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

Abstract

The present invention relates to a negative radiation-sensitive composition, a method for manufacturing a light-emitting device, a cured film, and an organic EL device. The negative radiation-sensitive composition has sufficient resolution and can obtain a cured film having sufficient chemical resistance and excellent adhesion even when heated at a low temperature. The present invention also relates to a method for manufacturing a light-emitting device, a cured film, and an organic EL device. The light-emitting device comprises a substrate, a light-emitting element on the substrate, a sealing layer on the element, and a hardened resin part which is directly or indirectly positioned on the sealing layer and is provided with at least one hardened resin layer. The manufacturing method comprises the following steps in sequence: forming the light-emitting element and the sealing layer on the element on the substrate; forming a coating film by directly or indirectly applying a composition on the sealant layer; irradiating at least a portion of the coating film with radiation; carrying out alkali development on the coating film irradiated by the radioactive rays; when heated at 100 DEG C or less, the composition contains: an alkali-soluble resin (A) containing a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of an oxeteropropyl group and an oxeterobutyl group; a polyfunctional radical polymerizable compound (B); and a photo-radical polymerization initiator (C).

Description

Technical Field

[0001] This invention relates to a method for manufacturing a light-emitting device, a negative-type emitting linear composition, a hardened film, and an organic EL device. Background Technology

[0002] As one of the light-emitting elements that has been developed in recent years, organic electroluminescence (EL) elements with a stacked structure including an anode layer, an organic light-emitting layer, and a cathode layer are known. As a display device with an organic EL element, an organic EL device with a touch screen on the front surface of the device is known (see Patent Document 1).

[0003] Organic EL devices with touchscreens are manufactured by bonding the touchscreen to a substrate forming the organic EL element via an adhesive layer or bonding layer. Touchscreens are typically manufactured by placing touchscreen components such as sensor electrodes on a touchscreen support substrate.

[0004] When a touchscreen is bonded to a substrate forming an organic EL element via an adhesive or bonding layer, the overall thickness of the organic EL device increases. This can lead to breakage or functional degradation when the organic EL device is bent. To address this issue, methods for directly fabricating touchscreens on organic EL elements using photolithography and etching have been known in recent years. However, since the formation of the patterned resin insulating film and other curing resin layers within the touchscreen requires baking at temperatures exceeding 100°C, directly forming the curing resin layer on the organic EL element using existing methods can cause degradation of the organic EL light-emitting layer.

[0005] [Existing technical documents]

[0006] [Patent Literature]

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

[0008] [The problem the invention aims to solve]

[0009] When a curable resin layer is directly formed on an organic EL element, curing is required at low temperatures to prevent degradation of the organic EL light-emitting layer, preferably by light irradiation alone. Therefore, a composition with high sensitivity and excellent curability is needed. However, if the sensitivity is too high, for example, when using a negative curable composition to form a hole pattern, the light leaking from the mask can cure to the area where the hole should be formed, sometimes resulting in poor resolution due to hole pattern filling, and reduced adhesion to the underlying layer due to curing shrinkage. On the other hand, if a curable composition that reduces sensitivity is used to preferentially form the hole pattern, the curing of the pattern becomes insufficient, and chemical resistance sometimes decreases. In other words, in the prior art, when a curable resin layer is directly formed on an organic EL element, it is difficult to simultaneously achieve resolution, adhesion, and chemical resistance.

[0010] The present invention is based on the facts described above, and its objective is to provide a negatively induced linear emissive composition having sufficient resolution and a curing film with sufficient chemical resistance and excellent adhesion even when heated at relatively low temperatures (e.g., below 100°C), a method for manufacturing a light-emitting device using the negatively induced linear emissive composition, a curing film formed by curing the negatively induced linear emissive composition, and an organic EL device including the curing film.

[0011] [Technical means to solve the problem]

[0012] The inventors have discovered that the aforementioned problem can be solved by incorporating a specific alkali-soluble resin into a negatively induced linear emissive composition. That is, the present invention provides a method for manufacturing a light-emitting device, a negatively induced linear emissive composition, a hardened film, and an organic EL device.

[0013] [1] A method for manufacturing a light-emitting device, the light-emitting device having a substrate, a light-emitting element located on the substrate, a sealing layer located on the light-emitting element, and a hardened resin portion having at least one hardened resin layer directly or indirectly located on the sealing layer, and the method for manufacturing the light-emitting device sequentially includes: a step of forming a light-emitting element and a sealing layer located on the light-emitting element on the substrate; a step of directly or indirectly coating a negatively induced radioactive linear composition onto the sealing layer to form a coating film; a step of irradiating at least a portion of the coating film with radiation; a step of alkaline developing the irradiated coating film; and a step of heating at a temperature below 100°C, wherein the negatively induced radioactive linear composition contains: an alkali-soluble resin (A), a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of oxadiol and oxadiol; a multifunctional free radical polymerizable compound (B); and a photoradioactive polymerization initiator (C).

[0014] [2] The method for manufacturing the light-emitting device according to [1], wherein the acidic group is a carboxyl group or a phenolic hydroxyl group.

[0015] [3] The method for manufacturing the light-emitting device according to [1] or [2], wherein the content of the structural unit having phenolic hydroxyl groups in the alkali-soluble resin (A) is 8% by mass or more and 35% by mass or less.

[0016] [4] The method for manufacturing a light-emitting device according to any one of [1] to [3], wherein the content of structural units having at least one group selected from the group consisting of oxocyclopropyl and oxocyclobutyl in the alkali-soluble resin (A) is 15% by mass or more and 80% by mass or less.

[0017] [5] The method for manufacturing a light-emitting device according to any one of [1] to [4], wherein the alkali-soluble resin (A) contains structural units having phenolic hydroxyl groups, and the content of structural units having carboxyl groups in the alkali-soluble resin (A) is less than 2% by mass or does not contain structural units having carboxyl groups.

[0018] [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 free radical polymerization.

[0019] [7] According to the method of manufacturing the light-emitting device described in [6], wherein the alkali-soluble resin (A) contains structural units derived from a free radical polymerizable monomer having phenolic hydroxyl groups and structural units derived from a free radical polymerizable monomer having at least one group selected from the group consisting of oxacyclopropyl and oxacyclobutyl.

[0020] [8] The method for manufacturing the light-emitting device according to [7] wherein the free radical polymerizable monomer having phenolic hydroxyl groups comprises at least one selected from the group consisting of hydroxyphenyl methacrylate, 4-hydroxystyrene and 4-isopropenylphenol.

[0021] [9] The method of manufacturing the light-emitting device according to [7] or [8], wherein the radical polymerizable monomer having at least one group selected from the group consisting of oxetyl and oxetyl comprises at least one group selected from the group consisting of glycidyl (meth)acrylate, 1,2-epoxy-3-(3-vinylbenzyloxy)propane, 1,2-epoxy-3-(4-vinylbenzyloxy)propane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, (meth)acrylate (3,4-epoxycyclohexyl)methyl ester, and 4-hydroxybutyl(meth)acrylate glycidyl ether.

[0022]

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

[0023]

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

[10] , wherein, relative to 100 parts by mass of the alkali-soluble resin (A), the content of the multifunctional free radical polymeric compound (B) in the negative-type radiosensitive linear composition is 40 parts by mass or more and 150 parts by mass or less.

[0024]

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

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

[0025]

[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.

[0026]

[14] A negatively induced radiolinear composition comprising: an alkali-soluble resin (A) containing a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of oxetyl and oxetyl; a multifunctional radical polymerizable compound (B); and a photoradical polymerization initiator (C).

[0027]

[15] The negative-type induced radiation linear composition according to

[14] is used to form a light-emitting device having a substrate, a light-emitting element located on the substrate, a sealing layer located on the light-emitting element, and a hardened resin portion having at least one hardened resin layer located directly or indirectly on the sealing layer.

[0028]

[16] A hardened film formed by hardening a negatively induced radiolinear composition according to

[14] or

[15] .

[0029]

[17] An organic EL device comprising a hardened membrane according to

[16] .

[0030] [The effects of the invention]

[0031] The present invention provides a negative-type radiosensitive linear composition having sufficient resolution and a hardened film with sufficient chemical resistance and excellent adhesion that can be obtained even when heated at relatively low temperatures (e.g., below 100°C), a method for manufacturing a light-emitting device using the negative-type radiosensitive linear composition, a hardened film formed by hardening the negative-type radiosensitive linear composition, and an organic EL device including the hardened film. Attached Figure Description

[0032] Figure 1 This is a cross-sectional view showing one embodiment of the light-emitting device obtained by the manufacturing method of the present invention.

[0033] Explanation of icon numbers

[0034] 1a: First metal wiring layer

[0035] 2a: Second metal wiring layer

[0036] 3: Contact hole

[0037] 3': Wiring

[0038] 10: Substrate

[0039] 20: Light-emitting element

[0040] 30: Sealing layer

[0041] 40: Hardened resin section

[0042] 41: Wiring base layer

[0043] 42: Patterned curing resin layer

[0044] 43: Upper protective layer Detailed Implementation

[0045] The following provides a detailed description of matters related to the implementation method. Furthermore, in this specification, the numerical range indicated by “~” refers to the values ​​before and after the “~” as lower and upper limits.

