TW202410492A - Method for manufacturing laminate film - Google Patents

Abstract

Provided is a laminate manufacturing method that is able to efficiently manufacture a laminate which includes a plurality of light-emitting elements and in which the leakage of light from adjacent light-emitting elements is suppressed. This laminate manufacturing method has: a step 1 in which a substrate equipped with light-emitting elements, which includes a substrate and a plurality of light-emitting elements arranged on the substrate, and a transfer film, which includes a temporary support body and a photosensitive layer, are bonded to each other such that the surface of the substrate on which the light-emitting elements are arranged faces the surface of the transfer film on the opposite side from the temporary support body, and the light-emitting elements are covered by the photosensitive layer; a step 2 in which the photosensitive layer undergoes pattern exposure; a step 3 in which the exposure photosensitive layer is developed, thereby forming a resin pattern having openings at positions corresponding to the light-emitting elements; and, between the step 1 and the step 2 or between the step 2 and the step 3, a step in which the temporary support body is peeled off.

Description

Method for manufacturing a laminate

The present invention relates to a method for manufacturing a laminate.

In recent years, as a next-generation display element, a micro LED display element (e.g., a micro LED display) having an array substrate on which a plurality of tiny LED chips are mounted has been developed. For example, Patent Document 1 discloses a micro LED mounting method and a micro LED display using laser stripping.

[Patent Document 1] Japanese Patent Application Publication No. 2021-163945

The inventors of the present invention referred to the micro LED display of patent document 1, manufactured a multilayer body in which a plurality of light-emitting elements (e.g., micro LED chips) are arranged on a substrate, and studied its performance. As a result, it was clearly found that there is a situation where the display performance is reduced due to light leakage from adjacent light-emitting elements. For example, in the case where pixels are composed of light-emitting elements having light-emitting colors of red (R), green (G), and blue (B), there is a situation where the desired display cannot be performed due to light mixing caused by light leakage from adjacent light-emitting elements. Based on the above insights, the inventors of the present invention clearly found that there is room for research on a method for manufacturing a multilayer body including a plurality of light-emitting elements in which light leakage from adjacent light-emitting elements is suppressed. In addition, in the manufacturing method of the laminate, it is generally expected that the manufacturing time is short (in other words, it can be manufactured efficiently).

Therefore, an object of the present invention is to provide a method for manufacturing a laminated body that can efficiently manufacture a laminated body including a plurality of light-emitting elements in which leakage of light from adjacent light-emitting elements is suppressed.

The present inventors found that the above-mentioned problems can be solved by the following structure.

[1] A method for manufacturing a laminate, comprising: Step 1 of laminating the substrate with light-emitting elements and the transfer film in such a manner that the surface of the substrate with light-emitting elements on the light-emitting element side of the substrate including a substrate and a plurality of light-emitting elements arranged on the substrate faces the surface of the transfer film including a temporary support and a photosensitive layer on the side opposite to the temporary support and the light-emitting elements are covered by the photosensitive layer; Step 2 of pattern-exposing the photosensitive layer; and Step 3 of developing the exposed photosensitive layer to form a resin pattern having an opening at a position corresponding to the light-emitting element, There is a step of peeling off the temporary support between step 1 and step 2 or between step 2 and step 3. 〔2〕A method for manufacturing a laminate as described in 〔1〕, wherein the thickness of the photosensitive layer in the transfer film is greater than the height of the light-emitting element. 〔3〕A method for manufacturing a laminate as described in 〔1〕 or 〔2〕, wherein the photosensitive layer in the transfer film comprises an alkali-soluble resin, a polymerizable compound and a photopolymerization initiator. 〔4〕A method for manufacturing a laminate as described in 〔1〕 or 〔2〕, wherein the photosensitive layer in the transfer film comprises a polymer and a photoacid generator. [5] A method for producing a laminate as described in any one of [1] to [4], wherein In the photosensitive layer in the transfer film, the content of water is 5.0 mass % or less relative to the total mass of the photosensitive layer. [6] A method for producing a laminate as described in any one of [1] to [5], wherein In the photosensitive layer in the transfer film, the content of an organic solvent is 5.0 mass % or less relative to the total mass of the photosensitive layer. [7] A method for producing a laminate as described in any one of [1] to [6], wherein In the photosensitive layer in the transfer film, the content of chloride ions is 100 mass ppm or less relative to the total mass of the photosensitive layer. [8] A method for manufacturing a laminate as described in any one of [1] to [7], wherein the photosensitive layer in the transfer film contains a white pigment. [9] A method for manufacturing a laminate as described in any one of [1] to [7], wherein the photosensitive layer in the transfer film has a photosensitive light absorbing layer precursor layer and a photosensitive light reflecting layer precursor layer in order from the side of the temporary support body. [10] A method for manufacturing a laminate as described in any one of [1] to [7], wherein the photosensitive layer in the transfer film is a photosensitive light absorbing layer precursor layer. [11] A method for manufacturing a laminate as described in any one of [1] to [7], wherein after step 3, there is also a step 4 of configuring a light reflecting film on the side wall of the opening. [Effect of the invention]

According to the present invention, it is possible to provide a method for manufacturing a laminated body that can efficiently manufacture a laminated body including a plurality of light-emitting elements in which light leakage from adjacent light-emitting elements is suppressed.

The present invention is described in detail below. In this specification, the numerical range represented by "～" refers to a range that includes the numerical values recorded before and after "～" as the lower limit and upper limit. In the numerical range recorded in stages in this specification, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of another numerical range recorded in stages. In addition, in the numerical range recorded in this specification, the upper limit or lower limit recorded in a certain numerical range can also be replaced by the value shown in the embodiment.

In this specification, the term "step" includes not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the intended purpose of the step can be achieved.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values converted to polystyrene using a standard substance measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance. In addition, in this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this manual, unless otherwise specified, the content of metal elements is the value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectrometer. In this manual, unless otherwise specified, the hue is the value measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

In this specification, "(meth)acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth)acrylyl group" is a concept including both acrylic acid group and methacrylic acid group. , "(meth)acrylate" is a concept that includes both acrylate and methacrylate.

In addition, in this specification, "alkali solubility" means that the solubility with respect to 100g of 1 mass % sodium carbonate aqueous solutions with a liquid temperature of 22 degreeC is 0.1g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

In this specification, "water-soluble" means that the solubility in 100 g of water at a pH of 7.0 at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above solubility condition.

In this specification, the "solid component" of a composition refers to the component that forms the composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. In addition, if it is a component that forms the composition layer, the liquid component is also regarded as a solid component.

In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. Therefore, a "transparent layer" refers to a layer with an average transmittance of visible light with a wavelength of 400 to 700 nm of 80% or more. For the average transmittance, the straight-line transmitted light is measured every 1 nm. In this specification, the average transmittance of visible light is a value measured at 25°C using a spectrophotometer, such as the spectrophotometer U-3310 manufactured by Hitachi, Ltd.

In addition, in this specification, unless otherwise specified, the thickness of each layer (for example, the photosensitive layer, the light reflecting layer precursor layer and the light absorbing layer precursor layer) is measured using SEM (Scanning Electron Microscope) or TEM ( Transmission electron microscope) The average value of the thickness measured at 10 points by observing the section cut by a microtome. Among them, those with a thickness of 1 μm or more are measured by SEM, and those with a thickness of less than 1 μm are measured by TEM.

In this specification, unless otherwise specified, the refractive index refers to the refractive index at a wavelength of 550 nm measured at 25°C using a measuring device in accordance with the elliptical polarization method.

[Manufacturing method of laminated body] The manufacturing method of the laminated body of the present invention includes: A surface of a light-emitting element side of a substrate with a light-emitting element including a substrate and a plurality of light-emitting elements arranged on the substrate, and a transfer film including a temporary support and a photosensitive layer opposite to the temporary support The step 1 of laminating the above-mentioned substrate with the light-emitting element and the above-mentioned transfer film in such a manner that the surfaces on both sides face each other and the above-mentioned light-emitting element is covered by the above-mentioned photosensitive layer; Step 2 of pattern-exposing the above-mentioned photosensitive layer; and Step 3 of developing the exposed photosensitive layer to form a resin pattern having openings at positions corresponding to the light-emitting elements, There is a step of peeling off the temporary support between the above step 1 and the above step 2 or between the above step 2 and the above step 3.

According to the manufacturing method of the laminate of the present invention having the above structure, by using photolithography of a transfer film, a substrate with light-emitting elements on which a plurality of light-emitting elements are arranged and a laminate formed by a partition layer arranged around each light-emitting element on the substrate with light-emitting elements can be efficiently manufactured. The laminate obtained by the above manufacturing method has a partition layer around each light-emitting element, so that light leakage of adjacent light-emitting elements is suppressed. In addition, compared with a manufacturing method in which a partition layer is pre-formed at a predetermined position on a substrate where a light-emitting element is arranged (that is, a resin pattern having an opening is formed at a predetermined position where a light-emitting element is arranged) by photolithography using a transfer film, and then a light-emitting element is arranged at a predetermined position, the manufacturing method of the laminate of the present invention can significantly shorten the manufacturing time. As an example of the use of the laminate obtained by the laminate manufacturing method of the present invention, micro LED display elements can be cited.

In addition, in the following, in the laminated body obtained by the manufacturing method of the laminated body of the present invention, it may be said that the light leakage of adjacent light-emitting elements can be further suppressed and/or the efficiency of the manufacturing method of the laminated body of the present invention is more excellent. "The effect of the present invention is even better."

The following describes the method for manufacturing a laminate of the present invention with reference to the drawings. [First embodiment] The first embodiment of the method for manufacturing a laminate of the present invention (hereinafter, also referred to as "the first embodiment of the present invention") comprises the following steps (1-1) to (1-3).

･Step (1-1) (bonding step): a step of bonding the substrate with light-emitting elements and the transfer film in such a manner that the surface of the substrate with light-emitting elements on the light-emitting element side of the substrate including a substrate and a plurality of light-emitting elements arranged on the substrate faces the surface of the transfer film including a temporary support and a photosensitive layer on the side opposite to the temporary support and the light-emitting elements are covered by the photosensitive layer ･Step (1-2) (exposure step): a step of pattern-exposing the photosensitive layer ･Step (1-3) (development step): a step of developing the exposed photosensitive layer to form a resin pattern having an opening at a position corresponding to the light-emitting element In addition, the first embodiment of the present invention has the following step (1-A) between step (1-1) and step (1-2) or between step (1-2) and step (1-3). ･Step (1-A) (temporary support body peeling step): a step of peeling off the temporary support body.

<<Step (1-1), bonding step>> Step (1-1) is a step of bonding the substrate with light-emitting elements to the transfer film in such a manner that the surface of the substrate with light-emitting elements on the light-emitting element side of the substrate including a substrate and a plurality of light-emitting elements arranged on the substrate faces the surface of the transfer film including a temporary support and a photosensitive layer on the side opposite to the temporary support and the light-emitting elements are covered by the photosensitive layer. The specific sequence of step (1-1) is described with reference to FIG. 1. In step (1-1), the substrate 10 with the light-emitting element and the transfer film 20 are bonded together in such a manner that the surface of the substrate 10 with the light-emitting element opposite to the substrate 12 (i.e., the surface having the light-emitting element 14) and the surface of the transfer film 20 opposite to the temporary support 22 (i.e., the surface on the photosensitive layer 24 side) face each other. In addition, FIG. 1 shows the state after the substrate 10 with the light-emitting element and the transfer film 20 are bonded together.

In addition, from the viewpoint that the light-emitting element is easily covered with the photosensitive layer in the bonding step and the effect of the present invention is more likely to be excellent, the thickness of the photosensitive layer in the transfer film is preferably greater than the height of the light-emitting element. . Here, the height of the light-emitting element refers to the thickness of the light-emitting element in the normal direction of the reference plane, using the surface of the substrate in a portion of the substrate with the light-emitting element where the light-emitting element is not arranged as the reference plane. That is, in the case of the laminated body shown in FIG. 1 , the height of the light-emitting element 14 refers to the base surface 12A of the substrate 10 with the light-emitting element in the portion where the light-emitting element 14 is not arranged. The thickness T1 of the light-emitting element 14 in the normal direction of the surface 12A.

When the transfer film has a protective film as described below, it is preferred to perform the laminating step after peeling off the protective film.

During lamination, it is preferable to bring the surface of the transfer film on the side opposite to the temporary support side into contact with the surface of the light-emitting element side of the substrate with the light-emitting element and press-bond them. Examples of the pressure-bonding method include known transfer methods and lamination methods, in which the surface of the transfer film on the side opposite to the temporary support side is overlapped with the surface of the substrate with the light-emitting element on the side of the light-emitting element. The method of applying pressure and heating using rollers or the like is preferred. Examples of the laminating method include a method using a known laminator such as a vacuum laminator and an automatic cutting laminator. The lamination temperature is preferably 70 to 130°C.

＜Substrate with light-emitting element＞ The substrate with light-emitting elements includes a substrate and a plurality of light-emitting elements arranged on the substrate. Examples of the substrate include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates. Examples of the material of the resin substrate include polyethylene terephthalate resin, polynaphthalene terephthalate resin, cycloolefin resin, polyimide resin, polycarbonate resin, and polyacrylate. resin, polyether resin, silicone resin, epoxy resin, etc. The thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm. As the substrate, a transparent substrate is preferable in view of the exposure step (step (1-2)). Examples of the transparent substrate include a resin substrate (for example, a resin film) and a glass substrate. The resin substrate is preferably a resin substrate that transmits visible light. Preferable components of the resin substrate that transmits visible light include, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, and polyimides. resin and polycarbonate resin. As the transparent substrate, polyamide film, polyethylene terephthalate film, cyclic olefin polymer, polyethylene naphthalate film, polyimide film or polycarbonate film are preferred. Polyethylene terephthalate film is preferred. Ethylene phthalate film is better. 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 further preferably 20 to 100 μm.

As a substrate, a substrate having at least one of an electrode and a lead wiring is also preferred. The electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide) and a metal fine wire such as a metal mesh and a metal nanowire. As the metal fine wire, for example, metal fine wires such as silver and copper can be cited, and silver conductive materials such as a silver mesh and a silver nanowire are preferred.

Metal is preferred as the material for lead wiring. As the above-mentioned metal, for example, gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese and alloys thereof can be cited, copper, molybdenum, aluminum or titanium is preferred, and copper is more preferred.

As a light-emitting element, a micro LED chip can be cited. In a substrate with a light-emitting element, there is no special restriction on the configuration of a plurality of light-emitting elements. As a configuration of a plurality of light-emitting elements, for example, a plurality of units (for example, equivalent to 1 pixel or 1 pixel) are provided on the substrate, and each light-emitting element having a light-emitting color of red (R), green (G) and blue (B) is configured in each unit (for example, 1, 2, 3 each) N forms. As the shape of the unit, there is no special restriction, for example, a grid shape can be cited. In addition, the configuration method of each light-emitting element in the unit (for example, a linear array) is not particularly restricted. In addition, R, G, and B are cited as an example of the light-emitting color of the light-emitting element, but the light-emitting element is not particularly restricted as long as it emits light, and its light-emitting color can be appropriately selected. In addition, the light-emitting element usually has a terminal for connecting to an external electrode.

When the light-emitting element is a micro LED chip, the type of LED may be an LED having a peak wavelength in the visible light region (hereinafter also referred to as a "visible light LED"), or an LED having a peak wavelength in the ultraviolet light region (hereinafter also referred to as a "UV-LED").

＜Transfer film＞ The transfer film that can be used in step (1-1) will be described in the later section.

