive material contained in the photosensitive layer can be any known material, depending on whether the photosensitive layer is a negative-type or positive-type. When the photosensitive layer is a negative-type photosensitive layer, the photosensitive material preferably contains one or more selected from a photopolymerizable compound and a photopolymerization initiator. When the photosensitive layer is a positive-type photosensitive layer, the photosensitive material preferably contains a resin (hereinafter also referred to as an "acid-decomposable resin") having a group (acid-decomposable group) in which a polar group is protected by a leaving group that leaves under the action of acid, and a photoacid generator.

[0070] <Photopolymerizable Compound> The photosensitive layer preferably contains a photopolymerizable compound. The photopolymerizable compound is a compound having a photopolymerizable group (a group that undergoes a polymerization reaction when exposed to light). Examples of the photopolymerizable group include a radical polymerizable group and a cation polymerizable group. A radical polymerizable group is preferred, an ethylenically unsaturated group is more preferred, and a (meth)acryloyloxy group is even more preferred.

[0071] The photopolymerizable compound preferably includes a compound having an ethylenically unsaturated group (hereinafter abbreviated as "ethylenically unsaturated compound"). The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited as long as it is one or more, but is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 to 3. The ethylenically unsaturated compound in this specification preferably has a molecular weight of less than 5,000. The ethylenically unsaturated compound in this specification is preferably a compound different from the compound of the alkali-soluble resin described below.

[0072] The ethylenically unsaturated compound may have an alkyleneoxy group. The alkylene group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the photopolymerizable compound per molecule is preferably 2 to 60, more preferably 2 to 30, and even more preferably 2 to 20.

[0073] Photopolymerizable Compound B1 The photosensitive layer preferably contains a photopolymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The photopolymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in the molecule, among the above photopolymerizable compounds.

[0074] Examples of the aromatic ring contained in the photopolymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; and condensed rings thereof, with an aromatic hydrocarbon ring being preferred, and a benzene ring being more preferred. The aromatic ring may have a substituent. The photopolymerizable compound B1 may have one or more aromatic rings.

[0075] The photopolymerizable compound B1 preferably has a bisphenol structure, since this suppresses swelling of the photosensitive layer due to a developer, thereby improving resolution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0076] Examples of photopolymerizable compounds B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be bonded directly to both ends of the bisphenol structure, or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, and more preferably ethyleneoxy groups. The number of alkyleneoxy groups (preferably ethyleneoxy groups) added to the bisphenol structure is preferably 2 to 60 per molecule, more preferably 2 to 30, and even more preferably 2 to 20. Examples of photopolymerizable compounds B1 having a bisphenol structure include those described in paragraphs

[0072] to

[0080] of JP 2016-224162 A, the contents of which are incorporated herein by reference.

[0077] As the photopolymerizable 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 ethoxylated bisphenol A dimethacrylates (BPE series, manufactured by Shin-Nakamura Chemical Co., Ltd.) such as 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0078] As the photopolymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0079]

[0080] In general formula B1, R １ and R ２ each independently represents a hydrogen atom or a methyl group. ２ H ４ B represents C ３ H ６ represents. n1 and n3 are each independently an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the structural units -(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 bisphenyl group side. In one aspect, n1 + n2 + n3 + n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0081] The content of the photopolymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, based on the total mass of the photosensitive layer, from the viewpoint of better resolution. The upper limit is preferably 90% by mass or less, more preferably 70% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive composition seeps out from the edge of a transfer member).

[0082] The content of the photopolymerizable compound B1 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, based on the total mass of the photopolymerizable compounds, from the viewpoint of superior resolution. The upper limit, based on the total mass of the photopolymerizable compounds, is preferably 100% by mass or less, more preferably 99% by mass or less, and even more preferably 95% by mass or less, based on the total mass of the photopolymerizable compounds, from the viewpoint of peelability.

[0083] Other Ethylenically Unsaturated Compounds Other than Photopolymerizable Compound B1 The other ethylenically unsaturated compounds other than photopolymerizable compound B1 are not particularly limited, and examples thereof include compounds having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds not having an aromatic ring, and trifunctional or higher ethylenically unsaturated compounds.

[0084] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0085] Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate (NK Ester 4G, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate (Aronix M-270, etc., manufactured by Toagosei Co., Ltd.). Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylate. Commercially available urethane di(meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0086] Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified versions thereof. "(Tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. "(Tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0087] Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) manufactured by Daicel-Allnex Co., Ltd.), 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), ARONIX M-510 (manufactured by Toagosei Co., Ltd.), and SR454 (manufactured by Tomoe Chemical Cooperative Association).

[0088] The photopolymerizable compound may be an ethylenically unsaturated compound having an acid group (for example, a carboxy group). The acid group may form an acid anhydride group. Examples of the ethylenically unsaturated compound having an acid 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.). Examples of the ethylenically unsaturated compound having an acid group include the polymerizable compounds described in paragraphs

[0025] to

[0030] of JP 2004-239942 A.

[0089] The photopolymerizable compound may be used alone or in combination of two or more. The content of the photopolymerizable compound is preferably 0.1 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 0.1 to 15% by mass, based on the total mass of the photosensitive layer. The content of the ethylenically unsaturated compound having an acid group is preferably 0.01 to 40% by mass, more preferably 0.01 to 30% by mass, and even more preferably 0.01 to 15% by mass, based on the total mass of the photosensitive layer.

[0090] <Photopolymerization Initiator> The photosensitive layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates polymerization of a photopolymerizable compound upon exposure to actinic radiation such as ultraviolet light, visible light, and X-rays. Examples of the photopolymerization initiator include known photopolymerization initiators. Examples of the photopolymerization initiator include photoradical polymerization initiators and photocationic polymerization initiators. Photoradical polymerization initiators are preferred, and examples thereof include acridine-based photopolymerization initiators, benzophenone-based polymerization initiators, oxime ester-based photopolymerization initiators, acetophenone-based photopolymerization initiators (e.g., aminoacetophenone-based photopolymerization initiators, hydroxyacetophenone-based photopolymerization initiators), acylphosphine oxide-based photopolymerization initiators, biimidazole-based photopolymerization initiators (e.g., bistriphenylimidazole-based photopolymerization initiators), and alkylphenone-based photopolymerization initiators.

[0091] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the photosensitive layer. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2% by mass or less, based on the total mass of the photosensitive layer.

[0092] <Acid-decomposable resin> As a resin (acid-decomposable resin) having a group (acid-decomposable group) protected by a leaving group in which a polar group is released by the action of an acid, a known acid-decomposable resin used in a transfer film having a positive photosensitive layer can be used. Specific examples of acid-decomposable resins include those described in paragraphs

[0023] to

[0101] of WO 2021 / 1132389.

[0093] <Photoacid Generator> As the photoacid generator, a known photoacid generator used in a transfer film having a positive photosensitive layer can be used. Specific examples of the photoacid generator can be found in, for example, paragraphs

[0107] to

[0120] of WO 2021 / 1132389.

[0094] <<Resin>> The photosensitive layer preferably contains a resin.

[0095] Any known resin can be used as the resin, for example, a (meth)acrylic resin, a (meth)acrylamide resin, an epoxy resin, an ene-thiol resin, a polycarbonate resin, a polyether resin, a polyarylate resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene resin, a polyarylene ether phosphine oxide resin, a polyimide resin, a polyamide resin, a polyolefin resin, a cyclic olefin resin, a polyester resin, a styrene resin, a silicone resin, a urethane resin, and the like.

[0096] The resin is preferably an alkali-soluble resin in terms of pattern formability.

[0097] The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.

[0098] As the resin, a resin having an acid group can be suitably used. The resin having an acid group can be used as an alkali-soluble resin. Examples of the resin having an acid group include a resin having a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group, with the carboxyl group being preferred. Furthermore, the carboxyl group is preferably an aromatic carboxyl group. Here, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In the aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of the repeating unit having an aromatic carboxyl group include repeating units having the structure shown below.

[0099]

[0100] Furthermore, in a repeating unit having a carboxyl group, the number of atoms constituting the chain connecting the resin main chain and the carboxyl group is preferably 4 or more, more preferably 8 or more. There is no particular upper limit on the number of atoms constituting the chain connecting the resin main chain and the carboxyl group, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Examples of repeating units in which the number of atoms constituting the chain connecting the resin main chain and the carboxyl group is 4 or more include repeating units with the structure shown below. The number written next to the structural formula indicates the number of atoms constituting the chain connecting the main chain and the carboxyl group.

[0101]

[0102] The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, even more preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less. For details of the resin having an acid group, please refer to the descriptions in paragraphs

[0558] to

[0571] of JP-A No. 2012-208494 and paragraphs

[0076] to

[0099] of JP-A No. 2012-198408, the contents of which are incorporated herein by reference.

[0103] As the resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers").

[0104]

[0105] In formula (ED1), R １ and R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[0106]

[0107] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of formula (ED2) can be found in JP-A-2010-168539.

[0108] For specific examples of ether dimers, reference can be made to paragraph

[0317] of JP2013-029760A, the contents of which are incorporated herein by reference.

[0109] As the resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by the following formula (X).

[0110]

[0111] In formula (X), R １ represents a hydrogen atom or a methyl group, R ２represents an alkylene group having 2 to 10 carbon atoms, and R ３ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and n represents an integer of 1 to 15.

[0112] The resin is preferably a resin containing a repeating unit having a graft chain, and is preferably incorporated as a dispersant for inhibiting aggregation of specific particles in a photosensitive composition for forming a photosensitive layer.

[0113] In the present invention, the graft chain refers to a polymer chain that branches off from the main chain of a repeating unit. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.

[0114] The graft chain preferably contains at least one repeating unit selected from a repeating unit of a polyester structure, a repeating unit of a polyether structure, a repeating unit of a poly(meth)acrylic structure, a repeating unit of a polyurethane structure, a repeating unit of a polyurea structure, and a repeating unit of a polyamide structure; more preferably contains at least one repeating unit selected from a repeating unit of a polyester structure, a repeating unit of a polyether structure, and a repeating unit of a poly(meth)acrylic structure; and even more preferably contains a repeating unit of a polyester structure. Examples of repeating units of the polyester structure include repeating units of structures represented by the following formula (G-1), formula (G-4), or formula (G-5). Examples of repeating units of the polyether structure include repeating units of structures represented by the following formula (G-2). Examples of repeating units of the poly(meth)acrylic structure include repeating units of structures represented by the following formula (G-3).

