CURABLE COMPOSITION, CURED FILM, ORGANIC EL DEVICE, AND METHOD FOR FORMING CURED RESIN LAYER

Abstract

The problem to be solved by the present invention is to provide a curable composition which can be cured at low temperatures (for example, 100° C. or lower) or by only light irradiation, and which can form a cured film that can achieve both high resolution and high development adhesion. [Solution] The present invention relates to a curable composition used to form a cured resin layer of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer on the sealing layer, the curable composition comprising an alkali-soluble resin (A), a polyfunctional radical polymerizable compound (B), a photoradical polymerization initiator (C), an ultraviolet absorber (D), and a silane coupling agent (E), wherein the ultraviolet absorber (D) has a transmittance of less than 10% at a wavelength of 360 nm in a 0.006 mass % solution, and a transmittance of 80% or more at a wavelength of 410 nm.

Description

[Technical field]

[0001] The present invention relates to a curable composition, a cured film, an organic electroluminescence device, and a method for forming a cured resin layer. [Background technology]

[0002] As one type of light-emitting element, an organic electroluminescence (EL) element having a laminated structure including an anode layer, an organic light-emitting layer, and a cathode layer is known. As a display device having an organic EL element, a touch panel-equipped organic EL device having a touch panel provided on the front surface of the device is known (for example, see Patent Document 1).

[0003] The organic EL device with a touch panel is manufactured, for example, by bonding a touch panel to a substrate on which an organic EL element is formed via an adhesive layer. The touch panel is usually manufactured by providing a touch panel member such as a sensor electrode on a touch panel support substrate.

[0004] When a touch panel support substrate is bonded to a substrate on which an organic EL element is formed via an adhesive layer or a bonding layer, the thickness of the entire organic EL device increases, and when the organic EL device is bent, the device may be damaged or its function may be impaired. As a method for solving such problems, a method of producing a touch panel directly on an organic EL element by techniques such as lithography and etching has been known in recent years. However, since the formation of a cured resin layer such as a patterned resin insulating film in a touch panel requires baking at a temperature of more than 100°C, there is a problem that the organic EL light-emitting layer is deteriorated when the cured resin layer is formed directly on an organic EL element by the conventional method. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2015-161806 A Summary of the Invention [Problem to be solved by the invention]

[0006] When forming a cured resin layer directly on an organic EL element, in order to prevent deterioration of the organic EL light-emitting layer, it is necessary to cure at a low temperature, preferably by only light irradiation. For this purpose, a composition with high sensitivity and excellent curability is required, but if the sensitivity is too high, for example, when a hole pattern is formed using a negative curable composition, the light leaking from the mask may cure even the part that should be a hole, resulting in poor resolution such as the hole pattern being filled. On the other hand, when a curable composition with a lowered sensitivity is used in order to prioritize the formation of a hole pattern, the pattern to be cured may not be cured sufficiently, and the adhesion during development (development adhesion) may not be maintained. In other words, in the conventional technology, it was difficult to achieve both resolution and development adhesion when forming a cured resin layer directly on an organic EL element.

[0007] Therefore, the problem to be solved by the present invention is to provide a curable composition which can be cured at low temperatures (for example, 100° C. or lower) or by only light irradiation, and which can form a cured film that can achieve both high resolution and high development adhesion. [Means for solving the problem]

[0008] According to the present invention, there are provided the following curable composition, cured film, organic EL device, and method for forming a cured resin layer.

[0009] In one embodiment, the present invention comprises: a curable composition used to form a cured resin layer of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin part having at least one cured resin layer on the sealing layer, An alkali-soluble resin (A); A polyfunctional radically polymerizable compound (B); A photoradical polymerization initiator (C); An ultraviolet absorber (D); A silane coupling agent (E), The ultraviolet absorber (D) has a transmittance of less than 10% at a wavelength of 360 nm in a 0.006% by mass solution and a transmittance of 80% or more at a wavelength of 410 nm. The present invention relates to a curable composition.

[0010] In another embodiment, the present invention comprises: A cured film obtained by curing the curable composition, and The present invention also relates to an organic EL device including the cured film.

[0011] In another embodiment, the present invention comprises: 1. A method for forming a cured resin layer of a light emitting device having a substrate, a light emitting element on the substrate, a sealing layer on the light emitting element, and a cured resin part having at least one cured resin layer on the sealing layer, comprising: A step of forming a coating film by directly or indirectly applying the curable composition of the present invention onto the sealing layer; a step of irradiating at least a portion of the coating film with radiation after the step of forming the coating film; developing the coating film after the radiation exposure step; and After the developing step, a step of exposing the coating film to light and / or a step of heating the coating film at a temperature of 120° C. or less are provided. The present invention relates to a method for forming a cured resin layer.

[0012] In another embodiment, the present invention comprises: An alkali-soluble resin (A); A polyfunctional radically polymerizable compound (B); A photoradical polymerization initiator (C); An ultraviolet absorber (D); A silane coupling agent (E), The ultraviolet absorber (D) has a transmittance of less than 10% at a wavelength of 360 nm in a 0.006% by mass solution and a transmittance of 80% or more at a wavelength of 410 nm. The present invention relates to a curable composition. Effect of the Invention

[0013] The curable composition of the present invention contains a specific ultraviolet absorber (D) and a silane coupling agent (E) that absorb light with a wavelength of 360 nm and transmit light with a wavelength of 410 nm, and thus can form a cured film that can achieve both resolution and development adhesion. In addition, since the curable composition of the present invention can be cured at a low temperature of 100° C. or less, even when used on a substrate having a light-emitting element, the deterioration of the light-emitting element due to heat can be suppressed. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 shows a cross-sectional view of one embodiment of a light-emitting device to which a cured resin layer formed from the curable composition of the present invention is applied. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

[0016] Matters related to the embodiments will be described in detail below. In this specification, a numerical range described using "to" means that the numerical range includes the numerical ranges before and after "to" as the lower and upper limits.

[0017] In this specification, the term "hydrocarbon group" includes chain-shaped hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain-shaped hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that do not include a cyclic structure in the main chain and are composed only of a chain structure. However, the chain-shaped hydrocarbon group may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, the alicyclic hydrocarbon group does not necessarily have to be composed only of an alicyclic hydrocarbon structure, and also includes those that have a chain structure as a part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that includes an aromatic ring structure as a ring structure. However, the aromatic hydrocarbon group does not necessarily have to be composed only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure as a part of it. The ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent group consisting of a hydrocarbon structure.

[0018] In this specification, "(meth)acrylo" is intended to include "acrylo" and "methacrylo", "(meth)acrylic" is intended to include "acrylic" and "methacrylic", and "(meth)acrylate" is intended to include "acrylate" and "methacrylate".

[0019] A light emitting device to which a cured resin layer formed from the curable composition of the present invention is applied will be described.

[0020] <Light-emitting device> The light emitting device has a substrate, a light emitting element on the substrate, a sealing layer on the light emitting element, and a cured resin part on the sealing layer, the cured resin part having at least one cured resin layer. That is, the light emitting device has a substrate, a light emitting element, a sealing layer, and a cured resin part in this order, and these layers may be in contact with each other, or other layers may be formed between them.

[0021] The sealing layer and the cured resin part may be formed in contact with each other, and other layers may be present between the sealing layer and the cured resin part, but it is preferable that there is no support (such as a glass substrate or a resin substrate formed from a resin such as polyethylene terephthalate) having a thickness of more than 50 μm between the sealing layer and the cured resin part, and it is more preferable that no support itself is used. The light-emitting element and the touch panel layer (cured resin layer) may be separately prepared and bonded using a support, but in this embodiment, it is more preferable that after the sealing layer is formed, the sealing layer and the cured resin part are formed in contact with each other directly or indirectly via another layer (such as a flattening layer) on the upper part.

[0022] The light-emitting device is, for example, a device having a laminated structure including an organic layer such as an organic light-emitting layer and an organic semiconductor thin film, and specifically includes an organic electroluminescence (EL) device and an organic transistor, with an organic EL device being preferred. Examples of the organic EL device include an organic EL lighting device and an organic EL display device.

[0023] The substrate may be any substrate that is generally used in light-emitting devices, such as a glass substrate or a resin substrate. Specifically, the substrates described in International Publication No. 2019 / 009360 can be suitably used.

[0024] The substrate is, for example, a thin film transistor (TFT) substrate having TFTs for driving the light emitting elements, and in one embodiment, the TFTs are arranged in a matrix. The TFT substrate may also have a planarization film covering the TFTs.

[0025] The light-emitting element is preferably an organic EL element. The organic EL element may be an organic EL element used in a known organic EL device, and may have a structure in which an organic light-emitting layer containing a light-emitting material is sandwiched between a pair of electrodes facing each other (i.e., a structure in which an organic light-emitting layer is sandwiched between an anode and a cathode facing each other), and may have a known structure having an anode / organic light-emitting layer / cathode. Specifically, for example, the one described in International Publication No. WO 2019 / 009360 may be suitably adopted.