＜＜Step (1-2), exposure step>> The exposure step is a step of exposing the photosensitive layer in a pattern. "Pattern exposure" means exposure in a pattern-like form, and means exposure in a form in which exposed portions and non-exposed portions exist. The positional relationship between the exposed portion (exposed area) and the non-exposed portion (non-exposed area) during pattern exposure can be appropriately adjusted. The exposure direction may be from the photosensitive layer side or the side opposite to the photosensitive layer side (substrate side). Typically, the exposure step is a step of pattern exposure through a photomask. In the exposure step, the photomask and the laminated body as the photosensitive object may or may not be in contact.

When the temporary support peeling step described below is performed between the bonding step and the exposure step, as the exposure step, the side of the laminated body from which the temporary support has been peeled off, which is obtained in the temporary support peeling step, is opposite to the substrate side. The exposure step is preferably to perform pattern exposure by contacting the surface of the side with the photomask. In other words, the exposure step is preferably to bring the surface of the laminated body from which the temporary support has been peeled off and which is exposed by peeling off the temporary support (the surface of the photosensitive layer, etc.) into contact with the photomask to pattern-expose the photosensitive layer.

When the photosensitive layer is a negative photosensitive layer, hardening of the components contained in the photosensitive layer can occur in the exposure area (the area corresponding to the opening of the mask) through the exposure step of performing pattern exposure. reaction. By performing a development step (step (1-3)) after exposure, the non-exposed area of the photosensitive layer is removed to form a pattern. In the exposure step, it is not appropriate to use a portion corresponding to the position where the light-emitting element is arranged so that a resin pattern having a predetermined opening can be formed at a position corresponding to the light-emitting element after the development step (step (1-3)). The exposure step can be performed using a mask with a pattern of the opening, corresponding to the position corresponding to the adjacent light-emitting elements (in other words, the position where the barrier layer is formed). Through the above-mentioned exposure step, the photosensitive layer can be exposed according to the pattern shape of the photomask. In addition, FIG. 2 shows the pattern exposure step when the photosensitive layer is a negative photosensitive layer. In the laminated body of FIG. 2 , a curing reaction of the components contained in the photosensitive layer 24 can occur in the opening (exposure area) of the photomask 30 . On the other hand, the photosensitive layer in the non-opening portion (non-exposed area) of the photomask 30 is removed by performing a development step (step (1-3)) after exposure.

On the other hand, when the photosensitive layer is a positive photosensitive layer, a structural change of the components contained in the photosensitive layer may occur in the exposure area (the area corresponding to the opening of the mask), and the exposed area of the photosensitive layer is removed by performing a development step (step (1-3)) after exposure, thereby forming a pattern. That is, by the structural change of the components contained in the photosensitive layer in the exposure area, a solubility contrast in the developer is generated between the exposure area and the non-exposure area, and as a result, the exposed area of the photosensitive layer is removed by the development step (step (1-3)) after exposure, thereby forming a pattern. In the exposure step, a resin pattern having a predetermined opening can be formed at a position corresponding to the light-emitting element after the development step (step (1-3)). The exposure step can be performed using a mask having a pattern in which the portion corresponding to the position where the light-emitting element is arranged is an opening portion, and the portion corresponding to the position corresponding to the adjacent light-emitting element (in other words, the position where the partition layer is formed) is a non-opening portion. By the above exposure step, the photosensitive layer can be exposed according to the pattern shape of the mask.

The method for manufacturing a laminated body of the present invention preferably includes a mask peeling step for peeling off the mask used in the exposure step between the exposure step and the development process. Examples of the mask peeling step include known peeling steps.

As a light source for pattern exposure, for example, if it can irradiate light in a wavelength range that can harden the photosensitive layer (for example, 365 nm and 405 nm), it can be appropriately selected and used. Among them, it is preferable that the dominant wavelength of the exposure light is 365nm. In addition, the dominant wavelength refers to the wavelength with the highest intensity.

Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. As the exposure amount, 5 to 200 mJ/cm ² is preferred, and 10 to 200 mJ/cm ² is more preferred. Preferred aspects of the light source, exposure amount, and exposure method used for exposure are described in, for example, paragraphs [0146] to [0147] of International Publication No. 2018/155193, and these contents are incorporated into this specification.

Furthermore, it is also preferred that the cross section (cross section perpendicular to the substrate) of the resin pattern obtained after the development step (step (1-3)) is tapered. Furthermore, more specifically, it is preferred that the resin pattern has an opening portion whose opening area expands from the substrate side toward the opposite side. In the case where the photosensitive layer is a negative photosensitive layer, the cross section of the resin pattern can be set to a tapered shape by, for example, introducing a light scattering plate into an exposure machine and irradiating exposure light from an oblique direction. When the cross section of the resin pattern is tapered, the angle between the side wall of the opening and the substrate surface of the substrate with the light-emitting element where the light-emitting element is not arranged ("taper angle". Specifically, it is equivalent to the angle θ in Figure 3.) is preferably less than 90°, 10 to 80° is more preferably, 15 to 80° is further preferably, 20 to 80° is particularly preferably, and 40 to 60° is the best.

＜＜Step (1-A), temporary support peeling step>> The temporary support peeling step is performed between the bonding step and the exposure step or between the exposure step and the development step. Among them, it is more preferable to have a peeling step between the above-mentioned bonding step and the above-mentioned exposure step. The peeling step is a step of peeling off the temporary support from the laminate of the transfer film and the substrate with the light-emitting element. As a peeling method of a temporary support, a well-known peeling method is mentioned, for example. Specific examples include the cover film peeling mechanism described in paragraphs [0161] to [0162] of Japanese Patent Application Laid-Open No. 2010-072589.

＜＜Step (1-3), development step>> The development step is a step of developing the exposed photosensitive layer using a developer to form a resin pattern. As the developer, an alkaline aqueous solution is preferred. Examples of the alkaline compound that may be included in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. , tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).

Examples of the development methods include spin immersion development, shower development, spin development, and immersion development.

Examples of the developer preferably used in this specification include the developer described in paragraph [0194] of International Publication No. 2015/093271. Examples of the development method preferably used include International Publication No. 2015/093271. The development method described in paragraph [0195] of No. 2015/093271.

It is also preferable to perform a rinsing treatment after development and before moving to the next step. Water or the like can be used for the rinsing treatment.

By going through the development step, a resin pattern can be formed on the substrate with light-emitting elements. The resin pattern is arranged at a position corresponding to the position between adjacent light-emitting elements, and the position corresponding to the light-emitting element becomes an opening. That is, a partition layer can be formed around each light-emitting element to separate the adjacent light-emitting element and suppress its light leakage. FIG3 shows a cross-sectional schematic diagram of the laminate 40 after the development step. The laminate 40 is composed of a substrate 10 with light-emitting elements and a resin pattern 42. Specifically, the resin pattern 42 is arranged at a position corresponding to the position between adjacent light-emitting elements 14, and the position corresponding to the light-emitting element 14 becomes an opening 44. In addition, in the case of a laminate having a negative photosensitive layer as shown in FIG2 , the resin pattern 42 corresponds to a cured film of the negative photosensitive layer.

＜＜Step (1-B) (post-exposure step) and step (1-C) (post-baking step)＞＞ The first embodiment of the present invention may also include a step of further exposing the resin pattern obtained by the development step (step (1-3)) (hereinafter, also referred to as "step (1-B)" or "post-exposure step") and/or a step of heating (hereinafter, also referred to as "step (1-C)" or "post-baking step"). In the case where the first embodiment of the present invention has both the post-exposure step and the post-baking step, it is preferred to perform the post-baking step after performing the post-exposure step. The exposure amount in the post-exposure step is preferably 100 to 5000 mJ/ ^cm2 , more preferably 200 to 3000 mJ/ ^cm2 . The post-baking temperature in the post-baking step is preferably 80 to 250°C, more preferably 90 to 160°C. The post-baking time in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

<<Transfer film>> Hereinafter, a transfer film that can be used in the first embodiment of the present invention will be described. The structure of the transfer film is not particularly limited as long as it has a temporary support and a photosensitive layer (a layer showing photosensitivity). The photosensitive layer may be any of a positive photosensitive layer and a negative photosensitive layer, and a negative photosensitive layer is preferred. The photosensitive layer may be a single layer or may be two or more layers. The transfer film may have other component layers (for example, a water-soluble resin layer, etc.) in addition to the photosensitive layer. The transfer film may have a protective film.

FIG4 shows a specific example of a transfer film. The transfer film 20A shown in FIG4 has a temporary support 22, a photosensitive layer 24, and a protective film 50 in order. The photosensitive layer 24 is a layer showing photosensitivity, and can be any one of a positive photosensitive layer and a negative photosensitive layer, and a negative photosensitive layer is preferred. When the photosensitive layer 24 is a negative photosensitive layer, the components contained in the layer undergo a curing reaction by exposure to form a resin layer (cured layer). In addition, the transfer film 20A shown in FIG4 is in a form with a protective film 50, but the protective film 50 may not be configured. In addition, the transfer film 20A shown in FIG4 may also have other component layers other than the photosensitive layer 24.

As the structure of the transfer film, in the laminate formed according to the first embodiment of the present invention, the following aspects are also preferred from the viewpoint of better brightness of the light-emitting element, easier suppression of external light reflection, and/or the ability to absorb stray light that is unnecessarily generated when the light-emitting element is lit. (N1) Temporary support/photosensitive light absorbing layer pre-driver layer/protective film (N2) Temporary support/photosensitive light reflecting layer pre-driver layer/protective film (N3) Temporary support/photosensitive light absorbing layer pre-driver layer/photosensitive light reflecting layer pre-driver layer/protective film

In addition, the transfer films shown in (N1) to (N3) above are provided with a protective film, but they may not be provided with a protective film. In addition, the photosensitive light-absorbing layer precursor layer (hereinafter referred to as the "light-absorbing layer precursor layer") and the photosensitive light-reflecting layer precursor layer (hereinafter referred to as the "light-reflecting layer precursor layer") are The layer representing photosensitivity is typically a negative photosensitive layer.

In the transfer film 20A shown in FIG. 4 , the transfer film in the above-mentioned aspects (N1) and (N2) corresponds to the case where the photosensitive layer 24 is a photosensitive light-absorbing layer precursor layer, respectively. The photosensitive layer 24 is a photosensitive light reflective layer precursor layer. In addition, in the first embodiment of the present invention, when the transfer film of the aspect (N1) is used, in the exposed portion in the pattern exposure of step (1-2), the light absorbing layer precursor The layer undergoes a hardening reaction to form a patterned light-absorbing layer. That is, the resin pattern can be made to function as a light-absorptive barrier layer. A laminate having such a resin pattern as a partition layer easily absorbs external light or stray light. As a result, black fastening is more excellent when the light-emitting element is not lit. Furthermore, in the first embodiment of the present invention, when the transfer film of the above aspect (N2) is used, in the exposed portion in the pattern exposure of step (1-2), the light reflective layer precursor The layer undergoes a hardening reaction to form a patterned light reflective layer. That is, the resin pattern can be made to function as a light-reflective barrier layer. In a laminate having such a resin pattern as a partition wall layer, when the light-emitting element is lit, the light from the light-emitting element is easily reflected by the partition wall, thereby improving the brightness.

In the transfer film 20A shown in FIG. 4 , the transfer film in the above aspect (N3) is equivalent to having the photosensitive layer 24 as a two-layer structure, with one side serving as the photosensitive light-absorbing layer precursor layer. The other side is used as a photosensitive light reflective layer precursor layer. FIG. 5 shows a schematic cross-sectional view of the transfer film in the aspect (N3) described above. The transfer film 20A shown in FIG. 5 has a temporary support 22, a photosensitive layer 24, and a protective film 50 in this order. The photosensitive layer 24 has a light-absorbing layer precursor layer 26 and a light-reflecting layer precursor layer 28 from the temporary support 22 side toward the protective film 50 .

In addition, in the first embodiment of the present invention, when the transfer film of the above-mentioned (N3) aspect is used, in the exposure portion in the pattern exposure of step (1-2), the light absorbing layer precursor layer and the light reflecting layer precursor layer undergo a hardening reaction, and by the development step (step (1-3)), a resin pattern having a light reflecting layer and a light absorbing layer in order from the substrate side with the light emitting element can be formed. In the laminate having such a resin pattern as a partition layer, external light or stray light is easily absorbed by the light absorbing layer, and as a result, when the light emitting element is not lit, black fastening is more excellent. In addition, due to the light reflecting layer, when the light emitting element is lit, the light from the light emitting element is easily reflected by the partition, thereby improving the brightness.

As described below, the light absorbing layer front-driver layer is equivalent to a negative photosensitive layer containing a light absorbing substance, and the light reflecting layer front-driver layer is equivalent to a negative photosensitive layer containing a reflectivity adjuster.

As the structure of the transfer film, in the laminate formed according to the first embodiment of the present invention, the following aspects are also preferred from the viewpoint of better brightness of the light-emitting element, easier suppression of external light reflection, and/or the ability to absorb stray light that is unnecessarily generated when the light-emitting element is lit. (P1) Temporary support/photosensitive light absorbing layer/protective film (P2) Temporary support/photosensitive light reflecting layer/protective film (P3) Temporary support/photosensitive light absorbing layer/photosensitive light reflecting layer/protective film In addition, the transfer films shown in (P1) to (P3) above are in the form of a protective film, but may not be provided with a protective film. In addition, the photosensitive light absorbing layer and the photosensitive light reflecting layer are layers showing photosensitivity, and are typically positive photosensitive layers.

In addition, the light-absorbing layer corresponds to a positive-type photosensitive layer containing a light-absorbing substance, and the light-reflecting layer corresponds to a positive-type photosensitive layer containing a reflectivity adjuster.

Hereinafter, each element constituting the transfer film will be described.

＜Temporary support＞ The transfer film has a temporary support. The temporary support is a member that supports the photosensitive layer and is eventually removed by a peeling process.

The temporary support may be a single-layer structure or a multi-layer structure. The temporary support is preferably a film, and a resin film is more preferred. As a temporary support, a film that is flexible and does not undergo significant deformation, contraction or elongation under pressure or under pressure and heat is preferred. As the above-mentioned film, for example, polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film and polycarbonate film can be cited. Among them, polyethylene terephthalate film is preferred as a temporary support. Furthermore, it is preferred that the film used as a temporary support has no deformation such as wrinkles or scratches.

From the viewpoint of being able to perform pattern exposure through a temporary support, the higher the transparency of the temporary support, the better. The transmittance at 365nm, 405nm and 436nm is preferably 60% or more, more preferably 70%, further preferably 80% or more, and particularly preferably 90% or more. Examples of preferred values of transmittance include 87%, 92% and 98%. From the viewpoint of pattern formability when performing pattern exposure through a temporary support and the transparency of the temporary support, it is preferred that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and further preferably 0.1% or less. From the viewpoint of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, the smaller the number of particles, foreign matter and defects contained in the temporary support, the better. The number of particles, foreign matter and defects with a diameter of 1 μm or more in the temporary support is preferably 50 pieces/ ¹⁰ mm2 or less, more preferably 10 pieces/ ¹⁰ mm2 or less, further preferably 3 pieces/10 ^mm2 or less, and particularly preferably 0 pieces/10 ^mm2 or less.

The thickness of the temporary support is not particularly limited, but 5 to 200 μm is preferred, 5 to 150 μm is more preferred, 5 to 50 μm is further preferred, and 5 to 25 μm is particularly preferred from the viewpoint of ease of operation and versatility. The thickness of the temporary support can be calculated by the average value of any five points measured by cross-section observation using a SEM (Scanning Electron Microscope).

In order to improve the adhesion between the temporary support and the photosensitive layer formed on the temporary support, the surface of the temporary support in contact with the photosensitive layer may be surface-modified by UV (ultraviolet) irradiation, coma discharge, plasma, etc.