[0115]

[0116] In the above formula, R Ｇ１ and R Ｇ２ Each independently represents an alkylene group. Ｇ１and R Ｇ２ The alkylene group represented by the formula (I) is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and even more preferably a linear or branched alkylene group having 3 to 12 carbon atoms. Ｇ３ represents a hydrogen atom or a methyl group. Ｇ１ represents —O— or —NH—, L Ｇ１ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ２ -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these. Ｇ４ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.

[0117] The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group. Among these, an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched groups are preferred.

[0118] The graft chain is preferably a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a).

[0119]

[0120] In the above formula, R Ｇ１ and R Ｇ２ each independently represents an alkylene group; R Ｇ３ represents a hydrogen atom or a methyl group, and Q Ｇ１ represents —O— or —NH—, L Ｇ１ represents a single bond or a divalent linking group, R Ｇ４ represents a hydrogen atom or a substituent, W １００ represents a hydrogen atom or a substituent. n1 to n5 each independently represent an integer of 2 or more. R Ｇ１ ~R Ｇ４ , Q Ｇ１ , and L Ｇ１ Regarding the formulas (G-1) to (G-5), Ｇ１ ~R Ｇ４ , Q Ｇ１ , and L Ｇ１ The same applies to the preferred range.

[0121] In formulae (G-1a) to (G-5a), W １００ is preferably a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group. Among these, an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched groups are preferred.

[0122] In formulae (G-1a) to (G-5a), n1 to n5 each independently represent preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and even more preferably an integer of 8 to 60.

[0123] In formula (G-1a), when n1 is 2 or more, R Ｇ１ may be the same or different. Ｇ１ In the case where the repeating units have two or more different repeating units, the arrangement of the repeating units is not particularly limited and may be random, alternating, or block. The same applies to the formulae (G-2a) to (G-5a).

[0124] Examples of the repeating unit having a graft chain include the repeating unit represented by the following formula (A-1-2).

[0125]

[0126] In formula (A-1-2), X ２ represents the main chain of the repeating unit, L ２ represents a single bond or a divalent linking group; W １ represents a graft chain.

[0127] X in formula (A-1-2) ２ The main chain of the repeating unit represented by X in formula (A-1-1) １ The preferred ranges are also the same as those described above. ２ Examples of the divalent linking group represented by include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ２ -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these. １ Examples of the graft chain represented by include the graft chains described above.

[0128] Specific examples of the repeating unit represented by formula (A-1-2) include a repeating unit represented by the following formula (A-1-2a) and a repeating unit represented by the following formula (A-1-2b).

[0129]

[0130] In formula (A-1-2a), R ｂ１ ~R ｂ３ each independently represents a hydrogen atom or an alkyl group; ｂ１ represents —CO—, —COO—, —OCO—, —CONH—, or a phenylene group; L ２ represents a single bond or a divalent linking group; W １ represents a graft chain. ｂ１ ~R ｂ３The number of carbon atoms in the alkyl group represented by is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1. ｂ１ is preferably —COO— or —CONH—, more preferably —COO—.

[0131] In formula (A-1-2b), R ｂ１０ and R ｂ１１ each independently represents a hydrogen atom or an alkyl group; m2 represents an integer of 1 to 5; L ２ represents a single bond or a divalent linking group; W １ represents a graft chain. ｂ１０ and R ｂ１１ The alkyl group represented by the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms.

[0132] The weight-average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1,000 or more, more preferably 1,000 to 10,000, and even more preferably 1,000 to 7,500. In the present invention, the weight-average molecular weight of the repeating unit having a graft chain is a value calculated from the weight-average molecular weight of the raw material monomers used in the polymerization of the repeating unit. For example, the repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, the macromonomer refers to a polymeric compound having a polymerizable group introduced at the polymer terminal. When the repeating unit having a graft chain is formed using a macromonomer, the weight-average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.

[0133] It is also preferable that the resin containing a repeating unit having a graft chain further contains a repeating unit derived from a (meth)acrylic acid ester.

[0134] It is also preferred that the resin containing a repeating unit having a graft chain further contains a repeating unit having an acid group and a repeating unit having neither a graft chain nor an acid group.

[0135] It is also preferable to use a resin having a structure in which a polymer chain is bonded to a trivalent or higher linking group. Examples of such a resin include a resin having a structure represented by the following formula (SP-1) (hereinafter also referred to as resin (SP-1)):

[0136]

[0137] During the ceremony, Z １ represents a (m+n)-valent linking group; Y １ and Y ２ each independently represents a single bond or a linking group; １ represents a group containing a substituent selected from a heterocyclic group, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxy group; P １ represents a polymer chain, n represents 1 to 20, m represents 1 to 20, and m+n is 3 to 21, and n Y １ and A １ may be the same or different from each other, and m Y ２ and P １ may be the same or different from each other.

[0138] Z in formula (SP-1) １ , A １ , and P １ At least one of the groups may contain an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth)acryloyl group, a styrene group, a cinnamoyl group, and a maleimide group, of which a (meth)acryloyl group, a styrene group, and a maleimide group are preferred, a (meth)acryloyl group is more preferred, and an acryloyl group is particularly preferred.

[0139] When the resin (SP-1) contains an ethylenically unsaturated bond-containing group, such a resin corresponds to the polymerizable resin described later. １ , A １ , and P １ However, it is sufficient if it is included in any of P １ It is preferable that P １ When P contains an ethylenically unsaturated bond-containing group, １ is preferably a polymer chain having a repeating unit containing an ethylenically unsaturated bond-containing group in the side chain.

[0140] In formula (SP-1), A １ represents a group containing the above-mentioned substituent. The substituent is preferably a heterocyclic group, an acid group, a group having a basic nitrogen atom, a hydrocarbon group having 4 or more carbon atoms, or a hydroxy group, and more preferably an acid group. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferred.

[0141] The above-mentioned substituents are each independently selected from one A １ It is sufficient that at least one is contained in the compound, but two or more may be contained. １ Preferably, A contains 1 to 10 of the above-mentioned substituents, and more preferably 1 to 6 of them. １ Examples of groups containing the above-mentioned substituents represented by the formula (I) include groups formed by bonding the above-mentioned substituents to a linking group consisting of 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 to 40 sulfur atoms. Examples include groups formed by bonding one or more acid groups via a linear saturated hydrocarbon group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. The linear saturated hydrocarbon group, cyclic saturated hydrocarbon group, and aromatic hydrocarbon group may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxy group, a carboxyl group, an amino group, a sulfonamido group, an N-sulfonylamido group, an acyloxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate ester group, and an ethylenically unsaturated bond-containing group. In addition, the above substituent itself is A １ may be.

[0142] A １ The chemical formula weight is preferably 30 to 2000. The upper limit is preferably 1000 or less, more preferably 800 or less. The lower limit is preferably 50 or more, more preferably 100 or more.

[0143] In formula (SP-1), Z １represents an (m+n)-valent linking group. Examples of the (m+n)-valent linking group include groups consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. Examples of the (m+n)-valent linking group include the following structural units or groups consisting of two or more of the following structural units combined together (which may form a ring structure).

[0144]

[0145] The (m+n)-valent linking group may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxy group, an amino group, a carboxyl group, a sulfonamido group, an N-sulfonylamido group, an acyloxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate ester group, and an ethylenically unsaturated bond-containing group.

[0146] Z １ The (m+n)-valent linking group represented by is preferably a group represented by any of the following formulae:

[0147]

[0148] L ３ represents a trivalent group. ３ represents a single bond or a divalent linking group, and three T ３ may be the same or different. ４ represents a tetravalent group. ４ represents a single bond or a divalent linking group, and four T ４ may be the same or different. ５ represents a pentavalent group. ５ represents a single bond or a divalent linking group, and there are five T ５ may be the same or different. ６ represents a hexavalent group. ６ represents a single bond or a divalent linking group, and six T ６ may be the same or different from each other.

[0149] T３ ~T ６ The divalent linking group represented by is —CH ２ Examples of the divalent linking group include -, -O-, -CO-, -COO-, -OCO-, -NH-, an aliphatic cyclic group, an aromatic hydrocarbon cyclic group, a heterocyclic group, and a group formed by a combination thereof. The aliphatic cyclic group, the aromatic hydrocarbon cyclic group, and the heterocyclic group may be a monocyclic group or a fused ring. The divalent linking group may further have the above-mentioned substituent.

[0150] L ３ Examples of the trivalent group represented by L include groups in which one hydrogen atom has been removed from the above divalent linking groups. ４ Examples of the tetravalent group represented by L include groups in which two hydrogen atoms have been removed from the above divalent linking groups. ５ Examples of the pentavalent group represented by L include groups in which three hydrogen atoms have been removed from the above divalent linking groups. ６ Examples of the hexavalent group represented by L include groups in which four hydrogen atoms have been removed from the above divalent linking groups. ３ ~L ６ The trivalent to hexavalent group represented by may further have the above-mentioned substituent.

[0151] Z １ The chemical formula weight of Z is preferably 20 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 50 or more, more preferably 100 or more. １ When the chemical formula weight of Z is within the above range, the dispersibility of the pigment in the composition can be improved. １ The formula weight is a value calculated from the structural formula.

[0152] For specific examples of the (m+n)-valent linking group, refer to paragraphs 0043 to 0055 of JP2014-177613A, the contents of which are incorporated herein by reference.

[0153] In formula (SP-1), Y １ and Y ２Each of Y independently represents a single bond or a linking group. Examples of the linking group include groups consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The above groups may further have the above-mentioned substituents. １ and Y ２ Examples of the linking group represented by include the following structural units or groups formed by combining two or more of the following structural units.

