Curable composition, cured film, organic el device, and method for forming cured resin layer

Abstract

The invention relates to a curable composition, a cured film, an organic EL device, and a method for forming a cured resin layer. The present invention relates to a curable composition 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 of the cured resin layers on the sealing layer, the curable composition comprises: 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). 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 EL device, and a method for forming a cured resin layer. Background Art

[0002] As one type of light-emitting element, an organic electroluminescence (EL) element having a stacked 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, an organic EL device with a touch screen having a touch screen provided on the front surface of the device is known (for example, see Patent Document 1).

[0003] The organic EL device with a touch screen is manufactured by, for example, bonding the touch screen to a substrate on which an organic EL element is formed via an adhesive layer. The touch screen is generally manufactured by providing touch screen components such as sensor electrodes on a touch screen support substrate.

[0004] When a support substrate for a touch screen is bonded to a substrate forming an organic EL element via an adhesive layer or a bonding layer, the overall thickness of the organic EL device increases, and when the organic EL device is bent, the device may sometimes be damaged or its function may be reduced. As a method to eliminate this problem, in recent years, a method of directly manufacturing a touch screen on an organic EL element using methods such as photolithography and etching has become known. However, since the formation of a hardened resin layer such as a patterned resin insulating film in a touch screen requires baking at a temperature exceeding 100°C, when a hardened resin layer is directly formed on an organic EL element using existing methods, there is a problem of causing degradation of the organic EL light-emitting layer.

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-161806 Summary of the Invention

[0008] [Problems to be solved by the invention]

[0009] When directly forming a hardened resin layer on organic EL element, in order to prevent the deterioration of organic EL light-emitting layer, it is necessary to harden at low temperatures, preferably only harden by light irradiation.Therefore, it is necessary to have a composition with high sensitivity, excellent curability, but if the sensitivity is too high, then for example, in the case of using a negative curable composition to form a hole pattern, due to the light leaked from the mask, it is hardened to the part that should form a hole, and sometimes the resolution such as hole pattern embedding is poor. On the other hand, in the case of preferentially forming a hole pattern and using the curable composition that reduces sensitivity, the hardening of the pattern to be hardened becomes insufficient, and sometimes it is impossible to keep the adhesion (development adhesion) when developing. That is, in existing technology, in the case of directly forming a hardened resin layer on organic EL element, it is difficult to take into account both resolution and development adhesion.

[0010] Therefore, the problem to be solved by the present invention is to provide a curable composition that can be cured at low temperatures (eg, 100° C. or lower) or can be cured only by light irradiation and can form a cured film that satisfies both resolution and development adhesion.

[0011] [Technical means to solve the problem]

[0012] According to the present invention, the following curable composition, cured film, organic EL device, and method for forming a cured resin layer are provided.

[0013] In one embodiment, the present invention relates to a curable composition,

[0014] The curable composition is used to form a curable resin layer of a light-emitting device, wherein the light-emitting device includes a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a curable resin portion having at least one curable resin layer on the sealing layer, the curable composition comprising:

[0015] Alkali-soluble resin (A);

[0016] a polyfunctional free radical polymerizable compound (B);

[0017] Photoradical polymerization initiator (C);

[0018] UV absorber (D); and

[0019] Silane coupling agent (E),

[0020] 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.

[0021] In another embodiment, the present invention relates to a

[0022] A cured film formed by curing the curable composition, and

[0023] An organic EL device including the cured film.

[0024] In another embodiment, the present invention relates to a method for forming a hardened resin layer, which is a method for forming the hardened resin layer of a light-emitting device.

[0025] The light emitting device comprises a substrate, a light emitting element on the substrate, a sealing layer on the light emitting element, and a hardened resin portion having at least one hardened resin layer on the sealing layer, wherein a method for forming the hardened resin layer comprises:

[0026] a step of forming a coating film by directly or indirectly applying the curable composition of the present invention on the sealing layer;

[0027] After forming the coating film, irradiating at least a portion of the coating film with radiation;

[0028] a step of developing the coating film after the step of irradiating the radiation; and

[0029] After the development step, the coating film is exposed to light and / or heated at a temperature of 120° C. or lower.

[0030] In yet another embodiment, the present invention relates to a hardening composition comprising:

[0031] Alkali-soluble resin (A);

[0032] a polyfunctional free radical polymerizable compound (B);

[0033] Photoradical polymerization initiator (C);

[0034] UV absorber (D); and

[0035] Silane coupling agent (E),

[0036] 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.

[0037] [Effects of the Invention]

[0038] The curable composition of the present invention contains a specific ultraviolet absorber (D) that absorbs light at a wavelength of 360 nm and transmits light at a wavelength of 410 nm, and a silane coupling agent (E), thereby forming a cured film that achieves both high resolution and good development adhesion. Furthermore, the curable composition of the present invention can be cured at low temperatures of 100°C or lower, thus suppressing thermal degradation of the light-emitting element even when used on a substrate having a light-emitting element. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 A cross-sectional view showing one embodiment of a light-emitting device using a curable resin layer formed from the curable composition of the present invention.

[0040] Explanation of Figure Numbers

[0041] 1a: First metal wiring layer

[0042] 2a: Second metal wiring layer

[0043] 3: Contact hole

[0044] 3': Wiring

[0045] 10: Substrate

[0046] 20: Light-emitting element

[0047] 30: Sealing layer

[0048] 40: Hardened resin part

[0049] 41: Wiring base layer

[0050] 42: Patterned hardened resin layer

[0051] 43: Upper protective layer DETAILED DESCRIPTION

[0052] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

[0053] Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower limit and the upper limit.

[0054] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The so-called "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that does not contain a cyclic structure on the main chain but is composed only of a chain structure. Among them, the chain hydrocarbon group may be saturated or unsaturated. The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that only contains the structure of an alicyclic hydrocarbon as a ring structure and does not contain an aromatic ring structure. Among them, the alicyclic hydrocarbon group does not need to be composed only of the structure of an alicyclic hydrocarbon, and also includes a group having a chain structure in a part thereof. The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. Among them, the aromatic hydrocarbon group does not need to be composed only of the aromatic ring structure, and may also contain a chain structure or an alicyclic hydrocarbon structure in a part thereof. In addition, the ring structure possessed by the alicyclic hydrocarbon group and the aromatic hydrocarbon group may also have a substituent containing a hydrocarbon structure.

[0055] In this specification, "(meth)acryloyl" includes both "acryloyl" and "methacryloyl," "(meth)acrylate" includes both "acrylate" and "methacrylate," and "(meth)acrylate" includes both "acrylate" and "methacrylate."

[0056] A light-emitting device using a cured resin layer formed from the curable composition of the present invention will be described.

[0057] Luminous Installation

[0058] A light-emitting device comprises a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a hardened resin portion on the sealing layer, wherein the hardened resin portion comprises at least one hardened resin layer. Specifically, the light-emitting device comprises a substrate, a light-emitting element, a sealing layer, and a hardened resin portion in this order. These layers may be in contact with each other or may have other layers formed therebetween.

[0059] The sealing layer and the hardened resin portion may be formed in contact with each other, or another layer may be interposed between them. However, it is preferred that no support (such as a glass substrate or a resin substrate formed from a resin such as polyethylene terephthalate) with a thickness exceeding 50 μm be placed between the sealing layer and the hardened resin portion. More preferably, no support itself is used. Sometimes, the light-emitting element and the touch screen layer (hardened resin layer) are formed separately and then laminated together using a support. However, in this embodiment, it is preferred that the sealing layer and the hardened resin portion be formed directly or indirectly in contact with each other via another layer (such as a planarization layer) on top of the sealing layer after the sealing layer is formed.

[0060] The light-emitting device is, for example, a device comprising a stacked structure of organic layers including an organic light-emitting layer and an organic semiconductor thin film. Specifically, an organic electroluminescent (EL) device and an organic transistor are examples, and an organic EL device is preferred. Examples of the organic EL device include an organic EL lighting device and an organic EL display device.