[0026] The sealing layer seals the light-emitting element and can reduce the intrusion of moisture into the light-emitting element, thereby suppressing the occurrence of dark spots and the deterioration of light-emitting properties such as brightness and light-emitting efficiency caused by moisture.

[0027] Examples of the sealing layer include (1) an organic sealing layer, (2) an inorganic sealing layer, and (3) an organic-inorganic sealing layer having, for example, an organic sealing layer and an inorganic sealing layer alternately. For example, it may be an organic-inorganic sealing layer having an organic sealing layer between two inorganic sealing layers, or an organic-inorganic sealing layer having a total of four or more layers of inorganic sealing layers and organic sealing layers alternately. It is preferable that the outermost layer of the sealing layer is an inorganic sealing layer.

[0028] Examples of the inorganic sealing layer include layers described in JP 2010-160906 A, JP 2016-012433 A, and JP 2016-143605 A. Specifically, layers made of silicon nitride (SiNx) and silicon oxide (SiOx) are included, and methods for forming these include sputtering and chemical vapor deposition. The thickness of one inorganic sealing layer is usually about 10 nm to 2 μm.

[0029] The organic sealing layer may be, for example, a layer formed from a curable composition. The thickness of one organic sealing layer is usually 1 to 50 μm, preferably 1 to 20 μm, and more preferably 1 to 15 μm.

[0030] As the curable composition for forming the organic sealing layer and the method for forming the sealing layer, the composition and method described in WO 2019 / 009360 can be suitably used.

[0031] The cured resin portion includes a cured resin layer made of the curable composition of the present invention. The cured resin layer may have a pattern. The cured resin layer having a pattern (hereinafter, also referred to as a patterned cured resin layer) is preferably a layer formed directly on the sealing layer by a photolithography method using the curable composition of the present invention.

[0032] The shape of the pattern is not particularly limited, and examples thereof include an embodiment in which the portion where the cured resin layer is not present has a circular, elliptical, polygonal or other hole shape or a line shape.

[0033] The cured resin part usually has two or more metal wiring layers, which are insulated from each other by the patterned cured resin layer and, where necessary, are electrically connected by wiring formed in contact holes formed in the patterned cured resin layer.

[0034] The thickness of the patterned cured resin layer is usually 1 to 5 μm. The thickness of the metal wiring layer is usually 100 to 1000 nm. The diameter of the contact hole is usually 1 to 20 μm.

[0035] The cured resin part may further include a cured layer as a wiring underlayer on the side of the patterned cured resin layer facing the light emitting element, and / or may further include a cured layer as an upper protective layer on the side of the patterned cured resin layer facing the light emitting element. These cured layers may be unpatterned layers and act as a wiring underlayer or an upper protective layer for a metal wiring layer. The wiring underlayer or the upper protective layer can be formed from the curable composition of the present invention.

[0036] The thickness of the wiring underlayer and the upper protective layer is usually 0.5 to 10 μm, respectively.

[0037] The total thickness of the cured resin portion is preferably 15 μm or less, more preferably 9 μm or less, and even more preferably 6 μm or less.

[0038] An embodiment of a display device including a cured resin layer formed from the curable composition of the present invention will be further described with reference to FIG. 1. As shown in FIG. 1, one embodiment of the cured resin part 40 includes a wiring base layer 41, a first metal wiring layer 1a formed on the wiring base layer 41, a patterned cured resin layer 42 partially covering the first metal wiring layer 1a, a second metal wiring layer 2a formed on the patterned cured resin layer 42 and electrically connected to the first metal wiring layer 1a by a wiring 3' formed in a contact hole 3 of the patterned cured resin layer 42, and an upper protective layer 43 formed on the patterned cured resin layer 42 and the second metal wiring layer 2a and covering the second metal wiring layer 2a. The wiring base layer 41 may not be required. In FIG. 1, the cured resin part 40 is formed in direct contact with the sealing layer 30 in the element substrate consisting of the substrate 10, the light emitting element 20, and the sealing layer 30.

[0039] The hardened resin portion 40 is preferably a touch panel member.

[0040] The material constituting the metal wiring layer 1a and the metal wiring layer 2a is not particularly limited, but examples thereof include metals such as titanium, silicon, niobium, indium, zinc, tin, gold, silver, copper, aluminum, cobalt, chromium, nickel, lead, iron, palladium, platinum, tungsten, zirconium, tantalum, hafnium, and molybdenum, materials containing two or more of these metals, and alloys mainly composed of these metals. Among these, TiAlTi wiring, which is a laminated structure of titanium and aluminum, is preferable as the metal wiring.

[0041] The cured resin layer formed from the curable composition of the present invention is required to have good adhesion to metal wiring layers such as TiAlTi wiring and layers made of silicon nitride (SiNx) or silicon oxide (SiOx), since the cured resin layer is in contact with these layers.

[0042] The curable composition of the present invention will now be described.

[0043] 《Curable composition》 The curable composition according to this embodiment (hereinafter also referred to as "the composition") is used to form a cured resin layer of the light-emitting device, An alkali-soluble resin (A); A polyfunctional radically polymerizable compound (B); A photoradical polymerization initiator (C); An ultraviolet absorber (D); A silane coupling agent (E), The ultraviolet absorber (D) has a transmittance of less than 10% at a wavelength of 360 nm in a 0.006% by mass solution, and a transmittance of 80% or more at a wavelength of 410 nm.

[0044] Each component contained in the present composition, as well as other components that may be blended as necessary, will be described below.

[0045] <(A) Alkali-soluble resin> The alkali-soluble resin (A) is a component capable of exhibiting good developability with an alkali developer. The alkali-soluble resin (A) is usually a resin having an acidic group such as a carboxy group or a phenolic hydroxyl group, and is preferably a resin having a carboxy group.

[0046] The alkali-soluble resin (A) is preferably at least one selected from the group consisting of an acrylic resin, a polysiloxane resin, and a novolac resin, more preferably at least one selected from the group consisting of an acrylic resin and a novolac resin, and even more preferably a novolac resin.

[0047] The alkali-soluble resin (A) preferably has a group containing an unsaturated double bond such as a (meth)acryloyl group or vinyl, from the viewpoint of further improving the developability and the physical properties of the cured film. As such an alkali-soluble resin (A), an acid-modified epoxy (meth)acrylate resin obtained by reacting a compound having an epoxy group with (meth)acrylic acid is preferred, and examples thereof include an acid-modified cresol novolac epoxy (meth)acrylate resin, a phenol novolac epoxy (meth)acrylate resin, a bisphenol A epoxy (meth)acrylate resin, a bisphenol F epoxy (meth)acrylate resin, a biphenyl epoxy (meth)acrylate resin, and a trisphenol methane epoxy (meth)acrylate resin. As the alkali-soluble resin (A), an acid-modified cardo-based resin having a (meth)acryloyl group and a carboxy group is also preferred. Among these, an acid-modified cresol novolac epoxy (meth)acrylate resin and a phenol novolac epoxy (meth)acrylate resin are preferred.

[0048] (Acrylic resin) The acrylic resin may be a copolymer of a monomer having an alkali-soluble functional group and another copolymerizable monomer.

[0049] Examples of the monomer having an alkali-soluble functional group include Carboxy group-containing monomers such as (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, mono(2-(meth)acryloyloxyethyl) succinate, and ω-carboxy-polycaprolactone mono(meth)acrylate; Phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene; Maleimide and the like.

[0050] Examples of the other copolymerizable monomer include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, and dicyclopentadienyl (meth)acrylate; Aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene; Conjugated dienes such as butadiene and isoprene; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate; Examples of the polymerizable monomer include macromonomers having a polymerizable unsaturated group such as a (meth)acryloyl group at one end of a polymer chain, such as polystyrene, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybenzyl(meth)acrylate, etc. These may be used alone or in combination of two or more kinds.

[0051] The lower limit of the content of the monomer having an alkali-soluble functional group is preferably 5% by mass, more preferably 10% by mass, based on 100% by mass of all monomers constituting the acrylic resin, and the upper limit of the content is not particularly limited, but is, for example, preferably 40% by mass, more preferably 30% by mass.

[0052] The method for producing the acrylic resin is not particularly limited, and the resin can be produced by a known method such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, etc. The production conditions can also be conventionally known conditions.

[0053] (Polysiloxane resin) The polysiloxane resin may be a hydrolysis condensate of a hydrolyzable silane compound. Here, the term "hydrolyzable silane compound" refers to a compound containing a group capable of generating a silanol group through hydrolysis or a group capable of forming a siloxane condensate, and the term "hydrolysis condensate" refers to a condensate in which the silanol groups of the hydrolyzed silane compound are condensed together. For example, the polysiloxane resin described in JP 2017-048355 A may be mentioned.

[0054] (Novolac resin) The novolak resin can be obtained by polycondensing a phenol with an aldehyde such as formaldehyde using a known method.

[0055] Examples of the phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene bisphenol, methylene bis-p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, and β-naphthol. These may be used alone or in combination of two or more.