When the surface modification of the temporary support is carried out by UV irradiation, the exposure amount is preferably 10 to 2000 mJ/cm ² and more preferably 50 to 1000 mJ/cm ² . Examples of the light source include low-pressure mercury lamps, high-pressure mercury lamps, super-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. (LED) etc. As long as the amount of light irradiation can be within this range, the lamp output or illuminance is not particularly limited.

As the temporary support, for example, a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm can be cited.

The temporary support can also be recycled. Examples of recycled products include those obtained by washing and wafering used films and the like, and then using the materials as materials to form thin films. Specific examples of recycled products include the Ecouse series of TORAY INDUSTRIES, INC. Preferable forms of the temporary support include, for example, paragraphs [0017] to [0018] of Japanese Patent Application Laid-Open No. 2014-085643, paragraphs [0019] to [0026] of Japanese Patent Application Laid-Open No. 2016-027363, and International The contents of paragraphs [0041] to [0057] of Publication No. 2012/081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370 are incorporated into this specification.

From the perspective of providing operability, a layer (lubricant layer) containing tiny particles can be provided on the surface of the temporary support. The lubricant layer can be provided on one side of the temporary support or on both sides. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. In addition, the thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available products for temporary supports include Lumirror 16KS40, Lumirror 16FB40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by TORAY INDUSTRIES, INC.); COSMOSHINE A4100, COSMOSHINE A4300, COSMOSHINE A4160, COSMOSHINE A4360, and COSMOSHINE A8300 (all manufactured by TOYOBO Co., Ltd.).

<Photosensitive layer> (Components of the photosensitive layer) The photosensitive layer may be any of a positive photosensitive layer and a negative photosensitive layer, and a negative photosensitive layer is preferred. In the case where the photosensitive layer is a negative photosensitive layer, the photosensitive layer preferably has a structure including at least an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. In addition, as described above, the photosensitive layer may also be a light-reflecting layer precursor layer and a light-absorbing layer precursor layer. When the photosensitive layer is a light-reflecting layer precursor, the photosensitive layer includes a reflective adjuster described below. When the photosensitive layer is a light-absorbing layer precursor, the photosensitive layer includes a light-absorbing substance described below.

When the photosensitive layer is a positive photosensitive layer, it is preferable that the photosensitive layer has a structure including at least a polymer and a photoacid generator. Moreover, as mentioned above, the photosensitive layer may be a photosensitive light reflection layer and a photosensitive light absorption layer. When the photosensitive layer is a photosensitive light reflective layer, the photosensitive layer contains a reflectivity modifier described below. When the photosensitive layer is a photosensitive light absorbing layer, the photosensitive layer contains a light absorbing agent described below. material.

(Impurities in the photosensitive layer) The photosensitive layer may also contain impurities selected from the group including metals and metal ions (hereinafter also referred to as "impurity A"). Specific examples of the impurity A include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens and ions thereof. Among them, halide ions, sodium ions and potassium ions are easily mixed in as impurities, so the following contents are preferred. The upper limit of the content of the impurity A is preferably 150 ppm by mass or less, more preferably 100 ppm by mass or less, further preferably 10 ppm by mass or less, and specifically 2 ppm by mass or less relative to the total mass of the photosensitive layer. good. The lower limit of the content of the impurity A can be 1 mass ppb or more or 0.1 mass ppm or more relative to the total mass of the photosensitive layer. Among them, the upper limit of the content of chloride ions is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, further preferably 10 ppm by mass or less, and 2 ppm by mass, relative to the total mass of the photosensitive layer. The following are the best. The lower limit of the chloride ion content can be 1 mass ppb or more or 0.1 mass ppm or more relative to the total mass of the photosensitive layer. Methods for setting the impurity A within the above range include selecting a raw material for the photosensitive layer with a small content of impurities, preventing contamination of impurities when forming the photosensitive layer, and washing and removing impurities. By this method, the amount of impurities can be set within the above range.

Impurity A can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

In addition, the less the content of the organic solvent in the photosensitive layer, the better. As the content of the organic solvent, it is preferably 100 mass ppm or less relative to the total mass of the photosensitive layer, 20 mass ppm or less is more preferably, and 4 mass ppm or less is further preferably. As the lower limit of the content of the organic solvent, it can also be 10 mass ppb or more relative to the total mass of the photosensitive layer. The content of the organic solvent can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography. Specifically, the above-mentioned organic solvent may be selected from the group consisting of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane.

The water content in the photosensitive layer is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and 1.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint of improving reliability and lamination properties. % or less is further preferred. In addition, the lower limit of the water content in the photosensitive layer is preferably smaller, but it may be, for example, 0.01 mass % or more based on the total mass of the layer.

Hereinafter, the negative photosensitive layer and the positive photosensitive layer will be described respectively.

"Negative photosensitive layer" The components contained in the negative photosensitive layer will be described in detail below. -Alkali-soluble resin- The photosensitive layer preferably contains an alkali-soluble resin. Examples of the alkali-soluble resin include (meth)acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenolic resin, ester resin, urethane resin, etc. Epoxy acrylate resin obtained by the reaction of epoxy resin and (meth)acrylic acid and acid-modified epoxy acrylate resin obtained by the reaction of epoxy acrylate resin and acid anhydride.

(Preferred embodiment 1 of alkali-soluble resin) As one of the preferred embodiments of alkali-soluble resin, (meth)acrylic resin can be cited from the viewpoint of excellent alkali developability and film forming property. In addition, in this specification, (meth)acrylic resin refers to a resin having a constituent unit derived from a (meth)acrylic compound. The content of the constituent unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more relative to all the constituent units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of constituent units derived from a (meth)acrylic compound, or may have constituent units derived from a polymerizable monomer other than a (meth)acrylic compound. That is, the upper limit of the content of the constituent units derived from the (meth)acrylic compound relative to all the constituent units of the (meth)acrylic resin is 100 mass % or less. Moreover, the content of the constituent units derived from the (meth)acrylic compound relative to all the constituent units of the (meth)acrylic resin is preferably 50 mol % or more, 70 mol % or more is more preferably, and 90 mol % or more is further preferably. The (meth)acrylic resin may be composed only of constituent units derived from the (meth)acrylic compound, or may have constituent units derived from polymerizable monomers other than the (meth)acrylic compound. That is, the upper limit of the content of the constituent units derived from the (meth)acrylic compound relative to all the constituent units of the (meth)acrylic resin is 100 mol % or less. In addition, in this specification, when the content of "constituent unit" is specified by molar ratio, the above-mentioned "constituent unit" and "monomer unit" have the same meaning. In addition, in this specification, the above-mentioned "monomer unit" can be modified after polymerization by polymer reaction, etc. The same applies to the following.

Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylates include alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and (meth)acrylate. Diethylaminoethyl acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate and 2,2,3 , 3-Tetrafluoropropyl (meth)acrylate and alkyl (meth)acrylate are preferred. Examples of (meth)acrylamide include acrylamide such as diacetone acrylamide.

The alkyl group of the alkyl (meth)acrylate may be a straight chain or may have a branch. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate, which have an alkyl group with a carbon number of 1 to 12. In addition, the alkyl group of the alkyl (meth)acrylate may be a cyclic group. The cyclic alkyl group may be a monocyclic group or a polycyclic group. Specific examples include cyclohexyl (meth)acrylate, etc. As the (meth)acrylate, an alkyl (meth)acrylate having an alkyl group with 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

The (meth)acrylic resin may have constituent units other than constituent units derived from (meth)acrylic acid compounds. As polymerizable monomers forming the above constituent units, there are no particular restrictions as long as they are compounds other than (meth)acrylic acid compounds that can copolymerize with (meth)acrylic acid compounds. Examples thereof include styrene compounds that may have substituents at the α position or on the aromatic ring, such as styrene, vinyl toluene, and α-methyl styrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, and maleic acid monoisopropyl ester, maleic acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

Moreover, from the viewpoint of making the alkali developability more favorable, it is preferable that the (meth)acrylic resin contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphate group and a phosphonic acid group. Among them, it is more preferable that the (meth)acrylic resin contains a structural unit having a carboxyl group, and it is still more preferable that it has a structural unit derived from the above-mentioned (meth)acrylic acid.

From the viewpoint of better developing property, the content of the constituent units having an acid group in the (meth)acrylic resin (preferably the constituent units derived from (meth)acrylic acid) is preferably 10% by mass or more relative to all the constituent units of the (meth)acrylic resin. In addition, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, 50% by mass or less is preferred, and 40% by mass or less is more preferred. From the viewpoint of better developing property, the content of the constituent units having an acid group in the (meth)acrylic resin (preferably the constituent units derived from (meth)acrylic acid) is preferably 10% by mole or more relative to all the constituent units of the (meth)acrylic resin. In addition, the upper limit is not particularly limited, but from the perspective of excellent alkali resistance, 50 mol% or less is preferred, and 40 mol% or less is more preferred.

Furthermore, it is more preferable that the (meth)acrylic resin has a constituent unit derived from the above-mentioned alkyl (meth)acrylate. The content of the constituent unit derived from the alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50 to 90 mass %, more preferably 60 to 90 mass %, and further preferably 65 to 90 mass % relative to all the constituent units of the (meth)acrylic resin. Furthermore, it is more preferable that the content of the constituent unit derived from the alkyl (meth)acrylate in the (meth)acrylic resin is 50 to 90 mol %, more preferably 60 to 90 mol %, and further preferably 65 to 90 mol % relative to all the constituent units of the (meth)acrylic resin.

As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid alkyl ester is preferred, and only a resin derived from (meth)acrylic acid A resin composed of structural units derived from acrylic acid and alkyl (meth)acrylate is more preferred. Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

Furthermore, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from alkyl methacrylate. Both structural units derived from alkyl methacrylate and structural units derived from alkyl methacrylate are preferred. The total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate in the (meth)acrylic resin is 40% by mass or more relative to all the structural units of the (meth)acrylic resin. Preferably, it is more than 60 mass %. The upper limit is not particularly limited and may be 100 mass% or less, preferably 80 mass% or less. The total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate in the (meth)acrylic resin is 40 mol% or more relative to all the structural units of the (meth)acrylic resin. Preferably, it is more than 60 mol%. The upper limit is not particularly limited and may be 100 mol% or less, preferably 80 mol% or less.

Furthermore, the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylate, and a structural unit selected from the group consisting of structural units derived from acrylic acid. And at least one kind from the group of structural units derived from alkyl acrylate is also preferred. Relative to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is calculated as a mass ratio. 60/40～80/20 is better.

From the viewpoint of excellent developability of the photosensitive layer after transfer, the (meth)acrylic resin preferably has an ester group at the terminal. In addition, the terminal portion of the (meth)acrylic resin is composed of a portion derived from the polymerization initiator used for synthesis. A (meth)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

(Preferred embodiment 2 of the alkali-soluble resin) In addition, as another preferred embodiment of the alkali-soluble resin, from the viewpoint of better developing property, an alkali-soluble resin having an acid value of 60 mgKOH/g or more can be cited. Among such alkali-soluble resins, from the viewpoint of easily thermally crosslinking with a crosslinking component by heating to form a strong film, a resin having a carboxyl group having an acid value of 60 mgKOH/g or more (hereinafter also referred to as a "resin containing a carboxyl group") is more preferred, and a (meth) acrylic resin having a carboxyl group having an acid value of 60 mgKOH/g or more (hereinafter also referred to as a "(meth) acrylic resin containing a carboxyl group") is further preferred. If the alkali-soluble resin is a resin having a carboxyl group, the three-dimensional crosslinking density can be increased by adding a heat-crosslinking compound such as a blocked isocyanate compound to perform heat crosslinking. In addition, at this time, if the carboxyl group of the resin having a carboxyl group is dehydrated and hydrophobized, the moisture-heat resistance can be improved.

The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the above acid value conditions, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph [0025] of Japanese Patent Application Laid-Open No. 2011-095716, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more, and those of Japanese Patent Application Laid-Open No. 2010-237589 can be suitably used. Among the polymers described in paragraphs [0033] to [0052], a carboxyl group-containing acrylic resin, etc., has an acid value of 60 mgKOH/g or more.

(Better version of alkali-soluble resin 3) In addition, as another preferred aspect of the alkali-soluble resin, from the viewpoint of more excellent developability, an alkali-soluble resin having an aromatic ring structure can be cited. As the alkali-soluble resin having an aromatic ring structure, an alkali-soluble resin containing a structural unit having an aromatic ring structure is more preferred. Examples of the monomer that forms the structural unit having an aromatic ring structure include a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tertiary butyl Oxystyrene, acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred. Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, and substituted or unsubstituted benzyl groups are preferred.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride, and the like; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol, and the like. Among them, benzyl (meth)acrylate is preferred.

Moreover, it is more preferable that the alkali-soluble resin has a structural unit (a structural unit derived from styrene) represented by the following formula (S).

[Chemical formula 1]

When the alkali-soluble resin contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, and 10 to 80% by mass relative to all the structural units of the alkali-soluble resin. It is more preferable, 10-70 mass % is further more preferable, and 20-60 mass % is especially preferable. Furthermore, the content of the structural units having an aromatic ring structure in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and 20 to 60 mol% relative to all the structural units of the alkali-soluble resin. Mol% is further preferred. In addition, the content of the structural units represented by the above formula (S) in the alkali-soluble resin is preferably 5 to 70 mol%, and more preferably 10 to 60 mol%, based on all the structural units of the alkali-soluble resin. 20 to 60 mol% is more preferred, and 20 to 50 mol% is particularly preferred.

The alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure. That is, the alkali-soluble resin preferably contains a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be a single ring or a polycyclic ring. Among them, it is more preferable that the alkali-soluble resin has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

Examples of the ring of the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborane ring. Among them, a ring formed by condensation of two or more aliphatic hydrocarbon rings is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 ^2,6 ]decane ring) is more preferred. Examples of the monomer forming the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Furthermore, the alkali-soluble resin preferably has a constituent unit represented by the following formula (Cy), and more preferably has a constituent unit represented by the above formula (S) and a constituent unit represented by the following formula (Cy).

[Chemical formula 2]

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

^RM in the formula (Cy) is preferably a methyl group. ^RCy in the formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms. Furthermore, the aliphatic hydrocarbon ring structure in R ^Cy of the formula (Cy) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isoborane ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure. Furthermore, the aliphatic hydrocarbon ring structure in R ^Cy of the formula (Cy) is preferably a ring structure formed by condensing aliphatic hydrocarbons of 2 or more rings, and more preferably a ring structure formed by condensing aliphatic hydrocarbons of 2 to 4 rings. In addition, R ^Cy in the formula (Cy) is a group in which the oxygen atom of -C(=O)O- in the formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group is preferred, cyclohexyl or dicyclopentyl is more preferred, and dicyclopentyl is further preferred.

The alkali-soluble resin may have only one constituent unit having an aliphatic hydrocarbon ring structure, or may have two or more constituent units. When the alkali-soluble resin contains a constituent unit having an aliphatic hydrocarbon ring structure, the content of the constituent unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90 mass %, more preferably 10 to 80 mass %, and further preferably 20 to 70 mass % relative to all constituent units of the alkali-soluble resin. In addition, the content of the constituent unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and further preferably 20 to 50 mol % relative to all constituent units of the alkali-soluble resin. In addition, relative to all constituent units of the alkali-soluble resin, the content of the constituent unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%.

When the alkali-soluble resin contains a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, with respect to all the structural units of the alkali-soluble resin, the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure The total content of the structural units is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 40 to 75% by mass. Furthermore, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 to 80 mol%, and 20 to 80 mol% relative to all the structural units of the alkali-soluble resin. 70 mol% is more preferred, and 40 to 60 mol% is further preferred. In addition, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the alkali-soluble resin is 10 to 80 mol% relative to all the structural units of the alkali-soluble resin. The best, 20 to 70 mol% is more preferred, and 40 to 60 mol% is still more preferred.