[0154]

[0155] In formula (SP-1), P １ represents a polymer chain. １ The polymer chain represented by is preferably a polymer chain having, in the main chain, a repeating unit of at least one structure selected from a repeating unit of a poly(meth)acrylic structure, a repeating unit of a polyether structure, a repeating unit of a polyester structure, a repeating unit of a polyamide structure, a repeating unit of a polyimide structure, a repeating unit of a polyimine structure, and a repeating unit of a polyurethane structure. １ The polymer chain represented by formula (P1-1) is preferably a polymer chain containing repeating units represented by the following formulas (P1-1) to (P1-5).

[0156]

[0157] In the above formula, R Ｇ１ and R Ｇ２ Each independently represents an alkylene group. Ｇ１ and R Ｇ２ The alkylene group represented by the formula (I) is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and even more preferably a linear or branched alkylene group having 3 to 12 carbon atoms. The alkylene group may have a substituent. Examples of the substituent include an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an ethylenically unsaturated bond-containing group. In the formula (I), R Ｇ３represents a hydrogen atom or a methyl group. Ｇ１ represents —O— or —NH—, L Ｇ１ represents a single bond or an arylene group; L Ｇ２ represents a single bond or a divalent linking group. Ｇ１ is preferably —O—. Ｇ１ is preferably a single bond. Ｇ２ Examples of the divalent linking group represented by include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ２ -, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO-, -CONH-, and groups formed by combining two or more of these. Ｇ４ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an ethylenically unsaturated bond-containing group, and an acid group.

[0158] P １ The number of repeating units in the above-mentioned formula (I) is preferably 3 to 2000. The upper limit is preferably 1500 or less, more preferably 1000 or less. The lower limit is preferably 5 or more, more preferably 7 or more. １ is preferably a polymer chain having a repeating unit containing an ethylenically unsaturated bond-containing group in the side chain. １ The proportion of repeating units containing an ethylenically unsaturated bond-containing group in a side chain among all repeating units constituting P is preferably 1 mol % or more, more preferably 2 mol % or more, and even more preferably 3 mol % or more. The upper limit can be 100 mol %. １ is a polymer chain having a repeating unit containing an ethylenically unsaturated bond-containing group in a side chain, １ It is also preferable that P contains other repeating units in addition to the repeating unit containing an ethylenically unsaturated bond-containing group in the side chain. Examples of other repeating units include a repeating unit containing an acid group in the side chain. １By including a repeating unit containing an acid group in the side chain in addition to the repeating unit containing an ethylenically unsaturated bond-containing group in the side chain, the generation of development residues can be more effectively suppressed when a pattern is formed by photolithography. １ When P contains a repeating unit containing an acid group in the side chain, １ The proportion of repeating units containing an acid group in the side chain of all repeating units constituting the formula (I) is preferably 50 mol % or less, more preferably from 2 to 48 mol %, and even more preferably from 4 to 46 mol %.

[0159] P １ The weight average molecular weight of the polymer chain represented by is preferably 1,000 or more, more preferably 1,000 to 10,000. The upper limit is preferably 9,000 or less, more preferably 6,000 or less, and even more preferably 3,000 or less. The lower limit is preferably 1,200 or more, more preferably 1,400 or more. １ The weight average molecular weight is a value calculated from the weight average molecular weight of the raw material used to introduce the polymer chain.

[0160] Specific examples of the resin (SP-1) include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962, polymer compounds (C-1) to (C-61) described in paragraphs 0256 to 0269 of JP-A-2014-177613, and resins having a structure described in paragraph 0061 of WO 2018 / 163668, the contents of which are incorporated herein by reference.

[0161] The photosensitive layer preferably contains a resin having a polymerizable group (hereinafter also referred to as a polymerizable resin) as the resin. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group such as an epoxy group or an oxetane group. The amount of the polymerizable group-containing group in the polymerizable resin is preferably 0.01 to 5.0 mmol / g. The upper limit is more preferably 4.0 mmol / g or less, even more preferably 3.0 mmol / g or less, even more preferably 2.0 mmol / g or less, and particularly preferably 1.5 mmol / g or less. The lower limit is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more. The amount of polymerizable groups in the polymerizable resin is a numerical value representing the molar amount of polymerizable groups per gram of solid content of the polymerizable resin. When the polymerizable group value of the polymerizable resin can be calculated from the raw materials used in the synthesis of the polymerizable resin, the value calculated from the raw materials used is used. Furthermore, when the polymerizable group value of a polymerizable resin cannot be calculated from the raw materials used in the synthesis of the polymerizable resin, for example, in the case of an ethylenically unsaturated group, a value measured using a hydrolysis method is used. Specifically, the low molecular weight component (a) at the polymerizable group site is extracted from the polymerizable resin by alkali treatment, and its content is measured by high performance liquid chromatography (HPLC), and then calculated using the following formula. Furthermore, when the polymerizable group cannot be extracted from the polymerizable resin by alkali treatment, a value measured by NMR (nuclear magnetic resonance) is used. Polymerizable group value of polymerizable resin [mmol / g] = (content of low molecular weight component (a) [ppm] / molecular weight of low molecular weight component (a) [g / mol]) / (weighed value of polymerizable resin [g] × (solids concentration of polymerizable resin [mass%] / 100) × 10)

[0162] Examples of the polymerizable resin include a resin containing a repeating unit having a polymerizable group on a side chain. Examples of the repeating unit having a polymerizable group on a side chain include a repeating unit represented by the following formula (A-1-1). In the polymerizable resin, the content of the repeating unit having a polymerizable group is preferably 10 mol % or more, more preferably 10 to 80 mol %, still more preferably 10 to 60 mol %, and particularly preferably 10 to 50 mol %, of all repeating units of the polymerizable resin.

[0163]

[0164] In formula (A-1-1), X １ represents the main chain of the repeating unit, L １ represents a single bond or a divalent linking group, Y １ represents a polymerizable group.

[0165] In formula (A-1-1), X １ The main chain of the repeating unit represented by is not particularly limited. There is no particular limitation as long as it is a linking group formed from a known polymerizable monomer. Examples thereof include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, and a polystyrene linking group.

[0166] In formula (A-1-1), L １ Examples of the divalent linking group represented by include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ２ Examples of the alkylene group include -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and linear or branched is preferred. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.

[0167] In formula (A-1-1), Y １Examples of the polymerizable group represented by include an ethylenically unsaturated bond-containing group and a cyclic ether group, with the ethylenically unsaturated bond-containing group being preferred. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth)acryloyl group, a styrene group, a cinnamoyl group, and a maleimide group, with the (meth)acryloyl group, a styrene group, or a maleimide group being preferred, the (meth)acryloyl group being more preferred, and the acryloyl group being particularly preferred.

[0168] The resin containing the repeating unit represented by formula (A-1-1) may further contain a repeating unit having a graft chain. Examples of the repeating unit having a graft chain include the repeating unit represented by formula (A-1-2) described above. In the polymerizable resin, the content of the repeating unit having a graft chain is preferably 1.0 to 60 mol %, and more preferably 1.5 to 50 mol %, of all repeating units in the polymerizable resin.

[0169] The resin containing the repeating unit represented by formula (A-1-1) may further contain a repeating unit having an acid group. The content of the repeating unit having an acid group is preferably 80 mol % or less, more preferably 10 to 80 mol %, of all repeating units in the polymerizable resin.

[0170] Furthermore, as the resin component of the photosensitive layer, alkali-soluble resins described in paragraphs

[0037] to

[0087] of WO 2023 / 127889 can also be suitably used.

[0171] The photosensitive layer may contain only one type of resin, or may contain two or more types. The lower limit of the resin content is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, based on the total mass of the photosensitive layer. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0172] <<Compound Y>> The photosensitive layer preferably contains a compound (hereinafter also referred to as "compound Y") that does not have a photopolymerizable group and has a boiling point of 230 to 500° C. Compound Y is volatilized and removed from the system during a heat treatment that may be performed after the development treatment of the exposure treatment, which facilitates the promotion of aggregation of specific particles within the heat-treated photosensitive layer.

[0173] In this specification, the boiling point of compound Y refers to a value determined by the following measurement method. When compound Y is distilled under atmospheric pressure (760 mmHg), the boiling point is the gas temperature at which condensation of the evaporated gas begins (measurements are made from 23°C to 300°C, with a temperature increase rate of 1°C / min). Distillation is carried out using a Liebig condenser, and if distillation does not begin at 300°C under atmospheric pressure, distillation is carried out under reduced pressure. Similar distillation is carried out at pressures of 100 mmHg, 50 mmHg, and 5 mmHg in this order (23°C to 300°C, and if distillation does not begin at 300°C, the next pressure is used). The boiling point at atmospheric pressure is determined from the temperature and pressure at which condensation of the evaporated gas begins using the nomograph shown in Figure 3 (source: Science of Petroleum, Vol. II, p. 1281 (1938)). This is taken as the boiling point (calculated value). If distillation does not begin at 300°C under 5 mmHg, the boiling point at normal pressure is considered to be greater than 500°C. The method of using a nomograph is well known. Specifically, a straight line is drawn between the boiling point at reduced pressure on line A and the degree of reduced pressure on line C (Procedure 1), and the value at the intersection of the line drawn in Procedure 1 and line B is read (Procedure 2), and this value is considered to be the boiling point at normal pressure.

[0174] The lower limit of the boiling point of compound Y is preferably 250° C. or higher, more preferably 280° C. or higher, even more preferably 300° C. or higher, and particularly preferably 350° C. or higher. The upper limit is preferably 480° C. or lower, more preferably 450° C. or lower, and even more preferably 400° C. or lower.

[0175] Compound Y preferably has a molecular weight of 200 to 1,000. When compound Y has a molecular weight distribution, the above molecular weight of compound Y refers to the weight-average molecular weight. The lower limit of the molecular weight of compound Y is preferably 250 or more, more preferably 280 or more. The upper limit is preferably 800 or less, more preferably 600 or less, and even more preferably 400 or less.

[0176] The specific type of compound Y is not particularly limited, and examples thereof include ethyl phthalyl ethyl glycolate, benzyl benzoate, triacetin glycerin triacetate, 1,6-hexanediol diacetate, diethylene glycol monobutyl ether acetate, hexaethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, heptaethylene glycol monomethyl ether, octaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, and nonaethylene glycol dimethyl ether.