[0046] In this specification, "hydrocarbon group" refers to chain-like hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Chain-like hydrocarbon group" refers to a straight-chain hydrocarbon group or branched hydrocarbon group whose main chain consists only of chain structures and does not contain any ring structures. The chain-like hydrocarbon group can be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as its ring structure and does not contain any aromatic ring structures. The alicyclic hydrocarbon group does not necessarily need to consist solely of an alicyclic hydrocarbon structure; it may also include groups with chain structures in a portion of it. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as its ring structure. The aromatic hydrocarbon group does not necessarily need to consist solely of an aromatic ring structure; it may also include chain structures or alicyclic hydrocarbon structures in a portion of it. Furthermore, the ring structures of alicyclic hydrocarbon groups and aromatic hydrocarbon groups may also have substituents containing hydrocarbon structures.

[0047] In this specification, "(meth)acryloyl" means including both "acryloyl" and "methacryloyl", "(meth)acrylate" means including both "acrylate" and "methacrylate", and "(meth)acrylate" means including both "acrylate" and "methacrylate".

[0048] [Manufacturing method of light-emitting device]

[0049] The method for manufacturing a light-emitting device of the present invention comprises a substrate, a light-emitting element located on the substrate, a sealing layer located on the light-emitting element, and a hardened resin portion having at least one hardened resin layer located directly or indirectly on the sealing layer, and sequentially includes: a step of forming a light-emitting element and a sealing layer located on the light-emitting element on the substrate; a step of directly or indirectly coating a negative radiosensitive linear composition (hereinafter, the negative radiosensitive linear composition used in the present invention is also referred to as a "hardening composition" or "this composition") onto the sealing layer to form a coating film; a step of irradiating at least a portion of the coating film with radiation; a step of alkaline developing the irradiated coating film; and a step of heating at a temperature below 100°C, wherein the negative radiosensitive linear composition comprises: an alkali-soluble resin (A), a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of oxetyl and oxetyl; a multifunctional free radical polymerizable compound (B); and a photoradical polymerization initiator (C).

[0050] The method for manufacturing a light-emitting device according to the present invention provides a light-emitting device having a hardened resin layer, which has sufficient resolution, sufficient chemical resistance and excellent adhesion even when heated at relatively low temperatures (e.g., below 100°C).

[0051] The reasons for achieving the aforementioned effect are not necessarily clear. It is believed that the polymer chain length and crosslinking density of the polyfunctional free radical polymerizable compound (B) can be moderately controlled by the presence of a polymer with acidic groups, preferably phenolic hydroxyl groups, which can suppress the generation of strain in the hardened film caused by hardening, thereby improving the adhesion.

[0052] In addition, by using an alkali-soluble resin (A) containing structural units with acidic groups, sufficient solubility can be obtained in the developing process.

[0053] Furthermore, it is believed that by heating after the development process to carry out a crosslinking reaction based on the oxetine-soluble resin (A) containing oxetine propyl and oxetine butyl groups, chemical resistance and adhesion are further improved.

[0054] The sealing layer and the hardened resin portion can be formed in contact, or other layers can exist between the sealing layer and the hardened resin portion. However, it is preferable that there is no support (glass substrate or resin substrate formed of resin such as polyethylene terephthalate) with a thickness exceeding 50 μm between the sealing layer and the hardened resin portion. More preferably, the support itself is not used. Sometimes a support is used to separately fabricate the light-emitting element and the touch screen layer (hardened resin layer) and then bond them together. However, in this embodiment, it is more preferable that after the sealing layer is formed, the sealing layer and the hardened resin portion are formed in contact directly or indirectly through other layers (such as a planarization layer) on top of it.

[0055] The light-emitting device is, for example, a device comprising a stacked structure including an organic light-emitting layer and an organic semiconductor thin film, specifically, organic electroluminescent (EL) devices and organic transistors, preferably organic EL devices. Examples of organic EL devices include organic EL lighting devices and organic EL display devices.

[0056] The substrate can be any substrate commonly used in light-emitting devices, such as glass substrates and resin substrates. Specifically, the substrate described in International Publication No. 2019 / 009360 is preferred.

[0057] The substrate is, for example, a TFT substrate having thin-film transistors (TFTs) that drive the light-emitting elements. In one embodiment, the TFTs are arranged in a matrix. Alternatively, the TFT substrate may also have a planarization film covering the TFTs.

[0058] As the light-emitting element, an organic EL element is preferred. Examples of organic EL elements include those used in known organic EL devices, as long as they have a structure in which an organic light-emitting layer containing a light-emitting material is sandwiched between a pair of opposing electrodes (i.e., a structure in which an organic light-emitting layer is sandwiched between an opposing anode and a cathode). For example, a known structure having an anode / organic light-emitting layer / cathode can be cited. Specifically, for example, the structure described in International Publication No. 2019 / 009360 is preferred, and it can be formed on a substrate by a known method, preferably the method described in that publication.

[0059] The sealing layer seals the light-emitting element, which reduces the possibility of moisture entering the light-emitting element. As a result, it can suppress the generation of dark spots or the reduction of light-emitting characteristics such as brightness and luminous efficiency caused by moisture.

[0060] Examples of sealing layers include: (1) an organic sealing layer, (2) an inorganic sealing layer, and (3) an organic-inorganic sealing layer that alternates between organic and inorganic sealing layers. For example, it may be an organic-inorganic sealing layer with an organic sealing layer between two inorganic sealing layers, or an organic-inorganic sealing layer that alternates between a total of four or more inorganic and organic sealing layers. The outermost layer of the sealing layer is preferably an inorganic sealing layer.

[0061] Examples of inorganic sealing layers include those described in Japanese Patent Application Publication Nos. 2010-160906, 2016-012433, and 2016-143605. Specifically, layers comprising silicon nitride (SiNx) or silicon oxide (SiOx) can be included, and methods for forming these layers include sputtering and chemical vapor deposition. The thickness of a single inorganic sealing layer is typically around 10 nm to 2 μm.

[0062] As the organic sealing layer, for example, a layer formed from a curable composition can be cited. The thickness of one layer of the organic sealing layer is typically 1 μm to 50 μm, preferably 1 μm to 20 μm, and more preferably 1 μm to 15 μm.

[0063] The composition or method described in International Publication No. 2019 / 009360 is preferably used as the curing composition or method for forming the organic sealing layer.

[0064] The cured resin portion includes a cured resin layer comprising a negative-type radiosensitive linear composition (hereinafter also referred to as "the composition"). The cured resin layer may also be patterned. The patterned cured resin layer (hereinafter also referred to as a patterned cured resin layer) is preferably a layer formed directly on the sealing layer using the negative-type radiosensitive linear composition of the present invention and by photolithography.

[0065] The shape of the pattern is not particularly limited. For example, the shapes of the parts without a hardened resin layer can be shaped as circles, ovals, polygons, etc., such as pores or lines.

[0066] 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 layers, and where necessary, are electrically connected by wiring formed in contact holes formed on the patterned cured resin layers.

[0067] The thickness of the patterned curing resin layer is typically 1 μm to 5 μm. The thickness of the metal wiring layer is typically 100 nm to 1000 nm. The diameter of the contact holes is typically 1 μm to 20 μm.

[0068] The method for forming the hardened resin layer will be described in detail in the section on "Method for Forming the Hardened Resin Layer" which will be discussed later.

[0069] The cured resin portion may further include a cured layer serving as a wiring substrate layer on the light-emitting element side of the patterned cured resin layer, and / or may further include a cured layer serving as an upper protective layer on the side of the patterned cured resin layer opposite to the light-emitting element. These cured layers may be unpatterned layers, functioning as wiring substrate layers or upper protective layers of the metal wiring layer. The wiring substrate layer or upper protective layer may be formed from the curable composition of the present invention.

[0070] The thickness of the wiring base layer and the upper protective layer are typically 0.5 μm to 10 μm, respectively.

[0071] The overall thickness of the hardened resin portion is preferably 15 μm or less, more preferably 9 μm or less, and even more preferably 6 μm or less.

[0072] use Figure 1 An embodiment of a display device comprising a hardened resin layer formed from the negative-type radiometric linear composition of the present invention will be further described. For example... Figure 1As shown, one embodiment of the curing resin section 40 includes: a wiring substrate layer 41, a first metal wiring layer 1a formed on the wiring substrate layer 41, a patterned curing resin layer 42 partially covering the first metal wiring layer 1a, a second metal wiring layer 2a formed on the patterned curing resin layer 42 and electrically connected to the first metal wiring layer 1a through wirings 3' formed on contact holes 3 of the patterned curing resin layer 42, and an upper protective layer 43 formed on the patterned curing resin layer 42 and the second metal wiring layer 2a and covering the second metal wiring layer 2a. The wiring substrate layer 41 may also be omitted. Figure 1 In this process, the hardened resin portion 40 is formed directly in the ground on the sealing layer 30 in the element substrate that includes the substrate 10, the light-emitting element 20 and the sealing layer 30.

[0073] The hardened resin part 40 is preferably a touch screen component.

[0074] The materials constituting the first metal wiring layer 1a or the second metal wiring layer 2a are not particularly limited, and examples include: titanium, silicon, niobium, indium, zinc, tin, gold, silver, copper, aluminum, cobalt, chromium, nickel, lead, iron, palladium, platinum, tungsten, zirconium, tantalum, hafnium, molybdenum, and other metals, or materials containing two or more of these metals, or alloys with these metals as the main components. Among these, TiAlTi wiring with a titanium and aluminum laminate structure is preferred as the metal wiring.