Furthermore, from the viewpoint of achieving a more excellent effect of the present invention, the molar amount nS of the constituent unit represented by the above formula (S) and the molar amount nCy of the constituent unit represented by the above formula (Cy) in the alkali-soluble resin preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2). 0.2≦nS/(nS+nCy)≦0.8   Formula (SCy) 0.30≦nS/(nS+nCy)≦0.75   Formula (SCy-1) 0.40≦nS/(nS+nCy)≦0.70   Formula (SCy-2)

It is also preferable that the alkali-soluble resin contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphonic acid group and a phosphoric acid group, with a carboxyl group being preferred. As the structural unit having the above-mentioned acid group, the structural unit derived from (meth)acrylic acid shown below is preferable, and the structural unit derived from methacrylic acid is more preferable.

[Chemical formula 3]

The alkali-soluble resin may have one type of structural unit having an acid group alone, or may have two or more types. When the alkali-soluble resin contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50 mass %, and more preferably 5 to 40 mass %, relative to all the structural units of the alkali-soluble resin. The content is preferably 10 to 40% by mass, and is further preferably 10 to 30% by mass, and is particularly preferably 10 to 30% by mass. Furthermore, the content of the structural units having acidic groups in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and 20 to 40 mol% relative to all the structural units of the alkali-soluble resin. Ear% is further preferred.

It is preferable that the alkali-soluble resin has a reactive group, and it is more preferable that it contains a structural unit having a reactive group. As the reactive group, a radically polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. Moreover, when the alkali-soluble resin has an ethylenically unsaturated group, it is preferable that the alkali-soluble resin has a structural unit having an ethylenically unsaturated group in a side chain. In this specification, the "main chain" refers to the relatively longest bonding chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to the atomic groups branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferred. Examples of the structural unit having a reactive group include, but are not limited to, those shown below.

[Chemical formula 4]

The alkali-soluble resin may have one type of structural unit having a reactive group alone, or may have two or more types. When the alkali-soluble resin contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, and 10 to 50% by mass relative to all the structural units of the alkali-soluble resin. It is more preferable, and 20-40 mass % is still more preferable. Furthermore, the content of the structural units having reactive groups in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and 10 to 50 mol% relative to all the structural units of the alkali-soluble resin. Mol% is further preferred.

As a mechanism for introducing reactive groups into alkali-soluble resins, functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfonic acid groups are combined with epoxy compounds, Method for reacting blocked isocyanate compounds, isocyanate compounds, vinyl compounds, aldehyde compounds, hydroxymethyl and carboxylic acid anhydride and other compounds. As a preferred example of the method of introducing a reactive group into an alkali-soluble resin, a polymer having a carboxyl group is synthesized by polymerization reaction, and then glycidyl (meth)acrylate and glycidyl (meth)acrylate are reacted by a polymer reaction. A method in which a part of the carboxyl groups of the obtained polymer reacts to introduce (meth)acryloxy groups into the polymer. By this mechanism, an alkali-soluble resin having a (meth)acryloxy group in the side chain can be obtained. The above-mentioned polymerization reaction is preferably carried out at a temperature of 70 to 100°C, and more preferably at a temperature of 80 to 90°C. As the polymerization initiator used in the above-mentioned polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferred. The above-mentioned polymer reaction is preferably carried out at a temperature of 80 to 110°C. In the above-mentioned polymer reaction, it is better to use catalysts such as ammonium salts.

Furthermore, it is also preferred that the alkali-soluble resin has a constituent unit derived from an alkyl (meth)acrylate. As the constituent unit derived from an alkyl (meth)acrylate, the above-mentioned constituent units can be cited, among which methyl (meth)acrylate is preferred. The alkali-soluble resin may have one constituent unit derived from an alkyl (meth)acrylate alone, or may have two or more constituent units. When the alkali-soluble resin has a constituent unit derived from an alkyl (meth)acrylate, the content of the constituent unit derived from an alkyl (meth)acrylate is preferably 1 to 10% by mass, and more preferably 1 to 5% by mass, relative to all the constituent units of the alkali-soluble resin. Furthermore, relative to all constituent units of the alkali-soluble resin, the content of constituent units derived from alkyl (meth)acrylate in the alkali-soluble resin is preferably 1 to 10 mol%, and more preferably 1 to 5 mol%.

(A specific example of the alkali-soluble resin of preferred aspects 1 to 3) As the alkali-soluble resin, polymers X1 to X4 shown below are preferred. In addition, the content ratios (a to d) of each structural unit and the weight average molecular weight Mw shown below with respect to all structural units can be appropriately changed depending on the purpose. However, from the viewpoint that the effect of the present invention is more excellent, among them, The following configuration is preferred. (Polymer X1) a: 20 to 60 mass%, b: 10 to 50 mass%, c: 5.0 to 25 mass%, d: 10 to 50 mass%. (Polymer X2) a: 20 to 60 mass%, b: 10 to 50 mass%, c: 5.0 to 25 mass%, d: 10 to 50 mass%. (Polymer X3) a: 30 to 65 mass%, b: 1.0 to 30 mass%, c: 0.5 to 15 mass%, d: 10 to 50 mass%. (Polymer X4) a: 1.0 to 20 mass%, b: 20 to 60 mass%, c: 5.0 to 230 mass%, d: 10 to 50 mass%.

[Chemical formula 5]

(Preferred embodiment 4 of the alkali-soluble resin) As the alkali-soluble resin, it is preferred to use a polymer containing a constituent unit having a carboxylic acid anhydride structure (hereinafter, also referred to as "polymer X"). The carboxylic acid anhydride structure may be any of a chain carboxylic acid anhydride structure and a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferred. As the ring of the cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferred, a 5-membered ring or a 6-membered ring is more preferred, and a 5-membered ring is further preferred.

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

[Chemical formula 6]

In formula P-1, ^RA1a represents a substituent, ^{n1a RA1a} may be the same or different, ^Z1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, and ^n1a represents an integer greater than 0.

As the substituent represented by R ^A1a , for example, an alkyl group can be mentioned. As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferred, an alkylene group having 2 or 3 carbon atoms is more preferred, and an alkylene group having 2 carbon atoms is further preferred. n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and further preferably 0. When n ^1a represents an integer of 2 or more, plural R ^A1a may be the same or different. In addition, plural R ^A1a may be bonded to each other to form a ring, but it is preferred that they do not bond to each other to form a ring.

As the constituent unit having a carboxylic acid anhydride structure, a constituent unit derived from an unsaturated carboxylic acid anhydride is preferred, a constituent unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a constituent unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is further preferred, a constituent unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a constituent unit derived from maleic anhydride is the most preferred.

Specific examples of the structural unit having a carboxylic acid anhydride structure are given below, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples. In the structural unit below, Rx represents a hydrogen atom, a methyl group, a _CH2OH group or a _CF3 group, and Me represents a methyl group.

[Chemical formula 7]

[Chemical formula 8]

The constituent units having a carboxylic acid anhydride structure in the polymer X may be a single type or may be two or more types. The total content of the constituent units having a carboxylic acid anhydride structure relative to all the constituent units of the polymer X is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 35 mol%.

Polymer X is preferably used in combination with any alkali-soluble resin in the above-mentioned preferred aspects 1 to 3. When the photosensitive layer contains the polymer X, the content of the polymer More preferably, 1 to 20% by mass is particularly preferred. The photosensitive layer may contain only 1 type of polymer X, or may contain 2 or more types.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 3,500 or more, more preferably 5,000 or more, further preferably 10,000 or more, and particularly preferably 20,000 or more. The upper limit is preferably 50,000 or less, and more preferably 30,000 or less.

The acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH/g, more preferably 60 to 200 mgKOH/g, further preferably 60 to 150 mgKOH/g, and particularly preferably 70 to 125 mgKOH/g. In addition, the acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070: 1992. From the viewpoint of developing properties, the dispersion degree of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

The photosensitive layer may contain only one type of alkali-soluble resin, or may contain two or more types. The lower limit of the content of the alkali-soluble resin is preferably 10.0 mass% or more, more preferably 15.0 mass% or more, further preferably 20.0 mass% or more, and 30.0 mass% or more relative to the total mass of the photosensitive layer. Excellent. Moreover, as an upper limit value, 90.0 mass % or less is preferable, 80.0 mass % or less is more preferable, and 70.0 mass % or less is still more preferable.

-Polymerizable compound- The photosensitive layer preferably contains a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include free radical polymerizable groups and cationic polymerizable groups, and free radical polymerizable groups are preferred.

The polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an “ethylenically unsaturated compound”). As the ethylenically unsaturated group, a (meth)acryloxy group is preferred. In addition, the ethylenically unsaturated compound in this specification is a compound other than the alkali-soluble resin mentioned above, and it is preferable that the molecular weight is less than 5,000.

One of the preferred aspects of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M"). Q ² -R ¹ -Q ¹ Formula (M) In the formula (M), Q ¹ and Q ² each independently represent a (meth)acryloxy group, and R ¹ represents a divalent linking group having a chain structure.

From the viewpoint ^{of ease of synthesis, Q 1 and Q 2 in} formula (M) are preferably the same group. Furthermore, from the viewpoint of reactivity, Q ¹ and Q ² in formula (M) are preferably acryloyloxy groups. As R ¹ in the formula (M), an alkylene group, an alkoxyalkylene group (-L ¹ -OL ¹ -) or a polyalkyleneoxyalkylene group (-(L ¹ -O) _p -L ¹ - ) is preferred, a hydrocarbon group or a polyalkyleneoxy alkylene group having 2 to 20 carbon atoms is more preferred, an alkylene group having 4 to 20 carbon atoms is further preferred, and a straight chain alkylene group having 6 to 18 carbon atoms is Excellent. The above-mentioned hydrocarbon group only needs to have a chain structure in at least part of it. The part other than the above-mentioned chain structure is not particularly limited. For example, it may be a branched, cyclic or linear alkylene group having 1 to 5 carbon atoms. Any of an aryl group, an ether bond and a combination thereof, an alkylene group or a combination of two or more alkylene groups and one or more aryl groups is preferred, and an alkylene group is more preferred , a straight chain alkylene group is further preferred. In addition, the above-mentioned L ¹ each independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, and an integer of 2 to 10 is preferred.

In addition, the number of atoms in the shortest link between ^Q1 and ^Q2 in compound M is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12. In the present specification, "the number of atoms in the shortest link between ^Q1 and ^Q2 " means the number of atoms in the shortest bond from the atom in ^R1 linked to ^Q1 to the atom in ^R1 linked to ^Q2 .

Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol/propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, at least one compound selected from the group including 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from the group including 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group including 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is further preferred.

Furthermore, one of the preferred aspects of the polymerizable compound includes a bifunctional or higher ethylenically unsaturated compound. In this specification, a "bifunctional or higher ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acrylyl group is preferred. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

As the bifunctional ethylenically unsaturated compound, it is possible to appropriately select from known compounds. As bifunctional ethylenically unsaturated compounds other than the above-mentioned compound M, tricyclodecanedimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate can be cited.

Commercially available products of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol diacrylate (product name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (product name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (product name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (product name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

The trifunctional or higher ethylenically unsaturated compound can be appropriately selected from known compounds. Examples of trifunctional or higher ethylenically unsaturated compounds include dineopenterythritol (tri/tetra/penta/hexa)(meth)acrylate and neopentylerythritol (tri/tetra)(meth)acrylate. , trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate and glyceryl tri(meth)acrylate skeleton (meth)acrylate compounds.

Here, "(tri/tetra/penta/hexa)(meth)acrylate" includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate. ) The concept of acrylate, "(tri/tetra)(meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

As one of the preferred forms of polymerizable compounds, amine (meth)acrylate compounds can also be cited. As amine (meth)acrylates, amine di(meth)acrylates can be cited, for example, propylene oxide modified amine di(meth)acrylates and ethylene oxide and propylene oxide modified urethane di(meth)acrylates can be cited. In addition, as amine (meth)acrylates, amine (meth)acrylates with three or more functions can also be cited. As the lower limit of the number of functional groups, 6 or more functions are more preferred, and 8 or more functions are further preferred. In addition, as the upper limit of the number of functional groups, 20 or less functions are preferred. Examples of trifunctional or higher amine (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

As one of the preferred forms of polymerizable compounds, ethylenically unsaturated compounds having an acid group can also be cited. As the acid group, phosphoric acid group, sulfonic acid group and carboxyl group can be cited. Among them, carboxyl group is preferred as the acid group. As the ethylenically unsaturated compounds having an acid group, ethylenically unsaturated compounds having 3-4 functions (carboxyl groups introduced into the backbone of pentaerythritol tri- and tetraacrylate (PETA) (acid value: 80-120 mgKOH/g)), ethylenically unsaturated compounds having 5-6 functions (carboxyl groups introduced into the backbone of dipentaerythritol penta- and hexaacrylate (DPHA) (acid value: 25-70 mgKOH/g)) and the like can be cited. The trifunctional or higher ethylenically unsaturated compounds having an acid group may be used together with a bifunctional ethylenically unsaturated compound having an acid group as needed.

As the ethylenically unsaturated compound having an acid group, at least one selected from the group including bifunctional or higher ethylenically unsaturated compounds having a carboxyl group and their carboxylic anhydrides is preferred. If the ethylenically unsaturated compound having an acid group is at least one selected from the group including bifunctional or higher ethylenically unsaturated compounds having a carboxyl group and their carboxylic anhydrides, the developing property and the film strength are further improved. The bifunctional or higher ethylenically unsaturated compound having a carboxyl group is not particularly limited and can be appropriately selected from known compounds. As bifunctional or higher ethylenically unsaturated compounds having a carboxyl group, there are 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.).

As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of Japanese Patent Application Publication No. 2004-239942 is preferred, and the contents described in this publication are incorporated in this manual.

Examples of the polymerizable compound include a compound obtained by reacting an α,β-unsaturated carboxylic acid and a polyhydric alcohol, and a compound obtained by reacting an α,β-unsaturated carboxylic acid and a compound containing an glycidyl group. Compounds, amine ester monomers such as (meth)acrylate compounds with amine ester bonds, γ-chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl-phthalic acid Ester, β-hydroxyethyl-β'-(meth)acryloxyethyl-phthalate and β-hydroxypropyl-β'-(meth)acryloxyethyl-phthalate Phthalate compounds such as phthalate esters and alkyl (meth)acrylates. These are used individually or in combination of 2 or more types.

Examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, and polyethylene glycol polypropylene glycol having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. glycol) di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylpropane ethoxy tri(meth)acrylate, trihydroxymethylpropane diethoxy tri(meth)acrylate, trihydroxymethylpropane triethoxy tri(meth)acrylate, trihydroxymethylpropane tetraethoxy tri(meth)acrylate, trihydroxymethylpropane pentaethoxy tri(meth)acrylate, di(trihydroxymethylpropane) tetraacrylate, tetrahydroxymethylmethane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, dipentatriol tetra(meth)acrylate, dipentatriol penta(meth)acrylate and dipentatriol hexa(meth)acrylate. Among them, ethylene unsaturated compounds having a tetrahydroxymethylmethane structure or a trihydroxymethylpropane structure are preferred, and tetrahydroxymethylmethane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate or di(trihydroxymethylpropane)tetraacrylate are more preferred.

As polymerizable compounds, there can also be cited caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), oxirane-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glyceryl triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), etc. Also, as polymerizable compounds, there can be cited diacrylic acid (2,2-dimethylethylene) (5-ethyl-1,3-dimethoxy-2,5-diyl) methylene (KAYARAD R-604 manufactured by Nippon Kayaku Co., Ltd.) and the like.

