Method for manufacturing a light-emitting device, negative-type radiation-sensitive composition, cured film, and organic EL device

Abstract

To provide a negative-type radiation-sensitive composition that has sufficient resolution, exhibits sufficient chemical resistance even when heated at relatively low temperatures (e.g., below 100°C), and yields a cured film with excellent adhesion; a method for manufacturing a light-emitting device using the negative-type radiation-sensitive composition; a cured film obtained by curing the negative-type radiation-sensitive composition; and an organic EL device equipped with the cured film. [Solution] A method for manufacturing a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer directly or indirectly on the sealing layer, comprising the steps of forming a light-emitting element and a sealing layer on the substrate, applying a negative-type radiation-sensitive composition directly or indirectly on the sealing layer to form a coating film, irradiating at least a part of the coating film with radiation, alkali developing the coating film after radiation irradiation, and heating at a temperature of 100°C or lower, wherein the negative-type radiation-sensitive composition contains an alkali-soluble resin (A) having a constituent unit having an acidic group and a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group, a polyfunctional radical polymerizable compound (B), and a photoradical polymerization initiator (C).

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a light-emitting device, a negative-type radiation-sensitive composition, a cured film, and an organic EL device. [Background technology]

[0002] One type of light-emitting element that has been under development in recent years is the organic electroluminescent (EL) element, which has a stacked structure including an anode layer, an organic light-emitting layer, and a cathode layer. As a display device having an organic EL element, an organic EL device with a touch panel is known, in which a touch panel is provided on the front of the device (see Patent Document 1).

[0003] Organic EL devices with touch panels are manufactured, for example, by bonding the touch panel to a substrate on which organic EL elements are formed via an adhesive or bonding layer. Touch panels are typically manufactured by providing touch panel components, such as sensor electrodes, on a support substrate for the touch panel.

[0004] When a support substrate for a touch panel is bonded to a substrate on which organic EL elements are formed via an adhesive or bonding layer, the overall thickness of the organic EL device increases, which can lead to damage or functional degradation of the device when it is bent. In recent years, a method has been known to directly fabricate touch panels on organic EL elements using techniques such as lithography and etching to resolve this problem. However, since the formation of cured resin layers such as patterning resin insulating films within the touch panel requires baking at temperatures exceeding 100°C, there was a problem that directly forming the cured resin layer on the organic EL element using conventional methods would lead to degradation of the organic EL light-emitting layer. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2015-161806 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] When forming a cured resin layer directly on an organic EL element, curing at low temperatures, preferably by light irradiation alone, is necessary to prevent degradation of the organic EL light-emitting layer. This requires a composition with high sensitivity and excellent curability. However, if the sensitivity is too high, for example, when forming a hole pattern using a negative-type curable composition, light leaking from the mask may cure areas that should be holes, resulting in poor resolution such as filled hole patterns and reduced adhesion to the underlying layer due to curing shrinkage. On the other hand, if a curable composition with reduced sensitivity is used to prioritize hole pattern formation, the curing of the pattern that should be cured may be insufficient, leading to reduced chemical resistance. In other words, with conventional techniques, it has been difficult to achieve both high resolution, adhesion, and chemical resistance when forming a cured resin layer directly on an organic EL element.

[0007] The present invention has been made based on the above circumstances, and aims to provide a negative-type radiation-sensitive composition that has sufficient resolution, sufficient chemical resistance even when heated at relatively low temperatures (e.g., 100°C or below), and can produce a cured film with excellent adhesion; a method for manufacturing a light-emitting device using the negative-type radiation-sensitive composition; a cured film obtained by curing the negative-type radiation-sensitive composition; and an organic EL device equipped with the cured film. [Means for solving the problem]

[0008] The inventors have found that the above problems can be solved by incorporating a specific alkali-soluble resin into a negative-type radiation-sensitive composition. That is, according to the present invention, the following methods for manufacturing a light-emitting device, a negative-type radiation-sensitive composition, a cured film, and an organic EL device are provided.

[0009] [1] A method for manufacturing a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer directly or indirectly on the sealing layer, comprising in this order the steps of forming a light-emitting element and a sealing layer on the substrate, applying a negative-type radiation-sensitive composition directly or indirectly on the sealing layer to form a coating film, irradiating at least a part of the coating film with radiation, alkali developing the coating film after radiation irradiation, and heating at a temperature of 100°C or lower, wherein the negative-type radiation-sensitive composition contains an alkali-soluble resin (A) having a constituent unit having an acidic group and a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group, a polyfunctional radical polymerizable compound (B), and a photoradical polymerization initiator (C). [2] The method for manufacturing a light-emitting device according to [1], wherein the acidic group is a carboxyl group or a phenolic hydroxyl group. [3] The method for manufacturing a light-emitting device according to [1] or [2], wherein the content of constituent units having phenolic hydroxyl groups in the alkali-soluble resin (A) is 8% by mass or more and 35% by mass or less. [4] A method for manufacturing a light-emitting device according to any one of [1] to [3], wherein the content of a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group in the alkali-soluble resin (A) is 15% by mass or more and 80% by mass or less. [5] A method for manufacturing a light-emitting device according to any one of [1] to [4], wherein the alkali-soluble resin (A) contains a constituent unit having a phenolic hydroxyl group, and the content of constituent units having a carboxyl group in the alkali-soluble resin (A) is 2% by mass or less, or does not contain any constituent units having a carboxyl group. [6] The method for manufacturing a light-emitting device according to any one of [1] to [5], wherein the alkali-soluble resin (A) is a resin obtained by radical polymerization. [7] The method for manufacturing a light-emitting device according to [6], wherein the alkali-soluble resin (A) comprises a structural unit derived from a radical polymerizable monomer having a phenolic hydroxyl group and a structural unit derived from a radical polymerizable monomer having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group. [8] A method for producing a light-emitting apparatus according to [7], comprising at least one radical polymerizable monomer having a phenolic hydroxyl group, selected from the group consisting of hydroxyphenyl (meth)acrylate, 4-hydroxystyrene, and 4-isopropenylphenol. [9] A method for producing a light-emitting device according to [7] or [8], wherein the radical polymerizable monomer having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group comprises at least one selected from the group consisting of glycidyl (meth)acrylate, 1,2-epoxy-3-(3-vinyl benzyloxy)propane, 1,2-epoxy-3-(4-vinyl benzyloxy)propane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, and 4-hydroxybutyl (meth)acrylate glycidyl ether.

[10] The method for manufacturing a light-emitting device according to any one of [1] to [9], wherein the (meth)acrylic equivalent of the alkali-soluble resin (A) is 1200 g / eq or more.

[11] The method for manufacturing a light-emitting device according to any one of [1] to

[10] , wherein the content of the polyfunctional radical polymerizable compound (B) in the negative-type radiation-sensitive composition is 40 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the alkali-soluble resin (A).

[12] The method for manufacturing a light-emitting device according to any one of [1] to

[11] , wherein the negative radiation-sensitive composition further comprises at least one selected from the group consisting of a chain transfer agent (D), an ultraviolet absorber (E), a radical polymerization inhibitor (F), an adhesive (G), an antioxidant (H), a dehydrating agent (I), and a surfactant (J).

[13] A method for manufacturing a light-emitting device according to any one of [1] to

[12] , wherein the light-emitting device is an organic EL device.

[14] A negative radiation-sensitive composition comprising an alkali-soluble resin (A) having a constituent unit having an acidic group and a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group, a polyfunctional radical polymerizable compound (B), and a photoradical polymerization initiator (C).

[15] The negative-type radiation-sensitive composition according to

[14] for forming the cured resin layer of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer directly or indirectly on the sealing layer. A cured film obtained by curing the negative radiation-sensitive composition described in

[16]

[14] or

[15] .

[17] An organic EL apparatus comprising the cured film described in

[16] . [Effects of the Invention]

[0010] The present invention provides a negative-type radiation-sensitive composition that can produce a cured film having sufficient resolution, sufficient chemical resistance even when heated at relatively low temperatures (e.g., 100°C or below), and excellent adhesion; a method for manufacturing a light-emitting device using the negative-type radiation-sensitive composition; a cured film obtained by curing the negative-type radiation-sensitive composition; and an organic EL device equipped with the cured film. [Brief explanation of the drawing]

[0011] [Figure 1] This shows a cross-sectional view of one embodiment of a light-emitting device obtained by the manufacturing method of the present invention. [Modes for carrying out the invention]

[0012] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the numbers indicated before and after "~" as the lower and upper limits, respectively.

