Polymer composition, hardened film, and organic electroluminescent element

Abstract

The present application provides a polymer composition, a hardened film and an organic electroluminescence element, which can obtain a hardened film having less outgassing and excellent heat resistance. The present application is a polymer composition containing a polymer component (A), a reaction initiator (B), and a multifunctional polymerizable compound (C), and the polymer component (A) contains a structural unit (Uα) derived from at least one selected from the group consisting of an N-substituted maleimide compound having a monovalent cyclic hydrocarbon group and a (meth)acrylic compound having a monovalent cyclic hydrocarbon group, and the structural unit (Uα) contains 28% by mass or more of a structural unit (U1) derived from an N-substituted maleimide compound having a monovalent cyclic hydrocarbon group, relative to the total amount of the structural unit (Uα) contained in the polymer component (A).

Description

TECHNICAL FIELD

[0001] The present application relates to a polymer composition, a hardened film, and an organic electroluminescence (EL) element. BACKGROUND

[0002] An organic electroluminescence element (organic EL element) is a light-emitting element having a layered structure including an anode, an organic light-emitting layer, and a cathode, and is being put to practical use in applications such as display devices and lighting devices. Various devices such as organic EL elements and liquid crystal display elements generally include an insulating hardened film such as a planarization film, an interlayer insulating film, and a barrier rib. As a material for forming a hardened film, a polyimide or a (meth)acrylic polymer, etc. is known (for example, see Patent Document 1).

[0003] In Patent Document 1, a hardened film is formed from a composition containing a resin having a structural unit derived from an acrylic compound and a structural unit containing a cyclic ether group, and a content of the structural unit derived from the acrylic compound is 30% by mass or more with respect to the total structural units. It is described in Patent Document 1 that a hardened film having less outgassing can be formed from the composition according to Patent Document 1.

[0004] [Related Art Documents]

[0005] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-39979 SUMMARY

[0007] [Problems to be Solved by the Invention]

[0008] It is considered that outgassing generated from a hardened film affects the reliability of devices such as organic EL elements. In particular, in organic EL elements, higher fineness is required, and it is necessary to reduce outgassing generated from a hardened film as much as possible. In addition, in the manufacturing process of an element, a hardened film is sometimes subjected to high-temperature treatment (for example, heating treatment at 200°C or higher). Therefore, as a hardened film suitable for an organic EL element, it is required to have excellent heat resistance while reducing outgassing.

[0009] The present application was made in view of the above-described problems, and the main object is to provide a polymer composition that can obtain a hardened film having less outgassing and excellent heat resistance.

[0010] [Technical Means for Solving the Problems]

[0011] In order to solve the above-described problems, according to the present application, the following polymer composition, hardened film, and organic EL element are provided.

[0012] [1] A polymer composition comprising: a polymer component (A), a reaction initiator (B), and a multifunctional polymerizable compound (C), wherein the polymer component (A) comprises a structural unit (Uα) derived from at least one selected from the group consisting of an N-substituted maleimide compound having a monovalent cyclic hydrocarbon group and a (meth)acrylic acid compound having a monovalent cyclic hydrocarbon group, wherein the structural unit (Uα) comprises at least 28% by mass of the structural unit (Uα) derived from the N-substituted maleimide compound, relative to the total amount of the structural unit (Uα) contained in the polymer component (A).

[0013] [2] A hardened film formed using the polymer composition of [1].

[0014] [3] An organic EL element comprising the hardened film of [2].

[0015] [The effects of the invention]

[0016] According to the polymer composition of the present invention containing the polymer component (A), a hardened film with low gas emission and excellent heat resistance (specifically, coefficient of linear expansion and transparency after heat application) can be obtained. Such polymer compositions of the present invention are useful as planarization film materials, isolation wall materials, or accumulation layer materials, particularly as planarization film materials, isolation wall materials, and accumulation layer materials for organic EL elements. Attached Figure Description

[0017] Figure 1 This is a diagram showing the schematic structure of an organic EL element with a top-emitting structure.

[0018] Figure 2 This is a diagram showing the schematic structure of an organic EL element with a bottom-emitting structure.

[0019] Explanation of symbols

[0020] 10: Organic EL components

[0021] 11: Supporting substrate

[0022] 12: Pixel Electrode

[0023] 13: Common electrode

[0024] 14: Organic light-emitting layer

[0025] 15: Sealing substrate

[0026] 16: Thin Film Transistor (TFT)

[0027] 17: Planarization film

[0028] 18: Through hole

[0029] 19: Isolation Wall

[0030] 21: Concave

[0031] 22: Passivation film

[0032] 23: Sealing layer

[0033] 24: Black Matrix

[0034] 25: Color Filter Detailed Implementation

[0035] 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 both lower and upper limits. A “structural unit” is a single unit constituting the main chain structure, meaning that the main chain structure contains at least two or more units.

[0036] <Polymer Composition>

[0037] The polymer composition disclosed herein is used to form an insulating film, preferably an insulating film for forming organic EL elements. The polymer composition disclosed herein contains a polymer component (A), a reaction initiator (B), and a multifunctional polymerizable compound (C). Details of each component are described below. Furthermore, unless otherwise specified, each component may be used alone or in combination of two or more.