[0061] As the substrate, any substrate used in a conventional light-emitting device may be used, and examples thereof include a glass substrate and a resin substrate. Specifically, the substrate described in International Publication No. 2019 / 009360 can be preferably used.

[0062] The substrate is, for example, a thin film transistor (TFT) substrate having thin film transistors (TFTs) for driving the light emitting elements. In one embodiment, the TFTs are arranged in a matrix. The TFT substrate may also have a planarization film covering the TFTs.

[0063] As the light-emitting element, an organic EL element is preferably used. As the organic EL element, the organic EL element used in the known organic EL device can be listed, as long as the organic EL layer containing the light-emitting material is sandwiched between a pair of electrodes facing each other (that is, as long as the organic light-emitting layer is sandwiched between the anode and cathode facing each other), for example, a known structure with anode / organic light-emitting layer / cathode can be listed. Specifically, for example, those described in International Publication No. 2019 / 009360 can be preferably used.

[0064] The sealing layer seals the light-emitting element and can reduce the intrusion of moisture into the light-emitting element. As a result, the generation of dark spots or the reduction in light-emitting characteristics such as brightness and light-emitting efficiency caused by moisture can be suppressed.

[0065] 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 alternating between organic and inorganic sealing layers. For example, an organic-inorganic sealing layer may have an organic sealing layer between two inorganic sealing layers, or an organic-inorganic sealing layer may have four or more inorganic and organic sealing layers alternating between them. The outermost layer of the sealing layer is preferably an inorganic sealing layer.

[0066] Examples of the inorganic sealing layer include those described in Japanese Patent Application Laid-Open No. 2010-160906, Japanese Patent Application Laid-Open No. 2016-012433, and Japanese Patent Application Laid-Open No. 2016-143605. Specifically, layers comprising silicon nitride (SiNx) or silicon oxide (SiOx) can be used, and methods for forming these layers include sputtering and chemical vapor deposition. The thickness of one layer of the inorganic sealing layer is generally about 10 nm to 2 μm.

[0067] Examples of the organic sealing layer include a layer formed of a curable composition. The thickness of one layer of the organic sealing layer is generally 1 μm to 50 μm, preferably 1 μm to 20 μm, and more preferably 1 μm to 15 μm.

[0068] As the curable composition for forming the organic sealing layer or the method for forming the sealing layer, the composition or method described in International Publication No. 2019 / 009360 can be preferably used.

[0069] The curable resin portion includes a curable resin layer comprising the curable composition of the present invention. The curable resin layer may also have a pattern. The patterned curable resin layer (hereinafter also referred to as a patterned curable resin layer) is preferably a layer formed directly on the sealing layer using the curable composition of the present invention by photolithography.

[0070] The shape of the pattern is not particularly limited, and examples thereof include the shape of a portion where the cured resin layer does not exist, such as a circular shape, an elliptical shape, a polygonal shape, a hole shape, or a linear shape.

[0071] The hardened resin portion generally has two or more metal wiring layers that are insulated from each other by the patterned hardened resin layer and electrically connected to necessary portions via wiring formed in contact holes formed in the patterned hardened resin layer.

[0072] The thickness of the patterned hardened resin layer is generally 1 μm to 5 μm. The thickness of the metal wiring layer is generally 100 nm to 1000 nm. The diameter of the contact hole is generally 1 μm to 20 μm.

[0073] The hardened resin portion may further include a hardened layer serving as a wiring base layer on the light-emitting element side of the patterned hardened resin layer, and / or may further include a hardened layer serving as an upper protective layer on the side of the patterned hardened resin layer opposite the light-emitting element. These hardened layers may be unpatterned layers and function as wiring base layers or upper protective layers for metal wiring layers. The wiring base layer or upper protective layer may be formed from the curable composition of the present invention.

[0074] The thickness of the wiring base layer and the upper protective layer are each independently usually 0.5 μm to 10 μm.

[0075] 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.

[0076] use Figure 1 One embodiment of a display device including a curable resin layer formed from the curable composition of the present invention will be described. Figure 1 As shown, one embodiment of the hardened resin portion 40 includes: a wiring base layer 41, a first metal wiring layer 1a formed on the wiring base layer 41, a patterned hardened resin layer 42 partially covering the first metal wiring layer 1a, a second metal wiring layer 2a formed on the patterned hardened resin layer 42 and electrically connected to the first metal wiring layer 1a via wiring 3' formed in the contact hole 3 of the patterned hardened resin layer 42, and an upper protective layer 43 formed on the patterned hardened resin layer 42 and the second metal wiring layer 2a and covering the second metal wiring layer 2a. The wiring base layer 41 may also be omitted. Figure 1 In the embodiment, the curing resin portion 40 is formed in direct contact with the sealing layer 30 in the element substrate including the substrate 10 , the light emitting element 20 , and the sealing layer 30 .

[0077] The hardened resin portion 40 is preferably a touch screen component.

[0078] The material constituting the metal wiring layer 1a or the metal wiring layer 2a is not particularly limited, and 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, or materials containing two or more of these metals, or alloys containing these metals as main components. Among these, TiAlTi wiring having a laminated structure of titanium and aluminum is preferred as the metal wiring.

[0079] The cured resin layer formed from the curable composition of the present invention is in contact with a metal wiring layer such as TiAlTi wiring or a layer containing silicon nitride (SiNx) or silicon oxide (SiOx), and therefore requires good adhesion thereto.

[0080] Hereinafter, the curable composition of the present invention will be described.

[0081] Curable composition

[0082] The curable composition of this embodiment (hereinafter also referred to as “this composition”) is used to form a curable resin layer included in the light-emitting device, and includes:

[0083] Alkali-soluble resin (A);

[0084] a polyfunctional free radical polymerizable compound (B);

[0085] Photoradical polymerization initiator (C);

[0086] UV absorber (D); and

[0087] Silane coupling agent (E),

[0088] 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.

[0089] Hereinafter, each component contained in this composition and other components mix|blended as needed are demonstrated.

[0090] <(A) Alkali-soluble resin>

[0091] The alkali-soluble resin (A) is a component that can exhibit good developability with an alkali developer. The alkali-soluble resin (A) is usually a resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group, and is preferably a resin having a carboxyl group.

[0092] The alkali-soluble resin (A) is preferably at least one selected from the group consisting of acrylic resins, silicone resins, and novolac resins, more preferably at least one selected from the group consisting of acrylic resins and novolac resins, and even more preferably novolac resins.

[0093] The alkali-soluble resin (A) preferably has a group containing an unsaturated double bond, such as a (meth)acryloyl group or a vinyl group, from the viewpoint of further improving developability and cured film properties. Such an alkali-soluble resin (A) is preferably an acid-modified epoxy (meth)acrylate resin obtained by reacting a compound having an epoxy group with (meth)acrylic acid. Examples thereof include acid-modified cresol novolac-type epoxy (meth)acrylate resins, phenol novolac-type epoxy (meth)acrylate resins, bisphenol A-type epoxy (meth)acrylate resins, bisphenol F-type epoxy (meth)acrylate resins, biphenyl-type epoxy (meth)acrylate resins, and trisphenol methane-type epoxy (meth)acrylate resins. Examples of the alkali-soluble resin (A) include acid-modified cardo-based resins having a (meth)acryloyl group and a carboxyl group. Among these, acid-modified cresol novolac type epoxy (meth)acrylate resins and phenol novolac type epoxy (meth)acrylate resins are preferred.

[0094] (Acrylic resin)

[0095] Examples of the acrylic resin include copolymers of a monomer having an alkali-soluble functional group and other copolymerizable monomers.

[0096] Examples of the monomer having an alkali-soluble functional group include:

[0097] Carboxyl-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;

[0098] Monomers containing phenolic hydroxyl groups such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene;

[0099] Maleimide, etc.

[0100] Examples of the other copolymerizable monomers include:

[0101] (Meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, and dicyclopentadienyl (meth)acrylate;

[0102] Aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene;

[0103] Conjugated dienes such as butadiene and isoprene;

[0104] Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and other vinyl cyanide compounds;

[0105] Hydroxyl-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate;

[0106] Macromonomers having a polymerizable unsaturated group such as a (meth)acryloyl group at one end of the polymer chain, such as polystyrene, polymethyl (meth)acrylate, polyethyl (meth)acrylate, and polybenzyl (meth)acrylate, etc. These can be used alone or in combination of two or more.