[0013] In this specification, the term "hydrocarbon group" means a group including a linear hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "linear hydrocarbon group" means a linear hydrocarbon group and a branched hydrocarbon group that do not contain a cyclic structure in the main chain and are composed only of a linear structure. However, the linear hydrocarbon group may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as the ring structure and does not contain an aromatic ring structure. However, the alicyclic hydrocarbon group does not necessarily have to be composed only of the structure of an alicyclic hydrocarbon, and also includes those having a linear structure in a part thereof. The "aromatic hydrocarbon group" means a hydrocarbon group that contains an aromatic ring structure as the ring structure. However, the aromatic hydrocarbon group does not necessarily have to be composed only of an aromatic ring structure, and may contain a linear structure or the structure of an alicyclic hydrocarbon in a part thereof. In addition, the ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent composed of a hydrocarbon structure.

[0014] In this specification, "(meth)acryloyl" means including "acryloyl" and "methacryloyl", and "(meth)acrylic" means including "acrylic" and "methacrylic". "(meth)acrylate" means including "acrylate" and "methacrylate".

[0015] [Method for manufacturing a light-emitting device] The manufacturing method of the light-emitting device of the present invention is a manufacturing method of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer directly or indirectly on the sealing layer, comprising: a step of forming a light-emitting element and a sealing layer on the light-emitting element on the substrate; a step of applying a negative-type radiation-sensitive composition (hereinafter, the negative-type radiation-sensitive composition used in the present invention is also referred to as a "curable composition" or "this composition") directly or indirectly on the sealing layer to form a coating film; a step of irradiating at least a part of the coating film with radiation; a step of alkali-developing the coating film after radiation irradiation; and a step of heating at a temperature of 100 °C or lower in this order. The negative-type radiation-sensitive composition contains an alkali-soluble resin (A) having a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group, a polyfunctional radical-polymerizable compound (B), and a photo radical polymerization initiator (C).

[0016] According to the manufacturing method of the light-emitting device of the present invention, a light-emitting device having a cured resin layer with sufficient resolution, sufficient chemical resistance even with heating at a relatively low temperature (for example, 100 °C or lower), and excellent adhesion can be obtained. The reason for obtaining the above effects is not necessarily clear, but due to the presence of a polymer having an acidic group, preferably a phenolic hydroxyl group, the polymerization chain length and crosslink density of the polyfunctional radical-polymerizable compound (B) are appropriately controlled, and the generation of strain in the cured film due to curing is suppressed, thereby improving the adhesion. Also, by adopting the alkali-soluble resin (A) having a structural unit having an acidic group, sufficient solubility can be obtained in the developing step. Furthermore, by heating after the developing step, the crosslinking reaction based on the oxiranyl group and oxetanyl group of the alkali-soluble resin (A) proceeds, thereby further improving the chemical resistance and adhesion.

[0017] The sealing layer and the cured resin portion may be formed in contact with each other, and other layers may exist between the sealing layer and the cured resin portion. However, it is preferable that there is no support (such as a glass substrate or a resin substrate formed from a resin such as polyethylene terephthalate) with a thickness exceeding 50 μm between the sealing layer and the cured resin portion, and it is even more preferable that no support is used at all. In some cases, a support is used to separately manufacture and bond the light-emitting element and the touch panel layer (cured resin layer). However, in this embodiment, it is more preferable that after the sealing layer is formed, the sealing layer and the cured resin portion are formed in contact with each other directly or indirectly via another layer (such as a planarization layer) on top of it.

[0018] The light-emitting device is, for example, a device having a laminated structure including an organic light-emitting layer and an organic semiconductor thin film, and specifically includes an organic electroluminescent (EL) device and an organic transistor, with an organic EL device being preferred. Examples of organic EL devices include an organic EL lighting device and an organic EL display device.

[0019] The substrate can be any substrate commonly used in light-emitting devices, such as a glass substrate or a resin substrate. Specifically, those described in International Publication No. 2019 / 009360 can be suitably used. The substrate is, for example, a TFT substrate having thin-film transistors (TFTs) that drive the light-emitting element, and in one embodiment, the TFTs are arranged in a matrix. The TFT substrate may also have a planarization film covering the TFTs.

[0020] As the light-emitting element, an organic EL element is preferred. Examples of organic EL elements include organic EL elements used in known organic EL devices, and they only need to have a structure in which an organic light-emitting layer containing a light-emitting material is sandwiched between a pair of electrodes facing each other (i.e., they only need to have a structure in which the organic light-emitting layer is sandwiched between an anode and a cathode facing each other), and for example, a known structure having an anode / organic light-emitting layer / cathode can be cited. Specifically, for example, the one described in International Publication No. 2019 / 009360 can be suitably adopted, and it is formed on a substrate by a known method, preferably the method described in the said publication.

[0021] The sealing layer seals the light-emitting element, reducing the intrusion of moisture into the light-emitting element. As a result, it is possible to suppress the occurrence of dark spots and the deterioration of light-emitting characteristics such as brightness and luminous efficiency caused by moisture. 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, alternating organic and inorganic sealing layers. For example, it may be an organic-inorganic sealing layer having an organic sealing layer between two inorganic sealing layers, or an organic-inorganic sealing layer having a total of four or more alternating inorganic and organic sealing layers. Preferably, the outermost layer of the sealing layer is an inorganic sealing layer.

[0022] Examples of the inorganic encapsulation layer include those described in Japanese Patent Publication No. 2010-160906, Japanese Patent Publication No. 2016-012433, and Japanese Patent Publication No. 2016-143605. Specifically, examples include layers made of silicon nitride (SiNx) or silicon oxide (SiOx), and methods for forming these layers include sputtering and chemical vapor deposition. The thickness of a single inorganic encapsulation layer is usually about 10 nm to 2 μm.

[0023] Examples of the organic encapsulation layer include a layer formed from a curable composition. The thickness of a single layer of the organic encapsulation layer is typically 1 to 50 μm, preferably 1 to 20 μm, and more preferably 1 to 15 μm. As the curable composition for forming the organic encapsulation layer and the method for forming the encapsulation layer, the compositions and methods described in International Publication No. 2019 / 009360 can be suitably employed.

[0024] The cured resin portion includes a cured resin layer made of a negative-type radiation-sensitive composition (hereinafter also referred to as "the composition"). The cured resin layer may have a pattern. The cured resin layer having a pattern (hereinafter also referred to as the patterned cured resin layer) is preferably a layer directly formed on the sealing layer by photolithography using the negative-type radiation-sensitive composition of the present invention. The shape of the pattern is not particularly limited, but examples include embodiments in which the shape of the portion where the cured resin layer is absent is a hole-like or line-like shape such as a circle, ellipse, or polygon.

[0025] The cured resin portion typically has two or more metal wiring layers. These metal wiring layers are insulated from each other by the patterned cured resin layer, and are electrically connected in the necessary areas by wiring formed in contact holes formed in the patterned cured resin layer. The thickness of the patterned cured resin layer is typically 1 to 5 μm. The thickness of the metal wiring layer is typically 100 to 1000 nm. The diameter of the contact holes is typically 1 to 20 μm. The method for forming the cured resin layer will be described in detail later in the section [Method for Forming the Cured Resin Layer].

[0026] The cured resin portion may further include a cured layer as a wiring underlayment on the light-emitting side of the patterned cured resin layer, and / or a cured layer as an upper protective layer on the side opposite to the light-emitting side of the patterned cured resin layer. These cured layers may be layers that are not patterned, and they function as a wiring underlayment or upper protective layer for the metal wiring layer. The wiring underlayment or upper protective layer can be formed from the curable composition of the present invention. The thickness of the wiring underlayer and the upper protective layer is typically 0.5 to 10 μm, independently of each other. The overall 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.

[0027] An embodiment of a display device including a cured resin layer formed from the negative-type radiation-sensitive composition of the present invention will be further described with reference to Figure 1. As shown in Figure 1, one embodiment of the cured resin portion 40 includes a wiring base layer 41, a first metal wiring layer 1a formed on the wiring base layer 41, a patterned cured resin layer 42 that partially covers the first metal wiring layer 1a, a second metal wiring layer 2a formed on the patterned cured resin layer 42 and electrically connected to the first metal wiring layer 1a by wiring 3' formed in the contact holes 3 of the patterned cured resin layer 42, and an upper protective layer 43 formed on the patterned cured resin layer 42 and the second metal wiring layer 2a and covering the second metal wiring layer 2a. The wiring base layer 41 may be omitted. In Figure 1, the cured resin portion 40 is formed in direct contact with the sealing layer 30 of an element substrate consisting of a substrate 10, a light-emitting element 20, and a sealing layer 30. The cured resin portion 40 is preferably a touch panel member.

[0028] The materials constituting the first metal wiring layer 1a and the second metal wiring layer 2a are not particularly limited, but examples 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, as well as materials containing two or more of these metals, and alloys mainly composed of these metals. Among these, TiAlTi wiring, which has a laminated structure of titanium and aluminum, is preferred as the metal wiring.

[0029] The cured resin layer formed from the negative-type radiation-sensitive composition of the present invention comes into contact with metal wiring layers such as TiAlTi wiring, and layers made of silicon nitride (SiNx) or silicon oxide (SiOx), therefore adhesion to these is also required.