[0056] Examples of the aldehydes include, in addition to formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. These may be used alone or in combination of two or more kinds.

[0057] The novolac resin preferably has a group containing an unsaturated double bond such as a (meth)acryloyl group or vinyl, and preferably has a side chain represented by the following formula (1), in which case it is preferable that the main chain further has an aromatic ring. Among them, a resin having a side chain represented by the following formula (1) and a phenol-based novolac main chain is more preferable.

[0058] Examples of resins having a side chain represented by the following formula (1) and a phenolic novolac main chain include acid-modified cresol novolac type epoxy (meth)acrylate resins, acid-modified phenol novolac type epoxy (meth)acrylate resins, etc. Such resins are preferable because they have sufficient lithography performance due to their combination of a rigid main chain skeleton and a side chain containing an ethylenically unsaturated group and a carboxy group, and a cured film can be obtained even by heating at a relatively low temperature of 100° C. or less.

[0059] [ka]

[0060] In the above formula (1), R 5 R is a hydrogen atom or a methyl group. 6 and R 7 are each independently a divalent organic group. * represents a bonding site with the main chain.

[0061] Above R 5 is preferably a hydrogen atom.

[0062] Above R 6 and R 7Examples of the divalent organic group represented by the formula (I) include a divalent hydrocarbon group, a heteroatom-containing group that contains a divalent heteroatom-containing group between carbon atoms or at the bond-side terminal of a divalent hydrocarbon group, and groups in which some or all of the hydrogen atoms in the above-mentioned hydrocarbon group and heteroatom-containing group have been substituted with monovalent heteroatom-containing groups.

[0063] Examples of the divalent hydrocarbon group include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

[0064] Examples of the divalent chain hydrocarbon group include alkanediyl groups such as a methanediyl group, an ethanediyl group, an n-propanediyl group, an i-propanediyl group, an n-butanediyl group, an i-butanediyl group, or a sec-butanediyl group; Alkenediyl groups such as an ethenediyl group, a propenediyl group, or a butenediyl group; Examples of the alkyl group include alkynediyl groups such as an ethynediyl group, a propynediyl group, and a butynediyl group.

[0065] Examples of the divalent alicyclic hydrocarbon group include monocyclic cycloalkanediyl groups, such as a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, or a cyclohexanediyl group; monocyclic cycloalkenediyl groups such as a cyclopropenediyl group, a cyclobutenediyl group, a cyclopentenediyl group, or a cyclohexenediyl group; polycyclic cycloalkanediyl groups such as a norbornanediyl group, an adamantanediyl group, a tricyclodecanediyl group, and a tetracyclododecanediyl group; Examples of the cycloalkene-diyl group include polycyclic cycloalkene-diyl groups such as a norbornene-diyl group, a tricyclodecene-diyl group, and a tetracyclododecene-diyl group.

[0066] Examples of the divalent aromatic hydrocarbon group include Arenediyl groups such as a benzenediyl group, a toluenediyl group, or a naphthalenediyl group; Examples of the alkyl group include arenediylalkanediyl groups such as a benzenediylmethanediyl group and a naphthalenediylmethanediyl group.

[0067] Examples of the divalent heteroatom-containing group include -O-, -CO-, -CO-O-, -S-, -CS-, -SO2-, -NR'-, and groups formed by combining two or more of these, where R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0068] Examples of the monovalent heteroatom-containing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, amino group and sulfanyl group (-SH).

[0069] Above R 6 and R 7 The number of carbon atoms in the divalent organic group represented by the formula (I) is not particularly limited, and the lower limit may be 1. On the other hand, the upper limit of the number of carbon atoms may be, for example, 20 or 10.

[0070] Above R 6 As the R, a divalent hydrocarbon group is preferable, and a divalent chain hydrocarbon group and a divalent alicyclic hydrocarbon group are more preferable. 7 As the alkyl group, a group in which an oxygen atom (-O-) is bonded to the main chain terminal of a divalent hydrocarbon group, such as -CH2-O-*, is preferred.

[0071] An example of the acid-modified cresol novolac epoxy (meth)acrylate resin is a polymer represented by the following formula (2): The acid-modified cresol novolac epoxy (meth)acrylate resin can be obtained, for example, by reacting a cresol novolac epoxy resin with (meth)acrylic acid to obtain an epoxy (meth)acrylate resin, and then reacting the epoxy (meth)acrylate resin with an acid anhydride such as phthalic anhydride or 1,2,3,6-tetrahydrophthalic anhydride.

[0072] [ka]

[0073] In the above formula (2), p and q each independently represent an integer of 1 to 30.

[0074] In addition, as the alkali-soluble resin (A), a cardo resin having a side chain represented by the above formula (1) and modified with a specific acid can also be used. Examples of commercially available products of such resins include "WR-301" (ADEKA Corporation), which is an acid-modified cardo resin.

[0075] The lower limit of the acid value of the alkali-soluble resin (A) is preferably 10 mgKOH / g, more preferably 20 mgKOH / g, and even more preferably 40 mgKOH / g. The upper limit of the acid value is preferably 300 mgKOH / g, more preferably 270 mgKOH / g, and even more preferably 250 mgKOH / g. The acid value represents the number of mg of KOH required to neutralize 1 g of the solid content of the alkali-soluble resin (A).

[0076] The weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1,000 or more and 40,000 or less from the viewpoints of coatability, lithography performance, and cured film properties.

[0077] When the alkali-soluble resin (A) has an unsaturated double bond, the double bond equivalent is preferably 100 to 1200 g / mol, more preferably 100 to 850 g / mol, and even more preferably 100 to 600 g / mol. The double bond equivalent is the mass per mole of the unsaturated double bond in the alkali-soluble resin (A) and can be calculated by (mass (g) of the alkali-soluble resin (A)) / (amount (mol) of the unsaturated double bond in the alkali-soluble resin (A)).

[0078] The alkali-soluble resin (A) may be used alone or in combination of two or more kinds.

[0079] The lower limit of the content of the alkali-soluble resin (A) (total amount when multiple types are used) is preferably 5% by mass, more preferably 10% by mass, even more preferably 20% by mass, and particularly preferably 30% by mass, based on the total solid content (100% by mass) of the composition (i.e., the total amount of components other than the organic solvent (H) in the composition). The upper limit is preferably 90% by mass, more preferably 80% by mass, even more preferably 70% by mass, and particularly preferably 60% by mass, based on the total solid content (100% by mass) of the composition. By having the content of the alkali-soluble resin (A) within the above range, more sufficient lithography performance and curability can be exhibited.

[0080] <(B) Polyfunctional radically polymerizable compound> The polyfunctional radical polymerizable compound (B) may be any polymerizable compound that reacts with radicals generated from a photoradical polymerization initiator and cures, but from the viewpoint of improving the storage stability of the curable composition and controlling the curability of the resulting cured film, a polyfunctional (meth)acrylate, which is a polymerizable compound having two or more (meth)acryloyl groups in the molecule, is preferred. Specific examples of such polyfunctional (meth)acrylates include polyfunctional (meth)acrylic acid esters such as bifunctional (meth)acrylic acid esters and trifunctional or higher (meth)acrylic acid esters.

[0081] Examples of bifunctional (meth)acrylic acid esters include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane methanol di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, and neopentyl glycol hydroxypivalic acid ester di(meth)acrylate.

[0082] Examples of trifunctional or higher (meth)acrylic acid esters include trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate, succinic acid-modified dipentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, and mixtures thereof. Other examples include polyfunctional urethane (meth)acrylate compounds obtained by reacting a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and having three, four or five (meth)acryloyloxy groups.

[0083] Among these, the polyfunctional radically polymerizable compound (B) preferably contains a trifunctional or higher (meth)acrylic acid ester, and more preferably contains one or more selected from the group consisting of trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and isocyanuric acid EO-modified tri(meth)acrylate.

[0084] The polyfunctional radically polymerizable compound (B) may be used alone or in combination of two or more kinds.

[0085] The mass ratio ((B) / (A)) of the content of the polyfunctional radical polymerizable compound (B) to the content of the alkali-soluble resin (A) is preferably 1 / 2 or more and 2 / 1 or less. It is preferable that the polyfunctional radical polymerizable compound (B) is a tetrafunctional or higher (meth)acrylate, and the mass ratio of the (B) component to the (A) component is 1 / 2 or more and 2 / 1 or less.

[0086] The lower limit of the content of the polyfunctional radical polymerizable compound (B) (total amount when multiple types are used) is preferably 20 parts by mass, more preferably 50 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). On the other hand, the upper limit of the content is preferably 200 parts by mass, more preferably 150 parts by mass, and even more preferably 120 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). By having the content ratio of the (B) component within the above range, it is preferable because the properties of the obtained cured film can be more effectively improved.

[0087] <(C) Photoradical polymerization initiator> The photoradical polymerization initiator (C) is a compound that can generate radicals in response to radiation and initiate polymerization. Specific examples of the photoradical polymerization initiator (C) include O-acyloxime compounds, α-aminoketone compounds, α-hydroxyketone compounds, acylphosphine oxide compounds, etc., and among these, oxime-based photopolymerization initiators such as O-acyloxime compounds are preferred.