[0038] Here, in this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Chain hydrocarbon group" refers to a straight-chain hydrocarbon group or branched hydrocarbon group whose main chain does not contain a ring structure and is composed only of chain structures. These can be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as its ring structure and does not contain an aromatic ring structure. This does not necessarily mean it is composed solely of an alicyclic hydrocarbon structure; it may also include groups with a chain structure in a portion thereof. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as its ring structure. This does not necessarily mean it is composed solely of an aromatic ring structure; it may also include a chain structure or an alicyclic hydrocarbon structure in a portion thereof. Furthermore, the ring structure of alicyclic hydrocarbon groups and aromatic hydrocarbon groups may also have substituents containing hydrocarbon structures. "Cyclic hydrocarbon group" includes both alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0039] [Polymer component (A)]

[0040] • Structural unit (U1)

[0041] Polymer component (A) comprises a structural unit (U1) derived from an N-substituted maleimide compound having a monovalent cyclic hydrocarbon group (hereinafter also referred to as "monomer A1"). The cyclic hydrocarbon group of monomer A1 is preferably a monovalent alicyclic hydrocarbon group having a monocyclic, bridging, or spirocyclic ring, or a monovalent aromatic hydrocarbon group. Specific examples of the monovalent cyclic hydrocarbon group, as alicyclic hydrocarbon groups, include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, cyclopentenyl, cycloheptenyl, isobornyl, adamantyl, isobornyl, dicyclopentyl, tricyclic [5.2.1.0] 2,6 Decyl, spirobicyclopentyl, etc. Additionally, as aromatic hydrocarbon groups, examples include: phenyl, methylphenyl, dimethylphenyl, ethylphenyl, benzyl, phenethyl, naphthyl, anthracene, etc.

[0042] In terms of further improving the resolution, developability and heat resistance of the coating obtained by using the polymer composition, the cyclic hydrocarbon group of monomer A1 is preferably a monovalent alicyclic hydrocarbon group having a monocyclic or bridging ring, or a monovalent aromatic hydrocarbon group, more preferably a monovalent alicyclic hydrocarbon group having a monocyclic or bridging ring, and even more preferably a monovalent alicyclic hydrocarbon group having a monocyclic ring.

[0043] Specifically, the structural unit (U1) is preferably represented by the following formula (1).

[0044] [Chemistry 1]

[0045]

[0046] (In equation (1), R) 1 It is a monovalent cyclic hydrocarbon group. R 2 and R 3 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0047] In the above equation (1), R 1 The ring structure can be directly bonded to the nitrogen atom by a cyclic hydrocarbon group, or the ring structure can be bonded via a divalent linker. Examples of divalent linkers include alkyl groups such as methylene, ethylene, and 1,3-propanediyl. Among these, R... 1 Preferably, the cyclic hydrocarbon group has a ring structure directly bonded to the nitrogen atom; more preferably, the alicyclic hydrocarbon group has a structure directly bonded to the nitrogen atom. R 2 and R 3 Preferably, it is a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0048] Specific examples of monomer A1, as compounds having aromatic hydrocarbon groups, include: N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc.; as compounds having alicyclic hydrocarbon groups... Compounds, for example, include: 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, etc. Among these, monomer A1 is preferably at least one selected from the group consisting of N-cyclohexylmaleimide, N-(4-methylcyclohexyl)maleimide, N-phenylmaleimide, and N-(4-methylphenyl)maleimide, more preferably at least one of N-cyclohexylmaleimide and N-phenylmaleimide.

[0049] In the polymer component (A), the content of structural unit (U1) is preferably more than 15% by mass and less than 35% by mass, relative to all structural units constituting polymer component (A). If the content of structural unit (U1) exceeds 15% by mass, the heat resistance of the hardened film obtained using the polymer composition can be sufficiently improved; for example, crack formation can be suppressed when wiring is formed on the hardened film, which is preferable in this respect. On the other hand, if the content of structural unit (U1) is less than 35% by mass, there is a tendency to maintain the solubility of the polymer well. Furthermore, if the content of structural unit (U1) is set to less than 35% by mass, the glass transition temperature of the polymer can be moderately increased, and good developability can be achieved by maintaining the reactivity as a negative in the case of forming a negative hardened film. According to this viewpoint, the content of structural unit (U1) is more preferably 16% by mass or more, more preferably 18% by mass or more, and particularly preferably 20% by mass or more, relative to all structural units constituting polymer component (A). Furthermore, the proportion of structural unit (U1) is more preferably 34% by mass or less, more preferably 32% by mass or less, and particularly preferably 30% by mass or less, relative to all structural units constituting polymer component (A).