[0030] The following describes the negative-type radiation-sensitive composition used in the manufacturing method of the light-emitting device of the present invention. [Negative-type radiation-sensitive composition] The negative radiation-sensitive composition of the present invention (this composition) contains an alkali-soluble resin (A) having a constituent unit having an acidic group and a constituent unit having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group, a polyfunctional radical polymerizable compound (B), and a photoradical polymerization initiator (C). The negative-type radiation-sensitive composition of the present invention is preferably used to form a cured resin portion in the manufacturing method of the light-emitting device of the present invention, and is also preferably used to form the cured resin layer of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer directly or indirectly on the sealing layer. The following describes each component contained in this composition, as well as any other components that may be added as needed.

[0031] <Alkali-soluble resin (A)> Alkali-soluble resin (A) is a component that can exhibit good developability with an alkaline developer. Alkali-soluble resin (A) has a constituent unit having an acidic group and a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group. The alkali-soluble resin (A) is preferably at least one selected from the group consisting of resins obtained by radical polymerization, polysiloxane resins, and novolac resins, more preferably at least one selected from the group consisting of resins obtained by radical polymerization and polysiloxane resins, and even more preferably a resin obtained by radical polymerization.

[0032] The alkali-soluble resin (A) has a constituent unit having an acidic group, and the acidic group is preferably at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably a phenolic hydroxyl group from the viewpoint of the storage stability of the composition. From the viewpoint of further improving developability and cured film properties, the content of constituent units having acidic groups in the alkali-soluble resin (A) is preferably 8% by mass or more and 35% by mass or less, more preferably 9% by mass or more and 30% by mass or less, even more preferably 12% by mass or more and 28% by mass or less, and even more preferably 15% by mass or more and 26% by mass or less. The content of acidic constituent units in alkali-soluble resin (A) is calculated from the content of monomers that make up alkali-soluble resin (A).

[0033] From the viewpoint of further improving developability and cured film properties, the content of constituent units having phenolic hydroxyl groups in the alkali-soluble resin (A) is preferably 8% by mass or more and 35% by mass or less, more preferably 9% by mass or more and 30% by mass or less, even more preferably 12% by mass or more and 28% by mass or less, and even more preferably 15% by mass or more and 26% by mass or less.

[0034] When the alkali-soluble resin (A) has a carboxyl group as an acidic group, the content of the constituent units having a carboxyl group in the alkali-soluble resin (A) is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of further improving developability and cured film properties. If the alkali-soluble resin (A) has a phenolic hydroxyl group as an acidic group, the content of constituent units having a carboxyl group in the alkali-soluble resin (A) is preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, from the viewpoint of the storage stability of the composition, and it is even more preferable that it does not contain any carboxyl group.

[0035] From the viewpoint of further improving developability and cured film properties, the lower limit of the content of constituent units having at least one group selected from the group consisting of oxyranyl groups and oxetanyl groups in the alkali-soluble resin (A) is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 35% by mass or more. The upper limit of the content is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. The content of constituent units having at least one group selected from the group consisting of oxyranyl groups and oxetanyl groups in the alkali-soluble resin (A) is calculated from the content of monomers constituting the alkali-soluble resin (A).

[0036] (Resin obtained by radical polymerization) As for the alkali-soluble resin (A), from the viewpoint of further improving developability and cured film properties, it is preferable that it is a resin obtained by radical polymerization, more preferably having a constituent unit derived from a radical polymerizable monomer having an acidic group and a constituent unit derived from a radical polymerizable monomer having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group, and even more preferably having a constituent unit derived from a radical polymerizable monomer having a phenolic hydroxyl group and a constituent unit derived from a radical polymerizable monomer having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group.

[0037] [Radical polymerizable monomers with acidic groups] Examples of radical polymerizable monomers having an acidic group include radical polymerizable monomers having a carboxyl group and radical polymerizable monomers having a phenolic hydroxyl group, with radical polymerizable monomers having a phenolic hydroxyl group being preferred. Furthermore, the radical polymerizable monomer having an acidic group may be used alone or in combination of two or more types.

[0038] Examples of radical polymerizable monomers having a carboxyl group include (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, with (meth)acrylic acid being preferred.

[0039] Examples of radical polymerizable monomers having a phenolic hydroxyl group include 2-hydroxyphenyl(meth)acrylate, 3-hydroxyphenyl(meth)acrylate, 4-hydroxyphenyl(meth)acrylate, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-isopropenylphenol, 3-isopropenylphenol, and 4-isopropenylphenol. Among these, from the viewpoint of reactivity with at least one group selected from the group consisting of oxiranil and oxetanyl groups, at least one selected from the group consisting of hydroxyphenyl(meth)acrylate (preferably 4-hydroxyphenyl(meth)acrylate), 4-hydroxystyrene, and 4-isopropenylphenol is preferred, 4-hydroxyphenyl(meth)acrylate is more preferred, and 4-hydroxyphenyl methacrylate is even more preferred.

[0040] [Radical polymerizable monomer having at least one group selected from the group consisting of oxyranyl groups and oxetanyl groups] A radical polymerizable monomer having at least one group selected from the group consisting of oxiranil groups and oxetanil groups is not particularly limited as long as it has at least one group selected from the group consisting of oxiranil groups and oxetanil groups and also has a radical polymerizable group (e.g., (meth)acryloyl group, vinyl group, etc.), but from the viewpoint of curability, it is preferable to have an oxiranil group. Specific examples of radical polymerizable monomers having at least one group selected from the group consisting of oxiranyl groups and oxetanyl groups include, for example, glycidyl (meth)acrylate, 1,2-epoxy-3-(3-vinyl benzyloxy)propane, 1,2-epoxy-3-(4-vinyl benzyloxy)propane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, (meth)acrylic acid (3,4-epoxycyclohexyl), (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, (meth)acrylic acid 2-(3,4-epoxycyclohexyl)ethyl, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl (meth)acrylate is one example. Among these, from the viewpoint of curability and other factors, it is preferable that at least one is selected from the group consisting of glycidyl (meth)acrylate, 1,2-epoxy-3-(3-vinyl benzyloxy)propane, 1,2-epoxy-3-(4-vinyl benzyloxy)propane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, and 4-hydroxybutyl (meth)acrylate glycidyl ether, and more preferably glycidyl (meth)acrylate, (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, 1,2-epoxy-3-(3-vinyl benzyloxy)propane, and 1,2-epoxy-3-(4-vinyl benzyloxy)propane. Furthermore, the radical polymerizable monomer having at least one group selected from the group consisting of an oxiranil group and an oxetanil group may be used alone or in combination of two or more.

[0041] [Other radical polymerizable monomers] The alkali-soluble resin (A) preferably has, in addition to the constituent units derived from radical polymerizable monomers having acidic groups as described above, and constituent units derived from radical polymerizable monomers having at least one group selected from the group consisting of oxyranyl groups and oxetanyl groups, constituent units derived from other radical polymerizable monomers. Other radical polymerizable monomers include, for example, Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, tricyclo(meth)acrylate [5.2.1.0 2,5 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.0 2,5 Decane-8-yloxyethyl, isobornyl (meth)acrylate, and other (meth)acrylic acid esters; Radical polymerizable monomers having UV-absorbing functional groups, such as 3-(2H-1,2,3-benzotriazol-2-yl)-4-hydroxyphenethyl methacrylate (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.); Aromatic vinyl monomers such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, vinyltoluene, etc. N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, and N-naphthylmaleimide; Styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloyloxyphenyltrimethoxysilane, (meth)acryloyloxyphenyltriethoxysilane, (meth)acryloyloxyphenylmethoxydimethoxysilane, (meth)acryloyloxyphenylethyldiethoxysilane, etc.; trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane Alkoxysilyl group-containing monomers such as (thyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloyloxynaphthyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, and 4-(meth)acryloyloxybutyltrimethoxysilane; Conjugated dienes such as 1,3-butadiene and isoprene; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate; Examples include macromonomers having a polymerizable unsaturated group such as a (meth)acryloyl group at one end of a polymer chain, such as polystyrene, poly(meth)acrylate, poly(meth)acrylate, and poly(meth)acrylate benzyl. These may be used individually or in combination of two or more.

[0042] Among these, it is preferable to include at least one selected from the group consisting of (meth)acrylic acid esters, aromatic vinyl compounds, and N-substituted maleimide compounds as other radical polymerizable monomers, and more preferably to include at least an alkyl (meth)acrylate ester.

[0043] The content of constituent units derived from other radical polymerizable monomers in the alkali-soluble resin (A) is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 65% ​​by mass or less, even more preferably 55% by mass or less, and even more preferably 45% by mass or less.

[0044] The method for obtaining the alkali-soluble resin (A) by radical polymerization is not particularly limited, and it can be produced by known methods such as suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization. Furthermore, conventionally known production conditions can also be used.