[0107] The lower limit of the content of the monomer having an alkali-soluble functional group in 100% by mass of all monomers constituting the acrylic resin is preferably 5% by mass, more preferably 10% by mass. The upper limit of the content is not particularly limited, but is preferably 40% by mass, more preferably 30% by mass.

[0108] The acrylic resin may be produced by any method, but not limited to, suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, or other known methods. Conventionally known conditions may also be employed for the production of the acrylic resin.

[0109] (Polysilicone resin)

[0110] Examples of the polysiloxane resin include hydrolysis-condensates of hydrolyzable silane compounds. Here, a "hydrolyzable silane compound" refers to a compound containing a group that can be hydrolyzed to form a silanol group or a group that can form a siloxane condensate, and a "hydrolysis-condensate" refers to a condensate formed by condensing the silanol groups of a hydrolyzed silane compound. Examples of such polysiloxane resins include those described in Japanese Patent Application Laid-Open No. 2017-048355.

[0111] (phenolic novolac resin)

[0112] The novolac resin can be obtained by polycondensing phenols with aldehydes such as formaldehyde using a known method.

[0113] 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, methylenebis(p-cresol), resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, 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, β-naphthol, etc. These may be used alone or in combination of two or more.

[0114] 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.

[0115] The novolac resin preferably has a group containing an unsaturated double bond, such as a (meth)acryloyl group or a vinyl group, and more preferably has a side chain represented by the following formula (1). In this case, it is preferred that the main chain further have an aromatic ring. Among them, a resin having a side chain represented by the following formula (1) and a phenolic novolac main chain is more preferred.

[0116] Examples of resins having a phenolic novolac main chain and a side chain represented by the following formula (1) include acid-modified cresol novolac-type epoxy (meth)acrylate resins and acid-modified phenol novolac-type epoxy (meth)acrylate resins. Such resins are preferred because they have a rigid main chain skeleton and side chains containing ethylenically unsaturated groups and carboxyl groups, exhibiting sufficient photolithographic performance and providing a cured film even by heating at relatively low temperatures of 100°C or lower.

[0117] [Chemistry 1]

[0118]

[0119] In the formula (1), R 5 is a hydrogen atom or a methyl group. 6 and R 7 Each is independently a divalent organic group. * indicates the bonding site to the main chain.

[0120] As the R 5 , preferably a hydrogen atom.

[0121] As the R 6 and R 7 Examples of the divalent organic group include a divalent hydrocarbon group, a heteroatom-containing group containing a divalent heteroatom-containing group at the end of the carbon-carbon or bonding side of the divalent hydrocarbon group, and a group in which a part or all of the hydrogen atoms possessed by the hydrocarbon group and the heteroatom-containing group are substituted with a monovalent heteroatom-containing group.

[0122] Examples of the divalent hydrocarbon group include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

[0123] Examples of the divalent chain hydrocarbon group include:

[0124] Alkanediyl groups such as methanediyl, ethanediyl, n-propanediyl, isopropanediyl, n-butanediyl, isobutanediyl, and sec-butanediyl;

[0125] Alkenediyl groups such as ethylenediyl, propylenediyl, and butenediyl;

[0126] Alkynediyl groups such as acetylenediyl, propynediyl, butynediyl, etc.

[0127] Examples of the divalent alicyclic hydrocarbon group include:

[0128] Monocyclic cycloalkanediyl groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl;

[0129] Monocyclic cycloalkene diyl groups such as cyclopropene diyl, cyclobutene diyl, cyclopentene diyl, and cyclohexene diyl;

[0130] Polycyclic cycloalkanediyl groups such as norbornanediyl, adamantanediyl, tricyclodecanediyl, and tetracyclododecandiyl;

[0131] Polycyclic cycloalkene diyl groups such as norbornene diyl, tricyclodecenediyl, and tetracyclododecenediyl, etc.

[0132] Examples of the divalent aromatic hydrocarbon group include:

[0133] Aromatic diyl groups such as benzene diyl, toluene diyl, and naphthalene diyl;

[0134] Aryldiylalkanediyl such as benzylmethanediyl and naphthalenediylmethanediyl.

[0135] Examples of the divalent heteroatom-containing group include -O-, -CO-, -CO-O-, -S-, -CS-, -SO2-, -NR'-, and combinations of two or more of these. R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0136] Examples of the monovalent heteroatom-containing group include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, a carboxyl group, a cyano group, an amino group, and a mercapto group (—SH).

[0137] As the R 6 and R 7 The carbon number of the divalent organic group is not particularly limited, but the lower limit thereof may be 1. On the other hand, the upper limit thereof may be 20 or 10, for example.

[0138] As the R 6 , preferably a divalent hydrocarbon group, more preferably a divalent chain hydrocarbon group and a divalent alicyclic hydrocarbon group. 7 , preferably a group in which an oxygen atom (—O—) is bonded to the terminal of the main chain side of the divalent hydrocarbon group, such as —CH 2 —O—*.

[0139] Examples of acid-modified cresol novolac-type epoxy (meth)acrylate resins include polymers represented by the following formula (2). Acid-modified cresol novolac-type epoxy (meth)acrylate resins can be obtained, for example, by reacting an acid anhydride such as phthalic anhydride or 1,2,3,6-tetrahydrophthalic anhydride with an epoxy (meth)acrylate resin obtained by reacting (meth)acrylic acid with a cresol novolac-type epoxy resin.

[0140] [Chemistry 2]

[0141]

[0142] In the above formula (2), p and q are each independently an integer of 1 to 30.

[0143] Alternatively, as the alkali-soluble resin (A), a cardo-based resin having a side chain represented by the formula (1) and subjected to a predetermined acid modification may be used. Commercially available products of such resins include "WR-301" (ADEKA Co.), an acid-modified cardo-based resin.

[0144] 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).

[0145] 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 coating properties, photolithographic performance, and cured film characteristics.

[0146] When the alkali-soluble resin (A) has unsaturated double bonds, the double bond equivalent is preferably 100 g / mol to 1200 g / mol, more preferably 100 g / mol to 850 g / mol, and even more preferably 100 g / mol to 600 g / mol. The double bond equivalent is the mass per 1 mol of the unsaturated double bonds in the alkali-soluble resin (A) and can be calculated as (mass of the alkali-soluble resin (A) (g)) / (amount of unsaturated double bonds in the alkali-soluble resin (A) (mol)).

[0147] The alkali-soluble resin (A) may be used alone or in combination of two or more.

[0148] The lower limit of the content of the alkali-soluble resin (A) (the total amount in multiple cases) is preferably 5% by mass, more preferably 10% by mass, further preferably 20% by mass, and particularly preferably 30% by mass, relative to the total solid content (100% by mass) of the present composition (i.e., the total amount of components other than the organic solvent (H) in the present composition). Furthermore, the upper limit is preferably 90% by mass, more preferably 80% by mass, further preferably 70% by mass, and particularly preferably 60% by mass, relative to the total solid content (100% by mass) of the present composition. When the content of the alkali-soluble resin (A) is within this range, more sufficient lithographic performance and curability can be achieved.

[0149] <(B) Polyfunctional radical polymerizable compound>

[0150] The polyfunctional radical polymerizable compound (B) may be any polymerizable compound that reacts and cures by utilizing radicals generated by a photoradical polymerization initiator. However, from the perspective of improving the storage stability of the curable composition or controlling the curability of the resulting cured film, a polymerizable compound having two or more (meth)acryloyl groups in the molecule, i.e., a polyfunctional (meth)acrylate, is preferred. Specific examples of such polyfunctional (meth)acrylates include difunctional (meth)acrylates and trifunctional or higher-functional (meth)acrylates.

[0151] Examples of the difunctional (meth)acrylate 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, tricyclodecanemethanol di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, and neopentyl glycol hydroxypivalate di(meth)acrylate.