[0177] Compound Y may be used alone or in combination of two or more. The lower limit of the content of compound Y is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 50% by mass or more, based on the total mass of the photosensitive layer. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0178] <<Surfactant>> The photosensitive layer may contain a surfactant. Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A No. 2009-237362.

[0179] Examples of surfactants include hydrocarbon surfactants, fluorine surfactants, and silicone surfactants. From the viewpoint of improving environmental friendliness, it is preferable that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon surfactant or a silicone surfactant. Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, 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, and F-780 (all manufactured by DIC Corporation); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC); PolyFox Examples include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by NEOS Corporation); and U-120E (manufactured by Unichem).

[0180] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21). Furthermore, the fluorosurfactant may be 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. The fluorosurfactant may be a block polymer. The fluorosurfactant may also be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group having an ethylenically unsaturated group in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0181] As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0182] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Examples of hydrocarbon surfactants include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Japan); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); and Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0183] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or terminals, and polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.Preferred silicone surfactants are polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.The polymers may be either random copolymers or block copolymers.

[0184] The repeating unit having a group having a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).

[0185]

[0186] In formula (SX1), each R independently represents an alkyl group having 1 to 3 carbon atoms. １ represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent organic group. When a plurality of R's are present, the R's may be the same or different.

[0187]

[0188] In formula (SX2), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms. ３ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50.

[0189] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0190]

[0191] In formula (SX3), R ４ and R ５ each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.

[0192] Examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, and X-22-6266 , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, K F-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-12 No. 5, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Perform BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0193] The surfactant also includes a nonionic surfactant.

[0194] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably from 0.01 to 3.0% by mass, more preferably from 0.01 to 1.0% by mass, and even more preferably from 0.05 to 1.0% by mass, based on the total mass of the photosensitive layer.

[0195] <<Other Additives>> The photosensitive layer may contain other additives in addition to the various components described above. Examples of other additives include dispersants for specific particles, heterocyclic compounds (e.g., triazole, tetrazole, benzotriazole, and derivatives thereof), aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen donor compounds, solvents, impurities, plasticizers, sensitizers, and alkoxysilane compounds. Examples of heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen donor compounds include the various components described in WO 2022 / 039027. Examples of plasticizers, sensitizers, and alkoxysilane compounds include those described in paragraphs 0097 to 0119 of WO 2018 / 179640.

[0196] The photosensitive layer may contain impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so the following contents are preferred.

[0197] The content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit is often 0 ppb by mass or more, but may be 1 ppb by mass or more, or 0.1 ppm by mass or more, relative to the total mass of the photosensitive layer.

[0198] Methods for adjusting the content of impurities include, for example, using raw materials with low impurity contents as raw materials for the various components that may be contained in the photosensitive layer, purifying the various components that may be contained in the photosensitive layer before use, and preventing the incorporation of impurities when forming the photosensitive layer.

[0199] The content of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0200] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. Specifically, the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, relative to the total mass of the photosensitive layer. The content of these compounds can be adjusted using the same method as for the impurities described above. Furthermore, these compounds can be quantified using known measurement methods.

[0201] <<Thickness of Photosensitive Layer>> The thickness of the photosensitive layer is 3 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 16 μm or more. There is no particular upper limit, and for example, it is preferably 100 μm or less, more preferably 50 μm or less.

[0202] [Protective Film] The transfer film of the present invention may have a protective film. As the protective film, a resin film having heat resistance and solvent resistance can be used, for example, a polyolefin film such as a polypropylene film or a polyethylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, and a polystyrene film. In addition, a resin film made of the same material as the temporary support may be used as the protective film. Among them, a polyolefin film is preferred as the protective film, a polypropylene film or a polyethylene film is more preferred, and a polyethylene film is even more preferred.

[0203] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of being relatively inexpensive.

[0204] In addition, the number of fish eyes with a diameter of 80 μm or more contained in the protective film is 5 / m. ２ The term "fisheyes" refers to foreign matter, undissolved matter, oxidized degradation products, etc., that are trapped in a film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0205] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 5 or less pieces / mm ２ The following is more preferable: This makes it possible to suppress defects caused by the transfer of irregularities due to particles contained in the protective film to the light-reflecting layer precursor layer and the light-absorbing layer precursor layer.

[0206] From the viewpoint of providing windability, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the protective film on the surface in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0207] [Photosensitive Light-Absorbing Layer Precursor Layer] The transfer film of the present invention may have a photosensitive light-absorbing layer precursor layer.

[0208] <<Optical Density of Photosensitive Light-Absorbing Layer Precursor Layer>> The optical density (OD) of the photosensitive light-absorbing layer precursor layer is preferably 0.5 or more, more preferably 1.0 or more, even more preferably 2.0 or more, and particularly preferably 3.0 or more. There is no particular upper limit, and for example, 6.0 or less is preferable. The optical density (OD) of the photosensitive light-absorbing layer precursor layer is preferably a value at a wavelength of 385 nm or 550 nm. The optical density of the photosensitive light-absorbing layer precursor layer at a wavelength of 550 nm can be measured using a Macbeth densitometer (manufactured by Macbeth, TD-904, using a visual filter) or the like. The optical density at a wavelength of 385 nm can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. or the like.

[0209] <<Thickness of Photosensitive Light-Absorbing Layer Precursor Layer>> The thickness of the photosensitive light-absorbing layer precursor layer is preferably 1 μm or more, and more preferably 2 μm or more. There is no particular upper limit, and the thickness is, for example, preferably 10 μm or less, and more preferably 5 μm or less.

[0210] <<Components of Photosensitive Light-Absorbing Layer Precursor Layer>> The photosensitive light-absorbing layer precursor layer may be either a positive-type photosensitive layer or a negative-type photosensitive layer, but is preferably a negative-type photosensitive layer. The photosensitive light-absorbing layer precursor layer preferably contains a light-absorbing substance and a photosensitive material. The photosensitive material contained in the photosensitive light-absorbing layer precursor layer can be an appropriate known material depending on whether the photosensitive light-absorbing layer precursor layer is negative-type or positive-type. When the photosensitive light-absorbing layer precursor layer is negative-type, the photosensitive material preferably contains one or more selected from a photopolymerizable compound and a photopolymerization initiator. When the photosensitive light-absorbing layer precursor layer is positive-type, the photosensitive material preferably contains an acid-decomposable resin and a photoacid generator. The material of the photosensitive light-absorbing layer precursor layer can have the same composition as the above-mentioned photosensitive layer, except that it contains a light-absorbing substance instead of the specific particles. In other words, the preferred embodiments of the components and content of the photosensitive light-absorbing layer precursor layer are the same as those of the above-mentioned photosensitive layer, except that a light-absorbing substance is used instead of the specific particles. Note that, as the resin component of the photosensitive light-absorbing layer precursor layer, the alkali-soluble resins described in paragraphs

[0037] to

[0087] of WO 2023 / 127889 can be suitably used.

[0211] <<Light-Absorbing Substance>> The light-absorbing substance is not particularly limited, and examples thereof include black pigments and black dyes, and specific examples thereof include carbon black, titanium black, titanium carbon, iron oxide, and graphite.

[0212] When the light-absorbing substance is granular, its shape is not particularly limited, and examples thereof include isotropic shapes (e.g., spherical and polyhedral), anisotropic shapes (e.g., needle-like, rod-like, and plate-like), and irregular shapes. Furthermore, the light-absorbing substance may be subjected to physical surface treatments such as plasma discharge treatment and corona discharge treatment, or chemical surface treatments using surfactants, coupling agents, resins, and the like. Furthermore, when the light-absorbing substance is granular, the average primary particle size of the light-absorbing substance is not particularly limited, and is preferably, for example, 1 to 1,000 nm, and more preferably 2 to 500 nm. The above-mentioned value of the average primary particle size of the light-absorbing substance is a value measured using a method similar to the method for measuring the average primary particle size of specific particles.

[0213] The content of the light-absorbing substance in the photosensitive light-absorbing layer precursor layer is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 60 mass %, based on the total mass of the photosensitive light-absorbing layer precursor layer.

[0214] Also preferred as the light-absorbing substance is a compound represented by formula (1) described below. The compound represented by formula (1) is a black colorant precursor, and is a compound that undergoes structural transformation and develops a black color when subjected to a thermal stimulus (for example, heating at 80°C to 260°C). The compound represented by formula (1) is preferably used in combination with a dispersant having an amine value of 70 mgKOH / g or less, in that unintended color development before the thermal stimulus can be suppressed and pattern formation performance is superior.

[0215]

[0216] In formula (1), X １ , X ２ , X ３ , X ４ , Y １ , and Y ２ each independently represents an oxygen atom, a sulfur atom, or N-L １Represents L １ represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, or an aminocarbonyl group. １ , R ２ , R ３ , and R ４ are each independently a hydrogen atom, -OL ２ , -OCO-L ３ , -S-L ２ , or -OSO-L ３ Represents L ２ represents a hydrogen atom or an alkyl group, L ３ represents an alkyl group or an amino group. １ and R ２ At least one of represents a hydrogen atom, and R ３ and R ４ At least one of A, B and C represents a hydrogen atom. A, B and C each independently represent an aromatic ring.

[0217] In formula (1), X １ , X ２ , X ３ and X ４ Among them, an oxygen atom is preferable. １ may be the same or different, but are preferably the same. １ is preferably an oxygen atom.

[0218] In formula (1), the two Y ２ may be the same or different, but are preferably the same. ２ is N-L １ is preferred. １ Among these, a hydrogen atom, an alkyl group, an acyl group, or an alkoxycarbonyl group is preferable, and an alkyl group, an acyl group, or an alkoxycarbonyl group is more preferable.

[0219] L １ The alkyl group represented by the formula (I) may or may not have a substituent. １ The alkyl group represented by the formula (I) may be linear, branched, or cyclic. １The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms. １ The alkyl group represented by the formula (I) is preferably, for example, an s-butyl group, an n-hexyl group, a 2-ethoxyethyl group, a methoxycarbonylmethyl group, an isopropyl group, an n-pentyl group, or a 2-ethylhexyl group.