[0045] (Polysiloxane resin) Examples of the polysiloxane resin include hydrolysis condensates of hydrolyzable silane compounds. Here, "hydrolyzable silane compound" refers to a compound containing a group that can be hydrolyzed to produce a silanol group or a group that can form a siloxane condensate, and "hydrolysis condensate" refers to a condensate formed by the condensation of silanol groups of a hydrolyzed silane compound. Examples of such polysiloxane resins include those described in Japanese Patent Publication No. 2017-048355.

[0046] (Novolac resin) The novolac resin can be obtained by polycondensing phenols with aldehydes such as formaldehyde using known methods.

[0047] The (meth)acrylic equivalent of the alkali-soluble resin (A) is preferably a large value from the viewpoint of adhesion, specifically preferably 1200 g / eq or more, more preferably 2000 g / eq or more, and even more preferably 5000 g / eq or more. In other words, it is preferable that the acrylic-soluble resin (A) is not a resin into which (meth)acrylic groups have been intentionally introduced, for example, it is preferable that it does not have (meth)acryloyloxy groups in its side chains.

[0048] The acid value of the alkali-soluble resin (A) is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, even more preferably 40 mg KOH / g or more, and preferably 300 mg KOH / g or less, more preferably 200 mg KOH / g or less, and even more preferably 100 mg KOH / g or less, from the viewpoint of further improving developability and cured film properties. The acid value represents the number of mg of KOH required to neutralize 1 g of solid content of the alkali-soluble resin (A).

[0049] The weight-average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1000 or more, more preferably 3000 or more, even more preferably 4000 or more, and preferably 40000 or less, more preferably 20000 or less, and even more preferably 15000 or less, from the viewpoint of further improving the coatability, developability, and cured film properties of the composition. Furthermore, the molecular weight distribution (Mw / Mn) of the alkali-soluble resin (A), expressed as the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less, from a similar viewpoint. The weight-average molecular weight and number-average molecular weight of the alkali-soluble resin (A) are measured by the method described in the examples.

[0050] The alkali-soluble resin (A) may be used alone or in combination of two or more types. The content of alkali-soluble resin (A) (total amount in the case of multiple types) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less, from the viewpoint of further improving developability and cured film properties, relative to the total solid content (100% by mass) of the composition (i.e., relative to the total amount of components other than organic solvents in the composition).

[0051] <Polyfunctional radical polymerizable compound (B)> The polyfunctional radical polymerizable compound (B) can be any polymerizable compound that reacts with radicals generated from a photoradical polymerization initiator and hardens. However, from the viewpoint of improving the storage stability of the curable composition and controlling the hardness of the resulting cured film, a polyfunctional (meth)acrylate, which is a polymerizable compound having two or more (meth)acryloyloxy groups in its molecule, is preferred. Specific examples of such polyfunctional (meth)acrylates include difunctional (meth)acrylic acid esters and polyfunctional (meth)acrylic acid esters with three or more functions.

[0052] Examples of difunctional (meth)acrylic acid esters include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane methanol di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, and neopentyl glycol hydroxypivalate di(meth)acrylate.

[0053] Examples of (meth)acrylic acid esters with three or more functions include trimethylolpropane tri(meth)acrylate, trimethylolpropaneethylene oxide (EO)-modified tri(meth)acrylate, trimethylolpropanepropylene oxide (PO)-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate (also known as tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate), pentaerythritol tetra Examples include la(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate, succinic acid-modified dipentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, or mixtures thereof. Other examples include polyfunctional urethane (meth)acrylate compounds obtained by reacting a compound having a linear alkylene group and an alicyclic structure and two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and three, four, or five (meth)acryloyloxy groups.

[0054] Among these, the polyfunctional radical polymerizable compound (B) preferably includes a difunctional (meth)acrylic acid ester as well as a trifunctional or more functional (meth)acrylic acid ester, and more preferably includes 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.

[0055] The polyfunctional radical polymerizable compound (B) may be used alone or in combination of two or more types. In this composition, the content of the polyfunctional radical polymerizable compound (B) (total content in the case of multiple types) per 100 parts by mass of the alkali-soluble resin (A) is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 60 parts by mass or more, from the viewpoint of further improving curability, developability, and cured film properties. The upper limit is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, even more preferably 100 parts by mass or less, and particularly preferably 90 parts by mass or less. The upper limit is particularly preferred when the lower layer is polyimide.

[0056] <Photoradical polymerization initiator (C)> A photoradical polymerization initiator (C) is a compound that generates radicals in response to radiation and can initiate polymerization. Specific examples of photoradical polymerization initiators (C) include, for example, O-acyloxime compounds, α-aminoketone compounds, α-hydroxyketone compounds, and acylphosphine oxide compounds. Among these, oxime ester-based photopolymerization initiators such as O-acyloxime compounds are preferred.

[0057] Using the aforementioned oxime ester-based photopolymerization initiator is preferable because it can improve sensitivity and easily suppress variations in line width within the plane when forming fine line patterns. Furthermore, using the oxime ester-based photopolymerization initiator tends to improve the residual film rate.

[0058] As for the oxime ester-based photopolymerization initiator, 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 heterocycle are even more preferred, in order to reduce contamination of the composition and equipment by decomposition products. Examples of oxime ester-based photopolymerization initiators include 1,2-octadione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), and oxime ester-based photopolymerization initiators described in Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, and Japanese Patent Publication No. 2013-041153. Examples of commercially available products include Irgacure OXE-01 (manufactured by BASF), Adeka Arcluz NCI-930 (manufactured by ADEKA) with a diphenyl sulfide skeleton, TR-PBG-345, TR-PBG-304 with a carbazole skeleton, TR-PBG-365 with a fluorene skeleton, and TR-PBG-3057 with a diphenyl sulfide skeleton (all manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

[0059] The above-mentioned photoradical polymerization initiator (C) may be used alone or in combination of two or more types. The content of the photoradical polymerization initiator (C) (total content in the case of multiple types) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (A). The above range for the content of the photoradical polymerization initiator (C) is preferable because it allows the composition to form a cured film with good resolution and developability even at low exposure levels.

[0060] In addition to the alkali-soluble resin (A), polyfunctional radical polymerizable compound (B), and photoradical polymerization initiator (C) described above, this composition preferably further comprises at least one selected from the group consisting of a chain transfer agent (D), an ultraviolet absorber (E), a radical polymerization inhibitor (F), an adhesive (G), an antioxidant (H), a dehydrating agent (I), and a surfactant (J). The following explains each of the ingredients.

[0061] <Chain transfer agent (D)> This composition may contain a chain transfer agent (D), and it is preferable that it contains a chain transfer agent (D). A chain transfer reaction is a reaction in radical polymerization in which a radical in a growing polymer chain moves to another molecule, and a chain transfer agent is a drug that causes a chain transfer reaction. When this composition contains a chain transfer agent (D), the polymerization chain length of the polyfunctional radical polymerizable compound (B) in the layers or films formed from this composition is controlled by the action of the chain transfer agent, which is preferable.

[0062] The chain transfer agent (D) contained in this composition is not particularly limited as long as it is a compound that functions as a chain transfer agent in a radical polymerization reaction. Examples of chain transfer agents (D) include pyrazole derivatives and alkylthiols. Among these, from the viewpoint of improving the adhesion of the cured film, compounds having mercapto groups (thiol groups) are preferred, more preferably having two or more thiol groups, even more preferably being polyfunctional thiol compounds having three or more thiol groups, and even more preferably being polyfunctional thiol compounds having four or more thiol groups. The number of thiol groups is preferably six or less per molecule. However, the thiol compounds do not include those corresponding to the adhesive (G) described later.

[0063] Examples of polyfunctional thiol compounds include primary polyfunctional thiols and secondary polyfunctional thiols, but secondary polyfunctional thiols are preferred from the viewpoint of high storage stability and suppressed odor. Examples of secondary polyfunctional thiols include pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and 1,3,5-tris[2-(3-mercaptobutanoyloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. Examples of primary polyfunctional thiols include trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate).

[0064] The chain transfer agent (D) may be used alone or in combination of two or more types. If the composition contains a chain transfer agent (D), the content of the chain transfer agent (D) (total content in the case of multiple types) is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the alkali-soluble resin (A), from the viewpoint of further improving the adhesion of the cured product.

[0065] <UV absorber (E)> This composition may further contain an ultraviolet absorber (E). The ultraviolet absorber (E) is added to control the photocuring distribution by absorbing specific wavelengths of the light source used for exposure. When this composition contains an ultraviolet absorber (E), effects such as improving the tapered angle shape after development and reducing the residue remaining in the unexposed areas after development tend to be obtained. As the ultraviolet absorber (E), for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm is used, from the viewpoint of not inhibiting light absorption by the photoradical polymerization initiator (C).