[0152] Examples of the trifunctional or higher functional (meth)acrylate include trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide (EO)-modified tri(meth)acrylate, trimethylolpropane propylene oxide (PO)-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloyloxyethyl)phosphate, succinic acid-modified dipentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, and mixtures thereof. In addition, polyfunctional urethane (meth)acrylate compounds obtained by reacting a compound having a linear alkylene structure and an alicyclic structure and having two or more isocyanate groups with a compound having one or more hydroxyl groups and three, four, or five (meth)acryloyloxy groups in the molecule can be mentioned.

[0153] Among these, the polyfunctional radical polymerizable compound (B) preferably contains a trifunctional or higher functional (meth)acrylate, 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.

[0154] The polyfunctional radically polymerizable compound (B) may be used alone or in combination of two or more.

[0155] The mass ratio of the content of the polyfunctional radically polymerizable compound (B) to the content of the alkali-soluble resin (A) ((B) / (A)) is preferably 1 / 2 or more and 2 / 1 or less. Preferably, the polyfunctional radically polymerizable compound (B) is a tetrafunctional or higher-functional (meth)acrylate, and the mass ratio of component (B) to component (A) is 1 / 2 or more and 2 / 1 or less.

[0156] The lower limit of the content of the multifunctional free radical polymerizable compound (B) (total amount in the case of multiple types) 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 further preferably 120 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). By keeping the proportion of component (B) within the above range, the various properties of the obtained cured film can be more effectively improved, and therefore, it is preferred.

[0157] <(C) Photoradical polymerization initiator>

[0158] The photoradical polymerization initiator (C) is a compound that can generate free radicals in response to radiation and initiate polymerization. Specific examples of the photoradical polymerization initiator (C) include O-acyl oxime compounds, α-amino ketone compounds, α-hydroxy ketone compounds, and acylphosphine oxide compounds. Among these, oxime-based photopolymerization initiators such as O-acyl oxime compounds are preferred.

[0159] The use of these oxime ester photoinitiators is preferred because they improve sensitivity and, when forming fine line patterns, can easily suppress line width variations within a plane. Furthermore, the use of oxime ester photoinitiators tends to increase the residual film rate and suppress water staining. Water stains refer to traces of water immersion that occur after rinsing with pure water after alkali development when using an ingredient that enhances alkali developability.

[0160] As the oxime ester-based photoinitiator, from the perspective of reducing contamination of the composition or the equipment by decomposition products, those having an aromatic ring are preferred, those having a condensed ring containing an aromatic ring are more preferred, and those having a condensed ring containing a benzene ring and a heterocyclic ring are even more preferred.

[0161] Examples of the oxime ester photoinitiator include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and oxime ester photoinitiators described in Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2010-527338, and Japanese Patent Application Publication No. 2013-041153. Commercially available products include Irgacure OXE-01 (manufactured by BASF), ADEKA Arkls NCI-930 (manufactured by ADEKA) having a diphenyl sulfide skeleton, 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 Qiangli Electronic New Materials Co., Ltd.).

[0162] The photoradical polymerization initiator (C) may be used alone or in combination of two or more.

[0163] As the lower limit of the content of the photoradical polymerization initiator (C) (total amount in multiple cases), it 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, as the upper limit of the content, it is preferably 40 parts by mass, more preferably 30 parts by mass, and further preferably 20 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). By keeping the proportion of the component (C) within the range, even if the present composition is a low exposure, a cured film with good resolution and development adhesion can be formed, and therefore it is preferred.

[0164] (D) Ultraviolet absorbers

[0165] 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 an absorption maximum wavelength at a wavelength of 400 nm or less, and having no absorption wavelength in visible light exceeding 420 nm. The ultraviolet absorber (D) may be a compound having no absorption wavelength in visible light exceeding 400 nm.

[0166] A 0.006% by mass solution of a UV absorber (e.g., a 0.006% by mass propylene glycol monomethyl ether acetate solution) is prepared, and the transmittance of the 0.006% by mass solution is measured using an ultraviolet-visible near-infrared spectrophotometer (e.g., JASCO Corporation, V-670), thereby obtaining transmittances of wavelengths of 360 nm and 410 nm. The solvent for forming a 0.006% by mass solution of a UV absorber is not particularly limited, as long as it is a solvent that dissolves the UV absorber, but propylene glycol monomethyl ether acetate is preferably used. Wherein, in the case where it is difficult to prepare a 0.006% by mass solution of a UV absorber using propylene glycol monomethyl ether acetate, a solvent suitable for the UV absorber to be dissolved can be selected for use. Examples of such solvents include dichloromethane, tetrahydrofuran, N-methylpyrrolidone, or an organic solvent (H) described later.

[0167] 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 even more preferably 3% or less. By using an ultraviolet absorber (D) with a low transmittance at a wavelength of 360 nm, a cured film with good resolution can be formed.

[0168] 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 an ultraviolet absorber (D) with a high transmittance at a wavelength of 410 nm, the brightness of the EL element in the actual panel can be maintained.

[0169] The ultraviolet absorber (D) used in the present invention is not particularly limited in structure as long as the transmittance at a wavelength of 360 nm and a wavelength of 410 nm satisfies the above ranges. Examples of the ultraviolet absorber (D) include benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzoate ultraviolet absorbers, benzoic acid ultraviolet absorbers, anthranilic acid ultraviolet absorbers, salicylic acid ultraviolet absorbers, and cinnamic acid ultraviolet absorbers. Among these, preferred are at least one ultraviolet absorbers selected from the group consisting of benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and benzophenone ultraviolet absorbers. More preferred are at least one ultraviolet absorbers selected from the group consisting of benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers. Even more preferred are benzotriazole ultraviolet absorbers.

[0170] (Benzotriazole-based UV absorber)

[0171] Examples of the benzotriazole-based ultraviolet absorber include at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers represented by the following formula (3).

[0172] [Chemistry 3]

[0173]

[0174] (In the above formula (3),

[0175] 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 them is a hydroxyl group, -ORa, or an organic group having 1 to 15 carbon atoms.

[0176] X 4 represents a hydrogen atom or a halogen atom)

[0177] In the formula (3), X 1 、X 2 and X 3 The organic group in the alkyl group may include a monovalent hydrocarbon group, a heteroatom-containing group containing a divalent heteroatom-containing group at the end of the carbon-carbon or bonding side of the monovalent hydrocarbon group, and a group in which a part or all of the hydrogen atoms possessed by the hydrocarbon group and the heteroatom-containing group are substituted with a monovalent heteroatom-containing group.

[0178] As the X 1 、X2 and X 3 Examples of the monovalent hydrocarbon group in Ra include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group.

[0179] Examples of the monovalent chain hydrocarbon group include R 6 and R 7 The monovalent chain hydrocarbon group corresponding to the divalent chain hydrocarbon group in the formula (1) can be exemplified as the monovalent alicyclic hydrocarbon group. 6 and R 7 The monovalent alicyclic hydrocarbon group corresponding to the divalent alicyclic hydrocarbon group in the formula (1) may be R 6 and R 7 The monovalent aromatic hydrocarbon group corresponding to the divalent aromatic hydrocarbon group in .

[0180] Furthermore, as the divalent heteroatom-containing group and the monovalent heteroatom-containing group, the groups listed in the above formula (1) can be preferably used.

[0181] As the organic group, 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., in addition, it can be 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl, 4-glycidyloxyphenyl, 4-isocyanuratephenyl, etc. The -C8H 17 、-C 12 H 25 etc. can be straight chain or branched.

[0182] Among the benzotriazole-based ultraviolet absorbers represented by the formula (3), X is preferably 2 is a hydrogen atom, X 1 and X 3 are independently a hydrogen atom or an organic group having 1 to 15 carbon atoms (wherein X 1 and X 3 At least one of them is an organic group having 1 to 15 carbon atoms), X4 is 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.

[0183] Specific examples of the benzotriazole-based ultraviolet absorber represented by the formula (3) include compounds represented by the following formulas (3-1) to (3-9).