[0088] The use of the oxime ester photoinitiator is preferable because it can improve the sensitivity and easily suppress the variation in the line width in the plane when forming a fine line pattern. Furthermore, the use of the oxime ester photoinitiator tends to improve the residual film rate and enhance the effect of suppressing the occurrence of water stains. Note that water stains refer to the occurrence of water stains after rinsing with pure water after alkaline development when a component that increases alkaline developability is used.

[0089] As the oxime ester photoinitiator, from the viewpoint of reducing contamination of the composition and contamination of the apparatus due to decomposition products, it is preferable that the oxime ester photoinitiator has an aromatic ring, it is more preferable that the oxime ester photoinitiator has a condensed ring containing an aromatic ring, and it is even more preferable that the oxime ester photoinitiator has a condensed ring containing a benzene ring and a heterocycle.

[0090] Examples of the oxime ester photoinitiator include 1,2-octadione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), and oxime ester photoinitiators described in JP-A Nos. 2000-80068, 2001-233842, JP-T Nos. 2010-527339, 2010-527338, and 2013-041153. Commercially available products include Irgacure OXE-01 (manufactured by BASF), ADEKA ARCLES NCI-930 having a diphenyl sulfide skeleton (manufactured by ADEKA), TR-PBG-345, TR-PBG-304 having a carbazole skeleton, TR-PBG-365 having a fluorene skeleton, and TR-PBG-3057 having a diphenyl sulfide skeleton (all manufactured by Changzhou New Strong Electronic Materials Co., Ltd.).

[0091] The above-mentioned photoradical polymerization initiators (C) can be used alone or in combination of two or more kinds.

[0092] The lower limit of the content of the photoradical polymerization initiator (C) (total amount when multiple types are used) is preferably 1 part by mass, more preferably 5 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). On the other hand, the upper limit of the content is preferably 40 parts by mass, more preferably 30 parts by mass, and even more preferably 30 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). By having the content ratio of the (C) component within the above range, the present composition can form a cured film having good resolution and development adhesion even at a low exposure dose, which is preferable.

[0093] <(D) Ultraviolet absorber> The ultraviolet absorber (D) contained in the curable composition of the present invention is a compound having a transmittance of less than 10% at a wavelength of 360 nm and a transmittance of 80% or more at a wavelength of 410 nm, preferably having a maximum absorption wavelength of 400 nm or less, and having no absorption in visible light having a wavelength of more than 420 nm. The ultraviolet absorber (D) may be a compound having no absorption wavelength in visible light having a wavelength of more than 400 nm.

[0094] The transmittance at wavelengths of 360 nm and 410 nm is obtained by preparing a 0.006 mass% solution of the ultraviolet absorber (for example, a 0.006 mass% propylene glycol monomethyl ether acetate solution) and measuring the transmittance of the 0.006 mass% solution using an ultraviolet-visible near-infrared spectrophotometer (for example, V-670, manufactured by JASCO Corporation). The solvent for forming the 0.006 mass% solution of the ultraviolet absorber is not particularly limited, and any solvent in which the ultraviolet absorber dissolves may be used, but it is preferable to use propylene glycol monomethyl ether acetate. However, when it is difficult to prepare a 0.006 mass% solution of the ultraviolet absorber using propylene glycol monomethyl ether acetate, a solvent suitable for the ultraviolet absorber to be dissolved can be selected and used. Examples of such solvents include dichloromethane, tetrahydrofuran, N-methylpyrrolidone, and the organic solvent (H) described below.

[0095] The transmittance of the ultraviolet absorber (D) used in the present invention at a wavelength of 360 nm is less than 10%, preferably 8% or less, more preferably 5% or less, and more preferably 3% or less. By using an ultraviolet absorber (D) having such a small transmittance at a wavelength of 360 nm, it is possible to form a cured film with good resolution.

[0096] The transmittance of the ultraviolet absorber (D) used in the present invention at a wavelength of 410 nm is 80% or more, more preferably 85% or more, and even more preferably 90% or more. By using the ultraviolet absorber (D) having such a high transmittance at a wavelength of 410 nm, it becomes possible to maintain the brightness of the EL element in the actual panel.

[0097] The ultraviolet absorber (D) used in the present invention may have a transmittance at wavelengths of 360 nm and 410 nm that satisfies the above range, and its structure is not particularly limited. For example, examples of the ultraviolet absorber (D) include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, benzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, and cinnamic acid-based ultraviolet absorbers. Among these, it is preferable for the ultraviolet absorber to be one or more ultraviolet absorbers selected from the group consisting of benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers, it is more preferable for the ultraviolet absorber to be one or more ultraviolet absorbers selected from the group consisting of benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers, and it is even more preferable for the ultraviolet absorber to be a benzotriazole-based ultraviolet absorber.

[0098] (Benzotriazole-based UV absorber) The benzotriazole-based ultraviolet absorber may be at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers represented by the following formula (3). [ka] (In the above formula (3), X 1 , X 2 and X 3 each independently represents a hydrogen atom, a hydroxyl group, -ORa, or an organic group having 1 to 15 carbon atoms, and Ra represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. 1 , X 2 and X 3 At least one of these is a hydroxyl group, -ORa, or an organic group having 1 to 15 carbon atoms. X 4 represents a hydrogen atom or a halogen atom.

[0099] In the above formula (3), X 1 , X 2and X 3 Examples of the organic group in the formula (I) include a monovalent hydrocarbon group, a heteroatom-containing group that contains a divalent heteroatom-containing group between the carbon atoms of a monovalent hydrocarbon group or at the terminal on the bond side, and groups in which some or all of the hydrogen atoms of the above-mentioned hydrocarbon group and heteroatom-containing group have been substituted with a monovalent heteroatom-containing group.

[0100] X 1 , X 2 and X 3 Examples of the monovalent hydrocarbon group for Ra include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group.

[0101] The monovalent chain hydrocarbon group is R 6 and R 7 Examples of the monovalent alicyclic hydrocarbon group include a monovalent chain hydrocarbon group corresponding to the divalent chain hydrocarbon group in the above formula (1). 6 and R 7 Examples of the monovalent aromatic hydrocarbon group include a monovalent alicyclic hydrocarbon group corresponding to the divalent alicyclic hydrocarbon group in the above formula (1). 6 and R 7 Examples of the aromatic hydrocarbon group include monovalent aromatic hydrocarbon groups corresponding to the divalent aromatic hydrocarbon groups in the above formula (1).

[0102] As the divalent heteroatom-containing group and the monovalent heteroatom-containing group, those exemplified in the above formula (1) can be suitably used.

[0103] The organic group is, for example, -C2H3(OH)-CH2-O-C8H 17 , -C2H3(OH)-CH2-OC 12 H 25 , -CH(CH3)-CO2-C8H 17 , -t-C4H9, -CH2CH2COOC7H 15 ,-CH2CH2COOC8H 17 , -CH2CH2COOC9H 19 , -t-C8H 17, -CH(CH3)2C6H5, -C(CH3)2CH2C(CH3)3, -CH2CH2CO(OCH2CH2)6OH, methacryloyloxyethyl, etc., and may also be 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl, 4-glycidyloxyphenyl, 4-isocyanurate phenyl, etc. 17 , -C 12 H 25 etc. may each be linear or branched.

[0104] In the benzotriazole-based ultraviolet absorber represented by the above formula (3), X 2 is a hydrogen atom, and X 1 and X 3 are each independently a hydrogen atom or an organic group having 1 to 15 carbon atoms (provided that X 1 and X 3 At least one of X is an organic group having 1 to 15 carbon atoms; 4 is preferably a hydrogen atom or a chlorine atom. 1 and X 3 The organic group having 1 to 15 carbon atoms may have 1 to 12 carbon atoms or 1 to 8 carbon atoms.

[0105] Specific examples of the benzotriazole-based ultraviolet absorber represented by the above formula (3) include compounds represented by the following formulas (3-1) to (3-9). [ka]

[0106] (Triazine-based UV absorber) The triazine-based ultraviolet absorbent may be at least one ultraviolet absorbent selected from the group consisting of triazine-based ultraviolet absorbents represented by the following formula (4). [ka] (In the above formula (4), Y 1 , Y 2, Y 3 , Y 4 , Y 5 and Y 6 each independently represents a hydrogen atom, a hydroxyl group, -ORb, or an organic group having 1 to 15 carbon atoms, and Rb represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 At least one of represents a hydroxyl group, -ORb, or an organic group having 1 to 15 carbon atoms.)

[0107] The above Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 The organic group having 1 to 15 carbon atoms in the formula (3) is X 1 , X 2 and X 3 Preferred examples of the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent in Rb include the same as the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent in Ra in formula (3).

[0108] Y 2 , Y 4 , and Y 6 At least one of them may be a hydroxyl group, and may be a hydroxyphenyltriazine-based ultraviolet absorber.