[0220] L １ The acyl group represented by the formula (I) is preferably an acyl group having 2 to 30 carbon atoms, more preferably an acyl group having 2 to 15 carbon atoms. １ The acyl group represented by the formula (I) is preferably, for example, an acetyl group, a 2-ethylhexanoyl group, a 3,3,5-trimethylhexanoyl group, a propionyl group, a butyryl group, an isobutyryl group, or a pivaloyl group.

[0221] L １ The alkoxycarbonyl group represented by the formula (I) is preferably an alkoxycarbonyl group having 1 to 30 carbon atoms in the alkoxy moiety. １ The alkoxycarbonyl group represented by the formula (I) is preferably, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a t-butoxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, a benzyloxycarbonyl group, or a 2,2,2-trichloroethyloxycarbonyl group.

[0222] In formula (1), R １ and R ２ When one of the groups is a hydrogen atom, the other group is a hydrogen atom or a hydroxy group (i.e., L ２ is a hydrogen atom ２ ) is preferred, and a hydrogen atom is more preferred. ３ and R ４ When one of the groups is a hydrogen atom, the other group is a hydrogen atom or a hydroxy group (i.e., L ２ is a hydrogen atom ２ ) is preferred, and a hydrogen atom is more preferred.

[0223] L ２ is preferably a hydrogen atom. ２ The alkyl group represented by the formula (I) may or may not have a substituent.２ The alkyl group represented by the formula (I) may be linear, branched, or cyclic. ２ The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms. ２ The alkyl group represented by the formula (I) is preferably, for example, a methyl group, an ethyl group, a propyl group, or a 2-ethylhexyl group.

[0224] L ３ The alkyl group represented by the formula (I) may or may not have a substituent. ３ The alkyl group represented by the formula (I) may be linear, branched, or cyclic. ３ The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms. ３ The alkyl group represented by the formula (I) is preferably, for example, a methyl group, an ethyl group, a propyl group, or a 2-ethylhexyl group.

[0225] In formula (1), the aromatic ring represented by A and the aromatic ring represented by B may be the same as or different from each other. The aromatic rings represented by A and B may or may not have a substituent. The aromatic rings represented by A and B may be, for example, aromatic hydrocarbon rings, aromatic heterocycles, or condensed rings thereof.

[0226] When the aromatic rings represented by A and B are aromatic hydrocarbon rings, the aromatic hydrocarbon rings represented by A and B are preferably 5- or 6-membered rings, and more preferably 6-membered rings. When the aromatic rings represented by A and B are aromatic hydrocarbon rings, the aromatic hydrocarbon rings represented by A and B are preferably aromatic hydrocarbon rings having 6 to 30 carbon atoms, more preferably aromatic hydrocarbon rings having 6 to 20 carbon atoms, and even more preferably aromatic hydrocarbon rings having 6 to 10 carbon atoms. When the aromatic rings represented by A and B are aromatic hydrocarbon rings, the aromatic hydrocarbon ring represented by A is preferably, for example, a benzene ring, a naphthalene ring, or an anthracene ring, and more preferably a benzene ring.

[0227] When the aromatic rings represented by A and B are aromatic heterocycles, the aromatic heterocycles represented by A and B are preferably 5- or 6-membered rings, more preferably 5-membered rings. When the aromatic rings represented by A and B are aromatic heterocycles, the aromatic heterocycles represented by A and B are preferably aromatic heterocycles containing one or more heteroatoms selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms in the ring. The number of heteroatoms in the aromatic heterocycle is preferably 1 or 2, more preferably 1. When the aromatic rings represented by A and B are aromatic heterocycles, the aromatic heterocycles represented by A and B are preferably, for example, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, or a pyridine ring, more preferably a thiophene ring.

[0228] The aromatic ring represented by C may or may not have a substituent. Examples of the aromatic ring represented by C include a benzene ring and an aromatic heterocycle. Examples of the heterocycle include a pyridine ring and a pyrazine ring. The aromatic ring represented by C is preferably a benzene ring.

[0229] In formula (1), X １ , X ２ , X ３ , X ４ , R １ , R ２ , R ３ , and R ４ For example, the following aspect A is preferred, and aspect B is more preferred. Aspect A: X １ , X ２ , X ３ and X ４ is an oxygen atom, and R １ and R ２ is a hydrogen atom on one side and a hydroxy group on the other side, and R ３ and R ４ In the embodiment B, one of X is a hydrogen atom and the other is a hydroxy group. １ , X ２ , X ３ , and X ４ is an oxygen atom, and R １ , R ２ , R ３ , and R ４is a hydrogen atom.

[0230] A preferred embodiment of the compound represented by formula (1) is X １ , X ２ , X ３ , and X ４ is an oxygen atom, and Y １ and Y ２ each independently represents an oxygen atom, a sulfur atom, or N-L １ and L １ is a hydrogen atom, an alkyl group, an acyl group, or an alkoxycarbonyl group, and R １ or R ２ one of which is a hydrogen atom and the other is a hydroxy group, and R ３ or R ４ A and B are each independently a benzene ring or a thiophene ring, and C is a benzene ring. １ , X ２ , X ３ , and X ４ is an oxygen atom, and Y １ is an oxygen atom, and Y ２ But N-L １ and L １ is an alkyl group, an acyl group, or an alkoxycarbonyl group, and R １ , R ２ , R ３ , and R ４ is a hydrogen atom, A and B are benzene rings, and C is a benzene ring.

[0231] The compound represented by formula (1) can be produced by referring to a known method.

[0232] When the photosensitive light-absorbing layer precursor layer contains the compound represented by formula (1) as a light-absorbing substance, the photosensitive light-absorbing layer precursor layer also preferably contains a dispersant having an amine value of 70 mgKOH / g or less (hereinafter also referred to as "dispersant A").

[0233] Dispersant A is not particularly limited as long as its amine value is 70 mgKOH / g or less. Dispersant A is preferably a polymer having a basic functional group. Examples of basic functional groups include amino groups, imino groups, amide groups, and imide groups. From the viewpoint of dispersibility, the basic functional group is preferably an amino group. The amine value of dispersant A is preferably 55 mgKOH / g or less, more preferably 40 mgKOH / g or less, and even more preferably 25 mgKOH / g or less. The lower limit of the amine value of dispersant A is not particularly limited, and examples include 0 mgKOH / g or more, preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and even more preferably 15 mgKOH / g or more. The amine value is the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize 1 g of sample. In the present disclosure, the amine value of the dispersant is measured by potentiometric titration in accordance with JIS K 7237:1995. In addition, when the dispersant is a commercially available product and the amine value is described in the catalog of the commercially available product, the amine value described in the catalog is used as a priority.

[0234] Commercially available products can be used as the dispersant A. Examples of commercially available products of the dispersant A include "AJISPER (registered trademark) PA111" (amine value: 0 mgKOH / g, acid value: 35 mgKOH / g, manufactured by Ajinomoto Fine-Techno Co., Ltd.), "DISPARLON (registered trademark) PW-36" [amine value: 0 mgKOH / g, acid value: 55 mgKOH / g, manufactured by Kusumoto Chemicals Co., Ltd.], "DISPERBYK (registered trademark)-111" [amine value: 0 mgKOH / g, acid value: 129 mgKOH / g, manufactured by BYK Japan Co., Ltd.], "DISPERBYK (registered trademark)-2001" [amine value: 29 mgKOH / g, acid value: 19 mgKOH / g, manufactured by BYK Japan Co., Ltd.], "DISPERBYK (registered trademark)-2025" [amine value: 37 mgKOH / g, acid value: 38 mgKOH / g, manufactured by BYK Japan Co., Ltd.], "DISPERBYK (registered trademark)-164" [amine value: 18 mgKOH / g, acid value: 0 mgKOH / g, manufactured by BYK Japan Co., Ltd.], and "AJISPER (registered trademark) PN411" (amine value: 0 mgKOH / g, acid value: 6 mgKOH / g, manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0235] The content of dispersant A in the photosensitive light-absorbing layer precursor layer is not particularly limited, but is, for example, preferably 0.002 to 0.05 times, more preferably 0.003 to 0.03 times, and even more preferably 0.004 to 0.02 times, by mass, the content of the compound represented by formula (1). Dispersant A may be used singly or in combination of two or more types.

[0236] [Uses] There are no particular limitations on the uses of the transfer film of the present invention, but it is particularly preferred to use it to form a partition layer between each LED chip of a micro LED array substrate in a micro LED display element.

[0237] [Method for Producing Transfer Film] The method for producing the transfer film can be a known method, and is preferably a method for producing the transfer film in which a photosensitive composition is applied to a temporary support to form a photosensitive layer.

[0238] For example, a method for producing the transfer film 1 shown in Fig. 1 includes a step of applying a photosensitive composition to the surface of a temporary support to form a coating film, and then drying the coating film to form a photosensitive layer. Furthermore, the transfer film 1 shown in Fig. 1 is produced by pressing a cover film onto the photosensitive layer of the transfer film produced by the above-mentioned production method. The transfer film 1 shown in Fig. 1 may also be wound up after production and stored as a roll-form transfer film 1. The roll-form transfer film 1 can be provided in its original form for the lamination step with a substrate in a roll-to-roll system described below.

[0239] Furthermore, examples of a method for producing the transfer film 2 shown in FIG. 2 include a process of applying a photosensitive composition for forming a photosensitive light-absorbing layer precursor layer on the surface of a temporary support to form a coating film, and then drying this coating film to form the photosensitive light-absorbing layer precursor layer, and a process of applying a photosensitive composition containing specific particles on the surface of the photosensitive light-absorbing layer precursor layer to form a coating film, and then drying this coating film to form a photosensitive layer.