[0075] Since the hardened resin layer formed by the negative-type radioactive linear composition of the present invention is in contact with metal wiring layers such as TiAlTi wiring or layers containing silicon nitride (SiNx) or silicon oxide (SiOx), a tightness relative to these is also required.

[0076] The following describes the negative-type induced radiation linear composition used in the manufacturing method of the light-emitting device of the present invention.

[0077] [Negative-sensory radiolinear composition]

[0078] The negative-type radiosensitive linear composition of the present invention (the composition) comprises: an alkali-soluble resin (A) containing a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of oxecyclopropyl and oxecyclobutyl; a multifunctional radical polymerizable compound (B); and a photoradical polymerization initiator (C).

[0079] The negative-type induced linear emissive composition of the present invention is preferably used in the manufacturing method of the light-emitting device of the present invention to form a hardened resin portion. In addition, it is preferably used to form the hardened resin layer of the light-emitting device having a substrate, a light-emitting element located on the substrate, a sealing layer located on the light-emitting element, and a hardened resin portion having at least one hardened resin layer located directly or indirectly on the sealing layer.

[0080] The following describes each component contained in this composition and any other components that may be formulated as needed.

[0081] <Alkali-soluble resin (A)>

[0082] Alkali-soluble resin (A) is a component that exhibits good developability based on alkali developing solutions. Alkali-soluble resin (A) contains structural units having an acidic group and structural units having at least one group selected from the group consisting of oxetyl and oxetyl.

[0083] The alkali-soluble resin (A) is preferably selected from at least one of the group consisting of resins obtained by free radical polymerization, polysiloxane resins and phenolic varnish resins, more preferably from at least one of the group consisting of resins obtained by free radical polymerization and polysiloxane resins, and even more preferably from a resin obtained by free radical polymerization.

[0084] The alkali-soluble resin (A) contains a structural unit having an acidic group, which is preferably at least one group selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, and is further preferably a phenolic hydroxyl group from the viewpoint of the storage stability of the composition.

[0085] From the viewpoint of further improving the developability and properties of the hardened film, the content of the structural unit with acidic group 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, more preferably 12% by mass or more and 28% by mass or less, and more preferably 15% by mass or more and 26% by mass or less.

[0086] The content of structural units with acidic groups in alkali-soluble resin (A) can be calculated based on the content of monomers constituting alkali-soluble resin (A).

[0087] From the viewpoint of further improving the developability and properties of the hardened film, the content of structural units with 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, more preferably 12% by mass or more and 28% by mass or less, and more preferably 15% by mass or more and 26% by mass or less.

[0088] In the case where the alkali-soluble resin (A) has a carboxyl group as an acidic group, from the viewpoint of further improving the developability and properties of the hardened film, the content of the structural unit with a carboxyl group in the alkali-soluble resin (A) is preferably 3% by mass or more, more preferably 5% by mass or more, and 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.

[0089] In the case where the alkali-soluble resin (A) has phenolic hydroxyl groups as acidic groups, from the viewpoint of the storage stability of this composition, the content of structural units with phenolic hydroxyl groups 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, and even more preferably not contained.

[0090] Regarding the content of structural units having at least one group selected from the group consisting of oxetyl and oxetyl in the alkali-soluble resin (A), from the viewpoint of further improving developability and the physical properties of the cured film, the lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and further 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, further preferably 70% by mass or less, and further more preferably 65% ​​by mass or less.

[0091] The content of structural units in alkali-soluble resin (A) having at least one group selected from the group consisting of oxetyl and oxetyl groups can be calculated based on the content of monomers constituting alkali-soluble resin (A).

[0092] (Resin obtained through free radical polymerization)

[0093] From the viewpoint that the alkali-soluble resin (A) can further improve the developability and hardened film properties, as described above, it is preferable to be a resin obtained by free radical polymerization, more preferably a structural unit containing a structural unit derived from a free radical polymerizable monomer having an acidic group and a structural unit derived from a free radical polymerizable monomer having at least one group selected from the group consisting of oxetyl and oxetyl, and even more preferably a structural unit containing a structural unit derived from a free radical polymerizable monomer having a phenolic hydroxyl group and a structural unit derived from a free radical polymerizable monomer having at least one group selected from the group consisting of oxetyl and oxetyl.

[0094] [Free radical polymerizable monomers with acidic groups]

[0095] Examples of free radical polymerizable monomers having acidic groups include free radical polymerizable monomers having carboxyl groups and free radical polymerizable monomers having phenolic hydroxyl groups, with free radical polymerizable monomers having phenolic hydroxyl groups being preferred.

[0096] Furthermore, free radical polymerizable monomers with acidic groups can be used alone or in combination with two or more.

[0097] Examples of free radical polymerizable monomers with carboxyl groups include (meth)acrylic acid, maleic acid, fumaric acid, butenoic acid, itaconic acid, citraconic acid, succinic acid, cinnamic acid, succinic acid mono(2-(meth)acryloyloxyethyl) ester, ω-carboxyl-polycaprolactone mono(meth)acrylate, etc., with (meth)acrylic acid being the most preferred.

[0098] Examples of free radical polymerizable monomers having phenolic hydroxyl groups 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 oxetyl and oxetyl, at least one group selected from the group consisting of hydroxyphenyl (meth)acrylate (preferably 4-hydroxyphenyl (meth)acrylate), 4-hydroxystyrene, and 4-isopropenylphenol is preferred, more preferably 4-hydroxyphenyl (meth)acrylate, and even more preferably 4-hydroxyphenyl methacrylate.

[0099] [A radically polymerizable monomer having at least one group selected from the group consisting of oxetyl and oxetyl]

[0100] A free radical polymerizable monomer having at least one group selected from the group consisting of oxetyl and oxetyl is not particularly limited as long as it has at least one group selected from the group consisting of oxetyl and oxetyl and has a free radical polymerizable group (e.g., (meth)acryloyl, vinyl, etc.), but from the viewpoint of curability, it is preferred to have an oxetyl group.

[0101] Specific examples of free radical polymerizable monomers having at least one group selected from the group consisting of oxetyl and oxetyl groups include: glycidyl (meth)acrylate, 1,2-epoxy-3-(3-vinylbenzyloxy)propane, 1,2-epoxy-3-(4-vinylbenzyloxy)propane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, (meth)acrylate (3,4-epoxycyclohexyl)ester, (meth)acrylate (3,4-epoxycyclohexyl)methyl ester, (meth)acrylate 2-(3,4-epoxycyclohexyl)ethyl ester, 4-hydroxybutyl (meth)acrylate glycidyl ether, (meth)acrylate 3,4-epoxytricyclo[5.2.1.0] 2,6 ] Decyl ester.

[0102] Of these, from the viewpoint of curability, etc., it is preferable to be at least one selected from the group consisting of glycidyl methacrylate, 1,2-epoxy-3-(3-vinylbenzyloxy)propane, 1,2-epoxy-3-(4-vinylbenzyloxy)propane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, (3,4-epoxycyclohexyl)methyl methacrylate, and 4-hydroxybutyl(meth)acrylate glycidyl ether, more preferably glycidyl methacrylate, (3,4-epoxycyclohexyl)methyl methacrylate, 1,2-epoxy-3-(3-vinylbenzyloxy)propane, and 1,2-epoxy-3-(4-vinylbenzyloxy)propane.

[0103] Furthermore, a radical polymerizable monomer having at least one group selected from the group consisting of oxecyclopropyl and oxecyclobutyl can be used alone or in combination with two or more groups.

[0104] [Other free radical polymerizable monomers]

[0105] The alkali-soluble resin (A) preferably contains structural units derived from other free radical polymerizable monomers, in addition to the structural units derived from the free radical polymerizable monomers having acidic groups and the structural units derived from the free radical polymerizable monomers having at least one group selected from the group consisting of oxecyclopropyl and oxecyclobutyl.

[0106] Other free radical polymerizable monomers, for example:

[0107] 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 ester, (meth)acrylate tricyclic [5.2.1.0] 2,5 Decane-8-yloxyethyl ester, isobornyl acrylate, and other methacrylates;

[0108] 3-(2H-1,2,3-benzotriazol-2-yl)-4-hydroxyphenylethyl methacrylate (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) and other free radical polymerizable monomers with ultraviolet-absorbing functional groups;

[0109] Aromatic vinyl monomers including styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, vinyltoluene, etc.

[0110] 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, N-naphthylmaleimide, and other N-substituted maleimide compounds;

[0111] Styrene trimethoxysilane, styrene triethoxysilane, styrene methyl dimethoxysilane, styrene ethyl diethoxysilane, styrene dimethoxyhydroxysilane, styrene diethoxyhydroxysilane, (meth)acryloyloxyphenyl trimethoxysilane, (meth)acryloyloxyphenyl triethoxysilane, (meth)acryloyloxyphenyl methoxydimethoxysilane, (meth)acryloyloxyphenyl ethyl diethoxysilane, etc.; trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinyl) Monomers containing alkoxysilanes, such as naphthyl(4-vinylnaphthyl)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;

[0112] Conjugated dienes such as 1,3-butadiene and isoprene;

[0113] Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and other vinyl cyanide compounds;

[0114] 2-Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and other monomers containing hydroxyl groups;

[0115] Polystyrene, poly(methyl)methacrylate, poly(ethyl)methacrylate, poly(benzyl)methacrylate, and other macromonomers with polymerizable unsaturated groups such as (meth)acryloyl groups at one end of the polymer chain. These can be used alone or in combination with two or more.