[0184] [Chemistry 4]

[0185]

[0186] (Triazine UV absorber)

[0187] Examples of the triazine-based ultraviolet absorber include at least one ultraviolet absorber selected from the group consisting of triazine-based ultraviolet absorbers represented by the following formula (4).

[0188] [Chemistry 5]

[0189]

[0190] (In the above formula (4),

[0191] 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 them represents a hydroxyl group, -ORb or an organic group having 1 to 15 carbon atoms)

[0192] The 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) may preferably be one of the following: 1 、X 2 and X 3The same group as the organic group having 1 to 15 carbon atoms in Rb. In addition, the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent in Rb is preferably the same group as the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent in Ra of formula (3).

[0193] Y 2 、Y 4 , and Y 6 At least one of the groups may be a hydroxyl group, and the triazine-based UV absorber may be a hydroxyphenyltriazine-based UV absorber.

[0194] Among the triazine-based ultraviolet absorbers represented by the formula (4), Y 1 、Y 2 、Y 3 、Y 4 、Y 5 and Y 6 are each independently a hydroxyl group or -ORb, Rb is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have an ester group, and more preferably Y 2 、Y 4 and Y 6 At least one of them is a hydroxyl group. As the triazine ultraviolet absorber represented by the formula (4), Y 1 and Y 2 are independently hydroxyl or -ORb, Y 4 and Y 6 is hydroxyl group, Y 3 and Y 5 is -ORb, Rb is -CH(CH3)-CO2-C8H 17 and the like, which may include an aliphatic hydrocarbon group having 1 to 12 carbon atoms and an ester group.

[0195] Specific examples of the triazine-based ultraviolet absorber represented by the formula (4) include compounds represented by the following formulas (4-1) and (4-2).

[0196] [Chemistry 6]

[0197]

[0198] (Benzophenone-based UV absorber)

[0199] Examples of the benzophenone-based ultraviolet absorber include hydroxybenzophenone-based ultraviolet absorbers, and for example, at least one ultraviolet absorber selected from the group consisting of hydroxybenzophenone-based ultraviolet absorbers represented by the following formula (5) can be mentioned.

[0200] [Chemistry 7]

[0201]

[0202] (In the above formula (5),

[0203] Z 1 represents a hydroxyl group, -ORc, or an organic group having 1 to 15 carbon atoms, and Z 2 represents a hydrogen atom, a hydroxyl group, -ORc, or an organic group having 1 to 15 carbon atoms, and 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)

[0204] In the formula (5), Z 1 and Z 2 The organic group having 1 to 15 carbon atoms in the formula (3) may preferably be one of the following: 1 、X 2 and X 3 The same group as the organic group having 1 to 15 carbon atoms in Rc. In addition, the hydrocarbon group having 1 to 15 carbon atoms in Rc which may have a substituent is preferably the same group as the hydrocarbon group having 1 to 15 carbon atoms in Ra in formula (3) which may have a substituent.

[0205] Among the hydroxybenzophenone-based ultraviolet absorbers, Z 1 is a hydroxyl group, -ORc, or an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, Z 2 is a hydrogen atom, a hydroxyl group, -ORc, or an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, 3 is a hydrogen atom or a hydroxyl group, Rc is an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, and Z is more preferably 1 is a hydroxyl group, -ORc, or an unsubstituted aliphatic hydrocarbon group having 1 to 4 carbon atoms, Z 2 and Z 3 is a hydrogen atom or a hydroxyl group, and Rc is an unsubstituted aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0206] As the ultraviolet absorber (D), a cyanoacrylate-based ultraviolet absorber may also be used. Examples thereof include Uvinul 3035, Uvinul 3039, and Uvinul 3030FF (produced by Ogiseki Co., Ltd.).

[0207] In order to efficiently absorb ultraviolet rays, 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. However, since polymers have low ultraviolet absorption capacity, non-polymer compounds having no repeating units are preferred.

[0208] In addition, if the transmittance of the ultraviolet absorber (D) used in the present invention at a wavelength of 360nm in a 0.006 mass% solution (preferably a propylene glycol monomethyl ether acetate solution) is less than 10%, and the transmittance at a wavelength of 410nm is 80% or more, then two or more can be mixed and used. That is, even if the ultraviolet absorber (D) used in the present invention contains a substance with a transmittance of 10% or more at a wavelength of 360nm or less than 80% at a wavelength of 410nm in a 0.006 mass% solution (preferably a propylene glycol monomethyl ether acetate solution), by mixing two or more, as long as the transmittance at a wavelength of 360nm and the transmittance at a wavelength of 410nm meet the above ranges, then these mixtures can also be used as the ultraviolet absorber (D). There is no particular limitation on the ultraviolet absorbers that can be mixed, and ultraviolet absorbers commonly used in the art can also be suitably used.

[0209] Specific examples of the ultraviolet absorber (D) used in the present invention include 2-phenol, 2-(2H-benzotriazole-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, phenylpropionic acid, 3-(2H-benzotriazole-2- 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, etc., but are not limited to these. Examples of commercially available ultraviolet absorbers used in the present invention include Tinuvin 329, Tinuvin 326, Tinuvin 477, Tinuvin PS, Tinuvin 99-2, Tinuvin 384-2, Tinuvin 900, and Tinuvin 928 (all manufactured by BASF), Kemisorb 111, and Kemisorb 73 (produced by Chemipro Chemicals). The present invention also includes, but is not limited to, Uvinul 3049, Uvinul 3050, Uvinul 3035, Uvinul 3039, and Uvinul 3030FF (all manufactured by Ogiseki Co., Ltd.).

[0210] The ultraviolet absorbers (D) may be used alone or in combination of two or more.

[0211] As the lower limit of the content of the ultraviolet absorber (D) (total amount in multiple cases), it is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, further 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, as the upper limit of the content, it is preferably 30 parts by mass, more preferably 15 parts by mass, and further preferably 10 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A). By containing the proportion of the (D) component within the above range, a cured film with excellent developability can be formed, and therefore it is preferred.

[0212] 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 this range, a cured film with excellent resolution can be formed, which is preferred.

[0213] <(E) Silane coupling agent>

[0214] The silane coupling agent (E) is preferably a compound that improves the adhesion between the cured film and a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Specific examples include known silane coupling agents, and a silane coupling agent having an ethylenically unsaturated bond is preferred.

[0215] The silane coupling agent (E) is preferably a silane coupling agent having a hydrolyzable group such as a methoxy group, ethoxy group, or acetoxy group, and a functional group such as a (meth)acryloyloxy group, a glycidyl group, an amino group, a thiol group, or an isocyanate group. Since the silane coupling agent can be fixed to the main component resin, it is preferably a silane coupling agent having a reactive group with the alkali-soluble resin (A) or the polyfunctional radical polymerizable compound (B), and particularly preferably a silane coupling agent having a (meth)acryloyloxy group.

[0216] The silane coupling agent (E) is preferably a silane coupling agent having 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 a silane coupling agent having a (meth)acryloyloxy group.

[0217] 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. Of these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, and γ-glycidoxypropyltrialkoxysilane are more preferred. These may 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, and KBE-585A (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0218] The silane coupling agent (E) may be a polymer type. For example, a silane coupling agent having an organic main chain structure and a hydrolyzable group and other functional groups bonded thereto may be preferably used. Commercially available organic polymer types include X-12-1048, X-12-1050, X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L.

[0219] The silane coupling agent (E) may be used alone or in combination of two or more.

[0220] The lower limit of the content of the silane coupling agent (E) (the total amount in the case of multiple components) is preferably 0.1 parts by mass, more preferably 1 part by mass, and further 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 further preferably 10 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A). When the content ratio of the (E) component is within the above range, a cured film with excellent development adhesion can be formed, which is therefore preferred.

[0221] <(F) Phosphoric acid compound having a (meth)acryloyloxy group>

[0222] 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 the substrate or the conductive layer.

[0223] 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 thereof include the Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP) manufactured by Uni-Chemical 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 Co., Ltd., and the Light Ester series (Light Ester P-2M (trade name)) manufactured by Kyoeisha Chemical Co., Ltd.