[0240] [Method of Forming Photosensitive Layer] The photosensitive layer can be formed by known methods, such as by applying and drying a photosensitive composition. The various components that can be contained in the photosensitive composition are synonymous with the various components that can be contained in the photosensitive layer described above, and preferred embodiments are also the same. However, the preferred ranges of the contents of the various components in the photosensitive composition are the same as the preferred ranges obtained by replacing the above-mentioned "contents (% by mass) of the various components relative to the total mass of the photosensitive layer" with "contents (% by mass) of the various components relative to the total solid content of the photosensitive composition." Specifically, the phrase "The resin content is preferably X% by mass or more relative to the total mass of the photosensitive layer" should be replaced with "The resin content is preferably X% by mass or more relative to the total solid content of the photosensitive composition." Furthermore, the photosensitive composition preferably contains a solvent (solvent) that does not fall under the category of compound Y in order to improve coatability.

[0241] The solvent is not particularly limited as long as it does not fall under the category of compound Y and can dissolve or disperse various components that may be contained in the photosensitive composition. Examples of solvents include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and solvents containing two or more of these. Solvents may be used alone or in combination. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0242] Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0243] [Method for forming photosensitive light-absorbing layer precursor layer] The method for forming the photosensitive light-absorbing layer precursor layer is the same as the method for forming the photosensitive layer, except that a light-absorbing substance is contained instead of specific particles, and the preferred embodiments are also the same.

[0244] [Pattern Forming Method] By using the transfer film of the present invention, a pattern having a high average reflectance of visible light can be formed on a substrate (transfer receiving material). Hereinafter, a pattern forming method using the transfer film of the present invention will be described. In the following description, the layer excluding the protective film formed on the temporary support of the transfer film may also be referred to as the "composition layer."

[0245] The pattern forming method of the present invention has steps 1 to 5. However, step 5 is carried out between step 1 (laminating step) and step 2 (exposure step), or between step 2 (exposure step) and step 3 (development step). Step 1: laminating a transfer film and a substrate so that the surface of the transfer film on the photosensitive layer side faces the substrate (laminating step); Step 2: exposing the photosensitive layer to a pattern (exposure step); Step 3: developing the pattern-exposed photosensitive layer to form a pattern (developing step); Step 4: heating the developed pattern (heating step); Step 5: peeling off the temporary support (temporary support peeling step).

[0246] The pattern formation method may include other steps in addition to steps 1 to 5. The procedure of the above steps will be described in detail below.

[0247] [Step 1 (Laminating Step)] The laminating step is a step of laminating a transfer film and a substrate so that the surface of the transfer film opposite to the temporary support (in other words, the surface of the composition layer) contacts the substrate, thereby obtaining a substrate with a composition layer having the substrate, the composition layer, and the temporary support in this order. Note that, when the transfer film has a configuration in which the transfer film has a protective film, the protective film is peeled off before the laminating step is carried out.

[0248] In the lamination, the substrate and the surface of the composition layer are pressure-bonded so that they come into contact with each other. There are no particular limitations on the pressure-bonding method, and known transfer methods and lamination methods can be used. Among these, it is preferable to place the surface of the composition layer on the substrate and apply pressure and heat using a roll or the like. For the lamination, known laminators such as a vacuum laminator and an auto-cut laminator can be used. There are no particular limitations on the lamination temperature, but it is preferably, for example, 70 to 130°C.

[0249] The substrate is not particularly limited, and examples thereof include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate. Examples of materials for the resin substrate include polyethylene terephthalate resins, polynaphthalene terephthalate resins, cycloolefin resins, polyimide resins, polycarbonate resins, polyacrylate resins, polyethersulfone resins, silicone resins, epoxy resins, and polyamide resins. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm. The resin substrate is also preferably a substrate that is transparent to visible light (transparent substrate). Among transparent substrates, polyamide film, polyethylene terephthalate film, cycloolefin polymer, polyethylene naphthalate film, polyimide film, or polycarbonate film is preferred, with polyethylene terephthalate film being more preferred. The thickness of the transparent substrate is not limited. The thickness of the transparent substrate is preferably 10 to 200 μm, more preferably 20 to 120 μm, and even more preferably 20 to 100 μm.

[0250] The substrate may also be provided with a conductive layer. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The conductive layer in the substrate having a conductive layer may be either one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, it is preferable that each conductive layer is made of a different material. Examples of materials for the conductive layer include simple metals and conductive metal oxides. Examples of simple metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO ２ The conductivity is such that the volume resistivity is 1×10 ６ It means that the volume resistivity is less than 1×10 ４ Preferably, the resistivity is less than Ωcm. When the substrate having a conductive layer has two or more conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide.

[0251] The substrate may also be provided with a light-emitting element. That is, the substrate may be a substrate with a light-emitting element. Examples of the light-emitting element include a micro LED chip. In a substrate with a light-emitting element, the arrangement of the multiple light-emitting elements is not particularly limited. Examples of the arrangement of the multiple light-emitting elements include providing multiple cells (e.g., corresponding to one pixel or one picture element) on a substrate, and arranging N light-emitting elements each having red (R), green (G), and blue (B) emission colors in the cells (e.g., arranging one, two, or three). The shape of the cell is not particularly limited, and examples include a lattice shape. The arrangement method of the light-emitting elements in the cell (e.g., a linear array) is not particularly limited. Note that R, G, and B are given as examples of the emission colors of the light-emitting elements, but the light-emitting elements are not particularly limited as long as they emit light, and the emission color can be selected appropriately.

[0252] [Step X2 (Exposure Step)] Step X2 is a step of patternwise exposing the photosensitive layer after the above-mentioned Step X1. Note that "patternwise exposure" refers to a form of patternwise exposure, that is, exposure in a form in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in the patternwise exposure is not particularly limited and may be adjusted as appropriate. Exposure may be performed from the side opposite the substrate of the photosensitive layer, or from the substrate side of the photosensitive layer.

[0253] The light source used for exposure can be appropriately selected as long as it irradiates light in a wavelength range (e.g., light in wavelength ranges of 254 nm, 313 nm, 365 nm, and 405 nm) to which various photosensitive components (e.g., photopolymerization initiators, photoacid generators, etc.) in the photosensitive layer are photosensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes).

[0254] The exposure dose is 5 to 200 mJ / cm ２ is preferred, and 10 to 200 mJ / cm ２ is more preferred.

[0255] In step X2, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off. To prevent mask contamination due to contact between the photosensitive layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. The pattern exposure may be performed through a mask or by direct exposure using a laser or the like. When exposure is performed through a mask, examples of the mask include a quartz mask, a soda-lime glass mask, and a film mask. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they can be easily made into large sizes. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. As a material for the film mask, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is exemplified. It is preferable to peel the temporary support from the photosensitive layer before step X3, which will be described later.

[0256] [Step X3 (Developing Step)] Step X3 is a step of developing the exposed photosensitive layer after Step X2 to form a pattern. Step X3 can be performed using a developer. Examples of the developer include an alkaline developer and an organic solvent developer. The developer preferably contains at least one selected from the group consisting of cyclopentanone, an aqueous tetramethylammonium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, and an aqueous potassium carbonate solution.

[0257] (Alkaline Developer) The alkaline developer is preferably an alkaline aqueous solution. An alkaline aqueous developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferred. The water content in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the alkaline developer. The upper limit is preferably less than 100% by mass, based on the total mass of the alkaline developer. Examples of alkaline developers include aqueous sodium carbonate solutions, aqueous potassium carbonate solutions, aqueous sodium hydroxide solutions, aqueous potassium hydroxide solutions, and aqueous tetramethylammonium hydroxide solutions. Examples of the concentration of the alkaline developer (the alkaline component constituting the alkaline developer) include 0.1% by mass aqueous solutions, 1.0% by mass aqueous solutions, and 2.38% by mass aqueous solutions. The alkaline developer may also contain a water-soluble organic solvent, a surfactant, and the like. Examples of the alkaline developer include the developer described in paragraph 0194 of WO 2015 / 093271.

[0258] (Organic Solvent Developer) Examples of the organic solvent developer include developers containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Examples of the organic solvent developer include cyclopentanone and propylene glycol monomethyl ether acetate, with cyclopentanone being preferred. In the organic solvent developer, a plurality of organic solvents may be mixed, or may be mixed with an organic solvent other than the above or water. The water content of the organic solvent developer is preferably less than 10% by mass, more preferably substantially free of water, based on the total mass of the organic solvent developer. The organic solvent content of the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the organic solvent developer. The upper limit is preferably 100% by mass or less, based on the total mass of the organic solvent developer.

[0259] Examples of development methods include puddle development, shower development, spin development, and dip development. In shower development, unnecessary portions can be removed by spraying a developer onto the photosensitive layer after exposure. It is also preferable to spray a detergent or the like onto the layer after development and remove development residues by rubbing with a brush or the like. The temperature of the developer is preferably 20 to 40°C.

[0260] [Step X4 (Heating Step)] Step X4 (heating step) is a step (post-baking step) in which the pattern obtained in Step X3 is heated. By performing Step X4, compound Y in the photosensitive layer volatilizes, which can change the aggregation state of specific particles in the photosensitive layer. The heating temperature is preferably 150 to 300°C, more preferably 180 to 250°C, and even more preferably 180 to 220°C. The heating time is preferably 20 to 180 minutes, more preferably 40 to 120 minutes, and even more preferably 60 to 100 minutes. The heating treatment may be performed in either an air environment or a nitrogen-substituted environment. The atmospheric pressure in the heating treatment environment is preferably 8.1 kPa or more, more preferably 50.66 kPa or more. The upper limit is preferably 121.6 kPa or less, more preferably 111.46 kPa or less, and even more preferably 101.3 kPa or less.

[0261] [Step X5 (Temporary Support Peeling Step)] Step 5 is a step carried out between Step 1 (Laminating Step) and Step 2 (Exposure Step), or between Step 2 (Exposure Step) and Step 3 (Development Step). Examples of methods for peeling the temporary support include known peeling methods. Specific examples include the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A No. 2010-072589.

[0262] [Laminate, Micro LED Display] The laminate of the present invention is a laminate having a pattern obtained by the above-described pattern formation method, and is preferably a component to be mounted on a micro LED display. The pattern obtained by the above-described pattern formation method has a high average reflectance of visible light, and is therefore preferably used as a partition layer disposed around the light-emitting element in a printed wiring board on which the light-emitting element, such as an LED, is mounted.