[0116] Among these, other free radical polymerizable monomers are preferably those containing at least one selected from the group consisting of (meth)acrylates, aromatic vinyl compounds, and N-substituted maleimide compounds, and more preferably those containing at least an alkyl (meth)acrylate.

[0117] Regarding the content of structural units derived from other free radical polymerizable monomers in the alkali-soluble resin (A), as a lower limit, it is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 15% by mass or more. As an upper limit, it is preferably 80% by mass or less, more preferably 65% ​​by mass or less, further preferably 55% by mass or less, and further preferably 45% by mass or less.

[0118] There are no particular limitations on the method for obtaining the alkali-soluble resin (A) by free radical polymerization, and it can be manufactured by known methods such as suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization. Furthermore, the manufacturing conditions can also be those currently known.

[0119] (Polysiloxane resin)

[0120] Examples of such polysiloxane resins include hydrolytic condensates of hydrolyzable silane compounds. Here, "hydrolyzable silane compound" refers to a compound containing a group that can be hydrolyzed to form a silanol group or a group that can form a siloxane condensate; "hydrolytic condensate" refers to a condensate formed by the condensation of the silanol groups of a hydrolyzed silane compound. Examples of such polysiloxane resins include the polysiloxane resin described in Japanese Patent Application Publication No. 2017-048355.

[0121] (Phenolic varnish resin)

[0122] The phenolic varnish resin can be obtained by using known methods and by polycondensation of phenols with aldehydes such as formaldehyde.

[0123] From the viewpoint of adhesion, the (meth)acrylic acid equivalent of the alkali-soluble resin (A) is preferably a large value, specifically, preferably 1200 g / eq or more, more preferably 2000 g / eq or more, and even more preferably 5000 g / eq or more.

[0124] That is, the alkali-soluble resin (A) is preferably a resin that is not intentionally introduced with (meth)acrylic acid groups, for example, preferably one that does not have (meth)acryloyloxy groups in its side chain.

[0125] From the viewpoint of further improving the developability and properties of the hardened film, the acid value of the alkali-soluble resin (A) is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 40 mgKOH / g or more. Furthermore, it is preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. The acid value refers to the number of mg of KOH required to neutralize 1 g of the solid component of the alkali-soluble resin (A).

[0126] From the viewpoint of further improving the coatability, developability and hardened film properties of the composition, the weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more, and preferably 40,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.

[0127] Furthermore, from the same viewpoint, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the alkali-soluble resin (A) is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0128] The weight-average molecular weight and number-average molecular weight of the alkali-soluble resin (A) can be determined by the methods described in the examples.

[0129] The alkali-soluble resin (A) can be used alone or in combination with two or more.

[0130] From the viewpoint of further improving the developability and properties of the hardened film, the content of alkali-soluble resin (A) (in many cases, the total amount) is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, particularly 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, more preferably 70% by mass or less, and more preferably 60% by mass or less, relative to the total solid content (100% by mass) of the composition (i.e., relative to the total amount of components other than the organic solvent in the composition).

[0131] <Multifunctional free radical polymeric compounds (B)>

[0132] The polyfunctional free radical polymerizable compound (B) can be any polymerizable compound that reacts and hardens using free radicals generated by a photoradical polymerization initiator. However, from the viewpoint of improving the storage stability of the hardened composition or controlling the hardening properties of the obtained hardened film, a polymerizable compound having two or more (meth)acryloyloxy groups in the molecule, i.e., a polyfunctional (meth)acrylate, is preferred. Specific examples of such polyfunctional (meth)acrylates include difunctional (meth)acrylates or trifunctional or higher (meth)acrylates.

[0133] Examples of difunctional (meth)acrylates include: 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tricyclodecanemethanol dimethacrylate, bisphenol A epoxy dimethacrylate, neopentyl glycol hydroxypentyl ester dimethacrylate, etc.

[0134] Examples of trifunctional or higher (meth)acrylates include: trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide (EO) modified tri(meth)acrylate, trimethylolpropane propylene oxide (PO) modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate (also known as tri(2-hydroxyethyl)isocyanuric acid tri(meth)acrylate), pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl) phosphate, succinic acid modified dipentaerythritol tri(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, or mixtures thereof. In addition, examples include polyfunctional urethane (meth)acrylate compounds obtained by reacting compounds having straight-chain alkylene or alicyclic structures and having two or more isocyanate groups with compounds having one or more hydroxyl groups in the molecule and having three, four or five (meth)acryloyloxy groups.

[0135] Among these, the polyfunctional free radical polymerizable compound (B) preferably contains trifunctional or higher (meth)acrylates in addition to difunctional (meth)acrylates, and more preferably contains one or more compounds 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.

[0136] Multifunctional free radical polymeric compounds (B) can be used alone or in combination with two or more.

[0137] In this composition, the content (in many cases, the total content) of the polyfunctional free radical polymerizable compound (B) relative to 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 properties of the cured film. 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. This upper limit is especially preferred when the lower layer is polyimide.

[0138] <Photoradical polymerization initiator (C)>

[0139] The photoradical polymerization initiator (C) is a compound that can sense radiation to generate free radicals and initiate polymerization. Specific examples of photoradical polymerization initiators (C) include: O-acyl oxime compounds, α-amino ketone compounds, α-hydroxy ketone compounds, acylphosphine oxide compounds, etc., among which oxime ester-based photopolymerization initiators such as O-acyl oxime compounds are preferred.

[0140] By using the oxime ester-based photopolymerization initiator, sensitivity can be improved, and in-plane linewidth deviations are easily suppressed when forming fine line patterns, which is therefore preferred. Furthermore, by using the oxime ester-based photopolymerization initiator, there is a tendency to increase the residual film yield.

[0141] As the oxime ester-based photopolymerization initiator, in terms of reducing contamination of the composition or the device by decomposition products, it is preferable to have an aromatic ring, more preferably to have a condensed ring containing an aromatic ring, and even more preferably to have a condensed ring containing a benzene ring and a heterocyclic ring.

[0142] Examples of oxime ester-based photopolymerization initiators include: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2010-527338, and Japanese Patent Application Publication No. 2013-041153. Commercially available products include: Irgacure OXE-01 (manufactured by BASF), ADEKA Arkls NCI-930 (manufactured by ADEKA) 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 Qiangli Electronic New Materials Co., Ltd.).

[0143] The photoradical polymerization initiator (C) can be used alone or in combination with two or more.

[0144] Relative to 100 parts by weight of the alkali-soluble resin (A), the content of the photoradical polymerization initiator (C) (in various cases, the total content) is preferably 1 part by weight or more, more preferably 2 parts by weight or more, even more preferably 3 parts by weight or more, even more preferably 4 parts by weight or more, and preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, even more preferably 8 parts by weight or less. With the content of the photoradical polymerization initiator (C) within the aforementioned range, even at low exposure levels, this composition can form a hardened film with good resolution and good adhesion for development, which is therefore preferable.

[0145] The composition preferably includes, in addition to the alkali-soluble resin (A), the multifunctional free radical polymerizable compound (B), and the photoradical polymerization initiator (C), at least one of the group consisting of a chain transfer agent (D), an ultraviolet absorber (E), a free radical polymerization inhibitor (F), a bonding agent (G), an antioxidant (H), a dehydrating agent (I), and a surfactant (J).

[0146] The following is a description of each component.

[0147] <Chain transfer agent (D)>

[0148] This composition may also contain a chain transfer agent (D), and preferably contains a chain transfer agent (D). A chain transfer reaction is a reaction in free radical polymerization in which free radicals of growing polymer chains move to other molecules; the chain transfer agent is an agent that generates the chain transfer reaction. If this composition contains a chain transfer agent (D), the polymer chain length of the polyfunctional free radical polymerizable compound (B) can be controlled by the action of the chain transfer agent, which is therefore preferred.

[0149] The chain transfer agent (D) contained in this composition is not particularly limited to any compound that functions as a chain transfer agent in a free radical polymerization reaction. Examples of chain transfer agents (D) include compounds containing pyrazole derivatives, alkyl thiols, etc.

[0150] From the viewpoint of improving the adhesion of the hardened film, compounds having thiol groups are preferred, more preferably compounds having two or more thiol groups, and even more preferably polyfunctional thiol compounds having three or more thiol groups, and even more preferably polyfunctional thiol compounds having four or more thiol groups. The number of thiol groups is preferably six or less per molecule. The thiol compound does not contain a compound equivalent to the adhesion agent (G) described later.

[0151] As polyfunctional thiols, primary and secondary polyfunctional thiols can be listed. From the viewpoint of high storage stability and odor suppression, secondary polyfunctional thiols are preferred.

[0152] Examples of secondary polyfunctional thiols include: pentaerythritol tetra(3-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), and 1,3,5-tris[2-(3-mercaptobutyryloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0153] Examples of primary polyfunctional thiols include: trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetra(3-mercaptopropionate), and dipentaerythritol hexa(3-mercaptopropionate).

[0154] Chain transfer agent (D) can be used alone or in combination with two or more.