[0224] The phosphoric acid compound (F) may be used alone or in combination of two or more.

[0225] When the present composition includes a phosphoric acid compound (F), the lower limit of the content of the phosphoric acid compound (F) (total amount in the case of multiple amounts) is preferably 0.05 parts by mass, more preferably 0.1 parts by mass, and further 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, and further preferably 8 parts by mass, and particularly preferably 6 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A). By including the phosphoric acid compound (F) within the range, it is preferred in terms of development adhesion.

[0226] <(G) Thiol compound>

[0227] In order to further improve the adhesion of the cured film to the substrate or the conductive layer and prevent undercutting, the present composition preferably contains a thiol compound (G) having one or more thiol groups per molecule. The thiol compound (G) only needs to have at least one thiol group, but is preferably a polyfunctional thiol compound having two or more thiol groups, more preferably a polyfunctional thiol compound having three or more thiol groups, and even more preferably a polyfunctional thiol compound having four or more thiol groups. The number of thiol groups per molecule is preferably six or less. However, the thiol compound (G) does not contain a substance equivalent to the silane coupling agent (E).

[0228] Examples of the polyfunctional thiol compound include primary polyfunctional thiols and secondary polyfunctional thiols. From the viewpoint of high storage stability and suppression of odor, secondary polyfunctional thiols are preferred.

[0229] Examples of the secondary polyfunctional thiol include pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and 1,3,5-tris[2-(3-mercaptobutyryloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0230] Examples of the primary polyfunctional thiol include trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexa(3-mercaptopropionate).

[0231] The thiol compound (G) can be used alone or in combination of two or more.

[0232] When the present composition contains a thiol compound (G), the upper limit of the content of the thiol compound (G) (the total amount in the case of two or more) is not particularly limited. However, in order to further improve the adhesion of the cured product to the substrate or the conductive layer, the content 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.

[0233] <(H)Organic solvent>

[0234] The present composition may further contain an organic solvent (H). The organic solvent (H) is not particularly limited, and examples thereof include alcohol solvents, ether solvents, ester solvents, ketone solvents, and amide solvents. The organic solvent (H) may be used alone or in combination of two or more.

[0235] Examples of the alcoholic solvent include alkyl alcohols such as methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, and diacetone alcohol; and aromatic alcohols such as benzyl alcohol.

[0236] Examples of the ether solvent 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.

[0237] Examples of the ester solvent include carboxylic acid esters such as ethyl acetate, isopropyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; polyol carboxylic acid ester solvents such as propylene glycol diacetate; and polyol partial ether carboxylic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.

[0238] Examples of the ketone-based solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0239] Among these, ether solvents and ester solvents are preferred, ester solvents are more preferred, and polyol partial ether carboxylate solvents are further preferred. Among ether solvents and ester 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.

[0240] The content of the organic solvent (H) in this composition is not particularly limited, but is preferably adjusted in the following range with the solid component (component other than the (H) organic solvent) concentration of this composition. As the lower limit of the solid component concentration in this composition, it is preferably 5 mass %, more preferably 10 mass %, and then preferably 20 mass %. On the other hand, as the upper limit of solid component concentration, it is preferably 60 mass %, more preferably 50 mass %, and then preferably 40 mass %.

[0241] <Other ingredients>

[0242] In addition to the aforementioned components, the present composition may further contain other components. Examples of these other components include hardeners, hardening accelerators, antioxidants, and surfactants. The content of these 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.

[0243] <Viscosity of Curable Composition>

[0244] The viscosity of the curable composition, as measured using an E-type viscometer at 25°C and 50 rpm, is preferably from 0.5 mPa·s to 20 mPa·s, more preferably from 0.5 mPa·s to 7 mPa·s, and even more preferably from 2.5 mPa·s to 5 mPa·s. The viscosity of the curable composition can be adjusted to within the above range by adjusting the amount of the organic solvent (H) added.

[0245] <Method for preparing curable composition>

[0246] The curable composition of the present invention can be prepared by mixing the components at a predetermined ratio and dissolving them in an organic solvent (H). The prepared composition is preferably filtered through a filter having a pore size of about 0.2 μm.

[0247] Hardening film

[0248] 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 produce a cured film having sufficient resolution and development adhesion even by heating at relatively low temperatures. The present composition is preferably curable at a post-bake temperature of 100°C or lower, and more preferably curable by heating at a temperature range of 60°C to 100°C.

[0249] The transmittance of the cured film formed by curing the curable composition of the present invention at a wavelength of 400 nm is preferably higher than 90%, more preferably higher than 95%.

[0250] The cured film of the present invention may be a patterned film.

[0251] The cured film of the present invention can be used as a cured resin layer in the cured resin portion of the light-emitting device. Specifically, it can be used as a wiring base layer, a patterned cured resin layer (interlayer insulation film for touchscreen wiring), or an upper protective layer (protective film for touchscreen wiring) in the cured resin portion.

[0252] The thickness of the cured film of the present invention is not particularly limited and can be appropriately set depending on the intended use.

[0253] Organic EL Device

[0254] The organic EL device of the present invention includes the present cured film. The organic EL device of the present invention preferably includes a touch screen laminated on a substrate having an organic EL element, and preferably uses the present cured film as a cured resin layer of at least a portion of the touch screen. It is particularly preferred to use the present cured film as an interlayer insulating film for a touch screen laminated on a substrate having an organic EL element without an adhesive layer or bonding layer. This method allows the touch screen to be directly laminated on a substrate having an organic EL element, thereby achieving a thinner organic EL device including a touch screen.

[0255] This curable composition can produce a cured film with a sufficient decomposition rate and development adhesion even by heating at relatively low temperatures. This can suppress degradation of the organic EL element during the manufacturing process of the organic EL device, thereby improving yields. Furthermore, since the curable composition can be used to form an insulating film by heating at relatively low temperatures, degradation of the organic EL element during the manufacturing process can be suppressed. Therefore, the curable composition is particularly suitable for forming insulating films in various organic EL devices including organic EL elements, including touch screens.

[0256] <Method for forming a cured resin layer>

[0257] A method for forming a hardened resin layer as one embodiment of the present invention is a method for forming the hardened resin layer of a light emitting device.

[0258] The light emitting device includes a substrate, a light emitting element on the substrate, a sealing layer on the light emitting element, and a hardened resin portion having at least one hardened resin layer on the sealing layer. A method for forming the hardened resin layer may include:

[0259] a step of forming a coating film by directly or indirectly applying the curable composition of the present invention on the sealing layer (hereinafter also referred to as a "coating film forming step");

[0260] After the step of forming the coating film, a step of irradiating (exposing) at least a portion of the coating film with radiation (hereinafter also referred to as "radiation irradiation step");

[0261] a step of developing the coating film after the step of irradiating the radiation (hereinafter also referred to as a "development step"); and

[0262] After the development step, the coating film is exposed to light and / or heated at a temperature of 120°C or less (hereinafter also referred to as an "exposure and heating step"). The formation method may also include, as an optional step, a step of heating the coating film between the radiation irradiation step and the development step (hereinafter also referred to as a "PEB (post-exposure bake) step").

[0263] According to the formation method, the use of the curable composition allows for a cured resin layer (cured film) that can be patterned in a good shape and exhibits high resolution and development adhesion. Furthermore, even when the substrate on which the coating film is formed includes an organic EL element, the degradation of the organic EL element can be suppressed by performing the heating process at a relatively low temperature. Each process is described below.

[0264] (Coating film forming step)

[0265] In this step, after applying the curable composition directly or via another layer on the sealing layer, the coated surface is preferably heated (prebaked) to remove the organic solvent and the like to form a coating film. The sealing layer is as described above.

[0266] The method for applying the curable composition is not particularly limited, and suitable methods such as spraying, roll coating, spin coating, slot die coating, and rod coating can be employed. Of these coating methods, spin coating and slot die coating are particularly preferred. Prebaking conditions vary depending on the type and proportion of the components, but for example, a temperature of 60°C to 120°C, more preferably 100°C or less, and a heating time of 1 minute to 10 minutes are sufficient.