As a polymerizable compound (particularly, an ethylenically unsaturated compound), from the viewpoint of excellent developability of the photosensitive layer after transfer, those containing an ester bond are also preferred. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule. However, from the viewpoint that the effect of the present invention is more excellent, compounds having a tetramethylolmethane structure or a trihydroxyl methane structure are not particularly limited. Ethylenically unsaturated compounds with a methylpropane structure are preferred, such as tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and trimethylolpropane tri(meth)acrylate. ester or di(trimethylolpropane)tetraacrylate is more preferred. From the viewpoint of providing reliability, the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned compound having a tetramethylolmethane structure or a trimethylolpropane structure. Ethylenically unsaturated compounds are preferred. Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and Tricyclodecane dimethanol di(meth)acrylate.

One of the preferred aspects of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). The polymerizable compound has a ring structure (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) formed by condensing two or more aliphatic hydrocarbon rings. Preferable compounds are bifunctional ethylenically unsaturated compounds, and bifunctional ethylenically unsaturated compounds having a ring structure formed by contracting two or more aliphatic hydrocarbon rings are more preferable, and tricyclodecane dimethanol di(meth)acrylate is further preferable. Better. As the aliphatic hydrocarbon ring structure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure or an isoborane structure is preferred.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

In one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, and more preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group.

Furthermore, as one of the preferred aspects of the photosensitive layer, the photosensitive layer contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (methyl ) acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound) are preferred. The mass ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the trifunctional or higher ethylenically unsaturated compound (mass of the bifunctional ethylenically unsaturated compound/mass of the trifunctional or higher ethylenically unsaturated compound) is 10/ 90～90/10 is better, 30/70～70/30 is better. The content of the bifunctional ethylenically unsaturated compound is preferably 20.0 mass% or more, more preferably 30.0 mass% or more, and still more preferably 40.0 mass% or more relative to the total amount of all ethylenically unsaturated compounds. The upper limit is not particularly limited, but for example, it is 100 mass% or less, preferably 90.0 mass% or less, and more preferably 80.0 mass% or less. The bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 5.0 to 60.0 mass%, more preferably 5.0 to 40.0 mass%, and still more preferably 5.0 to 40.0 mass%.

The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the difunctional or higher ethylenically unsaturated compound is preferably 50 to 100% by mass relative to the total content of all ethylenically unsaturated compounds contained in the photosensitive layer.

A polymerizable compound (especially an ethylenically unsaturated compound) may be used individually by 1 type, or may be used in combination of 2 or more types. The lower limit of the content of the polymerizable compound (especially the ethylenically unsaturated compound) in the photosensitive layer is preferably 10.0 mass% or more, and more preferably 15.0 mass% or more based on the total mass of the photosensitive layer. Moreover, as an upper limit value, 70.0 mass % or less is preferable, 60.0 mass % or less is more preferable, 50.0 mass % or less is still more preferable, and 40.0 mass % or less is especially preferable.

-Photopolymerization initiator- The photosensitive layer preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an “oxime-based photopolymerization initiator”), and a photopolymerization initiator having an α-aminoalkylphenol structure. Initiator (hereinafter, also referred to as "α-aminoalkylphenol photopolymerization initiator"), photopolymerization initiator having an α-hydroxyalkylphenol structure (hereinafter, also referred to as "α- Hydroxyalkylphenol-based polymerization initiator".), photopolymerization initiator having a acylphosphine oxide structure (hereinafter, also referred to as "hydroxyalkylphosphine oxide-based photopolymerization initiator.") and N-benzene Photopolymerization initiator with glycine structure (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiator"), etc.

The photopolymerization initiator includes an oxime-based photopolymerization initiator, an α-aminoalkylphenol-based photopolymerization initiator, an α-hydroxyalkylphenol-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. At least one type of photopolymerization initiator is preferably selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenol-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators. More preferably, it is at least one kind from the group of photopolymerization initiators.

Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064] to [0081] of JP-A-2015-014783 can also be used.

In addition, from the viewpoint of photosensitivity, visibility of the exposed part and the non-exposed part, and resolution, the photopolymerization initiator contains a compound selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives. At least one of the group is preferably used as a photoradical polymerization initiator. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl) -4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)- 4,5-diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Examples of derivatives of 2,4,5-triarylimidazole dimer include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl- 1,2'-biimidazole.

Examples of photoradical polymerization initiators include dimethylaminobenzoic acid ethyl ester (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p,p'-dimethoxybenzyl base) anisyl ester, TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 ( Trade name: Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (BASF company), Omnirad651 and 369 (trade name: IGM Resins B.V. company) and 2,2'-double (2- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzyl oxime) ( Trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone- 1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamine base)-2-[(4-methylphenyl)methyl]-1-[4-(4-ethylphenyl)phenyl]-1-butanone (trade name: Omnirad379EG, manufactured by IGM Resins B.V.) , 2-methyl-1-(4-methylthiophenyl)-2-ethylpropanyl-1-one (trade name: Omnirad907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4- [4-(2-Hydroxy-2-methylpropyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad127, manufactured by IGM Resins B.V.), 2-benzyl-2 -Dimethylamino-1-(4-ortholinylphenyl)butanone-1 (trade name: Omnirad369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan- 1-Ketone (trade name: Omnirad1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenyl Ethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.) ), bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (trade name: Omnirad819, manufactured by IGM Resins B.V.), oxime ester-based photopolymerization initiator (trade name: Lunar6, DKSH Manufactured by Japan K.K.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-bis Phenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Co., Ltd.) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co. ., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzyl oxime) (trade name: TR -PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H -Carbazol-3-yl]-,2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Trolly New Electronic Materials CO., LTD.) and 3-cyclohexyl-1-( 6-(2-(Benzyloxyimino)octyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl) Oxime) (trade name: TR-PBG-391, manufactured by Changzhou Trolly New Electronic Materials CO., LTD.). Examples of commercially available photoradical polymerization initiators include an alkylphenone-based compound with the product name “Omnirad 379” (manufactured by IGM Resins B.V.).

One type of photopolymerization initiator may be used alone, or two or more types may be used. When two or more types are used in combination, at least one selected from the group consisting of an oxime-based photopolymerization initiator and an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator is used. 1 type is better. When the photosensitive layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 0.5% by mass relative to the total mass of the photosensitive layer. The above is further preferred. Moreover, the upper limit is preferably 10.0 mass% or less, and more preferably 7.0 mass% or less based on the total mass of the photosensitive layer.

-Heterocyclic compound- The photosensitive layer may contain a heterocyclic compound. The heterocyclic compound may be a monocyclic or polycyclic heterocyclic compound. As heteroatoms of the heterocyclic compound, nitrogen atoms, oxygen atoms and sulfur atoms can be cited. It is preferred that the heterocyclic compound has at least one atom selected from the group consisting of nitrogen atoms, oxygen atoms and sulfur atoms, and it is more preferred that the heterocyclic compound has a nitrogen atom.

As heterocyclic compounds, for example, triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, trioxane compounds, dioxane compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzothiazole compounds and pyrimidine compounds can be cited. Among the above, as the heterocyclic compound, at least one compound selected from the group including triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, trioxane compounds, dioxane compounds, thiazole compounds, benzimidazole compounds and benzothiazole compounds is preferred, and at least one compound selected from the group including triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzothiazole compounds is more preferred.

Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

[Chemical formula 9]

[Chemical formula 10]

As the tetrazole compound, the following compounds can be exemplified.

[Chemical formula 11]

[Chemical formula 12]

Examples of the thiadiazole compound include the following compounds.

[Chemical formula 13]

Examples of the trisulfide compounds include the following compounds.

[Chemical formula 14]

As the diotanine compound, the following compounds can be exemplified.

[Chemical formula 15]

Examples of the thiazole compound include the following compounds.

[Chemical formula 16]

As the benzothiazole compound, the following compounds can be exemplified.

[Chemical formula 17]

Examples of the benzimidazole compound include the following compounds.

[Chemical formula 18]

[Chemical formula 19]

As benzoethazole compounds, the following compounds can be exemplified.

[Chemical formula 20]

The heterocyclic compound may be used alone or in combination of two or more. When the photosensitive layer contains the heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0 mass %, more preferably 0.10 to 10.0 mass %, further preferably 0.30 to 8.0 mass %, and particularly preferably 0.50 to 5.0 mass % relative to the total mass of the photosensitive layer.

-Aliphatic thiol compound- The photosensitive layer may contain an aliphatic thiol compound. By containing the aliphatic thiol compound in the photosensitive layer, an ene-thiol reaction occurs between the aliphatic thiol compound and the radical polymerizable compound having an ethylenic unsaturated group, thereby suppressing the hardening and shrinkage of the formed film and alleviating the stress.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher aliphatic thiol compound) is preferred.

Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is preferable from the viewpoint of the adhesion of the formed pattern (especially the adhesion after exposure).

In the present specification, a "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "thiol groups") in a molecule.

The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of 100 or more. Specifically, the polyfunctional aliphatic thiol compound has a molecular weight of 100 to 1,500, more preferably 150 to 1,000.

As for the number of functional groups of the polyfunctional aliphatic thiol compound, for example, from the viewpoint of the adhesion of the formed pattern, 2 to 10 functional groups are preferred, 2 to 8 functional groups are more preferred, and 2 to 6 functional groups are further preferred. good.

Examples of the polyfunctional aliphatic thiol compound include trihydroxymethylpropane tris(3-butylbutyrate), 1,4-bis(3-butylbutyryloxy)butane, pentaerythritol tetra(3-butylbutyrate), 1,3,5-tris(3-butylbutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(2-(3-thiobutylbutyryloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, trihydroxymethylethane tris(3-butylbutyrate), tris[(3 [-(3-butylpropionyloxy)ethyl] isocyanurate, trihydroxymethylpropane tris(3-butylpropionate), pentaerythritol tetra(3-butylpropionate), tetraethylene glycol bis(3-butylpropionate), dipentaerythritol hexa(3-butylpropionate), ethylene glycol bis(thio)propionate, 1,4-bis(3-butylbutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dibutylsuccinic acid and di(butylethyl) ether.

Among the above, the polyfunctional aliphatic thiol compound is selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyloxy)butane and At least 1 of the group of 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione compounds are preferred.

Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-butylpropionic acid, methyl 3-butylpropionate, 2-ethylhexyl-3-butylpropionate, n-octyl-3-butylpropionate, methoxybutyl 3-butylpropionate, and stearyl 3-butylpropionate.

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

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

-Thermal cross-linkable compound- It is also preferable that the photosensitive layer contains a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In addition, in this specification, the thermally crosslinkable compound which has an ethylenically unsaturated group mentioned later is not treated as an ethylenically unsaturated compound, but is treated as a thermally crosslinkable compound. Examples of thermally crosslinkable compounds include epoxy compounds, oxybutane compounds, methylol compounds, and blocked isocyanate compounds. Among these, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. The blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, and therefore, for example, when at least one of an alkali-soluble resin and a radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, it has the The hydrophilicity of the formed film tends to decrease and its function as a protective film tends to increase. In addition, the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of the isocyanate is protected (so-called masked) by a blocking agent."

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

Examples of end-capping agents having a dissociation temperature of 100 to 160° C. include active methylene compounds [malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, Di2-ethylhexyl malonate, etc.), oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime, etc. have -C (=N-OH) in the molecule )-the compound of the structure represented). Among these, as a terminal blocking agent having a dissociation temperature of 100 to 160° C., for example, from the viewpoint of storage stability, at least one type selected from oxime compounds is preferred.

For example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer body, the blocked isocyanate compound preferably has an isocyanurate structure. For example, hexamethylene diisocyanate is protected by isocyanuration to obtain a blocked isocyanate compound having an isocyanurate structure. Among the blocked isocyanurate compounds having an isocyanurate structure, compared with compounds without an oxime structure, it is easier to set the decomposition temperature within a better range and to reduce the development residue. The compound having an oxime structure using an oxime compound as a blocking agent is preferred.

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

As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (the above are manufactured by SHOWA DENKO K.K.) , End-capped Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

One type of thermally crosslinkable compound may be used alone, or two or more types may be used in combination. When the photosensitive layer contains a thermal cross-linkable compound, the content of the thermal cross-linkable compound is preferably 1.0 to 50.0 mass %, more preferably 5.0 to 30.0 mass %, and 5.0 mass % relative to the total mass of the photosensitive layer. ~25.0% by mass is further more preferable.

-Surfactant- The photosensitive layer may contain a surfactant. Examples of the surfactant include surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of Japanese Patent Application Laid-Open No. 2009-237362.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferred. Commercially available products of fluorine-based surfactants include, for example, MEGAFACE 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-5 59, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all DIC Corporation), FLUORAD FC430, FC431, 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, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), Footgent 710FM, 710FL, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 (all manufactured by NEOS COMPANY LIMITED), etc. In addition, the fluorine-based surfactant can also preferably use an acrylic compound, which has a molecular structure containing a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cut off, thereby volatilizing the fluorine atom. As such fluorine-based surfactants, the MEGAFACE DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), NIKKEI BUSINESS DAILY (February 23, 2016)) can be cited, such as MEGAFACE DS-21. In addition, as a fluorine-based surfactant, it is also preferable to use a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. In addition, as a fluorine-based surfactant, a capped polymer can also be used. Furthermore, as a fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which contains a constituent unit from a (meth)acrylate compound having a fluorine atom and a constituent unit from a (meth)acrylate compound having two or more (preferably five or more) alkoxy groups (preferably ethoxy and propoxy groups). Furthermore, as a fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenic unsaturated bond in the side chain can also be used. Examples include MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation), etc. As fluorine-based surfactants, from the perspective of improving environmental suitability, surfactants derived from alternative materials of compounds having perfluoroalkyl groups with more than 7 carbon atoms, such as perfluorooctane acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are preferred. As the nonionic surfactant, there can be mentioned glycerin, trihydroxymethylpropane, trihydroxymethylethane and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), Solsperse 20000 (all manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Co., Ltd.), etc.

As silicone-based surfactants, there are linear polymers formed by siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends.

Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above are Dow (manufactured by Corning Toray Silicone Co., Ltd.) and X-22-4952, , KF-643, , TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie Company), etc.

One type of surfactant may be used alone, or two or more types may be used in combination. When the photosensitive layer contains a surfactant, the surfactant content is preferably 0.01 to 3.0 mass%, more preferably 0.01 to 1.0 mass%, and 0.05 to 0.80 mass% relative to the total mass of the photosensitive layer. For further improvement.

-Polymerization inhibitor- The photosensitive layer may contain a polymerization inhibitor. Polymerization inhibitors refer to compounds that have the function of delaying or inhibiting polymerization reactions. As the polymerization inhibitor, for example, known compounds used as polymerization inhibitors can be used.

Examples of the polymerization inhibitor include phenanthridine, bis-(1-dimethylbenzyl)phenanthridine and 3,7-dioctylphenanthridine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate][vinylbis(ethylene oxide)]2,4-bis[(stearylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-tris(1,3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 1,3,5-tris(1,3,5-di-tert-butyl-2,6-dimethylbenzyl), 1,3,5-tris(1,3,5-di-tert-butyl-3-hydroxy ... Hindered phenol compounds such as pentylene glycol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxyamine and N-nitrosophenylhydroxyamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tert-butyl o-catechin; metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate. Among them, from the viewpoint of the better effect of the present invention, as the polymerization inhibitor, at least one selected from the group including thiophene compounds, nitroso compounds or their salts and hindered phenol compounds is preferred, and thiophene, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinylbis(ethylene oxide)]2,4-bis[(stearylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) and N-nitrosobenzoylamine aluminum salt are more preferred.

One type of polymerization inhibitor may be used alone, or two or more types may be used in combination. When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and 0.02 to 2.0 mass% relative to the total mass of the photosensitive layer. For further improvement. The content of the polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and further preferably 0.01 to 1.0 mass% relative to the total mass of the polymerizable compound.