[0155] When the composition contains a chain transfer agent (D), from the viewpoint of further improving the adhesion of the cured material, the content of the chain transfer agent (D) (in many cases, the total content) relative to 100 parts by mass of the alkali-soluble resin (A) is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, then 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.

[0156] <Ultraviolet Absorber (E)>

[0157] This composition may also contain a UV absorber (E). The UV absorber (E) is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of the light source used in the exposure. By containing a UV absorber (E) in this composition, there is a tendency to obtain effects such as improved cone shape after development or reduced residue remaining in the unexposed areas after development. From the viewpoint that the UV absorber (E) does not hinder light absorption by the photoradical polymerization initiator (C), for example, a compound with maximum absorption between 250 nm and 400 nm can be used.

[0158] Examples of ultraviolet (E) absorbers include: benzotriazole compounds, triazine compounds, benzophenone compounds, benzoic acid ester compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, dyes, etc.

[0159] Ultraviolet absorbers (E) can be used alone or in combination with two or more.

[0160] From the viewpoint of improving resolution, benzotriazole compounds and / or hydroxyphenyltriazine compounds are preferred, and benzotriazole compounds are more preferred.

[0161] Specifically, examples of benzotriazole compounds include: 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2,2-methylenebis{6-(benzotriazole-2-yl-4-tert-octylphenol)}, and 3-(2H-1,2,3-benzotriazole-2-yl)-4-hydroxyphenylethyl methacrylate (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.).

[0162] Examples of benzophenone compounds include 2,2-di-hydroxy-4,4-dimethoxybenzophenone.

[0163] Examples of triazine compounds include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Commercially available examples include: BASF's "TINUVIN PS", "TINUVIN P", "TINUVIN 324", "TINUVIN 326", and "TINUVIN 360"; Shipro Kasei's "Seesorb 107"; and Adekastab's "Adekastab LA-F70".

[0164] From the viewpoint of the shape and resolution of the obtained pattern, the content of ultraviolet absorber (E) (total content in various cases) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, relative to 100 parts by mass of alkali-soluble resin (A).

[0165] <Free Radical Polymerization Inhibitor (F)>

[0166] This composition may also contain a free radical polymerization inhibitor (F). The free radical polymerization inhibitor (F) is a component that improves the storage stability of this composition.

[0167] Examples of free radical polymerization inhibitors (F) include: sulfur, quinones (e.g., benzoquinone), hydroquinones (e.g., hydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone), polyoxyethylene compounds (e.g., p-methoxyphenol), amine compounds (e.g., N,N-diethylhydroxyamine), and nitrosoamine compounds (e.g., N-nitroso-N-phenylhydroxyamine aluminum).

[0168] Free radical polymerization inhibitors (F) can be used alone or in combination with two or more.

[0169] From the viewpoint of improving the obtained pattern shape and the preservation stability of the composition, the content of the free radical polymerization inhibitor (F) (total content in various cases) is preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, and 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, relative to 100 parts by mass of alkali-soluble resin (A).

[0170] <Sealing Agent (G)>

[0171] This composition may also contain an adhesive (G). The adhesive (G) is a component that improves the adhesion between the hardened film formed using this composition and the underlying layer. Examples of adhesives (G) include known silane coupling agents and phosphoric acid compounds having (meth)acryloyloxy groups.

[0172] 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, (meth)acryloyl, epoxy, vinyl, and isocyanate groups. Among these, (meth)acryloyl is preferred.

[0173] Specific examples of functional silane coupling agents include: trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, etc.

[0174] 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 Industry Co., Ltd.).

[0175] The silane coupling agent can be a polymer type, and preferably a silane coupling agent with hydrolyzable groups and other functional groups bonded to an organic polymer with an organic main chain. Examples of commercially available organic polymer types include: X-12-1048, X-12-1050, X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L.

[0176] As a phosphoric acid compound having a (meth)acryloyloxy group, there are no particular limitations if it is a compound formed by substituting at least one of the three hydrogens in phosphoric acid (O=P(OH)3) with an organic group having a (meth)acryloyloxy group. Examples include Uni-chemical's Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP), Nippon Kayaku's KAYAMER series (KAYAMER PM-21, KAYAMER PM-2), Toho Chemical Industry's PPME, PMR12, PPM-5P, and Kyoeisha Chemical's Light Ester series (Light Ester... Ester, P-2M (product name), etc.

[0177] Adhesive (G) can be used alone or in combination with two or more.

[0178] When the composition contains a binder (G), from the viewpoint of forming a hardened film with excellent adhesion, the content of the binder (G) (in many cases, the total content) relative to 100 parts by weight of the alkali-soluble resin (A) is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, and even more preferably 2 parts by weight or more, and preferably 30 parts by weight or less, more preferably 25 parts by weight or less, and even more preferably 20 parts by weight or less.

[0179] <Antioxidant (H)>

[0180] This composition may also contain an antioxidant (H). An antioxidant (H) is a component that inhibits the breaking of bonds in polymer molecules by capturing free radicals generated by exposure or heating, or by decomposing peroxides generated by oxidation. Because this composition contains an antioxidant (H), the degradation of polymer molecules in the formed hardened film can be inhibited, and durability is improved; therefore, it is preferred.

[0181] Antioxidants (H) can be used alone or in combination with two or more.

[0182] Examples of antioxidants (H) include compounds having a hindered phenolic structure, compounds having a hindered amine structure, compounds having an alkyl phosphite structure, and compounds having a thioether structure. Among these, the antioxidant (H) is preferably a compound having a hindered phenolic structure.

[0183] Examples of compounds with hindered phenolic structures (hindered phenolic compounds) include: pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], dithioethylenebis[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'-(trimethylbenzene-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-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamine)phenol, etc.

[0184] When the composition contains an antioxidant (H), the content of antioxidant (H) (in many cases, the total content) relative to 100 parts by weight of alkali-soluble resin (A) is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, and even more preferably 1 part by weight or more, and preferably 5 parts by weight or less, more preferably 3 parts by weight or less.

[0185] In addition, it is sometimes preferable to have no antioxidants. If the content of antioxidants is high, the sensitivity may sometimes decrease.

[0186] <Dehydrating Agent (I)>

[0187] This composition may also contain a dehydrating agent (I). Examples of dehydrating agents (I) include orthoester compounds. Orthoester compounds are esters of orthocarboxylic acids that react with water to provide a carboxylic acid ester. Alternatively, acid anhydrides may also be used as dehydrating agents (I).

[0188] Dehydrating agent (I) can be used alone or in combination with two or more.

[0189] Examples of orthoesters include: methyl orthoformate, ethyl orthoformate, propyl orthoformate, etc.; methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, etc.; methyl orthopropionate, ethyl orthopropionate, propyl orthopropionate, etc. Among these, orthoformate or orthoacetate is preferred, and methyl orthoformate, ethyl orthoformate, methyl orthoacetate, or ethyl orthoacetate is more preferred.

[0190] When the composition contains a dehydrating agent (I), the content of the dehydrating agent (I) (in many cases, the total content) relative to 100 parts by weight of the alkali-soluble resin (A) is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, and even more preferably 1 part by weight or more, and preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably 3 parts by weight or less.

[0191] <Surfactant (J)>

[0192] This composition may also contain a surfactant (J). If this composition contains a surfactant (J), the wettability to the substrate or the like to which the coating is formed can be improved, thus improving the coatability. Furthermore, a single surfactant (J) may be used, or two or more may be used in combination.

[0193] As a surfactant (J), fluorinated surfactants and silicone surfactants are preferred, and silicone surfactants are more preferred.

[0194] Commercially available surfactants (J) include, for example, Polyflow KL-401, KL-402, KL-403, and KL-404 (all manufactured by Kyoei Chemicals, Inc.).

[0195] 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).

[0196] Dow Corning Toray 8019 Additive and Dow Corning Toray 1313 Antiform Emulsion (both manufactured by Toray Dow Corning Corporation) are examples of such additives.

[0197] Relative to 100 parts by weight of alkali-soluble resin (A), the content of surfactant (J) in this composition (total content in various cases) is preferably 0.01 parts by weight or more, more preferably 0.03 parts by weight or more, and even more preferably 0.1 parts by weight or more, and preferably 1 part by weight or less, more preferably 0.5 parts by weight or less.

[0198] <Organic Solvent (K)>

[0199] This composition may also contain an organic solvent (K). By including an organic solvent (K), the viscosity of this composition can be adjusted to be suitable for application.

[0200] There are no particular limitations on the organic solvent (K), and examples include: alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, etc. An organic solvent (K) can be used alone or in combination with two or more.

[0201] Examples of alcohol-based solvents include: methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, diacetone alcohol, and other alkyl alcohols; and benzyl alcohol and other aromatic alcohols.

[0202] Examples of ether-based solvents include: diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and other ethylene glycol monoalkyl ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and other propylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and other diethylene glycol monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and other diethylene glycol dialkyl ethers; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and other dipropylene glycol monoalkyl ethers, etc.

[0203] Examples of ester-based solvents include: ethyl acetate, isopropyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and other carboxylic acid esters; propylene glycol diacetate and other polyol carboxylic acid esters; and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and other polyol partial ether carboxylic acid esters.

[0204] Examples of ketone solvents include: acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, etc.