[0267] (Radiation irradiation process)

[0268] In this process, at least a portion of the coating film formed in the coating film forming process is irradiated with radiation. Usually, when irradiating a portion of the coating film with radiation, the radiation is performed through a photomask having a predetermined pattern. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. can be used. Of these radiations, radiation having a wavelength of 190 nm or more and 450 nm or less is preferred, and radiation containing ultraviolet light of 365 nm is more preferred.

[0269] The lower limit of the exposure amount in this step is preferably 10 mJ / cm2, as measured by an illuminometer ("OAI model 356" manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm. 2 , more preferably 50 mJ / cm 2 The upper limit of the exposure dose is preferably 2,000 mJ / cm2 as measured by the illuminometer. 2 , more preferably 1,000 mJ / cm 2 .

[0270] (PEB process)

[0271] When a PEB process is provided, the PEB conditions vary depending on the types and blending ratios of the components. For example, the temperature may be 60°C to 120°C, more preferably 100°C to below, and the heating time may be 1 minute to 10 minutes.

[0272] (Development Process)

[0273] In this step, the coating film after radiation exposure is developed using a developer to form a predetermined pattern. The developer is preferably an alkaline developer. Examples of alkaline developers include alkaline aqueous solutions containing at least one alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. Furthermore, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer.

[0274] As a development method, suitable methods such as a coating method, immersion method, shaking immersion method, and spray method can be employed. The development time varies depending on the composition of the curable composition, but is, for example, from 10 seconds to 180 seconds. Following this development treatment, the desired pattern can be formed by washing with running water for, for example, from 30 seconds to 90 seconds, followed by air drying using, for example, compressed air or compressed nitrogen.

[0275] (Exposure and Heating Process)

[0276] In this step, the developed and patterned coating film is exposed and / or heated (post-baked) at a temperature of 120°C or lower 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 rays, and the exposure dose at this time can be, for example, 100 mJ / cm 2 Above and 2,000mJ / cm 2Below. The lower limit of the heating temperature is 60°C, preferably 80°C. By setting the heating temperature to above the lower limit, a fully cured hardened 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 below the upper limit, for example, a fully cured hardened resin layer (cured film) can be obtained while suppressing the degradation of the organic EL element included in the substrate. In addition, by setting the heating temperature to below the upper limit, the generation of excessive stress such as rapid film shrinkage can be suppressed, thereby suppressing the generation of cracks. In this way, heating is performed in a temperature range of 60°C to 120°C (preferably 60°C to 100°C) in the heating process. The heating time varies depending on the type of heating machine. For example, when heating on a hot plate, it can be set to 5 minutes to 30 minutes or less. When heating in an oven, it can be set to 10 minutes to 90 minutes or less. In addition, heating can be performed in air or in an inert gas environment such as nitrogen or argon. Alternatively, a step baking method in which the heating process is performed two or more times can be used.

[0277] (Other processes)

[0278] In the case of manufacturing an organic EL device, after the hardened resin layer (hardened film) is formed on the organic EL display substrate, other processes such as forming further electrodes, wiring, etc. are carried out. Examples of such processes include: an electrode forming process, a wiring forming process, an etching process, an ashing process, and the like. Well-known methods such as printing or vapor deposition can be used in the formation of electrodes or wiring. Etching can be carried out using, for example, well-known etching solutions such as amine solutions. Ashing can be carried out using well-known ashing methods such as oxygen ashing. In addition, when manufacturing a touch screen, etc., the formation of a hardened resin layer (hardened film) or the formation of electrodes, wiring, etc. can be carried out multiple times.

[0279] Curable composition

[0280] A curable composition according to one embodiment of the present invention includes:

[0281] Alkali-soluble resin (A);

[0282] a polyfunctional free radical polymerizable compound (B);

[0283] Photoradical polymerization initiator (C);

[0284] UV absorber (D); and

[0285] Silane coupling agent (E),

[0286] 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.

[0287] 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) described above can be preferably used. Examples of the curable composition include the same compositions as those described above.

[0288] The cured film formed from the curable composition has excellent resolution and development adhesion, and thus the curable composition can be preferably used as a material for forming interlayer insulating films, planarizing films, spacers, protective films, color filter colored pattern films, partition walls, banks, and the like.

[0289] [Example]

[0290] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "parts" and "%" are based on mass.

[0291] <Measurement of weight average molecular weight (Mw)>

[0292] 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.

[0293] Device: Resonac's "GPC-101"

[0294] Column: Connect to Resonac's "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804"

[0295] Mobile phase: tetrahydrofuran

[0296] Column temperature: 40°C

[0297] Flow rate: 1.0 mL / min

[0298] Sample concentration: 1.0 mass%

[0299] Sample injection volume: 100 μL

[0300] Detector: Differential refractometer

[0301] Standard material: monodisperse polystyrene

[0302] <Viscosity measurement>

[0303] The viscosity was measured at 25° C. using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) in accordance with Japanese Industrial Standards (JIS) K2283:2000.

[0304] <Measurement of transmittance of component (D)>

[0305] The ultraviolet absorber (D) 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-visible-near-infrared spectrophotometer (JASCO Corporation, V-670).

[0306] (Synthesis Example 1: Synthesis of Polymer (A-1))

[0307] Into a four-necked flask with a stirrer and a reflux cooler, 220 parts of a cresol novolac type epoxy resin (manufactured by DIC Co., Ltd., trade name: Epiclon N-695, epoxy equivalent: 220) were placed, 214 parts of carbitol acetate were added, and heated to dissolve. Next, 0.1 parts of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated to 95°C to 105°C, 72 parts of acrylic acid were slowly added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80°C to 90°C, 106 parts of tetrahydrophthalic anhydride were added, the mixture was reacted for 8 hours, and the mixture was taken out after cooling to obtain a carboxyl-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 a solid content of 85 mgKOH / g, and a weight average molecular weight Mw of approximately 3,500.

[0308] (Synthesis Example 2: Synthesis of Polymer (A-2))

[0309] 15 parts of 2,2'-azobis(2-methylpropionic acid)dimethyl ester and 200 parts of diethylene glycol ethyl methyl ether were added to a reaction apparatus including a stirrer, a cooling tube, a thermometer, and a nitrogen inlet. Subsequently, 16 parts of methacrylic acid, 25 parts of glycidyl methacrylate, 50 parts of styrene, and 9 parts of methyl methacrylate were added and the atmosphere was purged with nitrogen. While slowly stirring the solution in the flask, the temperature of the solution was raised to 80°C and the temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-2). The solid content concentration of the polymer solution was 34.5% by mass, the Mw of polymer (A-2) was 11,000, and the molecular weight distribution (Mw / Mn) was 2.2.

[0310] [Preparation of Negative Curing Composition]

[0311] The raw materials used for preparing each negative curable composition are shown below.

[0312] (A) Component: Alkali-soluble resin

[0313] A1: Polymer (A-1) obtained in Synthesis Example 1 (solid acid value: 85 mgKOH / g, molecular weight (Mw): 3,500)

[0314] A2: Polymer (A-2) obtained in Synthesis Example 2 (acid value: 104 mgKOH / g, molecular weight (Mw): 11,000, molecular weight distribution (Mw / Mn): 2.2)

[0315] Component (B): Polyfunctional radical polymerizable compound

[0316] B1: Trimethylolpropane triacrylate (trade name: Biscoat #295, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0317] B2: Pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: Aronix M-450, manufactured by Toagosei Co., Ltd.)

[0318] B3: Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: NK Ester A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0319] B4: EO-modified isocyanuric acid diacrylate and EO-modified isocyanuric acid triacrylate (trade name: Aronix M-313, manufactured by Toagosei Co., Ltd.)