[0109] In the triazine-based ultraviolet absorber having the above formula (4), Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are each independently a hydroxyl group or -ORb, and Rb is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have an ester group; Y 2 , Y 4 and Y6 It is more preferable that at least one of Y is a hydroxyl group. 1 and Y 2 are each independently a hydroxyl group or -ORb; Y 4 and Y 6 is a hydroxyl group, and Y 3 and Y 5 is -ORb and Rb is -CH(CH3)-CO2-C8H 17 It is preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have an ester group such as the above.

[0110] Specific examples of the triazine-based ultraviolet absorber represented by the above formula (4) include compounds represented by the following formulas (4-1) to (4-2). [ka]

[0111] (Benzophenone-based UV absorber) Benzophenone-based ultraviolet absorbents include hydroxybenzophenone-based ultraviolet absorbents, such as at least one ultraviolet absorbent selected from the group consisting of hydroxybenzophenone-based ultraviolet absorbents represented by the following formula (5). [ka] (In the above formula (5), Z 1 represents a hydroxyl group, -ORc, or an organic group having 1 to 15 carbon atoms; Z 2 represents a hydrogen atom, a hydroxyl group, -ORc, or an organic group having 1 to 15 carbon atoms; Z 3 represents a hydrogen atom or a hydroxyl group, and Rc represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent.

[0112] In the above formula (5), Z 1 and Z 2 The organic group having 1 to 15 carbon atoms in the formula (3) is X 1 , X2 and X 3 Preferred examples of the hydrocarbon group having 1 to 15 carbon atoms in Rc which may have a substituent include the same as the hydrocarbon group having 1 to 15 carbon atoms in Ra in formula (3).

[0113] Hydroxybenzophenone-based UV absorbers: Z 1 is a hydroxyl group, -ORc, or an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, and Z 2 is a hydrogen atom, a hydroxyl group, -ORc, or an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, and Z 3 is preferably a hydrogen atom or a hydroxyl group, Rc is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, Z 1 is a hydroxyl group, -ORc, or an unsubstituted aliphatic hydrocarbon group having 1 to 4 carbon atoms, and Z 2 and Z 3 More preferably, Rc is a hydrogen atom or a hydroxyl group, and Rc is an unsubstituted aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0114] Furthermore, as the ultraviolet absorbent (D), a cyanoacrylate ultraviolet absorbent may also be used, for example, Uvinul 3035, Uvinul 3039, Uvinul 3030FF, etc. (manufactured by Ozeki Co., Ltd.).

[0115] The weight average molecular weight of the ultraviolet absorber (D) is usually 80 or more, preferably 150 or more, more preferably 300 or more, and usually 2000 or less, preferably 1500 or less, more preferably 900 or less. The ultraviolet absorber (D) may be a polymer or a non-polymer compound having no repeating units, but since polymers have low ultraviolet absorbing ability, non-polymer compounds having no repeating units are preferred.

[0116] In addition, the ultraviolet absorbent (D) used in the present invention may be used in a mixture of two or more kinds, so long as the transmittance at a wavelength of 360 nm in a 0.006% by mass solution (preferably a propylene glycol monomethyl ether acetate solution) is less than 10% and the transmittance at a wavelength of 410 nm is 80% or more. That is, even if the ultraviolet absorbent (D) used in the present invention contains a single ultraviolet absorbent having a transmittance at a wavelength of 360 nm of 10% or more or a transmittance at a wavelength of 410 nm of less than 80% in a 0.006% by mass solution (preferably a propylene glycol monomethyl ether acetate solution), by mixing two or more kinds, as long as the transmittance at a wavelength of 365 nm and the transmittance at a wavelength of 410 nm satisfy the above range, the mixture can be used as the ultraviolet absorbent (D). Such ultraviolet absorbents that can be mixed are not particularly limited, and ultraviolet absorbents that can be normally used in this field can be used appropriately.

[0117] Specific examples of the ultraviolet absorber (D) used in the present invention include, for example, 2-phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl), 5-chloro-2-[3-(tert-butyl)-2-hydroxy-5-methylphenyl]-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, benzenepropanoic acid, 3-(2H-benzotriazol-2-yl), )-5-(1,1-dimethylethyl)-4-hydroxy, C7-9 alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-dihydroxy-4-methoxybenzophenone, and the like. In addition, examples of commercially available ultraviolet absorbents for use in the present invention include, but are not limited to, Tinuvin 329, Tinuvin 326, Tinuvin 477, Tinuvin PS, Tinuvin 99-2, Tinuvin 384-2, Tinuvin 900, Tinuvin 928 (all manufactured by BASF), KEMISORB111, KEMISORB73 (Chemipro Chemical Co., Ltd.), Uvinul 3049, Uvinul 3050, Uvinul 3035, Uvinul 3039, Uvinul 3030FF (all manufactured by Ozeki Corporation).

[0118] The ultraviolet absorbents (D) can be used alone or in combination of two or more.

[0119] The lower limit of the content of the ultraviolet absorber (D) (total amount when multiple types are used) is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, even more preferably 1 part by mass, and particularly preferably 2 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). On the other hand, the upper limit of the content is preferably 30 parts by mass, more preferably 15 parts by mass, and even more preferably 10 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). It is preferable that the content ratio of the (D) component is within the above range because a cured film with excellent developability can be formed.

[0120] The ratio of the mass of the ultraviolet absorber (D) to the total mass of the photoradical polymerization initiator (C) and the ultraviolet absorber (D), ((D) / ((C)+(D)), is preferably 5% by mass or more and 95% by mass or less, and more preferably 20% by mass or more and 90% by mass or less. When the content ratio of the ultraviolet absorber (D) is within the above range, it is preferable because a cured film having excellent resolution can be formed.

[0121] <(E) Silane coupling agent> The silane coupling agent (E) is preferably a compound that improves the adhesion between the substrate, for example, silicon compounds such as silicon, silicon oxide, silicon nitride, and metals such as gold, copper, molybdenum, titanium, aluminum, and the like, and the cured film.Specific examples thereof include known silane coupling agents, and the like, and a silane coupling agent having an ethylenically unsaturated bond is preferred.

[0122] As the silane coupling agent (E), those having a hydrolyzable group such as a methoxy group, an ethoxy group, or an acetoxy group, or a functional group such as a (meth)acryloyloxy group, a glycidyl group, an amino group, a thiol group, or an isocyanate group are preferred. In order to make it possible to fix to the main component resin, those having a reactive group contained in the alkali-soluble resin (A) or the polyfunctional radically polymerizable compound (B) are preferred, and those having a (meth)acryloyloxy group are particularly preferred.

[0123] The silane coupling agent (E) preferably has at least one functional group selected from the group consisting of a (meth)acryloyloxy group, a glycidyl group, and an isocyanate group, and more preferably has a (meth)acryloyloxy group.

[0124] Examples of the silane coupling agent (E) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, and vinyltrialkoxysilane. Among these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, and γ-glycidoxypropyltriakoxysilane are more preferred. These can be used alone or in combination of two or more. Commercially available products include KBM-403, KBM-5103, KBM-302, KBM-402, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, and the like (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0125] Said silane coupling agent (E) may be a polymer type, for example, a silane coupling agent in which hydrolyzable group and other functional groups are bonded to an organic polymer whose main chain is an organic structure can be suitably used.Commercially available organic polymer type products include X-12-1048, X-12-1050, X-12-9815, X-12-9845, X-12-1154, X-12-972F, X-12-1159L, etc.

[0126] The above silane coupling agents (E) can be used alone or in combination of two or more.

[0127] The lower limit of the content of the silane coupling agent (E) (total amount when multiple types are used) is preferably 0.1 parts by mass, more preferably 1 part by mass, and even more preferably 3 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). On the other hand, the upper limit of the content is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 10 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). It is preferable that the content ratio of the (E) component is within the above range because a cured film with excellent development adhesion can be formed.

[0128] <(F) Phosphoric acid compound having a (meth)acryloyloxy group> The curable composition of the present invention preferably contains a phosphoric acid compound (F) having a (meth)acryloyloxy group, in order to further improve the adhesion of the cured film to a substrate or a conductive layer.

[0129] The phosphoric acid compound (F) is not particularly limited as long as at least one of the three hydrogen atoms in phosphoric acid (O=P(OH)3) is substituted with an organic group having a (meth)acryloyloxy group. Examples of the phosphoric acid compound (F) include the Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP) manufactured by Unichemical Co., Ltd., the KAYAMER series (KAYAMER PM-21, KAYAMER PM-2) manufactured by Nippon Kayaku Co., Ltd., PPME, PMR12, PPM-5P manufactured by Toho Chemical Industry Co., Ltd., and the Light Ester series (Light Ester P-2M (trade name)) manufactured by Kyoeisha Chemical Co., Ltd.

[0130] The above phosphoric acid compounds (F) can be used alone or in combination of two or more.