[0205] Among these, ether-based solvents and ester-based solvents are preferred, more preferably ester-based solvents, and even more preferably polyol partial ether carboxylic acid ester solvents. Furthermore, among 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.

[0206] The content of organic solvent (K) in this composition is not particularly limited, but it is preferable to prepare the composition in such a way that the concentration of the solid components (components other than organic solvent (K)) is within the following range. From the viewpoint of solvent removal, the concentration of the solid components 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. Furthermore, from the viewpoint of coatability, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

[0207] In addition to the components (A) to (K) described above, this composition may also contain other components. Regarding these other components, their content 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.

[0208] Furthermore, from the viewpoint of preservation stability, this composition is preferably low in the content of photoacid generator. Relative to 100 parts by weight of alkali-soluble resin (A), the content of photoacid generator in this composition is preferably 0.1 parts by weight or less, more preferably 0.01 parts by weight or less, and even more preferably 0.001 parts by weight or less, and even more preferably not contained.

[0209] From the viewpoint of coating properties, the viscosity of this composition, measured using an E-type viscometer at 25°C and 50 rpm, is preferably 0.5 mPa·s or more, more preferably 2 mPa·s or more, and more preferably 20 mPa·s or less, more preferably 10 mPa·s or less. The viscosity of this composition can be set to the aforementioned range by adjusting the amount of organic solvent (K) added.

[0210] <Preparation Method of Negative-Type Radiosensitive Linear Composition>

[0211] This composition can be prepared by mixing and dissolving the components in an organic solvent (K) in a prescribed ratio. The prepared composition is preferably filtered, for example, using a filter with a pore size of approximately 0.2 μm.

[0212] [Hardened membrane]

[0213] The curing film of the present invention (hereinafter also referred to as "the curing film") can be formed by curing a negative radiosensitive linear composition prepared as described. The negative radiosensitive linear composition of the present invention can produce a curing film with sufficient resolution and good adhesion even by heating at relatively low temperatures. This composition is preferably one that can be cured at a post-baking temperature of 100°C or lower, and more preferably one that can be cured by heating in a temperature range of 60°C or higher and 100°C or lower.

[0214] The hardened film of the present invention can be a patterned film.

[0215] The curing film of the present invention can be used as a curing resin layer of the curing resin part of the light-emitting device. Specifically, it can be used as a wiring substrate layer of the curing resin part, a patterned curing resin layer (interlayer insulating film for touch screen wiring), and an upper protective layer (protective film for touch screen wiring).

[0216] The thickness of the hardened film of the present invention is not particularly limited and can be appropriately set according to the intended use.

[0217] [Organic EL Device]

[0218] The organic EL device of the present invention includes this curing film. The organic EL device of the present invention preferably includes a touchscreen laminated on a substrate having organic EL elements, and preferably uses this curing film as a curing resin layer for at least a portion of the touchscreen. Particularly preferably, this curing film is used as an interlayer insulating film for the touchscreen laminated on the substrate having organic EL elements without passing through an adhesive layer or bonding layer. By doing so, the touchscreen can be directly laminated on the substrate forming the organic EL elements, thus enabling the thinning of the organic EL device including the touchscreen.

[0219] This composition can produce a hardened film with sufficient resolution and good adhesion even with heating at relatively low temperatures, thus suppressing the degradation of organic EL elements during the manufacturing process of the organic EL device and improving yield. Furthermore, since 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 is particularly preferred for forming insulating films in various organic EL devices including organic EL elements, other than organic EL devices including touchscreens.

[0220] [Method for forming a hardened resin layer]

[0221] One embodiment of the present invention is a method for forming the hardened resin layer of a light-emitting device.

[0222] The light-emitting device includes a substrate, a light-emitting element located on the substrate, a sealing layer located on the light-emitting element, and a hardened resin portion located on the sealing layer having at least one hardened resin layer, wherein the method for forming the hardened resin layer includes, in sequence:

[0223] The process of forming a coating film by directly or indirectly applying the negative-type radiosensitive linear composition (the composition) of the present invention onto the sealing layer (hereinafter also referred to as the "coating film forming process").

[0224] The process of irradiating (exposing) at least a portion of the coating film with radiation after the process of forming the coating film (hereinafter also referred to as the "radiation irradiation process").

[0225] The process of alkaline developing the coating after radiation irradiation (hereinafter also referred to as the "developing process"); and

[0226] Processes involving heating at temperatures below 100°C (hereinafter also referred to as "heating processes").

[0227] Here, there may also be a process of exposing the developed coating after the development process, before the heating process, or after the heating process (hereinafter also referred to as "post-exposure process").

[0228] Alternatively, a heating process (hereinafter also referred to as "PEB (post exposure bake) process") may be included between the radiation irradiation process and the development process.

[0229] According to the formation method described above, by using the negative-type radiosensitive linear composition, a hardened resin layer (hardened film) that can be patterned in a good shape and has resolution and good developability can be obtained. Furthermore, even if the substrate on which the coating is formed contains organic EL elements, the degradation of the organic EL elements can be suppressed by performing a heating process at a relatively low temperature. Each process will be described below.

[0230] <Coating Formation Process>

[0231] In this process, after coating the composition directly or through other layers onto the sealing layer, it is preferable to heat (pre-bake) the coated surface to remove organic solvents and the like, thereby forming a coating film. The sealing layer is as described above.

[0232] There are no particular limitations on the coating method for this composition. For example, suitable methods such as spraying, roller coating, spin coating, slot die coating, and bar coating can be used. Among these coating methods, spin coating and slot die coating are particularly preferred. The pre-baking conditions also vary depending on the type and mixing ratio of each component, but it is acceptable to set a temperature preferably above 60°C and below 100°C, more preferably below 95°C, and a heating time of at least 1 minute and at least 10 minutes.

[0233] <Radiation Irradiation Procedure>

[0234] In this process, at least a portion of the coating film formed in the coating film forming process is irradiated with radiation. Typically, when irradiating a portion of the coating film with radiation, irradiation is performed through a photomask with a predetermined pattern. Examples of radiation used are visible light, ultraviolet light, far-ultraviolet light, electron beams, X-rays, etc. Among these radiations, those with wavelengths in the range of 190 nm or more and 450 nm or less are preferred, and those containing ultraviolet light at 365 nm are more preferred.

[0235] The lower limit of the exposure in this process is preferably 10 mJ / cm², measured using an illuminometer (OAI Optical Associates Inc.'s "OAI model 356") to determine the intensity of the radiation at a wavelength of 365 nm. 2 More preferably 50 mJ / cm 2 Furthermore, the upper limit of the exposure, measured using the illuminance meter, is preferably 2,000 mJ / cm². 2 More preferably 1,000 mJ / cm 2 .

[0236] <PEB Process>

[0237] When setting up a PEB process, the PEB conditions vary depending on the type and proportion of each component. For example, it is sufficient to set a temperature of 60°C or higher and 100°C or lower, and a heating time of 1 minute or more and 10 minutes or less.

[0238] <Developing Process>

[0239] In this process, a predetermined pattern is formed by developing the irradiated coating with a developing solution. The developing solution is preferably an alkaline developing solution. Examples of alkaline developing solutions include an alkaline aqueous solution containing at least one alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, or tetraethylammonium hydroxide. Furthermore, an appropriate amount of water-soluble organic solvents or surfactants such as methanol or ethanol can be added to the alkaline developing solution.

[0240] As a developing method, suitable methods such as liquid coating, immersion, shaking immersion, and spraying can be used. The developing time varies depending on the composition of the negative-type radiosensitive linear composition, and is, for example, 10 seconds or more and 180 seconds or less. Immediately following this developing process, after rinsing with running water for, for example, 30 seconds or more and 90 seconds or less, the sample is dried using, for example, compressed air or compressed nitrogen, thereby forming the desired pattern.

[0241] <Heating Process>

[0242] In this process, the developed and patterned coating is heated (post-baked) at a temperature below 100°C using a heating device such as a hot plate or oven, thereby obtaining a hardened film (preferably an insulating film for a display device as a hardened resin layer) with the desired pattern. The heating temperature is preferably 60°C or higher, more preferably 80°C or higher. By setting the heating temperature above this temperature, a sufficiently hardened resin layer (hardened film) can be obtained. On the other hand, the heating temperature is preferably below 100°C. By setting the heating temperature below this temperature, for example, a sufficiently hardened resin layer (hardened film) can be obtained while suppressing the deterioration of the organic EL elements included in the substrate. In addition, by setting the heating temperature below this temperature, excessive stress generation such as rapid film shrinkage can be suppressed, thus suppressing the generation of cracks. Thus, heating is performed in a temperature range preferably between 60°C and 100°C (more preferably between 80°C and 100°C) during the heating process. Heating time varies depending on the type of heating machine. For example, when heating on a hot plate, it should be set to 5 minutes to 30 minutes; when heating in an oven, it should be set to 10 minutes to 90 minutes. Furthermore, heating can be carried out in air or in an inert gas environment such as nitrogen or argon. Additionally, a step-by-step baking method involving two or more heating processes can also be used.

[0243] When using this composition, the detailed mechanism is not clearly understood, but a reduction in oxetyl and oxetyl groups is observed through a heating process following the development step. Furthermore, the reduction in oxetyl and oxetyl groups is observed as a decrease in the peaks originating from oxetyl and oxetyl groups in infrared (IR) measurements. As for the crosslinking, it can be assumed that it is a crosslinking between oxetyl or oxetyl groups, or a crosslinking between oxetyl or oxetyl groups and acidic groups.