-Hydrogen donating compound- The photosensitive layer may contain a hydrogen donating compound. The hydrogen-donating compound has the functions of further improving the sensitivity of the photopolymerization initiator to active light and inhibiting the polymerization inhibition of the polymerizable compound caused by oxygen.

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

Examples of the amines include "Journal of Polymer Society" by M.R. Sander et al., Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Laid-Open No. 51-082102, and Japanese Patent Application Laid-Open No. 51-082102 Japanese Patent Application Publication No. Sho 52-134692, Japanese Patent Application Publication No. Sho 59-138205, Japanese Patent Application Publication No. Sho 60-084305, Japanese Patent Application Publication No. Sho 62-018537, Japanese Patent Application Publication No. Sho 64-033104, and Research Disclosure 33825 Compounds listed in No. etc. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: colorless crystal violet), triethanolamine, Ethyl p-dimethylaminobenzoate, p-formyldimethylaniline and p-methylthiodimethylaniline. Among them, from the viewpoint that the effect of the present invention is more excellent, the amines are selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl). ), at least one of the methane group is preferred.

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, N-phenylglycine is preferable as the amino acid compound from the viewpoint that the effect of the present invention is more excellent.

Examples of hydrogen-donating compounds include organometallic compounds (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (trithiane, etc.) described in Japanese Patent Application Laid-Open No. 6-308727.

One type of hydrogen-donating compound may be used alone, or two or more types may be used in combination. When the photosensitive layer contains a hydrogen-donating compound, from the viewpoint of increasing the curing speed by balancing the polymerization growth rate and chain transfer, the content of the hydrogen-donating compound is 0.01 relative to the total mass of the photosensitive layer. It is preferably ∼10.0 mass%, more preferably 0.01 to 8.0 mass%, and still more preferably 0.03 to 5.0 mass%.

-Residual monomers- The photosensitive layer sometimes contains residual monomers of each constituent unit of the above-mentioned alkali-soluble resin. From the viewpoint of patterning and reliability, the content of residual monomers is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and further preferably 500 mass ppm or less relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but 1 mass ppm or more is preferably, and 10 mass ppm or more is more preferably. From the viewpoint of patterning and reliability, the content of residual monomers of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and further preferably 100 mass ppm or less relative to the total mass of the photosensitive layer. The lower limit is not particularly limited, but 0.1 mass ppm or more is preferred, and 1 mass ppm or more is even more preferred.

When the alkali-soluble resin is synthesized by polymer reaction, the residual monomer amount of the monomer is also preferably within the above range. For example, when a carboxylic acid side chain and glycidyl acrylate are reacted to synthesize an alkali-soluble resin, the content of glycidyl acrylate is preferably within the above range. The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

-Other ingredients- The photosensitive layer may contain components other than those described above (hereinafter also referred to as "other components"). Examples of other components include particles (for example, metal oxide particles), colorants, antioxidants, reflectivity adjusters, light absorbing substances, sensitizers, and chain transfer agents. Examples of other components include other additives described in paragraphs [0058] to [0071] of Japanese Patent Application Laid-Open No. 2000-310706.

--Particles-- Metal oxide particles are preferred as particles. The metal in the metal oxide particles also includes semimetals such as B, Si, Ge, As, Sb and Te. For example, from the perspective of the transparency of the cured film, the average primary particle size of the particles is preferably 1 to 200 nm, and more preferably 3 to 80 nm. The average primary particle size of the particles is calculated by measuring the particle size of any 200 particles using an electron microscope and arithmetically averaging the measurement results. In addition, when the shape of the particles is not spherical, the longest side is used as the particle size.

--Colorants-- The photosensitive layer may contain trace amounts of colorants (pigments, dyes, etc.).

--Antioxidants-- As antioxidants, for example, 3-pyrazolones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, gallol, methylhydroquinone and chlorohydroquinone; p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine and p-phenylenediamine can be cited. Among them, from the viewpoint of the more excellent effect of the present invention, 3-pyrazolones are preferred as antioxidants, and 1-phenyl-3-pyrazolone is more preferred.

-Reflectivity adjuster- It is preferred that the photosensitive layer contains one or more reflectivity adjusters selected from the group including white pigments, metal particles, hollow particles and liquid crystal compounds (especially, pigment particles of cholesteric liquid crystal compounds). When the photosensitive layer contains the reflectivity adjuster, it can be set as a light reflective layer precursor layer. When the photosensitive layer contains the reflectivity adjuster, the light reflectivity of the resin pattern of the laminate formed according to the first embodiment of the present invention is more excellent. In addition, when the photosensitive layer contains white pigments or hollow particles, the photosensitive layer easily becomes a white layer, and it is easy to obtain a light reflective layer of characteristic X1 described later. On the other hand, when the photosensitive layer contains metal particles or liquid crystal compounds (especially, pigment particles of cholesteric liquid crystal compounds), it is easy to obtain a light reflective layer of the characteristics X2 and X3 described later due to the reflectivity caused by the metal particles or the liquid crystal compounds.

--white pigment-- Examples of white pigments include titanium oxide, zinc oxide, zinc oxide, light calcium carbonate, white carbon black, aluminum oxide, aluminum hydroxide, barium sulfate, and the like. In addition, as the white pigment, from the viewpoint of more excellent effects of the present invention, particles having a higher refractive index than the cured product of the polymerizable compound included in the photosensitive layer are preferred, and among these, titanium oxide is more preferred, and rutile is more preferred. Type or anatase titanium oxide is further preferred, and rutile titanium oxide is particularly preferred. The surface of the white pigment can be treated with silica treatment, alumina treatment, titanium dioxide treatment, zirconium oxide treatment, and organic matter treatment. Furthermore, when the photosensitive layer contains a white pigment, the photosensitive layer may further contain a pigment dispersant.

The shape of the white pigment is not particularly limited, and examples thereof include spherical, amorphous, plate-shaped, needle-shaped, polyhedron, and the like. The average primary particle size of the white pigment is not particularly limited, but for example, 50 to 1000 nm is preferred, and 100 to 500 nm is more preferred. In addition, the average primary particle diameter of the white pigment is a value obtained by measuring the diameters of 100 arbitrary particles through observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. In addition, the diameter of the white pigment refers to the diameter when the observation image by a transmission electron microscope (TEM) is a circle of the same area.

--metal particles-- From the viewpoint of high reflectivity, the type of metal contained in the metal particles is preferably silver, nickel, cobalt, iron, copper, palladium, gold, platinum, tin, zinc, aluminum, tungsten or titanium, and silver , gold, tin, nickel, aluminum or cobalt are more preferred. From the viewpoint of exhibiting higher reflectivity in the visible light region, gold, silver or aluminum is further preferred, and silver is particularly preferred. The metal particles may be metal single particles or metal alloy particles. In addition, when the metal particles are metal alloy particles, the metal alloy particles are preferably two or more types of alloy particles among the above-mentioned metal types.

The shape of the metal particles is not particularly limited, and examples thereof include spherical, amorphous, plate-shaped, needle-shaped, polyhedron, and the like. The average primary particle diameter of the metal particles is not particularly limited, but for example, 1 to 5000 nm is preferred, and 5 to 1000 nm is more preferred. In addition, the average primary particle diameter of metal particles is a value obtained by measuring the diameters of 100 arbitrary particles through observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. In addition, the diameter of a metal particle refers to the diameter when the observation image by a transmission electron microscope (TEM) is a circle of the same area. Metal particles can be produced by methods such as reduction of organic metal compounds, as disclosed in Japanese Patent Application Laid-Open No. 10-183207.

--Hollow Particles-- The hollow particles are not particularly limited as long as they have a cavity inside. Examples thereof include hollow inorganic particles and hollow resin particles. As the hollow inorganic particles, for example, it is preferable that the shell portion of the hollow inorganic particles is made of a metal oxide selected from the group consisting of silica, alumina, zirconium oxide, titanium oxide, and composite oxides thereof. Examples of hollow resin particles include styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride resins, vinylidene chloride resins, amide resins, and urethane resins. Resins, polymers such as phenolic resins, styrene-conjugated diene resins, acrylic-conjugated diene resins, and olefin resins, and organic substances such as crosslinked products of these polymers constitute the hollow resin particles in the shell. . The hollow particles may also be subjected to physical surface treatment such as plasma discharge treatment and corona discharge treatment, or chemical surface treatment based on surfactants, coupling agents, and the like.

The shape of the hollow particles is not particularly limited, and examples thereof include spherical, crushed, fibrous, needle-shaped, and scale-shaped. The average primary particle size of the hollow particles is not particularly limited, but for example, 50 to 5000 nm is preferred, and 100 to 1000 nm is more preferred. In addition, the average primary particle diameter of hollow particles is a value obtained by measuring the diameters of 100 arbitrary particles through observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. In addition, the diameter of a hollow particle refers to the diameter when the observation image by a transmission electron microscope (TEM) is a circle of the same area.

--Liquid crystal compounds-- Examples of the liquid crystal compound include compounds having liquid crystallinity. In addition, the liquid crystal compound may also be fixed in a predetermined alignment state. That is, the photosensitive layer may contain a polymer obtained by polymerizing an aligned polymerizable liquid crystal compound. In the above polymer, the alignment state is fixed. As the liquid crystal compound, a polymer obtained by polymerizing a polymerizable liquid crystal compound with a cholesteric liquid crystal alignment (in other words, a polymer in which the cholesteric liquid crystal alignment is fixed) is preferred from the viewpoint of more excellent reflectivity. By using a cholesteric liquid crystal composition containing a nematic liquid crystal compound and a chiral agent, and hardening the liquid crystal composition in a state of exhibiting a cholesteric liquid crystal phase, a polymer in which the alignment of the cholesteric liquid crystal is fixed is obtained. The polymer in which the alignment of cholesteric liquid crystal is fixed usually has a circularly polarized light selective reflection function that selectively reflects circularly polarized light. Moreover, it is preferable that the polymer which fixes the alignment of cholesteric liquid crystal is contained in the photosensitive layer in the form of liquid crystal particles. In other words, the photosensitive layer preferably contains liquid crystal particles including a polymer in which the alignment of cholesteric liquid crystal is fixed. The shape of the liquid crystal particles is not particularly limited, but from the viewpoint of better dispersibility, flakes are preferred. The average primary particle size of the flakes is, for example, preferably 1 to 120 μm, more preferably 1 to 100 μm. In addition, the average primary particle diameter of liquid crystal particles is a value obtained by measuring the diameters of 100 arbitrary particles through observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. In addition, the diameter of a liquid crystal particle refers to the diameter when the observation image by a transmission electron microscope (TEM) is a circle of the same area.

Examples of commercially available liquid crystal particles include "HELICONE HC Sapphire", "HELICONE HC Aquarius", "HELICONE HC Scarabeus", "HELICONE HC Jade", and "HELICONE HC Maple" (all manufactured by Wacker Asahikasei Silicone Co., Ltd.).

When the photosensitive layer includes a reflective modifier, the content of the reflective modifier is preferably 10 to 90 mass %, more preferably 20 to 85 mass %, and further preferably 30 to 80 mass % relative to the total mass of the photosensitive layer. In particular, when the reflective modifier includes a white pigment, the content of the white pigment is preferably 30 to 80 mass %, and more preferably 40 to 70 mass %, relative to the total mass of the photosensitive layer. Furthermore, when the reflective modifier includes metal particles, the content of the metal particles is preferably 20 to 95 mass %, and more preferably 30 to 90 mass %, relative to the total mass of the photosensitive layer. Furthermore, when the reflectivity modifier contains hollow particles, the content of the hollow particles is preferably 20 to 80 mass % relative to the total mass of the photosensitive layer, and 30 to 70 mass % is more preferably. Furthermore, when the reflectivity modifier contains liquid crystal compounds (preferably liquid crystal particles), the content of the liquid crystal compounds (preferably liquid crystal particles) is preferably 10 to 90 mass % relative to the total mass of the photosensitive layer, and 20 to 80 mass % is more preferably, and 30 to 70 mass % is further preferably.

-Light absorbing substance- It is also preferable that the photosensitive layer contains a light absorbing substance. When the photosensitive layer contains a light absorbing substance, a light absorbing layer precursor layer can be formed. When the photosensitive layer contains a light-absorbing material, the external light reflectivity of the resin pattern of the laminate formed according to the first embodiment of the present invention is reduced, and/or stray light that may be generated when the light-emitting element is lit is easily absorbed. As a result, black fastening is more excellent when the light-emitting element is not lit. In addition, when the photosensitive layer contains a light-absorbing substance, a light-absorbing layer having characteristics Y1 and/or Y2 described below can be easily obtained.

The light absorbing material is not particularly limited, and examples thereof include black pigments, and specifically, carbon black, titanium black, titanium carbon, iron oxide, titanium oxide, and graphite, among which carbon black is more preferred.

When the light-absorbing substance is a black pigment, its shape is not particularly limited, and examples thereof include spherical, amorphous, plate-like, needle-like, and polyhedral. The average primary particle size of the light-absorbing substance is not particularly limited, and for example, 1 to 1000 nm is preferred, and 2 to 500 nm is more preferred. In addition, the average primary particle size of the light-absorbing substance is the value obtained by measuring the diameter of any 100 particles by observation using a transmission electron microscope (TEM) and calculating the arithmetic average of the 100 diameters. In addition, the diameter of the light-absorbing substance refers to the diameter when the observation image based on the transmission electron microscope (TEM) is set to a circle of the same area. Light-absorbing materials can also undergo physical surface treatments such as plasma discharge treatment and corona discharge treatment, or chemical surface treatments based on surfactants, coupling agents, and resins.

In addition to the black dye, examples of the light-absorbing substance include compounds that turn black by exposure, heating, or the like. Examples of compounds that turn black by exposure, heating, or the like include the following compound (1).

[Chemical formula 21]

When the photosensitive layer contains a light absorbing substance, the content of the light absorbing substance is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, further preferably 10 to 60 mass %, and particularly preferably 10 to 50 mass % relative to the total mass of the photosensitive layer.

The thickness of the photosensitive layer is, for example, preferably 1 μm or more, and more preferably 2 μm or more. The upper limit is not particularly limited, but for example, 100 μm or less is preferred, and 50 μm or less is more preferred.

(Preferred embodiments of a light-reflecting layer front-driver layer and a light-absorbing layer front-driver layer) As described above, when the photosensitive layer includes a reflective modifier, it can be set as a light-reflecting layer front-driver layer, and when the photosensitive layer includes a light-absorbing substance, it can be set as a light-absorbing layer front-driver layer. The following describes the preferred embodiments of the light-absorbing layer front-driver layer and the light-absorbing layer front-driver layer.

･Light reflective layer precursor layer ･･Thickness of light reflective layer precursor layer The thickness of the light reflective layer precursor layer is preferably 3 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and particularly preferably 16 μm or more. The upper limit is not particularly limited, but for example, 100 μm or less is preferred, and 50 μm or less is more preferred.

･･Characteristics of the light reflective layer formed from the light reflective layer precursor layer The light reflective layer formed from the light reflective layer precursor layer is preferably a layer that satisfies at least one of the following characteristics X1, X2, and X3. In particular, when the light-emitting element is a visible light LED, the light reflection layer is preferably a layer that satisfies at least one of the characteristics X1 and X2. When the LED in the light-emitting element is a UV-LED, as the light reflection layer As for the reflective layer, the layer that satisfies characteristic X3 is preferred. ^{" Characteristics ​ ​} For better. In addition, the L ^* value in the above-mentioned CIE 1976 (L ^* , a ^* , b ^* ) color space is a value measured using a spectrophotometer at 25°C on a light reflective layer with a thickness of 30 μm. As a spectrophotometer, for example, spectrophotometer V-570 manufactured by JASCO Corporation can be used. As the above-mentioned L ^* value, 90 or more is more preferable. The upper limit is 100 or less. <Characteristics The upper limit is 100% or less. In addition, the total reflectance at a wavelength of 550 nm is a value measured using a spectrophotometer at 25° C. on a light reflective layer with a thickness of 30 μm. As a spectrophotometer, for example, spectrophotometer V-570 manufactured by JASCO Corporation can be used. <Characteristics The upper limit is 100% or less. The total reflectance at a wavelength of 385 nm is measured using a spectrophotometer at 25°C on a light reflective layer with a thickness of 30 μm. As a spectrophotometer, for example, spectrophotometer V-570 manufactured by JASCO Corporation can be used.