[0131] When the composition contains a phosphoric acid compound (F), the lower limit of the content of the phosphoric acid compound (F) (the total amount when multiple types are used) is preferably 0.05 parts by mass, more preferably 0.1 parts by mass, and even more preferably 1 part by mass, relative to 100 parts by mass of the alkali-soluble resin (A). On the other hand, the upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, more preferably 8 parts by mass, and particularly preferably 6 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). It is preferable to contain the phosphoric acid compound (F) in the above range from the viewpoint of development adhesion.

[0132] <(G) Thiol compounds> The present composition preferably contains a thiol compound (G) having one or more thiol groups in one molecule in terms of further improving the adhesion of the cured film to the substrate or conductive layer and preventing undercut. The thiol compound (G) may have at least one thiol group, but preferably has two or more thiol groups, more preferably is a multifunctional thiol compound having three or more thiol groups, and even more preferably is a multifunctional thiol compound having four or more thiol groups. The number of thiol groups in one molecule is preferably six or less. However, the thiol compound (G) does not include those corresponding to the silane coupling agent (E).

[0133] Examples of the polyfunctional thiol compound include primary polyfunctional thiols and secondary polyfunctional thiols, with secondary polyfunctional thiols being preferred from the viewpoints of high storage stability and suppressed odor.

[0134] Examples of secondary polyfunctional thiols include pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and 1,3,5-tris[2-(3-mercaptobutanoyloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0135] Examples of primary polyfunctional thiols include trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate).

[0136] The thiol compound (G) can be used alone or in combination of two or more kinds.

[0137] When the composition contains a thiol compound (G), the upper limit of the content of the thiol compound (G) (total amount when multiple types are used) is not particularly limited, but in order to further improve the adhesion of the cured product to the substrate or conductive layer, it is preferably 40 parts by mass, more preferably 30 parts by mass, and even more preferably 25 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A). The lower limit is preferably 1 part by mass, and more preferably 3 parts by mass.

[0138] <(H) Organic Solvent> The composition may further contain an organic solvent (H). The organic solvent (H) is not particularly limited, and examples thereof include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, and amide-based solvents. The organic solvent (H) may be used alone or in combination of two or more kinds.

[0139] Examples of alcohol-based solvents include alkyl alcohols such as methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, and diacetone alcohol; and aromatic alcohols such as benzyl alcohol.

[0140] Examples of ether solvents include ethylene glycol monoalkyl ethers such as diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; and dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.

[0141] Examples of ester-based solvents include carboxylic acid esters such as ethyl acetate, i-propyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; polyhydric alcohol carboxylate-based solvents such as propylene glycol diacetate; and polyhydric alcohol partial ether carboxylate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.

[0142] Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0143] Among these, ether-based solvents and ester-based solvents are preferred, ester-based solvents are more preferred, and polyhydric alcohol partial ether carboxylate-based solvents are even more preferred.Of the ether-based solvents and ester-based solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate are preferred.

[0144] The content of the organic solvent (H) in the composition is not particularly limited, but it is preferable that the solid content (components other than the organic solvent (H)) of the composition is adjusted to be within the following range. The lower limit of the solid content concentration in the composition is preferably 5% by mass, more preferably 10% by mass, and even more preferably 20% by mass. On the other hand, the upper limit of the solid content concentration is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass.

[0145] <Other ingredients> The present composition may further contain other components in addition to the above-mentioned components. Examples of the other components include a curing agent, a curing accelerator, an antioxidant, a surfactant, etc. However, the content of the other components in the curable composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0146] <Viscosity of Curable Composition> The viscosity of the curable composition measured using an E-type viscometer at 25°C and 50 rpm is preferably 0.5 mPa·s or more and 20 mPa·s or less, more preferably 0.5 mPa·s or more and 7 mPa·s or less, and even more preferably 2.5 mPa·s or more and 5 mPa·s or less. The viscosity of the curable composition can be set within the above range by adjusting the amount of the organic solvent (H) added.

[0147] <Method of preparing curable composition> The curable composition of the present invention can be prepared by mixing the components in a predetermined ratio and dissolving them in an organic solvent (H). The prepared composition is preferably filtered, for example, through a filter having a pore size of about 0.2 μm.

[0148] ≪Cured film≫ The cured film of the present invention (hereinafter also referred to as "the present cured film") can be formed by curing the curable composition prepared as described above. The curable composition of the present invention can give a cured film having sufficient resolution and development adhesion even by heating at a relatively low temperature. The present composition is preferably a composition that can be cured at a post-bake temperature of 100°C or less, and more preferably a composition that can be cured by heating at a temperature range of 60°C to 100°C.

[0149] The transmittance of a cured film formed by curing the curable composition of the present invention at a wavelength of 400 nm is preferably greater than 90%, and more preferably greater than 95%.

[0150] The cured film of the present invention may be a patterned film.

[0151] The cured film of the present invention can be used as a cured resin layer of the cured resin part of the light-emitting device. Specifically, it can be used as a wiring underlayer of the cured resin part, a patterned cured resin layer (an interlayer insulating film of a touch panel wiring), or an upper protective layer (a protective film of a touch panel wiring).

[0152] The thickness of the cured film of the present invention is not particularly limited and can be appropriately set depending on the purpose of use.

[0153] ≪Organic EL device≫ The organic EL device of the present invention comprises the present cured film. The organic EL device of the present invention preferably comprises a touch panel laminated on a substrate having an organic EL element, and the present cured film is preferably used as at least a part of the cured resin layer in the touch panel. In particular, the present cured film is preferably used as an interlayer insulating film of a touch panel laminated on a substrate having an organic EL element without an adhesive layer or a bonding layer. In this way, the touch panel can be directly laminated on the substrate on which the organic EL element is formed, so that the organic EL device equipped with the touch panel can be made thinner.

[0154] The present curable composition can obtain a cured film having sufficient resolution and development adhesion even by heating at a relatively low temperature, so that deterioration of the organic EL element in the manufacturing process of the organic EL device can be suppressed, and the yield can be increased, etc. In addition, since the insulating film can be formed by heating at a relatively low temperature using the curable composition in this way, deterioration of the organic EL element in the manufacturing process can be suppressed, so that the curable composition can be particularly suitably used for forming an insulating film in various organic EL devices equipped with an organic EL element other than an organic EL device equipped with a touch panel.

[0155] <Method of forming cured resin layer> A method for forming a cured resin layer according to one embodiment of the present invention includes the steps of: 1. A method for forming a cured resin layer of a light emitting device having a substrate, a light emitting element on the substrate, a sealing layer on the light emitting element, and a cured resin part having at least one cured resin layer on the sealing layer, comprising: A step of forming a coating film by directly or indirectly applying the curable composition of the present invention onto the sealing layer (hereinafter also referred to as a "coating film forming step"); a step of irradiating (exposing) at least a part of the coating film with radiation after the step of forming the coating film (hereinafter also referred to as a "radiation irradiation step"); a step of developing the coating film after the step of irradiating with radiation (hereinafter also referred to as a "developing step"); and After the developing step, the method includes a step of exposing the coating film to light and / or a step of heating the coating film at a temperature of 120° C. or less (hereinafter also referred to as an "exposure and heating step"). The formation method may include, as an optional step, a step of heating the coating film (hereinafter also referred to as a "PEB step") between the radiation exposure step and the developing step.

[0156] According to this forming method, since the above-mentioned curable composition is used, it is possible to pattern a good shape, and a cured resin layer (cured film) having resolution and development adhesion can be obtained. Even if the substrate on which the coating film is formed contains an organic EL element, it is possible to suppress deterioration of the organic EL element by performing the heating process at a relatively low temperature. Each process will be described below.

[0157] (Coating film formation process) In this step, the curable composition is applied onto the sealing layer directly or via another layer, and then the applied surface is preferably heated (prebaked) to remove the organic solvent and the like, thereby forming a coating film. The sealing layer is as described above.

[0158] The method of applying the curable composition is not particularly limited, and may be any suitable method such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, etc. Among these coating methods, spin coating and slit die coating are particularly preferred. The pre-baking conditions vary depending on the type and blending ratio of each component, but may be, for example, a heating time of 1 minute to 10 minutes at a temperature of 60°C to 120°C, more preferably 100°C or less.

[0159] (Radiation irradiation process) In this step, radiation is irradiated to at least a part of the coating film formed in the coating film forming step. Usually, radiation is irradiated through a photomask having a predetermined pattern when a part of the coating film is irradiated with radiation. Examples of the radiation that can be used include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among these types of radiation, radiation having a wavelength in the range of 190 nm to 450 nm is preferred, and radiation containing ultraviolet light of 365 nm is more preferred.

[0160] The lower limit of the exposure dose in this process is 10 mJ / cm as a value measured by an illuminometer ("OAI model 356" by OAI Optical Associates Inc.) at a wavelength of 365 nm. 2 is preferred, and 50 mJ / cm 2 The upper limit of the exposure amount is preferably 2,000 mJ / cm as measured by the illuminometer. 2 is preferred, and 1,000 mJ / cm 2 is more preferred.

[0161] (PEB process) When a PEB step is performed, the PEB conditions vary depending on the types and blending ratios of each component, but may be, for example, a heating temperature of 60° C. to 120° C., more preferably 100° C. or less, for a heating time of 1 minute to 10 minutes.