[0244] By heating after the developing process to perform thermal crosslinking of epoxy, the adhesion, chemical resistance, and resolution of the hardened film are considered to be further improved.

[0245] <Post-exposure process>

[0246] A process for exposing the developed coating (hereinafter also referred to as a "post-exposure process") may be performed after the developing process, before the heating process, or after the heating process. The radiation used in the post-exposure process may be the same radiation used in the radiation irradiation process, preferably with the same range. Furthermore, the exposure dose in the post-exposure process may be, for example, set to 100 mJ / cm². 2 Above 2,000 mJ / cm 2 the following.

[0247] <Other Processes>

[0248] In the manufacture of display devices, preferably organic EL devices, after forming the aforementioned hardened resin layer (hardened film) on the organic EL display substrate, other processes are performed for forming further electrodes, wiring, etc. Examples of such processes include electrode formation, wiring formation, etching, and ashing. Known methods such as printing or vapor deposition can be used when forming the electrodes or wiring. Etching can be performed using known etching solutions such as amine-based solutions. Ashing can be performed using known ashing methods such as oxygen ashing. Furthermore, in the manufacture of touch screens, the formation of the hardened resin layer (hardened film) or the formation of electrodes, wiring, etc., can be performed multiple times.

[0249] [Negative-sensory radiolinear composition]

[0250] One embodiment of the negative-type radioactive linear composition of the present invention comprises:

[0251] An alkali-soluble resin (A) contains a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of oxetyl and oxetyl;

[0252] Multifunctional free radical polymeric compound (B); and

[0253] Photoradical polymerization initiator (C).

[0254] The alkali-soluble resin (A), the multifunctional free radical polymerizable compound (B), the photoradioactive polymerization initiator (C), and other components or their contents are preferably as described above. As a negative-type sensitizing linear composition, compositions identical to the one described herein (the negative-type sensitizing linear composition used in the method of manufacturing the display device) can be listed.

[0255] The negative-type induced radiation linear composition is preferably used to form a light-emitting device having a substrate, a light-emitting element on the substrate, a sealing layer on the light-emitting element, and a hardened resin portion having at least one hardened resin layer directly or indirectly located on the sealing layer.

[0256] Furthermore, the hardened film formed from the negative-type radiosensitive linear composition exhibits excellent resolution, development adhesion, and chemical resistance. Therefore, the negative-type radiosensitive linear composition is preferably used as a forming material for interlayer insulating films, planarization films, spacers, protective films, colored patterned films for color filters, isolation walls, and dams.

[0257] [Example]

[0258] The present invention will now be specifically described through examples, but the present invention is not limited to these examples. Furthermore, unless otherwise specified, "parts" and "%" in the examples and comparative examples refer to mass.

[0259] In this embodiment, the weight average molecular weight (Mw) of the polymer is determined by the following method.

[0260] [Weight-average molecular weight (Mw)]

[0261] The Mw of the polymer is the polystyrene conversion value determined by the following methods and conditions.

[0262] Determination method: Gel permeation chromatography (GPC)

[0263] Device: GPC-101 manufactured by Showa Denko Co., Ltd.

[0264] GPC tubing: Combining GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 manufactured by Shimadzu GLC (stock).

[0265] Mobile phase: Tetrahydrofuran

[0266] Column temperature: 40℃

[0267] Flow rate: 1.0 mL / min

[0268] Sample concentration: 1.0% by mass

[0269] Sample injection volume: 100 μL

[0270] Detector: Differential refractometer

[0271] Standard material: Monodisperse polystyrene

[0272] [Synthesis Example 1] (Synthesis of Polymer (A-1))

[0273] 200 parts by weight of propylene glycol monomethyl ether acetate and 6.5 parts by weight of 2,2'-azobis(2,4-dimethylpentanonitrile) were charged into a flask including a cooling tube and a stirrer. Then, 25 parts by weight of 4-hydroxyphenyl methacrylate, 58 parts by weight of glycidyl methacrylate, 4 parts by weight of methyl methacrylate, and 13 parts by weight of lauryl acrylate were added, and the mixture was purged with nitrogen. While stirring slowly, the temperature of the solution was raised to 80°C and maintained at this temperature for 5 hours for polymerization, thereby obtaining a polymer solution containing copolymer (A-1). The polymer solution had a solids concentration of 34.1% by weight, and the copolymer (A-1) had a molecular weight (Mw) of 7,600 and a molecular weight distribution (Mw / Mn) of 1.8.

[0274] [Synthesis Examples 2 to 10] (Synthesis of polymers (A-2) to (A-10))

[0275] Except for using the monomeric compounds of the types and amounts shown in Table 1 below, polymers (A-2) to (A-10) were synthesized by operating in the same manner as in Synthesis Example 1.

[0276] [Synthesis Example 11] (Synthesis of Polymer (A-11))

[0277] 200 parts by weight of propylene glycol monomethyl ether acetate and 12 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged into a flask including a cooling tube and a stirrer. Then, 9 parts by weight of methacrylic acid, 32 parts by weight of glycidyl methacrylate, 19 parts by weight of methyl methacrylate, and 40 parts by weight of benzyl methacrylate were added, and the mixture was purged with nitrogen. While stirring slowly, the temperature of the solution was raised to 70°C, maintained at this temperature for 5 hours, and polymerization was carried out to obtain a polymer solution containing copolymer (A-11). The solids concentration of the polymer solution was 34.0% by weight, and the Mw of copolymer (A-1) was 6,200, with a molecular weight distribution (Mw / Mn) of 1.8.

[0278] [Synthesis Examples 12 to 14] (Synthesis of polymers (A-12) to (A-14))

[0279] Except for using monomeric compounds of the types and amounts shown in Table 1 below, polymers (A-12) to (A-14) were synthesized by operating in the same manner as in Synthesis Example 11.

[0280] [Synthesis Example 15] (Synthesis of Polymer (A-15))

[0281] 70 parts of cresol phenolic varnish-type epoxy resin (manufactured by DIC (stock), trade name: Epiclon N-695, epoxy equivalent: 220) were added to a four-necked flask equipped with a stirrer and reflux cooler. 70 parts of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether were also added, and the mixture was heated to dissolve. Then, 13 parts of 4-hydroxythiophenol and 0.2 parts of tetrabutylammonium bromide were added. The solution was reacted at 60°C for 3 hours to obtain a cresol phenolic varnish resin (A-15) with epoxy and phenolic hydroxyl groups in its side chains. The resin (A-15) thus obtained had a solids concentration of 34% by mass, an acid value of 70 mgKOH / g, and a weight-average molecular weight (Mw) of approximately 4,500.

[0282] [Table 1]

[0283]

[0284] The monomers m-1 to m-16 used in Table 1 are as follows.

[0285] m-1: 4-Hydroxyphenyl methacrylate

[0286] m-2: 4-Isopropenylphenol

[0287] m-3: Methacrylic acid

[0288] m-4: Glycidyl methacrylate

[0289] m-5: (Meth)acrylate (3,4-epoxycyclohexyl)methyl ester

[0290] m-6: A mixture of 1,2-epoxy-3-(3-vinylbenzyloxy)propane and 1,2-epoxy-3-(4-vinylbenzyloxy)propane.

[0291] m-7: Styrene

[0292] m-8: Methyl methacrylate

[0293] m-9: n-Butyl methacrylate

[0294] m-10: Cyclohexylmaleimide

[0295] m-11: Cyclohexyl methacrylate

[0296] m-12: 2-Ethylhexyl methacrylate

[0297] m-13: Benzyl methacrylate

[0298] m-14: Lauryl acrylate

[0299] m-15: 3-Methacryloxypropyltrimethoxysilane

[0300] m-16: 3-(2H-1,2,3-benzotriazol-2-yl)-4-hydroxyphenethyl methacrylate (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.)

[0301] [Example 1]

[0302] Preparation of negative-type radiosensitive linear compositions

[0303] 100 parts by weight of (A-1) as (A) an alkali-soluble resin, 30 parts by weight of (B-1) as (B) a multifunctional free radical polymerizable compound, 40 parts by weight of (B-2) as (B) a polyfunctional free radical polymerizable compound, 5 parts by weight of (C-1) as (C) a photoradioactive polymerization initiator, 3 parts by weight of (E-1) as (E) a UV absorber, 0.5 parts by weight of (F-1) as (F) a free radical polymerization inhibitor, 2 parts by weight of (G-1) as (G) a binder, and 0.15 parts by weight of (J-1) as (J) a surfactant were mixed. The mixture was then diluted with propylene glycol monomethyl ether acetate (PGMEA) to a total solids concentration of 25% by weight, and filtered through a 0.2 μm membrane filter to prepare a negatively induced radiosensitive linear composition.

[0304] [Examples 2 to 19, Comparative Examples 1 to 2]

[0305] Preparation of negative-type radiosensitive linear compositions

[0306] The negative-type radiosensitive linear composition was prepared using the same method as in Example 1, with the types and amounts of each component listed in Table 2.

[0307] [Table 2]

[0308]

[0309] In the examples and comparative examples, the components used in the preparation of the negative-type radiosensitive linear compositions are shown.