[0320] Component (C): Photoradical polymerization initiator

[0321] C1: 1,2-octanedione-1-{4-(phenylthio)phenyl}-2-(O-benzoyloxime) (trade name: IRGACURE OXE-01, manufactured by BASF)

[0322] C2: TR-PBG-3057 described in International Publication No. 2023 / 074411 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0323] C3: TR-PBG-345 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0324] C4: ADEKA Arkls NCI-930 (manufactured by ADEKA)

[0325] (D) Ingredient: UV absorber

[0326] D1: 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (trade name: Tinuvin PS, manufactured by BASF, transmittance: 0% (360 nm), 100% (410 nm))

[0327] D2: Phenylpropionic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, C7-9-branched and linear alkyl ester (trade name: Tinuvin 384-2, manufactured by BASF, transmittance: 2% (360nm), 97% (410nm))

[0328] D3: Hydroxylphenyl triazine (HPT) ultraviolet absorber represented by the following formula (trade name: Tinuvin 477, manufactured by BASF, transmittance: 0% (360 nm), 92% (410 nm))

[0329] [Chemistry 8]

[0330]

[0331] 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 (trade name: Tinuvin 400, manufactured by BASF) (transmittance: 30% (360 nm), 100% (410 nm))

[0332] (E) Component: Silane coupling agent

[0333] E1: 3-Methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0334] E2: X-12-1048 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0335] (F) Component: Phosphate compound

[0336] F1: 2-Methacryloyloxyethylhexanoate acid phosphate (trade name: KAYAMER PM-21, manufactured by Nippon Kayaku Co., Ltd.)

[0337] F2: Acidic phosphoryloxy polypropylene glycol monomethacrylate (PPM-5P, manufactured by Toho Chemical Industry Co., Ltd.)

[0338] (G) Component: Thiol compound

[0339] G1: Pentaerythritol tetrakis(3-mercaptobutyrate) (Trade name: Karenz MT (registered trademark) PE1, manufactured by Resonac Co., Ltd.)

[0340] (H) ingredient: organic solvent

[0341] H1: Propylene glycol monomethyl ether acetate (PGMEA)

[0342] (Example 1)

[0343] A negative-type curable composition of Example 1 was prepared by dissolving 100 parts by mass of A1 as component (A), 50 parts by mass of Biscoat #295 as component (B), 10 parts by mass of IRGACURE 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 the organic solvent (H). The viscosity of the resulting curable composition, measured at 25°C and 50 rpm using an E-type viscometer, was 3.5 mPa·s.

[0344] (Example 2 to Example 23, Comparative Example 1 to Comparative Example 3)

[0345] Negative curable compositions of Examples 2 to 23 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the components in the types and contents shown in Table 1 were used. In Table 1, "-" indicates that the corresponding component was not used.

[0346] [Table 1]

[0347]

[0348] [evaluate]

[0349] The negative curable composition obtained above was evaluated for resolution, development adhesion, and transmittance by the following methods.

[0350] Resolution

[0351] The negative curable composition was applied to a silicon substrate by spin coating and pre-baked 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 light using a high-pressure mercury lamp (exposure at 365 nm, 100 mJ / cm 2 ), after exposing through a photomask with a blank pattern of a square with a side of 10 μm arranged at intervals of 10 μm, development was performed for 60 seconds at 25°C using a 2.38% by mass tetramethylammonium hydroxide aqueous solution using a liquid covering method. Subsequently, the film was rinsed with ultrapure water for 60 seconds and then dried to form a pattern on the silicon substrate. The cross-sectional shape of the blank pattern of a square with a side of 10 μm thus obtained was observed at a magnification of 1500 times using a scanning electron microscope (manufactured by Hitachi, Ltd., S-4200) and evaluated according to the following criteria. The evaluation results are shown in Table 2.

[0352] A: No residue, and the bottom size is 8μm or more

[0353] B: No residue, and the bottom size is 7 μm or more and less than 8 μm

[0354] C: There is residue, or the bottom size is less than 7μm

[0355] <Development Adhesion>

[0356] The negative curable composition was applied to silicon nitride (SiNx) and Ti substrates by spin coating, and then pre-baked 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 light using a high-pressure mercury lamp (exposure at 365 nm, 100 mJ / cm 2 ), after exposure to a photomask capable of forming a line pattern with different line widths in units of 1 μm in the range of 1 μm to 50 μm, development was performed for 60 seconds at 25°C using a 2.38% by mass tetramethylammonium hydroxide aqueous solution using a liquid covering method. This was followed by 60 seconds of running water washing with ultrapure water and then drying to form a film on each substrate. For the line pattern with different line widths in units of 1 μm in the range of 1 μm to 50 μm thus obtained, the substrate adhesion was observed at a magnification of 100 times using an optical microscope (manufactured by KEYENCE, VHX-5000), and evaluation was performed according to the following criteria. The evaluation results are shown in Table 2.

[0357] A: No peeling

[0358] B: There is peeling less than 4μm

[0359] C: There is peeling of 4μm or more

[0360] Transmittance

[0361] The negative curable composition was applied to a glass substrate by spin coating and pre-baked 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 light using a high-pressure mercury lamp (exposure at 365 nm, 100 mJ / cm 2 ), after exposure through a photomask without a pattern, development was performed using a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 25°C using a blanket method for 60 seconds. This was followed by rinsing with ultrapure water for 60 seconds. This was followed by exposure using a high-pressure mercury lamp at 200 mJ / cm 2 The cured resin film was formed by post-exposure and post-baking in an oven at 85° C. for 60 minutes. The transmittance of the substrate obtained in this manner was measured at a wavelength of 400 nm using a UV-vis spectrometer V-670 manufactured by JASCO Corporation.

[0362] A: Transmittance exceeds 95%

[0363] B: Transmittance is more than 90% and less than 95%

[0364] C: Transmittance is less than 90%

[0365] [Table 2]

[0366]

[0367] As shown in Table 2, cured films excellent in resolution and development adhesion were formed in Examples 1 to 23. On the other hand, in Comparative Examples, one of resolution and development adhesion was poor.

Claims

1. A curable composition for forming a curable resin layer in a light-emitting device, the light-emitting device comprising a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a curable resin portion on the sealing layer having at least one curable resin layer, the curable composition comprising: Alkali-soluble resin (A); a polyfunctional free radical polymerizable compound (B); Photoradical polymerization initiator (C); UV absorber (D); and 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. 2 . The curable composition according to claim 1 , further comprising a phosphoric acid compound (F) having a (meth)acryloyloxy group. 3 . 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 a molecule. 4 . The curable composition according to claim 1 , wherein the alkali-soluble resin (A) has a weight average molecular weight of 1,000 to 40,000. 5 . The curable composition according to claim 1 , wherein the alkali-soluble resin (A) is at least one selected from the group consisting of acrylic resin, polysiloxane resin, and novolac resin. 6 . 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. 7 . The curable composition according to claim 1 , further comprising a compound (G) having one or more thiol groups in one molecule. 8 . The curable composition according to claim 1 , wherein the curable resin layer is an interlayer insulating film or a protective film for touch screen wiring. 9 . The curable composition according to claim 1 , wherein the curable resin layer is in contact with TiAlTi wiring. 10 . The curable composition according to claim 1 , which can be cured at a post-bake temperature of 100° C. or lower. 11 . The curable composition according to claim 1 , wherein a cured film formed by curing the curable composition has a transmittance of greater than 90% at a wavelength of 400 nm.

12. A cured film formed by curing the curable composition according to claim 1. 13 . An organic electroluminescent device comprising the hardened film according to claim 12 .

14. A method for forming a hardened resin layer, wherein the method comprises forming a hardened resin layer of a light emitting device, The light emitting device comprises a substrate, a light emitting element on the substrate, a sealing layer on the light emitting element, and a hardened resin portion having at least one hardened resin layer on the sealing layer. The method for forming the hardened resin layer comprises: a step of forming a coating film by directly or indirectly applying the curable composition according to claim 1 on the sealing layer; After forming the coating film, irradiating at least a portion of the coating film with radiation; a step of developing the coating film after the step of irradiating the radiation; and After the development step, the coating film is exposed to light and / or heated at a temperature of 120° C. or lower.

15. A hardenable composition comprising: Alkali-soluble resin (A); a polyfunctional free radical polymerizable compound (B); Photoradical polymerization initiator (C); UV absorber (D); and 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.

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