[0162] (Development process) In this process, the coating film after irradiation is developed with a developer to form a predetermined pattern. The developer is preferably an alkaline developer. Examples of the alkaline developer include an alkaline aqueous solution in which at least one alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, and tetraethylammonium hydroxide is dissolved. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer.

[0163] As the developing method, for example, a suitable method such as a puddle method, a dipping method, a swing immersion method, a spray method, etc. can be adopted. The developing time varies depending on the composition of the radiation-sensitive composition, but is, for example, 10 seconds or more and 180 seconds or less. Following such a developing treatment, for example, washing with running water is performed for a processing time of 30 seconds or more and 90 seconds or less, and then drying is performed with, for example, compressed air or compressed nitrogen, thereby forming a desired pattern.

[0164] (Exposure heating process) In this step, the coating film that has been developed and patterned is exposed to light and / or heated (post-baked) at a temperature of 120° C. or less using a heating device such as a hot plate or an oven, thereby obtaining an insulating film for a display device having a desired pattern. The exposure can be performed by irradiation with radiation such as ultraviolet light, and the exposure dose at this time is, for example, 100 mJ / cm. 2 More than 2,000mJ / cm 2The heating temperature can be set to 60° C. or less. The lower limit of the heating temperature is 60° C., preferably 80° C. By setting the heating temperature to the lower limit or more, a sufficiently cured cured resin layer (cured film) can be obtained. On the other hand, the upper limit of the heating temperature is 120° C., preferably 100° C. By setting the heating temperature to the upper limit or less, for example, a sufficiently cured cured resin layer (cured film) can be obtained while suppressing deterioration of an organic EL element provided on a substrate. In addition, by setting the heating temperature to the upper limit or less, excessive stress generation such as sudden film shrinkage can be suppressed, so that the occurrence of cracks can be suppressed. Thus, in the heating step, heating is performed at a temperature range of 60° C. or more and 120° C. or less (preferably 60° C. or more and 100° C. or less). The heating time varies depending on the type of heating device, but for example, when heating on a hot plate, it may be 5 minutes or more and 30 minutes or less, and when heating in an oven, it may be 10 minutes or more and 90 minutes or less. The heating may be performed in air or in an inert gas atmosphere such as nitrogen or argon. It is also possible to use a step bake method in which two or more heating steps are performed.

[0165] (Other processes) When manufacturing an organic EL device, after the cured resin layer (cured film) is formed on the organic EL display substrate, other steps are performed to form further electrodes, wiring, etc. Examples of such steps include an electrode forming step, a wiring forming step, an etching step, an ashing step, etc. For forming the electrodes and wiring, known methods such as printing and deposition can be adopted. Etching can be performed using a known etching solution such as an amine-based solution. Ashing can be performed by a known ashing method such as oxygen ashing. In addition, when manufacturing a touch panel or the like, the formation of the cured resin layer (cured film) and the formation of the electrodes, wiring, etc. may each be performed multiple times.

[0166] ≪Curable composition≫ The curable composition according to one embodiment of the present invention comprises: An alkali-soluble resin (A); A polyfunctional radically polymerizable compound (B); A photoradical polymerization initiator (C); An ultraviolet absorber (D); A silane coupling agent (E), The ultraviolet absorber (D) has a transmittance of less than 10% at a wavelength of 360 nm in a 0.006% by mass solution, and a transmittance of 80% or more at a wavelength of 410 nm.

[0167] The alkali-soluble resin (A), the polyfunctional radical polymerizable compound (B), the photoradical polymerization initiator (C), the ultraviolet absorber (D), and the silane coupling agent (E) may be preferably those described above. The curable composition may be the same as the present composition described above.

[0168] A cured film formed from the curable composition has excellent resolution and development adhesion, and therefore the curable composition can be preferably used as a material for forming an interlayer insulating film, a planarizing film, a spacer, a protective film, a colored pattern film for a color filter, a partition wall, a bank, and the like. EXAMPLES

[0169] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are based on mass unless otherwise specified.

[0170] <Measurement of weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the polymer obtained in the following Synthesis Example 1 was measured by gel permeation chromatography (GPC) under the following conditions. Equipment: Resonac's "GPC-101" Column: Resonac's "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" connected together Mobile phase: Tetrahydrofuran Column temperature: 40℃ Flow rate: 1.0mL / min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: Differential refractometer Standard material: Monodisperse polystyrene

[0171] <Viscosity measurement> Measurements were performed at 25° C. using an E-type viscometer ("TVE22L" manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K2283:2000.

[0172] <Transmittance measurement of component (D)> The ultraviolet absorber (D) used was dissolved in propylene glycol monomethyl ether acetate to prepare a 0.006 mass% propylene glycol monomethyl ether acetate solution (test solution). The transmittance of the test solution at wavelengths of 360 nm and 410 nm was measured using a UV-Vis-NIR spectrophotometer (JASCO Corporation, V-670).

[0173] (Synthesis Example 1: Synthesis of Polymer (A-1)) 220 parts of cresol novolac epoxy resin (manufactured by DIC Corporation, trade name: Epiclon N-695, epoxy equivalent: 220) was placed in a four-neck flask equipped with a stirrer and a reflux condenser, 214 parts of carbitol acetate was added, and the mixture was dissolved by heating. Next, 0.1 parts of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95-105°C, 72 parts of acrylic acid were gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90°C, 106 parts of tetrahydrophthalic anhydride were added, and the mixture was reacted for 8 hours. After cooling, the mixture was taken out to obtain a carboxyl group-containing photosensitive resin (A-1). The carboxyl group-containing photosensitive resin (A-1) thus obtained had a nonvolatile content of 65% by weight, an acid value of the solid matter of 85 mgKOH / g, and a weight average molecular weight Mw of about 3,500.

[0174] (Synthesis Example 2: Synthesis of Polymer (A-2)) A reactor equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen inlet was charged with 15 parts of 2,2'-azobis(2-methylpropionate)dimethyl and 200 parts of diethylene glycol ethyl methyl ether. Subsequently, 16 parts of methacrylic acid, 25 parts of glycidyl methacrylate, 50 parts of styrene, and 9 parts of methyl methacrylate were charged and substituted with nitrogen. The solution in the flask was gently stirred while the temperature of the solution was raised to 80°C, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-2). The solid content concentration of this polymer solution was 34.5% by mass, and the Mw of polymer (A-2) was 11,000 and the molecular weight distribution (Mw / Mn) was 2.2.

[0175] [Preparation of negative radiation-sensitive resin composition] The raw materials used in the preparation of each negative radiation-sensitive resin composition are shown below.

[0176] Component (A): Alkali-soluble resin A1: Polymer (A-1) obtained in Synthesis Example 1 (acid value of solid matter: 85 mg KOH / g, molecular weight (Mw): 3,500) A2: Polymer (A-2) obtained in Synthesis Example 2 (acid value: 104 mg KOH / g, molecular weight (Mw): 11,000, molecular weight distribution (Mw / Mn): 2.2)

[0177] Component (B): Multifunctional radical polymerizable compound B1: Trimethylolpropane triacrylate (product name: Viscoat #295, manufactured by Osaka Organic Chemical Industry Co., Ltd.) B2: Pentaerythritol tri- and tetraacrylate (product name: Aronix M-450, manufactured by Toagosei Co., Ltd.) B3: Dipentaerythritol penta- and hexaacrylate (product name: NK Ester A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) B4: Isocyanuric acid EO modified di- and triacrylate (product name: Aronix M-313, manufactured by Toagosei Co., Ltd.)

[0178] Component (C): Photoradical polymerization initiator C1: 1,2-octanedione-1-{4-(phenylthio)phenyl}-2-(O-benzoyloxime) (trade name: IRGACURE OXE-01, manufactured by BASF) C2: TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) described in International Publication No. 2023 / 074411 ·C3:TR-PBG-345 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) C4: Adeka Arcles NCI-930 (manufactured by ADEKA)

[0179] (D) Ingredient: UV absorber ·D1:2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (Product name: TinuvinPS, manufactured by BASF, transmittance: 0% (360nm), 100% (410nm)) ·D2:Benzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-,C7-9-branched and linear alkyl esters (Product name: Tinuvin384-2, manufactured by BASF, transmittance: 2% (360nm), 97% (410nm)) D3: Hydroxyphenyltriazine (HPT)-based ultraviolet absorber represented by the following formula (trade name: Tinuvin 477, manufactured by BASF, transmittance: 0% (360 nm), 92% (410 nm)) [ka] ·D4:2-[4-([2-Hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-([2-Hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Product name: Tinuvin400, manufactured by BASF) (Transmittance: 30% (360 nm), 100% (410 nm))

[0180] Component (E): Silane coupling agent E1: 3-methacryloxypropyltrimethoxysilane (product name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) E2: X-12-1048 (Shin-Etsu Chemical Co., Ltd.)