[0066] Examples of UV absorbers (E) include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, dyes, and the like. UV absorber (E) may be used alone or in combination of two or more types.

[0067] Among these, from the viewpoint of improving resolution, benzotriazole compounds and / or hydroxyphenyltriazine compounds are preferred, and benzotriazole compounds are more preferred. Specifically, examples of benzotriazole compounds include 2-(2-hydroxy-5-t-butylphenyl)benzotriazole, 2,2-methylenebis{6-(benzotriazole-2-yl-4-tert-octylphenol)}, and 3-(2H-1,2,3-benzotriazole-2-yl)-4-hydroxyphenethyl methacrylate (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.). Examples of benzophenone compounds include 2,2-di-hydroxy-4,4-dimethoxybenzophenone. Examples of triazine compounds include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Commercially available products include BASF's "TINUVIN PS," "TINUVIN P," "TINUVIN 324," "TINUVIN 326," and "TINUVIN 360," Cipro Chemical Corporation's "Seesorb 107," and ADEKA's "ADEKA Stab LA-F70."

[0068] The content of the ultraviolet absorber (E) (total content in the case of multiple types) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, per 100 parts by mass of alkali-soluble resin (A), and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, from the viewpoint of the shape and resolution of the resulting pattern.

[0069] <Radical polymerization inhibitor (F)> This composition may contain a radical polymerization inhibitor (F). The radical polymerization inhibitor (F) is an ingredient that enhances the storage stability of this composition. Examples of radical polymerization inhibitors (F) include sulfur, quinones (e.g., benzoquinone), hydroquinones (e.g., hydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone), polyoxy compounds (e.g., p-methoxyphenol), amine compounds (e.g., N,N-diethylhydroxyamine), and nitrosamine compounds (e.g., N-nitroso-N-phenylhydroxylamine aluminum). The radical polymerization inhibitor (F) may be used alone or in combination of two or more types. The content of radical polymerization inhibitors (F) (total content in the case of multiple types) is preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of alkali-soluble resin (A), from the viewpoint of improving the resulting pattern shape and the storage stability of the composition.

[0070] <Adhesive (G)> This composition may contain an adhesive (G). The adhesive (G) is a component that improves the adhesion between the cured film formed using this composition and the underlying layer. Examples of adhesive (G) include known silane coupling agents and phosphoric acid compounds having a (meth)acryloyloxy group. As a silane coupling agent, a functional silane coupling agent having a reactive functional group is preferred. Examples of reactive functional groups in a functional silane coupling agent include carboxyl groups, (meth)acryloyl groups, epoxy groups, vinyl groups, isocyanate groups, etc., and among these, the (meth)acryloyl group is preferred.

[0071] Specific examples of functional silane coupling agents include, for example, trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. Commercially available products include KBM-403, KBM-5103, KBM-302, KBM-402, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, etc. (all manufactured by Shin-Etsu Chemical Co., Ltd.). The silane coupling agent may be of polymer type. For example, a silane coupling agent in which hydrolyzable groups and other functional groups are bonded to an organic polymer whose main chain has an organic structure can also be suitably used. Examples of commercially available organic polymer type silane coupling agents include X-12-1048, X-12-1050, X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L.

[0072] Phosphate compounds having a (meth)acryloyloxy group are 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 include the Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP) from Unichemical Co., Ltd., the KAYAMER series (KAYAMER PM-21, KAYAMER PM-2) from Nippon Kayaku Co., Ltd., PPME, PMR12, PPM-5P from Toho Chemical Industry Co., Ltd., and the Light Ester series (Light Ester P-2M (trade name)) from Kyoeisha Chemical Co., Ltd.

[0073] Adhesive agent (G) may be used alone or in combination of two or more types. If the composition contains an adhesive (G), the content of the adhesive (G) (total content in the case of multiple types) is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, even more preferably 2 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (A), from the viewpoint of forming a cured film with excellent adhesion.

[0074] <Antioxidant (H)> This composition may contain an antioxidant (H). The antioxidant (H) is a component that suppresses the cleavage of polymer molecule bonds by capturing radicals generated by exposure or heating, or by decomposing peroxides produced by oxidation. The inclusion of the antioxidant (H) in this composition is preferable because it suppresses the degradation of polymer molecules through cleavage in the formed cured film, thereby improving durability and other properties. The antioxidant (H) may be used alone or in combination of two or more types.

[0075] Examples of antioxidants (H) include compounds having a hindered phenol structure, compounds having a hindered amine structure, compounds having an alkyl phosphite structure, and compounds having a thioether structure. Among these, antioxidants (H) are preferably compounds having a hindered phenol structure.

[0076] Examples of compounds having a hindered phenol structure (hindered phenol compounds) include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 3,3',3',5 ',5'-Hexa-tert-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5- Examples include di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamine)phenol.

[0077] If the composition contains an antioxidant (H), the content of the antioxidant (H) (total content in the case of multiple types) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 1 part by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, per 100 parts by mass of the alkali-soluble resin (A). Furthermore, it is sometimes preferable that the product does not contain antioxidants. If the antioxidant content is high, sensitivity and other properties may decrease.

[0078] <Dehydrating agent (I)> This composition may contain a dehydrating agent (I). Examples of dehydrating agent (I) include orthoester compounds. Orthoester compounds are esters of orthocarboxylic acids, which react with water to give carboxylic acid esters. Alternatively, acid anhydrides may be used as dehydrating agent (I). Dehydrating agent (I) may be used alone or in combination of two or more types.

[0079] Examples of orthoesters include orthoformate esters such as methyl orthoformate, ethyl orthoformate, and propyl orthoformate; orthoacetate esters such as methyl orthoacetate, ethyl orthoacetate, and propyl orthoacetate; and orthopropionate esters such as methyl orthopropionate, ethyl orthopropionate, and propyl orthopropionate. Among these, orthoformate esters or orthoacetate esters are preferred, and methyl orthoformate, ethyl orthoformate, methyl orthoacetate, or ethyl orthoacetate are more preferred.

[0080] If the composition contains a dehydrating agent (I), the content of the dehydrating agent (I) (total content in the case of multiple types) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of alkali-soluble resin (A).

[0081] <Surfactant (J)> This composition may contain surfactant (J). When this composition contains surfactant (J), the wettability to the substrate or other surface on which the coating film is formed can be improved, thereby enhancing the coatability. Surfactant (J) may be used alone or in combination of two or more types.

[0082] As the surfactant (J), fluorine-based surfactants and silicone-based surfactants are preferred, and silicone-based surfactants are more preferred. Examples of commercially available surfactants (J) include Polyflow KL-401, KL-402, KL-403, and KL-404 (all manufactured by Kyoeisha Chemical Co., Ltd.); BYK-302, BYK-307, BYK-325, BYK-331, BYK-333, BYK348, BYK378, BYK-UV-3535, BYK-UV-3530, BYK-UV-3500, BYK-381, BYK-3441 (all manufactured by BYK-Chemie Japan Co., Ltd.); Examples include DAW CORNING TORAY8019 ADDITIVE and DOW CORNING TORAY 1313 ANTIFORM EMULSION (both manufactured by Toray Dow Corning).

[0083] The amount of surfactant (J) in this composition (total amount in the case of multiple types) is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.1 parts by mass or more, and preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, per 100 parts by mass of alkali-soluble resin (A).

[0084] <Organic solvent (K)> This composition may further contain an organic solvent (K). The inclusion of an organic solvent (K) adjusts the viscosity of the composition to one suitable for coating. The organic solvent (K) is not particularly limited and examples include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, etc. One type of organic solvent (K) may be used alone, or two or more types may be used in combination.

[0085] Examples of alcohol-based solvents include methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, and diacetone alcohol; and aromatic alcohols such as benzyl alcohol.

[0086] Examples of ether-based solvents include ethylene glycol monoalkyl ethers such as diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; and dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.

[0087] Examples of ester solvents include carboxylic acid esters such as ethyl acetate, i-propyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; polyhydric alcohol carboxylate solvents such as propylene glycol diacetate; and polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Examples of ketone solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0088] Among these, ether-based solvents and ester-based solvents are preferred, ester-based solvents are more preferred, and polyhydric alcohol partial ether carboxylate-based solvents are even more preferred. Furthermore, among the ether-based and ester-based solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate are preferred.

[0089] The content of organic solvent (K) in this composition is not particularly limited, but it is preferable that the composition be prepared so that the solid content (components other than organic solvent (K)) concentration is within the following ranges. From the viewpoint of solvent removal, the solid content concentration in this composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, and from the viewpoint of coating properties, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

[0090] In addition to the components (A) to (K) described above, this composition may further contain other components. The content of these other components in this composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. Furthermore, from the viewpoint of storage stability, it is preferable that this composition contains a small amount of photoacid generator. The amount of photoacid generator in this composition is preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less, and even more preferably 0.001 parts by mass or less, per 100 parts by mass of alkali-soluble resin (A), and it is even more preferable that it does not contain any photoacid generator.