･Light absorbing layer precursor layer ･･Thickness of light absorption layer precursor layer The thickness of the light absorbing layer precursor layer is preferably 1 μm or more, and more preferably 2 μm or more. The upper limit is not particularly limited, but for example, 10 μm or less is preferred, and 5 μm or less is more preferred. ･･Optical concentration of light absorption layer precursor layer The optical density (OD) of the light absorbing layer precursor layer at a wavelength of 550 nm is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and particularly preferably 3.0 or more. The upper limit is not particularly limited, but for example, 6.0 or less is preferred. The optical concentration of the light-absorbing layer precursor layer can be measured with a Macbeth concentration meter (TD-904, manufactured by Macbeth Corporation, using a visible filter) or the like. The optical density (OD) of the light absorbing layer precursor layer at a wavelength of 385 nm is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and particularly preferably 3.0 or more. The upper limit is not particularly limited, but for example, 6.0 or less is preferred. The optical concentration of the light-absorbing layer precursor layer at a wavelength of 385 nm can be measured with an ultraviolet spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) or the like.

･･Characteristics of the light-absorbing layer formed from the light-absorbing layer precursor layer It is preferable that the light absorbing layer formed from the light absorbing layer precursor layer satisfies the characteristics Y1 and/or the characteristics Y2. In particular, when the light-emitting element is a visible light LED, as the light-absorbing layer, a layer that satisfies the characteristic Y1 is preferable from the viewpoint of better anti-reflection of external light. When the light-emitting element is a UV-LED , as the light-absorbing layer, a layer that satisfies the characteristic Y2 is preferable from the viewpoint of better anti-reflection of external light and better suppression of stray light.

《Characteristic Y1》 As the optical density (OD) of the light absorbing layer at a wavelength of 550nm, 0.5 or more is preferred, 1.0 or more is more preferred, 2.0 or more is further preferred, and 3.0 or more is particularly preferred. As the upper limit value, there is no particular restriction, for example, 6.0 or less is preferred. The optical density of the light absorbing layer can be measured by a Macbeth density meter (manufactured by Macbeth, TD-904, using a visible filter). 《Characteristic Y2》 As the optical density (OD) of the light absorbing layer at a wavelength of 385nm, 0.5 or more is preferred, 1.0 or more is more preferred, 2.0 or more is further preferred, and 3.0 or more is particularly preferred. As the upper limit value, there is no particular restriction, for example, 6.0 or less is preferred. The optical concentration of the light absorbing layer at a wavelength of 385 nm can be measured by a UV spectrophotometer such as U-3310 (manufactured by Hitachi, Ltd.).

《Positive photosensitive layer》 The following describes the positive photosensitive layer in detail. As the photosensitive layer, a photosensitive layer including at least a polymer and a photoacid generator can be cited. As the above-mentioned polymer, a polymer including a repeating unit having a group whose hydrophilicity is increased by the action of an acid (for example, an acid-decomposable group formed by a polar group being protected by a dissociative group that is dissociated by the action of an acid, etc.) is preferred. As the photosensitive layer, a known positive photosensitive layer can be applied. In addition, the photosensitive layer can also be a photosensitive light reflecting layer and a photosensitive light absorbing layer. When the photosensitive layer is a photosensitive light reflective layer, the photosensitive layer includes a reflective adjuster, and when the photosensitive layer is a photosensitive light absorbing layer, the photosensitive layer includes a light absorbing substance. The types of the reflective adjuster and the light absorbing substance, and the contents of the reflective adjuster and the light absorbing substance relative to the total mass of the photosensitive layer are the same as those in the negative photosensitive layer, and the preferred range is also the same.

The thickness of the photosensitive layer is, for example, preferably 1 μm or more, and more preferably 2 μm or more. The upper limit is not particularly limited, but for example, 100 μm or less is preferred, and 50 μm or less is more preferred.

(Preferred forms of photosensitive light reflecting layer and photosensitive light absorbing layer) The following describes the preferred forms of the photosensitive light reflecting layer and the photosensitive light absorbing layer.

･Photosensitive light reflective layer ･･Thickness of photosensitive light reflective layer The thickness of the photosensitive light reflective layer is preferably 3 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and particularly preferably 16 μm or more. The upper limit is not particularly limited, but for example, 100 μm or less is preferred, and 50 μm or less is more preferred.

･･Characteristics of photosensitive light reflective layer The photosensitive light reflective layer is preferably a layer that satisfies at least one of the above characteristics X1, X2, and X3. In particular, when the light-emitting element is a visible light LED, the photosensitive light reflective layer is preferably a layer that satisfies at least one of the characteristics X1 and X2. When the LED in the light-emitting element is a UV-LED. , as a photosensitive light-reflecting layer, a layer satisfying characteristic X3 is preferred.

･Photosensitive light-absorbing layer ･･Thickness of photosensitive light-absorbing layer The thickness of the photosensitive light-absorbing layer is preferably 1 μm or more, and more preferably 2 μm or more. The upper limit is not particularly limited, but for example, 10 μm or less is preferred, and 5 μm or less is more preferred.

･･Characteristics of photosensitive light-absorbing layer The photosensitive light-absorbing layer preferably satisfies the above-mentioned characteristics Y1 and/or characteristics Y2. In particular, when the light-emitting element is a visible light LED, as a photosensitive light-absorbing layer, a layer that satisfies the characteristic Y1 is preferable from the viewpoint of better anti-reflection of external light. When the light-emitting element is a UV-LED In this case, as a photosensitive light-absorbing layer, a layer that satisfies the characteristic Y2 is preferable from the viewpoint of better anti-reflection of external light and better suppression of stray light.

＜＜Protective film＞＞ The transfer film may have a protective film. As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, and polycarbonate films. and polystyrene film. In addition, as the protective film, a resin film made of the same material as the temporary support can be used. Among them, as the protective film, a polyolefin film is preferred, a polypropylene film or a polyethylene film is more preferred, and a polyethylene film is further preferred.

The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film can be calculated by averaging five arbitrary points measured based on cross-sectional observation with a SEM (Scanning Electron Microscope). From the viewpoint of excellent mechanical strength, the thickness of the protective film is preferably 1 μm or more, and from the viewpoint of relatively low cost, the thickness of the protective film is preferably 100 μm or less.

Furthermore, in the protective film, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is preferably 5/ ^m2 or less. In addition, "fisheye" refers to foreign matter, undissolved matter, and oxidative degradation products of the material that are taken into the film when the material is heated and melted and the film is manufactured by methods such as kneading, extrusion, biaxial stretching, and casting.

The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, and still more preferably 5 particles/mm ² or less. This can suppress defects caused by the transfer of irregularities caused by particles contained in the protective film to the photosensitive layer.

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

[Second embodiment] The second embodiment of the method for manufacturing a laminate of the present invention (hereinafter also referred to as "the second embodiment of the present invention") comprises the following steps (2-1) to (2-4).

･Step (2-1) (bonding step): a step of bonding the substrate with light-emitting elements and the transfer film in such a manner that the surface of the substrate with light-emitting elements on the light-emitting element side of the substrate including a substrate and a plurality of light-emitting elements arranged on the substrate faces the surface of the transfer film including a temporary support and a photosensitive layer on the side opposite to the temporary support and the light-emitting elements are covered by the photosensitive layer ･Step (2-2) (exposure step): a step of pattern-exposing the photosensitive layer ･Step (2-3) (development step): a step of developing the exposed photosensitive layer to form a resin pattern having an opening at a position corresponding to the light-emitting element ･Step (2-4) (light-reflecting film forming step): a step of configuring a light-reflecting film on the side wall of the above-mentioned opening In addition, the second embodiment of the present invention has the following step (2-A) between step (2-1) and step (2-2) or step (2-2) and step (2-3). ･Step (2-A) (temporary support body peeling step): a step of peeling off the temporary support body.

<Steps (2-1) to (2-3), (2-A) to (2-C)> Steps (2-1) to (2-3) and (2-A) in the second embodiment of the present invention are the same as those described as steps (1-1) to (1-3) and (1-A) in the first embodiment of the present invention, respectively. In addition, in the second embodiment of the present invention, after implementing step (2-3) (development step), there may be a step of further exposing the formed resin pattern (hereinafter, also referred to as "step (2-B)" or "post-exposure step") and/or a step of heating (hereinafter, also referred to as "step (2-C)" or "post-baking step"). Steps (2-B) and (2-C) in the second embodiment of the present invention are the same as those described as steps (1-B) and (1-C) in the first embodiment of the present invention, respectively.

<Step (2-4) Light reflective film formation step> The second embodiment of the present invention is that after the development step (step (2-3)) (in addition, when the above-mentioned step (2-B) and/or step (2-C) is performed, after the step (2-3)), After), a step of forming a light reflective film on the side wall of the opening in the resin pattern formed on the substrate with the light-emitting element. In the resin pattern that functions as a partition layer that separates light-emitting elements from each other, when the light-reflecting film is disposed on the side wall of the opening, the light from the light-emitting elements is reflected by the light-reflecting film, so the brightness is more excellent. FIG. 6 shows a schematic cross-sectional view of the laminated body formed through the light reflective film forming step (step (2-4)). The laminated body 60 is composed of the substrate 10 with the light-emitting element, the resin pattern 42 , and the light reflective film 62 arranged on the side wall of the opening 43 in the resin pattern 42 .

The light reflective film preferably contains metal. The type of metal is not particularly limited. From the viewpoint of high reflectivity, silver, nickel, cobalt, iron, copper, palladium, gold, platinum, tin, zinc, aluminum, tungsten or titanium are preferred. Silver , gold, tin, nickel, aluminum or cobalt are more preferred. From the viewpoint of exhibiting higher reflectivity in the visible light region, gold, silver or aluminum is further preferred, and silver is particularly preferred.

The light reflective film forming step (step (2-4)) can be formed by sputtering, evaporation, electroplating, printing of ink containing metal particles (screen printing, inkjet, etc.), etc. Alternatively, the light reflective film can be formed by patterning in a manner that leaves only necessary areas by known methods such as wet etching and dry etching.

The film thickness of the light reflective film is preferably 10 nm or more, more preferably 50 nm or more, and still more preferably 250 nm or more. The upper limit is not particularly limited, but for example, 100 μm or less is preferred, 50 μm or less is more preferred, 10 μm or less is further preferred, 1 μm or less is particularly preferred, and 800 nm or less is optimal.

The light reflective film is preferably a film that satisfies at least one of the following characteristics Z1 and Z2. When the light-emitting element is a visible light LED, the light reflective film preferably satisfies characteristic Z1, and when the light-emitting element is a UV-LED, the light reflective film preferably satisfies characteristic Z2. (Characteristic Z1) The total reflectivity of the light reflective film at a wavelength of 550nm is preferably 60% or more, and more preferably 80% or more. The upper limit is 100% or less. The total reflectivity at a wavelength of 550nm is a value measured at 25°C using a spectrophotometer for a light reflective film with a thickness of 30μm. As a spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used. (Characteristic Z2) The total reflectance of the light reflective film at a wavelength of 385 nm is preferably 60% or more, and more preferably 80% or more. The upper limit is 100% or less. The total reflectance of the light reflective film at a wavelength of 385 nm is a value measured at 25°C using a spectrophotometer for a light reflective film with a thickness of 30 μm. As a spectrophotometer, for example, a spectrophotometer V-570 manufactured by JASCO Corporation can be used.

As the transfer film that can be used in the second embodiment of the present invention, for example, various transfer films shown as the transfer films that can be used in the first embodiment of the present invention can be used. An example of a preferred aspect of the transfer film that can be used in the second embodiment of the present invention is shown below. Hereinafter, the light reflective layer precursor layer, the light absorbing layer precursor layer, the protective film, and the temporary support and the light reflecting layer precursor layer and the light absorbing layer precursor in the transfer film that can be used in the first embodiment of the present invention are described. The physical layer, protective film and temporary support have the same meaning, and the preferred aspects are also the same. Other photosensitive layers refer to photosensitive layers that do not belong to any of the light reflective layer precursor layer and the light absorbing layer precursor layer. ･(N4) Temporary support/light absorbing layer precursor layer/protective film ･(N5) Temporary support/light absorbing layer precursor layer/other photosensitive layers/protective film

In addition, when the transfer film (N5) is used in the second embodiment of the present invention, it is only necessary to arrange it at least at a position corresponding to the resin layer from the other photosensitive layer in the side wall of the opening of the resin pattern. Light reflective film is enough. [Example]

The present invention is described in more detail below based on the embodiments. The materials, usage amounts, ratios, processing contents and processing sequences shown in the following embodiments can be appropriately changed as long as they do not deviate from the main purpose of the present invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below. In addition, unless otherwise specified, the following "parts" and "%" are based on mass.

[Preparation of a composition for forming a light absorbing layer precursor layer] A composition for forming a light absorbing layer precursor layer (A-1 to A-2) was prepared according to the components and blending amounts shown in Table 1. In addition, the blending amount of each component shown in Table 1 is expressed in parts by mass.

[Table 1] Table 1: Composition of the light absorbing layer precursor layer Ingredients Composition A-1 (blending amount: parts by mass) Composition A-2 (blending amount: parts by mass) Black foreshadow Compound (1) 16.00 5.26 Alkaline soluble resin Polymer P-1 solution (solid content = 40.5 mass %) 33.7 44.4 Polymeric compounds 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) 6.87 6.87 Dipentatriol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 3.21 3.21 ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.) 1.54 1.54 Polymerization initiator 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.87 1.87 Sensitizer SB-PI 701 (manufactured by Sanyo Trading Co., Ltd.) 0.016 0.016 Chain transfer agent N-Phenylaminomethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation) 0.19 0.19 Polymerization inhibitor TDP-G (manufactured by Kawaguchi Chemical Industry Company, Limited) 0.09 0.09 Additives MEGAFACE F-551A (manufactured by DIC Corporation) 0.31 0.31 Solvent Propylene glycol monomethyl ether acetate 11.6 11.6 Methyl Ethyl Ketone 24.6 24.6

Details of other abbreviations and product names in Table 1 are shown below. "Compound (1)": a compound with the following structure. In addition, compound (1) corresponds to a compound that changes from transparent to black by heat treatment.

[Chemical formula 22]

"Polymer P-1 solution": Polymer P-1 [copolymer of benzyl methacrylate/methacrylic acid, composition ratio of the copolymer (mass basis) = 70/30, weight average molecular weight (Mw) = 5000 〕 PGMEA solution (solid content: 40.5 mass%). "ARONIX TO-2349": Carboxyl group-containing monomer (manufactured by TOAGOSEI CO., LTD.) · “SB-PI 701”: 4,4’-bis(diethylamino)benzophenone (manufactured by Sanyo Trading Co., Ltd.) "TDP-G": TDP-G (manufactured by Kawaguchi Chemical Industry Company, Limited) "MEGAFACE F551A": Fluorine-based surfactant (manufactured by DIC Corporation)

[Preparation of the composition (B-1) and the photosensitive composition (B-2) for forming the light reflective layer precursor layer] Based on the components and blending amounts shown in Table 2, the composition (B-1) for forming the light reflective layer precursor layer and the photosensitive composition (B-2) were prepared. In addition, the unit of the blending amount of each component shown in Table 2 is parts by mass.