[0181] (F) Component: Phosphate compound F1: 2-methacryloyloxyethyl caproate acid phosphate (trade name: KAYAMER PM-21, manufactured by Nippon Kayaku Co., Ltd.) F2: Acid phosphooxy polypropylene glycol monomethacrylate (PPM-5P, manufactured by Toho Chemical Industry Co., Ltd.)

[0182] (G) Component: Thiol compound G1: Pentaerythritol tetrakis(3-mercaptobutyrate) (product name: KarenzMT (registered trademark) PE1, manufactured by Resonac Co., Ltd.)

[0183] (H) Component: Organic solvent H1: Propylene glycol monomethyl ether acetate (PGMEA)

[0184] Example 1 A negative curable composition of Example 1 was prepared by dissolving 100 parts by mass of A1 as component (A), 50 parts by mass of Viscoat #295 as component (B), 10 parts by mass of OXE-01 as component (C), 5 parts by mass of Tinuvin PS as component (D), 5 parts by mass of KBM-503 as component (E), and 2 parts by mass of KAYAMER PM-21 as component (F) in 500 parts by mass of PGMEA as organic solvent (H). The viscosity of the obtained curable composition was measured at 25°C and 50 rpm using an E-type viscometer and was 3.5 mPa·s.

[0185] (Examples 2 to 18, Comparative Examples 1 to 3) Negative curable compositions of Examples 2 to 18 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, except that the types and amounts of each component were used as shown in Table 1. In Table 1, "-" indicates that the corresponding component was not used.

[0186] [Table 1]

[0187] [evaluation] The negative curable compositions obtained above were evaluated for resolution, development adhesion, and transmittance according to the following methods.

[0188] <Resolution> A negative curable composition was applied onto a silicon substrate by spin coating, and then prebaked on a hot plate at 85° C. for 2 minutes to form a coating film with a thickness of 2.5 μm. The obtained coating film was exposed to a high-pressure mercury lamp (exposure dose at 365 nm was 100 mJ / cm 2 ). 2 ), exposure was performed through a photomask in which square cutout patterns with sides of 10 μm were arranged at 10 μm intervals, and development was then performed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25° C. for 60 seconds by puddle method. Next, the substrate was washed with running ultrapure water for 60 seconds, and then dried to form a pattern on the silicon substrate. The cross-sectional shape of the square cutout patterns with sides of 10 μm thus obtained was observed at a magnification of 1500 times using a scanning electron microscope (Hitachi, Ltd., S-4200) and evaluated according to the following criteria. The evaluation results are shown in Table 2. A: No residue and bottom dimension is 8μm or more B: No residue and bottom dimension is 7μm or more and less than 8μm C: Residue present or bottom dimension is less than 7μm

[0189] <Development adhesion> Negative curable compositions were applied by spin coating onto silicon nitride (SiNx) and Ti substrates, respectively, and then prebaked on a hot plate at 85°C for 2 minutes to form coating films with a thickness of 2.5 µm. The resulting coating films were then irradiated with a high-pressure mercury lamp (exposure dose at 365 nm was 100 mJ / cm2). 2 ) was used, and exposure was performed through a photomask capable of forming a line pattern with a line width varying in 1 μm increments in the range from 1 μm to 50 μm, and then development was performed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25°C for 60 seconds by puddle method. Next, the substrate was washed with running ultrapure water for 60 seconds, and then dried to form a film on each substrate. The thus obtained line patterns with a line width varying in 1 μm increments in the range from 1 μm to 50 μm were observed for substrate adhesion at a magnification of 100 times using an optical microscope (Keyence, VHX-5000) and evaluated according to the following criteria. The evaluation results are shown in Table 2. A: No peeling B: Less than 4μm with peeling C: Peeling occurs at 4μm or more

[0190] <Transmittance> A negative curable composition was applied onto a glass substrate by spin coating, and then prebaked on a hot plate at 85° C. for 2 minutes to form a coating film with a thickness of 2.5 μm. The obtained coating film was exposed to a high-pressure mercury lamp (exposure dose at 365 nm was 100 mJ / cm 2 ). 2 ) through a photomask without a pattern, and then developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C for 60 seconds by puddle method. Then, it was washed with running ultrapure water for 60 seconds. Then, it was irradiated with 200 mJ / cm2 from a high-pressure mercury lamp. 2 The substrate was then post-exposed to 100° C. and post-baked for 60 minutes in an oven at 85° C. to form a cured resin film. The transmittance of the substrate thus obtained was measured at a wavelength of 400 nm using a UV-vis spectrometer V-670 manufactured by JASCO Corporation. A: Transmittance exceeds 95% B: Transmittance is over 90% and below 95% C: Transmittance is 90% or less

[0191] [Table 2]

[0192] As shown in Table 2, in Examples 1 to 18, cured films excellent in resolution and development adhesion were formed. On the other hand, in the comparative examples, either the resolution or development adhesion was poor. [Explanation of symbols]

[0193] 10 Substrate 20 Light emitting element 30 Sealing layer 40 Cured resin part 41 Wiring base layer 42 Patterned cured resin layer 43 Upper protective layer 1a First metal wiring layer 2a Second metal wiring layer 3 Contact Hole 3' Wiring

Claims

1. A curable composition used for forming a cured resin layer of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin part having at least one cured resin layer formed directly or indirectly on the sealing layer, An alkali-soluble resin (A); A polyfunctional radically polymerizable compound (B); A photoradical polymerization initiator (C); An ultraviolet absorber (D); A silane coupling agent (E), The ultraviolet absorber (D) has a transmittance of less than 10% at a wavelength of 360 nm in a 0.006 mass% solution and a transmittance of 80% or more at a wavelength of 410 nm, The content of the ultraviolet absorber (D) is 2 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the alkali-soluble resin (A), The ultraviolet absorber (D) is one or more ultraviolet absorbers selected from the group consisting of benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers. Curable composition.

2. The curable composition according to claim 1, wherein the ultraviolet absorber (D) is at least one ultraviolet absorber selected from the group consisting of a benzotriazole-based ultraviolet absorber represented by the following formula (3) and a triazine-based ultraviolet absorber represented by the following formula (4): 【Chemistry 1】 (In the above formula (3), X １ , X ２ and X ３ each independently represents a hydrogen atom, a hydroxyl group, -ORa, or an organic group having 1 to 15 carbon atoms, and Ra represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. １ , X ２ and X ３ At least one of is a hydroxyl group, -ORa, or an organic group having 1 to 15 carbon atoms. X ４ represents a hydrogen atom or a halogen atom. 【Chemistry 2】 (In the above formula (4), Y １ , Y ２ , Y ３ , Y ４ , Y ５ and Y ６ each independently represents a hydrogen atom, a hydroxyl group, -ORb, or an organic group having 1 to 15 carbon atoms, where Rb represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. １ , Y ２ , Y ３ , Y ４ , Y ５ and Y ６ At least one of represents a hydroxyl group, -ORb, or an organic group having 1 to 15 carbon atoms.

3. The curable composition according to claim 1 , further comprising a phosphoric acid compound (F) having a (meth)acryloyloxy group.

4. The curable composition according to claim 1 , wherein the polyfunctional radically polymerizable compound (B) is a polymerizable compound having two or more (meth)acryloyl groups in the molecule.

5. The curable composition according to claim 1 , wherein the alkali-soluble resin (A) has a weight average molecular weight of 1,000 or more and 40,000 or less.

6. The curable composition according to claim 1, wherein the alkali-soluble resin (A) is at least one selected from the group consisting of an acrylic resin, a polysiloxane resin, and a novolac resin.

7. The curable composition according to claim 1, wherein the silane coupling agent (E) has at least one functional group selected from the group consisting of a (meth)acryloyloxy group, a glycidyl group, an amino group, a thiol group, and an isocyanate group.

8. The curable composition according to claim 1 , further comprising a compound (G) having one or more thiol groups in one molecule.

9. The curable composition according to claim 1 , wherein the cured resin layer is an interlayer insulating film or a protective film for a touch panel wiring.

10. The curable composition of claim 1 , wherein the cured resin layer contacts a TiAlTi interconnect.

11. The curable composition according to claim 1 , which is curable at a post-bake temperature of 100° C. or less.

12. The curable composition according to claim 1 , wherein a cured film having a thickness of 2.5 μm formed by curing the curable composition has a transmittance of more than 90% at a wavelength of 400 nm.

13. A cured film obtained by curing the curable composition according to claim 1.

14. An organic electroluminescence device comprising the cured film according to claim 13.

15. A method for forming a cured resin layer of a light emitting device having a substrate, a light emitting element on the substrate, a sealing layer on the light emitting element, and a cured resin part having at least one cured resin layer on the sealing layer, comprising: A step of forming a coating film by directly or indirectly applying the curable composition according to claim 1 onto the sealing layer; a step of irradiating at least a portion of the coating film with radiation after the step of forming the coating film; developing the coating film after the radiation exposure step; and After the developing step, the method includes a step of exposing the coating film to light and / or a step of heating the coating film at a temperature of 120° C. or less. A method for forming a cured resin layer.

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