[0091] The viscosity of this composition, measured using an E-type viscometer at 25°C and 50 rpm, is preferably 0.5 mPa·s or higher, more preferably 2 mPa·s or higher, and preferably 20 mPa·s or lower, more preferably 10 mPa·s or lower, from the viewpoint of coating properties. The viscosity of this composition can be set within the above range by adjusting the amount of organic solvent (K) added.

[0092] <Method for preparing a negative-type radiation-sensitive composition> This composition can be prepared by mixing each component in a predetermined ratio and dissolving them in an organic solvent (K). The prepared composition is preferably filtered using, for example, a filter with a pore size of about 0.2 μm.

[0093] [Cured film] The cured film of the present invention (hereinafter also referred to as "the cured film") is formed by curing the negative-type radiation-sensitive composition prepared as described above. The negative-type radiation-sensitive composition of the present invention can produce a cured film with sufficient resolution and development adhesion even when heated at relatively low temperatures. The composition is preferably curable at a post-bake temperature of 100°C or lower, and more preferably curable by heating in a temperature range of 60°C to 100°C.

[0094] The cured film of the present invention may be a patterned film. The cured film of the present invention can be used as the cured resin layer of the cured resin part of the light-emitting device. Specifically, it can be used as the wiring underlayer, the patterned cured resin layer (interlayer insulating film for touch panel wiring), and the upper protective layer (protective film for touch panel wiring) of the cured resin part. The thickness of the cured film of the present invention is not particularly limited and can be set as appropriate depending on the purpose of use.

[0095] [Organic EL device] The organic EL device of the present invention comprises this cured film. The organic EL device of the present invention preferably comprises a touch panel laminated on a substrate having organic EL elements, and it is preferable that this cured film is used as at least a portion of the cured resin layer in the touch panel. In particular, it is preferable that this cured film is used as an interlayer insulating film of a touch panel laminated on a substrate having organic EL elements without an adhesive or bonding layer in between. By doing so, the touch panel can be directly laminated on the substrate on which the organic EL elements are formed, making it possible to make the organic EL device equipped with the touch panel thinner.

[0096] This composition can produce a cured film with sufficient resolution and development adhesion even when heated at relatively low temperatures, thereby suppressing the degradation of organic EL elements during the manufacturing process of the above-mentioned organic EL device and improving yield. Furthermore, because the degradation of organic EL elements during the manufacturing process can be suppressed by forming an insulating film using this composition at relatively low temperatures, this composition can be particularly suitably used for forming insulating films in various organic EL devices equipped with organic EL elements, other than organic EL devices equipped with touch panels.

[0097] [Method for forming a cured resin layer] One embodiment of the present invention is a method for forming a cured resin layer, A method for forming the cured resin layer of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer on the sealing layer, A step of forming a coating film by directly or indirectly applying the negative-type radiation-sensitive composition of the present invention (the composition) onto the sealing layer (hereinafter also referred to as the "coating film formation step"), After the step of forming the above coating film, a step of irradiating (exposing) at least a part of the above coating film with radiation (hereinafter also referred to as the "radiation irradiation step"), The process of alkaline developing the coating film after the above-mentioned radiation irradiation (hereinafter also referred to as the "development process"), and This process includes heating to a temperature of 100°C or lower (hereinafter also referred to as the "heating process") in this order. Here, the process may include a step of exposing the developed coating film to light after the developing step, before the heating step, or after the heating step (hereinafter also referred to as the "post-exposure step"). Furthermore, a step of heating the coating film (hereinafter also referred to as the "PEB step") may be included between the radiation irradiation step and the development step.

[0098] According to this forming method, since the negative-type radiation-sensitive composition described above is used, it is possible to pattern it into a good shape and obtain a cured resin layer (cured film) with good resolution and development adhesion. Furthermore, even if the substrate on which the coating film is formed contains an organic EL element, it is possible to suppress the degradation of the organic EL element by performing the heating process at a relatively low temperature. The following describes each step.

[0099] <Coating film formation process> In this process, the composition is applied directly onto the sealing layer or via another layer, and then, preferably, the coated surface is heated (pre-baked) to remove organic solvents, etc., and a coating film is formed. The sealing layer is as described above.

[0100] The method of applying this composition is not particularly limited, and suitable methods such as spraying, roll coating, rotary coating (spin coating), slit die coating, and bar coating can be used. Among these coating methods, spin coating and slit die coating are particularly preferred. The pre-baking conditions vary depending on the type and proportion of each component, but preferably, a heating time of 1 minute to 10 minutes at a temperature of 60°C to 100°C, more preferably 95°C, is used.

[0101] <Radiation irradiation process> In this process, at least a part of the coating film formed in the coating film forming process is irradiated with radiation. Usually, when irradiating a part of the coating film with radiation, it is irradiated through a photomask having a predetermined pattern. As the above-mentioned radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. can be used. Among these radiations, radiation having a wavelength in the range of 190 nm or more and 450 nm or less is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

[0102] As the lower limit of the exposure amount in this process, as the value measured by an illuminometer ("OAI model356" of OAI Optical Associates Inc.) for the intensity at a radiation wavelength of 365 nm, 10 mJ / cm 2 is preferable, and 50 mJ / cm 2 is more preferable. Further, as the upper limit of the exposure amount, as the value measured by the above illuminometer, 2,000 mJ / cm 2 is preferable, and 1,000 mJ / cm 2 is more preferable.

[0103] <PEB process> When providing a PEB process, the PEB conditions vary depending on the type and blending ratio of each component, etc., but for example, the heating time may be 1 minute or more and 10 minutes or less at a temperature of 60 °C or more and 100 °C or less.

[0104] <Development process> In this process, a predetermined pattern is formed by developing the coating film after radiation irradiation with a developer. An alkaline developer is preferable as the above-mentioned developer. Examples of the alkaline developer include an alkaline aqueous solution in which at least one kind of alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. is dissolved. Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer.

[0105] As for the development method, appropriate methods such as the liquid-filling method, dipping method, agitation immersion method, and spray method can be employed. The development time varies depending on the composition of the negative-type radiation-sensitive composition, but is, for example, between 10 seconds and 180 seconds. Following such a development process, for example, a running water wash is performed for a processing time of 30 seconds to 90 seconds, and then the desired pattern can be formed by, for example, air-drying with compressed air or compressed nitrogen.

[0106] <Heating process> In this process, the developed and patterned coating film is heated (post-baked) at a temperature of 100°C or lower using a heating device such as a hot plate or oven to obtain a cured film (preferably a cured resin layer, which is an insulating film for a display device) having a desired pattern. The heating temperature is preferably 60°C or higher, more preferably 80°C or higher. By heating the film at or above the above temperature, a sufficiently cured resin layer (cured film) can be obtained. On the other hand, the heating temperature is preferably 100°C or lower. By heating the film at or below the above temperature, for example, a sufficiently cured resin layer (cured film) can be obtained while suppressing the degradation of organic EL elements on the substrate. Furthermore, by heating the film at or below the above temperature, the generation of excessive stress such as rapid film shrinkage can be suppressed, thereby suppressing the occurrence of cracks. Thus, in the heating process, heating is preferably carried out in a temperature range of 60°C to 100°C (more preferably 80°C to 100°C). The heating time varies depending on the type of heating equipment, but for example, it should be between 5 and 30 minutes when heating on a hot plate, and between 10 and 90 minutes when heating in an oven. Heating can be carried out in air or in an inert gas atmosphere such as nitrogen or argon. It is also possible to use a step bake method that involves two or more heating steps.

[0107] When the composition is used, although the detailed mechanism is unknown, a decrease in oxiranyl groups and oxetanyl groups is observed in the heating step after the development step. The decrease in oxiranyl groups and oxetanyl groups is observed as a decrease in the peaks derived from oxiranyl groups and oxetanyl groups in IR measurement. As the above crosslinking, crosslinking between oxiranyl groups or oxetanyl groups, or crosslinking between an oxiranyl group or an oxetanyl group and an acidic group can be assumed. By heating after the development step, the thermal crosslinking of epoxy proceeds, and as a result, it is considered that the adhesion, chemical resistance, and resolution of the cured film are improved.

[0108] <Post-exposure process> After the development step, before the heating step, or after the heating step, a step of exposing the developed coating film (hereinafter, also referred to as the "post-exposure step") may be included. Examples of the radiation used in the post-exposure step are the same as those used in the radiation irradiation step, and the preferable range is also the same. Further, as the exposure amount in the post-exposure step, for example, 100 mJ / cm 2 Up to 2,000 mJ / cm 2 It can be set to the following.