[0310] (A) Alkali-soluble resin

[0311] A-1 to A-15: Polymers (A-1) to (A-15) obtained in Synthetic Examples 1 to 15.

[0312] A-16: A resin containing a cresol phenolic varnish backbone with carboxyl and (meth)acryloyl groups in its side chain.

[0313] 220 parts of cresol varnish-type epoxy resin (manufactured by DIC (stock), trade name: Epiclon N-695, epoxy equivalent: 220) and 214 parts of carbitol acetate were added to a four-necked flask equipped with a stirrer and reflux cooler and heated to dissolve. Next, 0.1 parts of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated to 95°C–105°C, and 72 parts of acrylic acid were slowly added dropwise and reacted for 16 hours. The reaction product was cooled to 80°C–90°C, 106 parts of tetrahydrophthalic anhydride were added, and reacted for 8 hours. After cooling, the product was removed to obtain a resin (A-16) containing a cresol varnish backbone with carboxyl and (meth)acryloyl groups in the side chain. The resin (A-16) thus obtained has 65% non-volatile components by mass, an acid value of 85 mgKOH / g in solids, and a weight average molecular weight (Mw) of approximately 3,500.

[0314] (B) Multifunctional free radical polymeric compounds

[0315] B-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

[0316] B-2: Pentaerythritol tri / tetraacrylate blend (ARONIX M-40, manufactured by Dong-A Synthetic Co., Ltd.)

[0317] B-3: Tris(2-hydroxyethyl)isocyanurate triacrylate

[0318] B-4: Tricyclodecanedimethyl diacrylate

[0319] (C) Photoradical polymerization initiator

[0320] C-1: TR-PBG-3057 (oxime-based photopolymerization initiator, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0321] (D) Chain transfer agent

[0322] D-1: Karenz MT PE1 (Pentaerythritol tetra(3-mercaptobutyrate), manufactured by Resonac (stock))

[0323] (E) Ultraviolet absorber

[0324] E-1: 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole

[0325] (F) Free radical polymerization inhibitors

[0326] F-1: 2,5-Di-tert-butylhydroquinone

[0327] (G) Sealing agent

[0328] G-1: 3-Methacryloyloxypropyltrimethoxysilane

[0329] (J) Surfactants

[0330] J-1: DOWSIL 8019 Additive (manufactured by Toray Corning Co., Ltd.)

[0331] <Methods for evaluating resolution>

[0332] Solutions of various negative-type radiosensitive linear compositions were spin-coated onto a silicon substrate to a thickness of 2.5 μm, followed by pre-baking at 85°C for 2 minutes using a hot plate to form the coating. For the obtained coating, a 5 μm × 5 μm square aperture pattern mask was used, and scanning was performed using a SUSS-manufactured "DSC-200" laser (illuminance = 500 mW, numeric aperture (NA) = 0.10, λ = ghi rays, 60 mJ / cm²). 2Exposure was performed at 365 nm. Afterwards, development was carried out at 25°C for 1 minute using a tetramethylammonium hydroxide aqueous solution (2.38% concentration) via a coating method. Following this, the substrate was rinsed with running water using a spray method and dried with compressed air to form a pattern. Subsequently, the substrate was irradiated with 200 mJ / cm² mixed ghi rays using a TOPCON "TME-400PRJ". 2 The ultraviolet light is then used to heat the film at 85°C for 60 minutes in an oven to obtain a hardened film.

[0333] The bottom dimensions of the pores in the hardened film (patterned film) obtained by the method were observed using a scanning electron microscope (SEM) and evaluated according to the following criteria.

[0334] A: Resolves pores larger than 4 μm

[0335] B: Resolves pores larger than 3 μm but smaller than 4 μm

[0336] C: Poor resolution of holes smaller than 3 μm or poor resolution

[0337] <Methods for evaluating residual film rate>

[0338] Perform the same operation as the resolution evaluation method, and calculate the residual film rate in the exposed area according to the following formula.

[0339] Residual film yield (%) = [film thickness after development and rinsing] / [film thickness after pre-baking] × 100

[0340] <Evaluation of chemical resistance>

[0341] During exposure, a plain glass substrate was used for full exposure instead of a hole pattern mask. Otherwise, each composition was formed into a hardened film using the same method as for resolution evaluation. The obtained substrate was immersed in propylene glycol monomethyl ether acetate (PGMEA) heated to 60°C for 100 seconds. The residual film percentage of the hardened film before and after immersion was calculated using the following formula and evaluated according to the following criteria.

[0342] Residual film yield (%) = (film thickness after impregnation / film thickness before impregnation) × 100

[0343] A: The residual film rate is over 95%.

[0344] B: The residual film rate is above 90% but below 95%.

[0345] C: Residual film rate less than 90%

[0346] <Evaluation of close contact>

[0347] A polyimide film is first formed on a silicon substrate, and a hardened film is then formed on this substrate using the same procedure as for evaluating chemical resistance. According to ASTM D 3559-B, for the obtained hardened film, 11 cuts are made at 1 mm intervals in both the longitudinal and transverse directions to form a checkerboard pattern of 100 squares. Next, cellophane tape (registered trademark) is forcefully pressed onto the checkerboard area, and the end of the tape is torn off in one go at a 45° angle. The condition of the checkerboard pattern is then compared with a standard drawing for evaluation.

[0348] 5B The edges of the cutting line are smooth, and no checkerboard squares have been peeled off.

[0349] 4B shows slight peeling at the intersection of the cut lines. Less than 5% of the overall cut area is significantly affected.

[0350] 3B. Peeling can be seen along the cut line and at the intersection. More than 5% and less than 15% of the overall cut area is significantly affected.

[0351] 2B Extensive peeling is visible on part or all of the edges of the checkerboard, with peeling occurring everywhere. More than 15% but less than 35% of the overall cut area is significantly affected.

[0352] 1B. Extensive peeling can be seen along the edges of the checkerboard, with several checkerboard squares converging and partially or entirely peeling away. More than 35% and less than 65% of the entire cut area are significantly affected.

[0353] 0B is not equivalent to the aforementioned category.

[0354] [Table 3]

[0355]

[0356] As shown in Table 3, in Examples 1 to 19, cured films with excellent resolution, residual film rate, chemical resistance, and adhesion were formed. On the other hand, in the comparative examples, any one of the resolution, residual film rate, chemical resistance, and adhesion was poor. In particular, in Comparative Examples 1 and 2, which used an alkali-soluble resin having (meth)acryloyl groups in the side chain, the adhesion of the cured films was poor.

Claims

1. A method for manufacturing a light-emitting device, the light-emitting device comprising a substrate, a light-emitting element located on the substrate, a sealing layer located on the light-emitting element, and a hardened resin portion having at least one hardened resin layer directly or indirectly located on the sealing layer, and the method for manufacturing the light-emitting device comprising, in sequence: The process of forming a light-emitting element and a sealing layer on the light-emitting element on a substrate; The process of forming a coating film by directly or indirectly coating the sealing layer with a negative-type radiosensitive linear composition; The process of irradiating at least a portion of the coating with radiation; The process of alkaline development of coatings after radiation irradiation; and The process of heating at a temperature below 100℃ The negative-type radiosensitive linear composition contains: An alkali-soluble resin (A) contains a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of oxetyl and oxetyl; Multifunctional free radical polymeric compound (B); and Photoradical polymerization initiator (C).

2. The method for manufacturing the 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 the light-emitting device according to claim 1 or 2, wherein, The content of structural units with 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 the light-emitting device according to claim 1 or 2, wherein, The content of structural units having at least one group selected from the group consisting of oxocyclopropyl and oxocyclobutyl in the alkali-soluble resin (A) is 15% by mass or more and 80% by mass or less.

5. The method for manufacturing the light-emitting device according to claim 1 or 2, wherein, The alkali-soluble resin (A) contains structural units with phenolic hydroxyl groups, and the content of structural units with carboxyl groups in the alkali-soluble resin (A) is less than 2% by mass or does not contain structural units with carboxyl groups.

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

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

8. The method for manufacturing the light-emitting device according to claim 7, wherein, The free radical polymerizable monomer having a phenolic hydroxyl group includes at least one selected from the group consisting of 4-hydroxyphenyl methacrylate, 4-hydroxystyrene and 4-isopropenylphenol.

9. The method for manufacturing the light-emitting device according to claim 7, wherein, A radical polymerizable monomer having at least one group selected from the group consisting of oxetyl and oxetyl groups comprises at least one group selected from the group consisting of glycidyl (meth)acrylate, 1,2-epoxy-3-(3-vinylbenzyloxy)propane, 1,2-epoxy-3-(4-vinylbenzyloxy)propane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether.

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

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

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

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

14. A negative-type radiosensitive linear composition comprising: An alkali-soluble resin (A) contains a structural unit having an acidic group and a structural unit having at least one group selected from the group consisting of oxetyl and oxetyl; Multifunctional free radical polymeric compound (B); and Photoradical polymerization initiator (C).

15. The negative-type induced radiation linear composition of claim 14, used to form a light-emitting device having a substrate, a light-emitting element located on the substrate, a sealing layer located on the light-emitting element, and a hardened resin portion having at least one hardened resin layer located directly or indirectly on the sealing layer.

16. A hardened film formed by hardening the negative-type radiosensitive linear composition as described in claim 14 or 15.

17. An organic EL device comprising the hardened membrane as claimed in claim 16.

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