[0263] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. In the following, "parts" or "%" are based on mass unless otherwise specified.

[0264] [Preparation of Dispersion Compositions] Dispersion compositions of titanium oxide particles (W-1, W-2, W-3) were prepared based on the components and blending amounts shown in Table 1. The blending amount of each component shown in Table 1 is expressed in parts by mass.

[0265]

[0266] Details of the various components listed in Table 1 are shown below. Titanium oxide particles T-1: MPT-136 (manufactured by Ishihara Sangyo Kaisha, Ltd.) Titanium oxide particles T-2: TTO-51 (manufactured by Ishihara Sangyo Kaisha, Ltd.) Titanium oxide particles T-3: TTO-80A (manufactured by Ishihara Sangyo Kaisha, Ltd.) Dispersion resin B-1: Resin having the following structure (a resin having a structure in which a hexavalent linking group (group Z) is bonded to a substituent and a polymer chain containing a repeating unit of a poly(meth)acrylic structure; weight average molecular weight: 10,000, acid value: 80.4 mgKOH / g)

[0267]

[0268] PGMEA: propylene glycol monomethyl ether acetate

[0269] [Preparation of Photosensitive Compositions] Photosensitive compositions (A-1 to A-4) were prepared based on the components and blending amounts shown in Table 2. The blending amount of each component shown in Table 2 is expressed in parts by mass.

[0270]

[0271] The abbreviations and product names of the various components shown in Table 2 are detailed below. "W-1": Dispersion W-1 described in Table 1 "W-2": Dispersion W-2 described in Table 1 "W-3": Dispersion W-3 described in Table 1

[0272] "Polymer P-1": a resin having the following structure (a resin containing a repeating unit having a graft chain containing a repeating unit of a polyester structure. The number attached to the main chain indicates the molar ratio of the repeating unit, and the number attached to the side chain indicates the number of repeating units. Weight average molecular weight: 34,000, acid value: 57.2 mgKOH / g)

[0273]

[0274] "Polymer P-2 solution (solid content: 36.2% by mass)": Prepared by the following procedure. <Preparation method of polymer P-2 solution (solution of polymer P-2 with a solid content of 36.2% by mass)> Polymer P-2 solution (solution of polymer P-2 with a solid content of 36.2% by mass) was prepared by the polymerization process and addition process described below. 113.5 g of propylene glycol monomethyl ether was charged into a flask and heated to 90°C under a nitrogen stream. To this liquid, a solution obtained 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 obtained by dissolving 27.6 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 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 every hour. The mixture was then allowed to react for another 3 hours. The mixture was then 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 reaction solution was heated to 100°C, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. To this was added dropwise 71.9 g of glycidyl methacrylate (Blemmer G, manufactured by NOF Corporation) over 20 minutes. After the dropwise addition, the reaction solution was reacted at 100°C for 7 hours to obtain a solution of resin P-2. The solids concentration of the resulting solution was 36.2% by mass. The weight average molecular weight, calculated in terms of standard polystyrene, measured by GPC was 18,000, the number average molecular weight was 7,800, the polydispersity was 2.3, and the acid value of the polymer was 124 mg KOH / g. The residual monomer amounts measured using gas chromatography were less than 0.1% by mass of the polymer solids for all monomers. The structure of polymer P-2 is shown below.

[0275] Polymer P-2: The composition of the structural units in the following structural formula represents the molar ratio. Polymer P-2 corresponds to an alkali-soluble resin.

[0276]

[0277] "A-NOD-N": 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "A-DPH": dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "Aronix TO-2349": carboxyl group-containing monomer (manufactured by Toagosei Co., Ltd.)

[0278] "B-CIM": 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hampford Corporation) "SB-PI 701": 4,4'-bis(diethylamino)benzophenone (manufactured by Sanyo Trading Co., Ltd.) "TDP-G": phenothiazine (manufactured by Kawaguchi Chemical Industry Co., Ltd.) "CBT-1": carboxybenzotriazole (manufactured by Johoku Chemical Industry Co., Ltd.) "Megafac F551A": fluorosurfactant (manufactured by DIC Corporation)

[0279] [Example 1] [Preparation of Transfer Film] A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was prepared as a temporary support. Photosensitive composition A-1 was applied onto the temporary support so that the thickness after drying would be 10 μm, and dried at 100° C. for 1 minute to form a photosensitive layer. A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was pressure-bonded onto the photosensitive layer. By the above procedure, a transfer film 1 including a temporary support, a photosensitive layer, and a protective film in this order was obtained.

[0280] [Fabrication of Micro LED Display Element] A micro LED display element was fabricated using the transfer film 1 according to the following procedure. Specifically, before bonding the LED chip to the bonding member on the array substrate, a partition layer was formed using the transfer film 1. The specific procedure is described below.

[0281] First, the protective film of transfer film 1 was peeled off, and transfer film 1 was attached to the array substrate under the following lamination conditions to prepare a laminate consisting of the array substrate, the photosensitive layer, and the temporary support: Array substrate heating temperature: 40°C, Rubber roller temperature: 110°C, Linear pressure: 3 N / cm, Transport speed: 2 m / min

[0282] The distance between the surface of the exposure mask (mask for forming through-holes) and the surface of the temporary support was set to 125 μm. Using a proximity exposure machine (Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, i-rays were irradiated onto the photosensitive layer through the temporary support at a rate of 200 mJ / cm. ２ The pattern was irradiated with an exposure dose of 1000 uF. The through-hole size was 30 μmΦ. After the exposure process, the temporary support was peeled off. The exposed photosensitive layer was then developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate at 32°C. Next, ultrapure water was sprayed from an ultra-high pressure cleaning nozzle onto the laminate obtained after the development process to remove residue, and then air was blown onto it to remove moisture. Next, the developed laminate was subjected to a post-baking process at 200°C for 1.5 hours. By the above procedure, a partition layer with a through-hole pattern was formed on the joint of the array substrate.

[0283] An LED chip was bonded to the array substrate on which the partition wall layer was formed by the above procedure according to the method described in JP 2021-163945 A to fabricate a micro LED display element. An anti-reflection film (AR100-T062V-BD, manufactured by Dexerials Corporation) was then attached to the outermost surface of the display element.

[0284] [Examples 2 to 7, Comparative Example 1] Transfer films and micro LED display elements of Examples 2 to 7 and Comparative Example 1 were produced in the same manner as in Example 1, except that the photosensitive compositions shown in Table 3 were used and the thickness of the photosensitive layer after post-baking was adjusted to the thickness shown in Table 3 (see "Thickness of photosensitive layer (μm)" in Table 3).

[0285] [Various Measurements and Evaluations] [Average Particle Diameter of Titanium Oxide Particles in Transfer Film] The average particle diameter of titanium oxide particles was measured by the method described above.

[0286] [Average Primary Particle Diameter of Titanium Oxide Particles in Transfer Film] The average primary particle diameter of titanium oxide particles was measured by the method described above. The measured values ​​of the average primary particle diameter of titanium oxide particles are shown in Table 1.

[0287] (Refractive Index of Titanium Oxide Particles in Transfer Film) The refractive index of the titanium oxide particles was measured by the method described above.

[0288] [Measurement of Average Visible Light Reflectance] Measurement sample A (sample before heat treatment) and measurement sample B (sample after heat treatment) for average visible light reflectance were prepared according to the following procedure. The preparation procedure for each measurement sample is as follows. <Preparation of Measurement Sample A (Sample before Heat Treatment)> A transfer film was attached to a glass substrate under the same conditions as in Example 1, except that a glass substrate was used instead of the array substrate, to prepare a laminate consisting of a glass substrate, a photosensitive layer, and a temporary support. Next, the temporary support was peeled off from the laminate, and the laminate after peeling was used as Measurement Sample A.

[0289] <Preparation of Measurement Sample B (Sample after Heat Treatment)> A transfer film was attached to the glass substrate under the same conditions as in Example 1, except that a glass substrate was used instead of the array substrate, to prepare a laminate consisting of a glass substrate, a photosensitive layer, and a temporary support. Next, using a proximity exposure machine (Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, i-rays were irradiated at 200 mJ / cm2 onto the photosensitive layer via the temporary support. ２ After the exposure treatment, the temporary support was peeled off. Then, the developed laminate was subjected to a post-baking treatment at 200° C. for 1.5 hours.

[0290] (Measurement of Average Reflectance of Visible Light) Using a spectrophotometer V-570 manufactured by JASCO Corporation, the average reflectance of visible light having a wavelength of 400 to 700 nm of the prepared measurement sample A and measurement sample B was measured. The measurement results are shown in Table 3. In Table 3, the average reflectance of visible light having a wavelength of 400 to 700 nm of measurement sample A is shown in the column "X1 (before heat treatment)", and the average reflectance of visible light having a wavelength of 400 to 700 nm of measurement sample B is shown in the column "X2 (after heat treatment)". From the viewpoint of practicality, the value of X2 is preferably 50% or more.

[0291] [Evaluation of Pattern Resolution] The pattern resolution was evaluated using each of the transfer films prepared in the Examples and Comparative Examples. Specifically, a through-hole pattern was formed in the same manner as in the preparation procedure for the micro LED display element of Example 1, except that a glass substrate was used instead of the array substrate and exposure was performed using an exposure mask with a different through-hole size, and the pattern was evaluated based on the following evaluation criteria. <Evaluation Criteria> A: Through-holes of 10 μmφ or less can be patterned. B: Through-holes of more than 10 μmφ and less than 20 μmφ can be patterned. C: Through-holes of more than 20 μmφ and less than 30 μmφ can be patterned. D: Patterning was not possible, or only through-holes of more than 30 μmφ can be patterned.

[0292] [Brightness in White Display] Brightness was measured in white display (LED lit) for each of the fabricated micro LED display elements of Examples and Comparative Examples. The better the average reflectance of the pattern to visible light, the better the brightness measured by this evaluation. The brightness in white display of the fabricated micro LED display elements was measured using a luminance meter BM-5A (manufactured by Topcon Corporation) and evaluated based on the following evaluation criteria. The results are shown in Table 3. A rating of A is practically preferable. A: 300 cd / m ２ More than B:200cd / m ２ Above, 300cd / m ２ Less than C: 200 cd / m ２ less than

[0293] Table 3 is shown below.