[0109] <Other processes> When manufacturing a display device, preferably an organic EL device, after forming the cured resin layer (cured film) on the organic EL display substrate, other processes such as forming further electrodes, wirings, etc. are performed. Examples of such processes include an electrode formation step, a wiring formation step, an etching step, an ashing step, etc. For the formation of electrodes and wirings, known methods such as printing and vapor deposition can be adopted. Etching can be performed using a known etching chemical solution such as an amine-based solution. Ashing can be performed by a known ashing method such as oxygen ashing. When manufacturing a touch panel or the like, the formation of the cured resin layer (cured film) and the formation of electrodes, wirings, etc. may be performed a plurality of times, respectively.

[0110] [Negative-type radiation-sensitive composition] The negative-type radiation-sensitive composition which is one embodiment of the present invention is An alkali-soluble resin (A) having a constituent unit having an acidic group and a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group, Polyfunctional radical polymerizable compound (B), and It contains a photoradical polymerization initiator (C).

[0111] The alkali-soluble resin (A), polyfunctional radical polymerizable compound (B), photoradical polymerization initiator (C), and other components and their contents can be preferably those described above. The negative-type radiation-sensitive composition can be the same as the composition described above (the negative-type radiation-sensitive composition used in the manufacturing method of a display device).

[0112] The negative-type radiation-sensitive composition is suitable for forming the cured resin layer of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer directly or indirectly on the sealing layer. Furthermore, since the cured film formed from the negative-type radiation-sensitive composition exhibits excellent resolution, development adhesion, and chemical resistance, the negative-type radiation-sensitive composition can be preferably used as a forming material for interlayer insulating films, planarization films, spacers, protective films, colored pattern films for color filters, partitions, banks, and the like. [Examples]

[0113] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are based on mass unless otherwise specified.

[0114] In this example, the weight-average molecular weight (Mw) of the polymer was measured by the following method. [Weight average molecular weight (Mw)] The Mw of the polymer is a polystyrene equivalent value measured by the following method and conditions. • Measurement method: Gel permeation chromatography (GPC) method • Equipment: GPC-101 manufactured by Showa Denko Corporation • GPC columns: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 manufactured by Shimadzu GLC Co., Ltd. • Mobile phase: tetrahydrofuran Column temperature: 40°C ·Flow rate: 1.0mL / min • Sample concentration: 1.0% by mass • Sample injection volume: 100 μL • Detector: Differential refractometer • Standard material: Monodisperse polystyrene

[0115] [Synthesis Example 1] (Synthesis of polymer (A-1)) 200 parts by mass of propylene glycol monomethyl ether acetate and 6.5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged into a flask equipped with a condenser and a stirrer. Next, 25 parts by mass of 4-hydroxyphenyl methacrylate, 58 parts by mass of glycidyl methacrylate, 4 parts by mass of methyl methacrylate, and 13 parts by mass of lauryl acrylate were charged. The flask was then purged with nitrogen, and the temperature of the solution was raised to 80°C while gently stirring. Polymerization was carried out by maintaining this temperature for 5 hours to obtain a polymer solution containing copolymer (A-1). The solid content concentration of this polymer solution was 34.1% by mass, the Mw of copolymer (A-1) was 7,600, and the molecular weight distribution (Mw / Mn) was 1.8.

[0116] [Synthesis Examples 2-10] (Synthesis of polymers (A-2)-(A-10)) Polymers (A-2) to (A-10) were synthesized in the same manner as in Synthesis Example 1, except that the monomer compounds used were of the types and amounts shown in Table 1 below.

[0117] [Synthesis Example 11] (Synthesis of polymer (A-11)) 200 parts by mass of propylene glycol monomethyl ether acetate and 12 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged into a flask equipped with a condenser and a stirrer. Next, 9 parts by mass of methacrylic acid, 32 parts by mass of glycidyl methacrylate, 19 parts by mass of methyl methacrylate, and 40 parts by mass of benzyl methacrylate were charged. The flask was then purged with nitrogen, and the temperature of the solution was raised to 70°C while gently stirring. Polymerization was carried out by maintaining this temperature for 5 hours to obtain a polymer solution containing copolymer (A-11). The solid content concentration of this polymer solution was 34.0% by mass, the Mw of copolymer (A-11) was 6,200, and the molecular weight distribution (Mw / Mn) was 1.8.

[0118] [Synthesis Examples 12-14] (Synthesis of polymers (A-12)-(A-14)) Polymers (A-12) to (A-14) were synthesized in the same manner as in Synthesis Example 11, except that the monomer compounds used were of the types and amounts shown in Table 1 below.

[0119] [Synthesis Example 15] (Synthesis of Polymer (A-15)) 70 parts of cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name: Epiclon N-695, epoxy equivalent: 220) were placed in a four-necked flask equipped with a stirrer and reflux condenser. 70 parts of propylene glycol monomethyl ether acetate and 70 parts of propylene glycol monomethyl ether were added and heated until dissolved. Further, 13 parts of 4-hydroxythiophenol and 0.2 parts of tetrabutylammonium bromide were added. This solution was reacted at 60°C for 3 hours to obtain a cresol novolac resin (A-15) having epoxy groups and phenolic hydroxyl groups in its side chains. The resin (A-15) thus obtained had a solid content concentration of 34% by mass, an acid value of 70 mgKOH / g of solids, and a weight-average molecular weight (Mw) of approximately 4,500.

[0120] [Table 1]

[0121] The monomers m-1 to m-16 used in Table 1 are as follows: m-1:4-hydroxyphenylmethacrylate m-2:4-isopropenylphenol m-3: Methacrylic acid m-4: Glycidyl methacrylate m-5: Methyl (3,4-epoxycyclohexyl) methacrylate m-6: A mixture of 1,2-epoxy-3-(3-vinylbenzyloxy)propane and 1,2-epoxy-3-(4-vinylbenzyloxy)propane m-7: Styrene m-8: Methyl methacrylate m-9: n-butyl methacrylate m-10: Cyclohexylmaleimide m-11: Cyclohexyl methacrylate m-12:2-ethylhexyl methacrylate m-13: Benzyl methacrylate m-14: Lauryl acrylate m-15:3-Methacryloxypropyltrimethoxysilane m-16:3-(2H-1,2,3-benzotriazol-2-yl)-4-hydroxyphenethyl methacrylate (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.)

[0122] [Example 1] Preparation of negative-type radiation-sensitive compositions (A) 100 parts by mass of (A-1) as an alkali-soluble resin with resin solid content, (B) 30 parts by mass of (B-1) and 40 parts by mass of (B-2) as polyfunctional radical polymerizable compounds, (C) 5 parts by mass of (C-1) as a photoradical polymerization initiator, (E) 3 parts by mass of (E-1) as an ultraviolet absorber, (F) 0.5 parts by mass of (F-1) as a radical polymerization inhibitor, (G) 2 parts by mass of (G-1) as an adhesive, and (J) 0.15 parts by mass of (J-1) as a surfactant were mixed. Then, the mixture was diluted with PGMEA (propylene glycol monomethyl ether acetate) to a total solid content concentration of 25% by mass, and filtered through a membrane filter with a pore size of 0.2 μm to prepare a negative-type radiation-sensitive composition.

[0123] [Examples 2-19, Comparative Examples 1-2] Preparation of negative-type radiation-sensitive compositions Negative-type radiation-sensitive compositions were prepared using the same method as in Example 1, with the types and amounts of each component listed in Table 2.

[0124] [Table 2]

[0125] The components used in the preparation of the negative-type radiation-sensitive compositions in the examples and comparative examples are shown. (A) Alkali-soluble resin A-1 to A-15: Polymers (A-1) to (A-15) obtained in the above synthesis examples 1 to 15. A-16: A resin having a cresol novolac main chain with carboxyl groups and (meth)acryloyl groups in its side chains. 220 parts of cresol novolac epoxy resin (manufactured by DIC Corporation, trade name: Epiclon N-695, epoxy equivalent: 220) were placed in a four-necked flask equipped with a stirrer and reflux condenser, and 214 parts of carbitol acetate were added and heated until dissolved. Next, 0.1 parts of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95-105°C, and 72 parts of acrylic acid were gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90°C, 106 parts of tetrahydrophthalic anhydride were added, and the mixture was reacted for 8 hours. After cooling, the product was removed to obtain a resin (A-16) having a cresol novolac main chain with carboxyl groups and (meth)acryloyl groups in the side chains. The resin obtained in this manner (A-16) had a non-volatile content of 65% by mass, a solid acid value of 85 mgKOH / g, and a weight-average molecular weight Mw of approximately 3,500.