[Table 2] Table 2: Light reflective layer front driver layer composition (B-1), other photosensitive composition (B-2) Ingredients Composition B-1 (blending amount: parts by mass) Composition B-2 (blending amount: parts by mass) White pigment dispersion White dispersion (Pigment concentration: rutile titanium oxide, pigment concentration 30 mass%, manufactured by Tokyo Printing Ink Mfg. Co., Ltd.) 51.9 - Alkaline soluble resin Polymer P-2 solution (solid content: 36.2 mass %) 19.80 43.30 Polymeric compounds A-NOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.05 6.68 A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.43 3.12 ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.) 0.54 1.20 Polymerization initiator B-CIM (manufactured by Hampford) 0.83 1.82 Sensitizer SB-PI 701 (manufactured by Sanyo Trading Co., Ltd.) 0.01 0.01 Chain transfer agent N-Phenylaminomethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation) 0.16 0.16 Polymerization inhibitor TDP-G (manufactured by Kawaguchi Chemical Industry Company, Limited) 0.08 0.08 Additives CBT-1 (manufactured by Johoku Chemical Co., Ltd.) 0.03 0.03 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 0.01 0.01 MEGAFACE F-551A (manufactured by DIC Corporation) 0.26 0.26 Solvent Propylene glycol monomethyl ether acetate 5.89 27.33 Methyl Ethyl Ketone 16.00 16.00

[Preparation method of P-2 solution (solid content of polymer P-2 36.2 mass % solution)] The P-2 solution (solid content of polymer P-2 36.2 mass % solution) was prepared by the polymerization step and addition step shown below. 113.5 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen flow. 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 Corporation) in 57.7 g of propylene glycol monomethyl ether were simultaneously added dropwise to the solution over 3 hours. After the addition was completed, 2.5 g of V-601 was added three times at intervals of 1 hour. Then, it was allowed to react for a further 3 hours. Then, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. Under air flow, the reaction solution was heated to 100°C, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (Brenmar G manufactured by NOF CORPORATION) was added dropwise over 20 minutes. After the addition, the reaction solution was reacted at 100°C for 7 hours to obtain a solution of resin P-2. The solid content concentration of the obtained solution was 36.2% by mass. The weight average molecular weight converted to standard polystyrene in GPC was 18,000, the number average molecular weight was 7,800, the dispersity was 2.3, and the acid value of the polymer was 124 mgKOH/g. The amount of residual monomers measured by gas chromatography was less than 0.1 mass % relative to the polymer solid content in any monomer. The structure of polymer P-2 is shown below.

Polymer P-2: The composition of the constituent units in the following structural formula represents the molar ratio. In addition, polymer P-2 is equivalent to an alkali-soluble resin.

[Chemical formula 23]

The details of the abbreviations and product names of other components in Table 2 are shown below. "A-NOD-N": 1,9-nonanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "A-DPH": dipenterythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) "ARONIX TO-2349": Carboxyl group-containing monomer (manufactured by TOAGOSEI CO., LTD.) “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": TDP-G (manufactured by Kawaguchi Chemical Industry Company, Limited) "CBT-1": Carboxybenzotriazole (manufactured by Johoku Chemical Co., Ltd.) "MEGAFACE F551A": Fluorine-based surfactant (manufactured by DIC Corporation)

[Example 1] 〔Preparation of transfer film〕 As a temporary support, a polyethylene terephthalate film (Lumirror 16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16 μm) was prepared. On the temporary support, the light absorbing layer pre-driver layer forming composition A-1 was applied in a manner that the thickness after drying was 3 μm, and dried at 100°C for 1 minute, thereby forming a light absorbing layer pre-driver layer. On the light absorbing layer pre-driver layer, the light reflecting layer pre-driver layer forming composition B-1 was applied in a manner that the thickness after drying was 30 μm, and dried at 100°C for 3 minutes, thereby forming a light reflecting layer pre-driver layer. A polyethylene terephthalate film (Lumirror 16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16μm) was pressed onto the light-reflecting layer front-driver layer. By the above sequence, a transfer film 1 including a temporary support, a light-absorbing layer front-driver layer, a light-reflecting layer front-driver layer and a protective film was obtained in sequence.

[Production of micro LED display element] A micro LED display element was produced using the transfer film 1 in the following procedure. Specifically, after the LED chip was bonded to the bonding member on the array substrate, a resin pattern (partition layer) was formed using the transfer film 1. The specific procedure is shown below.

[[Installation of LED chips]] First, according to the method described in Japanese Patent Application Laid-Open No. 2021-163945 (Special Claims, Paragraphs 0013 to 0041), 200 LED chips on the peeling sapphire substrate were jointly bonded to the array substrate, and the peeling sapphire substrate was peeled off .

[[Formation of resin pattern (next wall layer)]] Next, the protective film of the transfer film 1 was peeled off, and the transfer film 1 was attached to the array substrate with the LED chip under the lamination conditions shown below, and a substrate with a pre-driver layer was prepared by laminating a light-reflecting layer pre-driver layer, a light-absorbing layer pre-driver layer and a temporary support body in sequence on the substrate with light-emitting elements (substrate with chip). Heating temperature of substrate with chip: 40°C Temperature of rubber roller: 110°C Line pressure: 3N/cm Transport speed: 2m/min

The distance between the surface of the exposure mask (a mask having an opening forming pattern) and the surface of the temporary support was set to 125 μm. Using a proximity exposure machine (Hitachi High-Tech Corporation) equipped with an ultra-high-pressure mercury lamp, the light-reflecting layer precursor layer and the light-absorbing layer precursor layer were irradiated in a pattern with an exposure dose of 100 mJ/cm ² through the temporary support. The i-ray. At this time, the pattern and position of the exposure mask are adjusted so that the taper angle (refer to the taper angle θ in Figure 3) of the partition layer formed in the portion where the LED chip is mounted becomes the angle shown in Table 3. The opening is formed. After the temporary support was peeled off after the exposure process, the exposed light reflective layer precursor layer and the light absorbing layer precursor layer were developed for 60 seconds using a 1 mass % sodium carbonate aqueous solution at a temperature of 32°C. Next, ultrapure water is sprayed from an ultrahigh-pressure washing nozzle to the laminated body obtained after the development process to remove residues, and then air is further blown to remove moisture. Next, the pattern in the obtained laminated body was subjected to exposure processing (post-exposure) at an exposure dose of 1000 mJ/cm ² (i-ray) using a post-exposure machine (manufactured by USHIO INC.) with a high-pressure mercury lamp. After exposure, a post-baking process was performed at 210° C. for 5 minutes. According to the above procedure, a resin pattern (a barrier layer layer in which a light reflection layer and a light absorption layer are stacked in this order) having an opening at the position of the LED chip is formed on the array substrate.

In this way, a micro LED display element was manufactured.

[Example 2] 〔Preparation of transfer film of Example〕 As a temporary support, a polyethylene terephthalate film (Lumirror 16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16μm) was prepared. On the temporary support, the light absorbing layer precursor layer forming composition A-1 was applied in a manner to have a thickness of 3μm after drying, and dried at 100°C for 1 minute to form a light absorbing layer precursor layer. On the light absorbing layer precursor layer, the photosensitive layer forming composition B-2 was applied in a manner to have a thickness of 30μm after drying, and dried at 100°C for 3 minutes to form a photosensitive layer (other photosensitive layer). A polyethylene terephthalate film (Lumirror 16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16μm) was pressed onto the photosensitive layer. Through the above sequence, a transfer film 2 including a temporary support, a light absorbing layer precursor layer, a photosensitive layer and a protective film was obtained in sequence.

[Preparation of micro LED display element of Example 2] First, LED chips were mounted on the array substrate in the same manner as [[Mounting of LED chips]] of Example 1. Then, the process conditions were appropriately adjusted so as to obtain the tapered angle of the partition layer shown in Table 3. In addition, a resin pattern having an opening (a partition layer formed by stacking a resin layer and a light absorbing layer in this order) was formed on the array substrate on which the LED chips were mounted in accordance with the same sequence as [[Formation of resin pattern (partition layer)]] in Example 1 above. After the partition was prepared, a 300nm silver layer was evaporated on the opening of the partition by a known evaporation method. At this time, by shielding the position of the surface on the chip and the side opposite to the substrate side corresponding to the partition layer, a light reflection layer is formed only on the side of the opening of the partition layer. In this way, the micro LED display element of Example 2 is manufactured.

[Example 3] A-2 was used as the light absorbing layer front-driver layer composition and coated in a manner such that the thickness after drying was 30 μm, and a structure in which the light reflecting layer front-driver layer was not laminated was adopted. Transfer film 3 was obtained in the same manner as in Example 1 except that the structure was such that the light reflecting layer front-driver layer was not laminated.

[Production of micro-LED display element of Example 3] First, the LED chip was mounted on the array substrate in the same manner as [Mounting of LED Chip] in Example 1. Next, the process conditions were appropriately adjusted so as to obtain the taper angle of the partition wall layer shown in Table 3. The same procedure as [Formation of the Resin Pattern (Partition Wall Layer)] in Example 1 was followed. A resin pattern (light absorbing layer) having openings is formed on the array substrate with the chip.

[Preparation of micro LED display element of comparative example 1] The micro LED display element of comparative example 1 was prepared in the same manner as in Example 1 except that the partition layer was not formed.

As mentioned above, in each micro-LED component produced, the size of the LED chip is 20 μm square and the thickness is 8 μm. In addition, the pitch between the LED chips was 400 μm, the through hole size was 30 μm square, and the partition width between the LED chips was 370 μm.

(Evaluation of light bleeding from adjacent pixels) Using the micro-LED display element fabricated as described above, the light bleeding of adjacent pixels was evaluated. Using a micro-UV-visible-near-infrared spectrophotometer MSV-5500 (manufactured by JASCO Corporation), the light intensity at 530 nm was measured at the position of an adjacent pixel when a green pixel with an emission center wavelength of 530 nm emitted light. At this time, the 530 nm light intensity of adjacent pixels when the 530 nm light intensity in the light emitting pixel was set to 100% was evaluated based on the following criteria. (Evaluation criteria) "A": Light intensity in adjacent pixels is less than 0.1% "B": The light intensity in adjacent pixels is more than 0.1% and less than 1% "C": The light intensity in adjacent pixels is more than 1%

The evaluation results of each embodiment are shown in Table 3.

[table 3] table 3 Method for manufacturing a laminate Transfer film structure Taper angle of the adjacent wall (manufacturing conditions of micro-LED display components) Is there silver deposition on the adjacent tapered part? Evaluation of light leakage from neighboring pixels Light absorbing layer precursor layer Light reflecting layer before driving material layer Other photosensitive layers Type of composition thickness Type of composition thickness Type of composition thickness Embodiment 1 Formed resin pattern (next layer) A-1 3μm B-1 30μm - - 60° without A Embodiment 2 Formed resin pattern (next layer) A-1 3μm - - B-2 30μm 60° have A Embodiment 3 Formed resin pattern (next layer) A-2 30μm - - - - 90° without A Comparison Example 1 No resin pattern (partition layer) is formed (light-emitting element only) - - - - - - - - C

It can be seen from the results in Table 3 that the laminated body including the plurality of light-emitting elements obtained by the method of manufacturing the laminated body of the Example suppresses light leakage from adjacent light-emitting elements. On the other hand, it was found that a laminate including a plurality of light-emitting elements obtained by the method of manufacturing a laminate of Comparative Example 1 does not achieve the above-mentioned effect. Moreover, it was confirmed that the laminated body obtained by the manufacturing method of the laminated body of Examples 1 and 2 can perform the display of higher brightness when a light-emitting element is turned on, compared with Example 1 and Comparative Example 1.

[Production of micro LED display element in Comparative Example 2] After forming a partition wall structure in advance using transfer film 1 on the array substrate before connecting the LED chip, the LED chip was mounted on the substrate, thereby producing a micro LED display element. At this time, since the array substrate has a partition wall structure with a thickness of 33 μm, it is difficult to mount a plurality of micro LED chips on the array substrate together as in [[Mounting of LED chip]] of Example 1, so the micro LED display element was produced by repeatedly bonding the LED chips one by one to the connection part and peeling them off from the peeling sapphire substrate. As a result, in Comparative Example 2, it took more than 100 times as long to produce the micro LED display element as compared with any of Examples 1 to 3.

10: Substrate with light-emitting element 12: Substrate 12A: Substrate surface T1: Height of light-emitting element 14: Light-emitting element 20, 20A, 20B: Transfer film 22: Temporary support 24: Photosensitive layer 26: Light-absorbing layer front-driver layer 28: Light-reflecting layer front-driver layer 30: Mask 40, 60: Laminated body 42: Resin pattern 44: Opening 50: Protective film 62: Light-reflecting film θ: Taper angle

Figure 1 is a schematic diagram for explaining step (1-1). Figure 2 is a schematic diagram for explaining step (1-2). Figure 3 is a schematic diagram for explaining step (1-3). FIG. 4 is a schematic diagram for explaining the structure of the transfer film. FIG. 5 is a schematic diagram for explaining the structure of the transfer film. Figure 6 is a schematic diagram for explaining step (2-4).

10: Substrate with light-emitting element

12:Substrate

12A: Substrate surface

14:Light-emitting components

T1: Thickness of light-emitting element

20:Transfer film

22: Temporary support body

24: Photosensitive layer

Claims (11)

A method for manufacturing a laminated body, which has: A surface of a light-emitting element side of a substrate with a light-emitting element including a substrate and a plurality of light-emitting elements arranged on the substrate, and a transfer film including a temporary support and a photosensitive layer opposite to the temporary support Step 1 of laminating the substrate with the light-emitting element and the transfer film in such a manner that the surfaces of the two sides face each other and the light-emitting element is covered by the photosensitive layer; Step 2 of performing pattern exposure on the aforementioned photosensitive layer; and Step 3 of developing the aforementioned photosensitive layer after exposure to form a resin pattern having openings at positions corresponding to the aforementioned light-emitting elements, There is a step of peeling off the temporary support between the aforementioned step 1 and the aforementioned step 2 or between the aforementioned step 2 and the aforementioned step 3. A method for manufacturing a laminate as described in claim 1, wherein the thickness of the photosensitive layer in the transfer film is greater than the height of the light-emitting element. A method for manufacturing a laminate as described in claim 1 or claim 2, wherein the photosensitive layer in the transfer film comprises an alkali-soluble resin, a polymerizable compound and a photopolymerization initiator. A method for manufacturing a laminate as described in claim 1 or claim 2, wherein the photosensitive layer in the transfer film comprises a polymer and a photoacid generator. The manufacturing method of the laminated body according to Claim 1 or Claim 2, wherein The content of water in the photosensitive layer in the transfer film is 5.0 mass % or less based on the total mass of the photosensitive layer. A method for manufacturing a laminate as described in claim 1 or claim 2, wherein in the photosensitive layer in the transfer film, the content of the organic solvent is 5.0 mass % or less relative to the total mass of the photosensitive layer. A method for manufacturing a laminate as described in claim 1 or claim 2, wherein in the photosensitive layer in the transfer film, the content of chloride ions is 100 mass ppm or less relative to the total mass of the photosensitive layer. A method for manufacturing a laminate as described in claim 1 or claim 2, wherein the photosensitive layer in the transfer film contains a white pigment. A method for manufacturing a laminate as described in claim 1 or claim 2, wherein the photosensitive layer in the transfer film has a photosensitive light absorbing layer precursor layer and a photosensitive light reflecting layer precursor layer in order from the side of the temporary support body. The manufacturing method of the laminated body according to Claim 1 or Claim 2, wherein The photosensitive layer in the transfer film is a photosensitive light-absorbing layer precursor layer. The manufacturing method of the laminated body according to Claim 1 or Claim 2, wherein After the aforementioned step 3, there is also a step 4 of arranging a light reflective film on the side wall of the opening.

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