[0294]

[0295] From the results in the table, it is clear that the transfer films of the examples have excellent pattern resolution. It is also clear that the patterns formed from the transfer films of the examples have high reflectance and, when applied to an LED display element, have excellent brightness during white display. Furthermore, comparison of the examples confirmed that the pattern resolution of the transfer film is better when the average reflectance of visible light of the photosensitive layer represented by X1 in formula (1) is 20% or less (preferably 10% or less). Furthermore, comparison of the examples confirmed that the smaller the average particle diameter of the specific particles contained in the photosensitive layer represented by X1 in formula (1), the better the pattern resolution of the transfer film.

[0296] Example 8 Synthesis of Binder Polymer P-1 82.4 g of propylene glycol monomethyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 1000 mL flask and heated to 90° C. under a nitrogen stream. To the heated propylene glycol monomethyl ether, a solution prepared by dissolving 38.4 g of styrene (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 30.1 g of dicyclopentanyl methacrylate (trade name: FANCRIL (registered trademark) FA-513M, manufactured by Hitachi Chemical Co., Ltd.), and 34.0 g of methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) in 20 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 5.4 g of dimethyl 2,2′-azobis(2-methylpropionate) (trade name: V-601, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a polymerization initiator in 43.6 g of propylene glycol monomethyl ether acetate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were simultaneously added dropwise over 3 hours. After the dropwise addition was completed, 0.75 g of polymerization initiator (V-601) was added three times to the solution after the dropwise addition, every hour. The solution after the addition was then allowed to react for an additional 3 hours. The resulting solution was then diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. The diluted solution was then heated to 100°C under an air stream. To the heated solution were then added 0.53 g of tetraethylammonium bromide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 0.26 g of p-methoxyphenol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). To the resulting solution, 25.5 g of glycidyl methacrylate (trade name: Blemmer (registered trademark) GH, manufactured by NOF Corporation) was then added dropwise over 20 minutes. The resulting solution was then allowed to react at 100°C for 7 hours, yielding 350.6 g of a solution of binder polymer P-1.

[0297] The solids concentration of the resulting solution was 36.3% by mass. The resulting binder polymer P-1 contained the structural units shown in Table 4 below, and had a weight average molecular weight (Mw) of 17,000, a polydispersity (Mw / Mn) of 2.4, and an acid value of 94.5 mgKOH / g.

[0298]

[0299] The weight average molecular weight (Mw) and number average molecular weight (Mn) of binder polymer P-1 were determined by gel permeation chromatography (GPC) in terms of standard polystyrene. The acid value of binder polymer P-1 was measured according to the method described in JIS K0070:1992. The amount of residual monomer measured using gas chromatography (GC) was less than 0.1% by mass of the solid content of binder polymer P-1 for each monomer. The term "solid content" refers to all components of the binder polymer P-1 solution excluding the solvent, and even if the components are in a liquid state, they are included in the solid content.

[0300] In Table 4, structural units other than those having a (meth)acryloyl group are shown by the abbreviation of the monomer that forms each structural unit. Structural units having a (meth)acryloyl group are shown in the form of an addition structure between monomers. For example, MAA-GMA means a structural unit in which glycidyl methacrylate (GMA) is added to a structural unit derived from methacrylic acid (MAA).

[0301] The following abbreviations represent the following monomers: "St": styrene, "MAA": methacrylic acid, "GMA": glycidyl methacrylate, "DCPMA": dicyclopentanyl methacrylate.

[0302] [Synthesis of Black Colorant Precursor] The following compound (1) was synthesized according to the following scheme: In the scheme, R corresponds to the ethylhexyl group in formula (1).

[0303]

[0304]

[0305] Synthesis of Compound (1) With reference to J. Am. Chem. Soc. 2015, 137, 15947-15956, a compound corresponding to the black compound in the above scheme (corresponding to compound (100) shown below) was synthesized using isatin as the starting material. 150 mL of tetrahydrofuran (hereinafter also referred to as "THF"; stabilizer-containing, Wako First Grade, Fujifilm Wako Pure Chemical Industries, Ltd.) was added to a 300 mL three-neck flask, followed by 10.0 g of the synthesized compound (100) and 4.9 g of zinc powder (Wako Special Grade, Fujifilm Wako Pure Chemical Industries, Ltd.). The three-neck flask was immersed in ice water to maintain the internal temperature below 5°C, and 15 mL of trifluoroacetic acid (Wako Special Grade, Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise. After the addition was complete, the external equipment was removed and the mixture was allowed to react in a water bath for 2 hours, ensuring the internal temperature did not exceed 40°C. The reaction solution was filtered through Celite, and 10 mL of ultrapure water was added to the filtrate. The mixture was heated to 40°C and THF was distilled off under reduced pressure. The precipitated gray solid was filtered by suction and washed with 300 mL of ultrapure water. The solid was dried for 12 hours using a blower dryer set at 50°C to obtain 4.5 g of compound (1) (yield: 46%).

[0306] The compound (1) is a black colorant precursor, and when subjected to a thermal stimulus (for example, heating at 200° C.), it undergoes structural transformation into the compound (100) and develops a black color.

[0307]

[0308] [Preparation of Black Colorant Precursor Dispersion] <Preparation of Dispersion D-1> The components were mixed according to the composition shown in Table 5. To the resulting mixture, zirconia beads (bead diameter: 0.1 mm) were added in an amount three times the mass of the mixture, and then dispersion was carried out using an MSE (Multi-Stacked Elements) mixer at a peripheral speed of 9 m / sec for 90 minutes. After dispersion, the zirconia beads were separated using a filter with a nominal filtration particle size of 73 μm, thereby obtaining Black Colorant Precursor Dispersion D-1. The blending amount of each component shown in Table 5 is expressed in parts by mass.

[0309]

[0310] [Preparation of Photosensitive Light-Absorbing Layer Precursor Layer Composition] Next, a photosensitive light-absorbing layer precursor layer composition (E-1) (hereinafter also referred to as "photosensitive composition E-1") was prepared using the components and blending amounts shown in Table 6. The blending amount of each component shown in Table 6 is expressed in parts by mass.

[0311]

[0312] [Preparation of Transfer Film] A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was prepared as a temporary support. Photosensitive composition E-1 shown in Table 6 was applied onto the temporary support to a thickness of 2 μm after drying, and dried at 100° C. for 1 minute to form a photosensitive light-absorbing layer precursor layer. Next, photosensitive composition A-1 shown in Table 2 was applied onto the photosensitive light-absorbing layer precursor layer to a thickness of 10 μm after drying, and dried at 100° C. for 1 minute to form a photosensitive layer. A polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was pressure-bonded onto the photosensitive layer. By the above procedure, a transfer film including, in this order, a temporary support, a photosensitive light-absorbing layer precursor layer, a photosensitive layer, and a protective film was obtained.

[0313] [Fabrication of micro LED display element] Micro LED elements were fabricated using the above-described transfer film using the same procedure as in Example 1. It was confirmed that the brightness during white display was equivalent to that of Example 1. Furthermore, the micro LED elements fabricated in Examples 1 and 8 were visually observed in a darkroom environment with a fluorescent lamp shining obliquely onto the micro LED display element during black display. As a result, it was confirmed that the micro LED display element of Example 1 had a whitish appearance, whereas the micro LED display element of Example 8 did not have a whitish appearance and provided a good level of black display.

[0314] REFERENCE SIGNS LIST 1, 2 Transfer film 10 Temporary support 12 Photosensitive layer 14 Protective film 22 Photosensitive light absorbing layer precursor layer

Claims

1. A transfer film comprising a temporary support and a photosensitive layer, the photosensitive layer comprising particles having a refractive index of 2.0 or more and an average particle size of 200 nm or less, and a photosensitive material, and satisfying the relationship of the following formula (A): Formula (A) X2>X1 In formula (A), X1 represents the average reflectance of visible light of the photosensitive layer. When the photosensitive layer is a negative photosensitive layer, X2 represents the exposure dose of i-line to the photosensitive layer of 200 mJ / cm. ２ and heating the exposed photosensitive layer at 200° C. for 1.5 hours. In the case where the photosensitive layer is a positive photosensitive layer, the average visible light reflectance of the treated film obtained by heating the photosensitive layer at 200° C. for 1.5 hours is expressed as the average visible light reflectance of the treated film obtained by exposing the photosensitive layer to light at 400° C. for 1.5 hours.

2. The transfer film according to claim 1, which satisfies the relationship of the following formula (B): Formula (B) X2>X1+30% In formula (B), X1 and X2 have the same meanings as X1 and X2 in formula (A).

3. The transfer film according to claim 1 or 2, wherein the photosensitive material contains a photopolymerizable compound and a photopolymerization initiator, and the photosensitive layer contains a compound that does not have a photopolymerizable group and has a boiling point of 230 to 500°C.

4. A transfer film according to claim 1 or 2, wherein the particles are titanium oxide.

5. A transfer film according to claim 1 or 2, wherein the average primary particle diameter of the particles is 100 nm or less.

6. The transfer film according to claim 1 or 2, wherein the photosensitive layer further contains an alkali-soluble resin.

7. The transfer film according to claim 1 or 2, further comprising a photosensitive light absorbing layer precursor layer between the temporary support and the photosensitive layer.

8. A pattern forming method comprising: step 1 of bonding the transfer film and the substrate so that the surface of the transfer film on the photosensitive layer side of the transfer film described in claim 1 or 2 faces the substrate; step 2 of pattern-exposing the photosensitive layer; step 3 of developing the pattern-exposed photosensitive layer to form a pattern; step 4 of heat-treating the developed pattern; and step 5 of peeling off the temporary support between steps 1 and 2, or between steps 2 and 3.

9. A laminate having a pattern obtained by the pattern forming method of claim 8.

10. A micro LED display comprising the laminate of claim 9.

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