[0126] (B) Polyfunctional radical polymerizable compounds B-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) B-2: Pentaerythritol tri / tetraacrylate mixture (ARONIX M-40, manufactured by Toagosei Co., Ltd.) B-3: Tris(2-hydroxyethyl) isocyanurate triacrylate B-4: Tricyclodecanedimethanol diacrylate

[0127] (C) Photoradical polymerization initiator C-1:TR-PBG-3057 (oxime photopolymerization initiator, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) (D) Chain transfer agent D-1: Karenz MT PE1 (Pentaerythritol tetrakis(3-mercaptobutyrate), manufactured by Resonaq Corporation) (E) UV absorber E-1: 2-(2-hydroxy-5-t-butylphenyl)benzotriazole (F) Radical polymerization inhibitors F-1: 2,5-di-t-butylhydroquinone (G) Adhesive G-1:3-Methacryloxypropyltrimethoxysilane (J) Surfactants J-1: DOWSIL 8019 Additive (manufactured by Toray Dow Corning)

[0128] <Method for evaluating resolution> A solution of each negative-type radiation-sensitive composition was spin-coated onto a silicon substrate to a thickness of 2.5 μm, and then pre-baked at 85°C for 2 minutes using a hot plate to form a coating. The resulting coating was then scanned using a SUSS "DSC-200" via a 5 μm × 5 μm square hole pattern mask, using the following scanning method (illuminance = 500 mW, NA (numerical aperture) = 0.10, λ = ghi line, 60 mJ / cm²). 2 Exposure was performed at (exposure amount at 365 nm). Subsequently, development was carried out using a tetramethylammonium hydroxide aqueous solution (concentration 2.38%) by the liquid buildup method at 25°C for 1 minute. After that, the substrate was rinsed with running water using the shower method and dried with compressed air to form a pattern. Next, development was carried out at 200 mJ / cm² using a TOPCON "TME-400PRJ" ghi mixing line. 2 The film was cured by irradiating it with ultraviolet light and then heating it in an oven at 85°C for 60 minutes. The bottom dimensions of the holes in the cured film (patterned thin film) obtained by the above method were observed using a scanning electron microscope (SEM) and evaluated according to the following criteria. A: Resolves holes larger than 4 μm. B: Resolves holes larger than 3 μm and smaller than 4 μm. C: Resolves holes smaller than 3μm, or has poor resolution.

[0129] <Method for evaluating residual film percentage> The same procedure as described above for evaluating resolution was performed, and the residual film rate in the exposed area was calculated using the following formula. Residual film percentage (%) = [Film thickness after development and rinsing] / [Film thickness after pre-baking] × 100

[0130] <Evaluation of chemical resistance> Except for not using a hole pattern mask during exposure and instead using plain glass for full-surface exposure, a cured film was formed for each composition using the same method as for resolution evaluation. The obtained substrates were immersed in PGMEA (propylene glycol monomethyl ether acetate) heated to 60°C for 100 seconds, and evaluated according to the following criteria based on the residual film percentage of the cured film before and after immersion, which is calculated using the following formula. Residual film percentage (%) = (film thickness after immersion / film thickness before immersion) × 100 A: Residual film rate is 95% or higher B: Residual film rate is 90% or more, but less than 95%. C: Residual film percentage is less than 90%

[0131] <Evaluation of adhesion> A polyimide film was first formed on a silicon substrate, and a cured film was formed on this substrate using the same procedure as for chemical resistance evaluation. In accordance with ASTM D 3559-B, 100 grid-like cuts were made in the cured film using a utility knife, with 11 cuts each in the vertical and horizontal directions at 1 mm intervals. Next, cellophane tape (registered trademark) was firmly pressed onto the grid areas, and the end of the tape was quickly peeled off at a 45° angle. The grid pattern was then compared to a standard diagram for evaluation. 5B The edges of the cut lines are smooth, and none of the grid lines are peeling off. 4B Slight peeling is observed at the intersection of the cut lines. Less than 5% of the entire cut area is significantly affected. 3B Peeling is observed along the cut lines and at the intersections. More than 5% and less than 15% of the entire cut area are significantly affected. 2B Widespread peeling is observed on part or all of the edges of the grid pattern, with peeling occurring in various places. Between 15% and 35% of the entire cut area is significantly affected. 1B: Wide peeling is observed along the edges of the grid pattern, with several grid sections peeling together, either partially or entirely. Between 35% and 65% of the entire cut area is significantly affected. 0B Items that do not fall under the above categories.

[0132] [Table 3]

[0133] As shown in Table 3, in Examples 1 to 19, cured films with excellent resolution, residual film ratio, chemical resistance, and adhesion were formed. On the other hand, in the comparative examples, resolution, residual film ratio, chemical resistance, and adhesion were inferior in any one of these aspects. In particular, in Comparative Examples 1 and 2, which used alkali-soluble resins having (meth)acryloyl groups in the side chains, the adhesion of the cured films was poor. [Explanation of Symbols]

[0134] 10 circuit boards 20 Light-emitting elements 30 Sealing layer 40 Cured resin part 41 Wiring base layer 42 Patterned cured resin layer 43 Upper protective layer 1a First metal wiring layer 2a Second metal wiring layer 3 Contact Holes 3' Wiring

Claims

1. A method for manufacturing a light-emitting device comprising a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer directly or indirectly on the sealing layer, A step of forming a light-emitting element on a substrate and a sealing layer on the light-emitting element, A step of applying a negative-type radiation-sensitive composition directly or indirectly onto the sealing layer to form a coating film. A step of irradiating at least a portion of the coating film with radiation, A process of alkaline developing the coating film after radiation irradiation, and This process includes heating at a temperature of 100°C or lower, in this order. The negative radiation-sensitive composition comprises an alkali-soluble resin (A) having a constituent unit having an acidic group and a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group. Polyfunctional radical polymerizable compound (B), and Contains a photoradical polymerization initiator (C), A method for manufacturing a light-emitting device.

2. The method for manufacturing a light-emitting device according to claim 1, wherein the acidic group is a carboxyl group or a phenolic hydroxyl group.

3. The method for manufacturing a light-emitting device according to claim 1 or 2, wherein the content of constituent units having phenolic hydroxyl groups in the alkali-soluble resin (A) is 8% by mass or more and 35% by mass or less.

4. The method for manufacturing a light-emitting device according to claim 1 or 2, wherein the content of a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group in the alkali-soluble resin (A) is 15% by mass or more and 80% by mass or less.

5. A method for manufacturing a light-emitting device according to claim 1 or 2, wherein the alkali-soluble resin (A) contains a constituent unit having a phenolic hydroxyl group, and the content of constituent units having a carboxyl group in the alkali-soluble resin (A) is 2% by mass or less, or does not contain any constituent units having a carboxyl group.

6. The method for manufacturing a light-emitting device according to claim 1 or 2, wherein the alkali-soluble resin (A) is a resin obtained by radical polymerization.

7. The method for manufacturing a light-emitting device according to claim 6, wherein the alkali-soluble resin (A) comprises a structural unit derived from a radical polymerizable monomer having a phenolic hydroxyl group and a structural unit derived from a radical polymerizable monomer having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group.

8. A method for producing a light-emitting device according to claim 7, wherein the radical polymerizable monomer having a phenolic hydroxyl group comprises at least one selected from the group consisting of 4-hydroxyphenyl (meth)acrylate, 4-hydroxystyrene, and 4-isopropenylphenol.

9. A method for producing a light-emitting device according to claim 7, wherein the radical polymerizable monomer having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group comprises at least one selected from the group consisting of glycidyl (meth)acrylate, 1,2-epoxy-3-(3-vinyl benzyloxy)propane, 1,2-epoxy-3-(4-vinyl benzyloxy)propane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, and 4-hydroxybutyl (meth)acrylate glycidyl ether.

10. A method for manufacturing a light-emitting device according to claim 1 or 2, wherein the (meth)acrylic equivalent of the alkali-soluble resin (A) is 1200 g / eq or more.

11. The method for manufacturing a light-emitting device according to claim 1 or 2, wherein the content of the polyfunctional radical polymerizable compound (B) in the negative-type radiation-sensitive composition is 40 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the alkali-soluble resin (A).

12. The method for manufacturing a light-emitting device according to claim 1 or 2, wherein the negative-type radiation-sensitive composition further comprises at least one selected from the group consisting of a chain transfer agent (D), an ultraviolet absorber (E), a radical polymerization inhibitor (F), an adhesive (G), an antioxidant (H), a dehydrating agent (I), and a surfactant (J).

13. The method for manufacturing a light-emitting device according to claim 1 or 2, wherein the light-emitting device is an organic EL device.

14. Alkali-soluble resin (A) having a constituent unit having an acidic group and a constituent unit having at least one group selected from the group consisting of an oxyranyl group and an oxetanyl group, Polyfunctional radical polymerizable compound (B), and Contains a photoradical polymerization initiator (C), Negative-type radiation-sensitive composition.

15. The negative-type radiation-sensitive composition according to claim 14, for forming the cured resin layer of a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a cured resin portion having at least one cured resin layer directly or indirectly on the sealing layer.

16. A cured film obtained by curing the negative-type radiation-sensitive composition according to claim 14 or 15.

17. An organic EL apparatus comprising the cured film described in claim 16.

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