[0050] Regarding the main chain of the polymer constituting polymer component (A), in terms of obtaining a hardened film exhibiting good heat resistance, chemical resistance, and developability, and in terms of high freedom of monomer selection, polymers obtained using monomers having polymerizable unsaturated carbon-carbon bonds (hereinafter also referred to as "unsaturated monomers") are preferred. Furthermore, polymers obtained using unsaturated monomers can achieve lower costs compared to polyimides conventionally used as insulating film materials. Examples of unsaturated monomers include (meth)acrylic acid compounds, styrene compounds, maleimide compounds, and vinyl compounds. Among these, the unsaturated monomers at least include maleimide compounds, and preferably include both maleimide compounds and (meth)acrylic acid compounds. In this specification, "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid." Additionally, "(meth)acrylic acid compound" includes both "acrylic acid compound" and "methacrylic acid compound."

[0051] Polymer component (A) contains a structural unit (U1) as a structural unit having a cyclic hydrocarbon group in its side chain. Polymers with cyclic hydrocarbon groups in their side chains exhibit moderately high hydrophobicity, resulting in curable films with high developability, making them suitable as insulating film materials (especially for organic EL elements). In polymer component (A), the structural unit having a cyclic hydrocarbon group in its side chain may be only structural unit (U1), or it may also include structural units different from structural unit (U1).

[0052] In terms of obtaining a hardened film with high transparency, resolution, and developability, the structural unit having cyclic hydrocarbon groups in the side chain and different from the structural unit (U1) is preferably a structural unit derived from a (meth)acrylic acid compound having a monovalent cyclic hydrocarbon group (hereinafter also referred to as "monomer A2"). Among these, monomer A2 is preferably an acrylic acid compound having a monovalent cyclic hydrocarbon group, especially in terms of reducing the decomposition (depolymerization) of the polymer backbone due to heat, etc., and reducing the generation of gas escape caused by the decomposition of the backbone. That is, the polymer component (A) preferably includes a structural unit (hereinafter referred to as "structural unit (U2)") derived from an acrylic acid compound having a monovalent cyclic hydrocarbon group, together with the structural unit (U1).

[0053] Furthermore, the structural units derived from monomer A1 and structural units derived from monomer A2 will be collectively referred to as "structural units (Uα)" below. The "monovalent cyclic hydrocarbon group" possessed by the structural unit (Uα) refers to a group containing a hydrocarbon structure, excluding groups containing heteroatoms such as epoxy groups. In monomer A2, the proportion of methacrylic acid compound containing a monovalent cyclic hydrocarbon group relative to the total amount of monomer A2 is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably substantially absent.

[0054] • Structural unit (U2)

[0055] The structural unit (U2) is preferably represented by the following formula (2).

[0056] [Chemistry 2]

[0057]

[0058] (In equation (2), R) 4 (A monovalent cyclic hydrocarbon group)

[0059] In equation (2), R 4 The ring structure can be directly bonded to the nitrogen atom by a cyclic hydrocarbon group, or the ring structure can be bonded via a divalent linker (e.g., an alkyl group). Regarding further improvements in the resolution, developability, and transparency of the film obtained using the polymer composition, R... 4 The cyclic hydrocarbon group is preferably an alicyclic hydrocarbon group.

[0060] Specific examples of acrylic compounds having a monovalent cyclic hydrocarbon group include, for example, phenyl acrylate, benzyl acrylate, ethyl acrylate, and 2-naphthyl acrylate, which are compounds having an aromatic hydrocarbon group; and for example, cyclopentyl acrylate, cyclohexyl acrylate, cyclooctyl acrylate, cyclohexene acrylate, norbornyl acrylate, adamantyl acrylate, and tricyclic acrylate [5.2.1.0], which are compounds having a monovalent cyclic hydrocarbon group. 2,6 Decane-8-yl ester, etc.

[0061] In the polymer component (A), the content of structural unit (U2) is preferably more than 0% by mass and less than 35% by mass relative to the total amount of structural units constituting the polymer component (A). By including structural unit (U2) in the polymer component (A), a film with high resolution and developability can be obtained while suppressing the glass transition temperature (Tg) from becoming too high, which is preferable in this respect. In addition, by setting the content of structural unit (U2) to less than 35% by mass, the decomposition of polymer side chains due to heat and other factors is less likely to occur, and the generation of gas escape caused by the decomposition of polymer side chains can be sufficiently reduced, which is preferable in this respect. According to this viewpoint, the content of structural unit (U2) is more preferably 1% by mass or more relative to all structural units constituting the polymer component (A), more preferably 5% by mass or more, and particularly preferably 10% by mass or more. Furthermore, relative to all structural units constituting polymer component (A), the content of structural unit (U2) is more preferably 33% by mass or less, more preferably 32% by mass or less, and even more preferably less than 30% by mass, more preferably 28% by mass or less, and particularly preferably 25% by mass or less.

[0062] In a polymer composition containing polymer component (A), a reaction initiator (B), and a multifunctional polymerizable compound (C), the preferred proportions of structural units (U1) and (U2) in polymer component (A) are as follows: relative to all structural units constituting polymer component (A), the proportion of structural unit (U1) is more than 15% by mass and less than 35% by mass, and the proportion of structural unit (U2) is more than 0% by mass and less than 35% by mass. By setting these ranges, the hardened film obtained using the polymer composition uniformly exhibits various properties such as low gas permeability, heat resistance, radiation sensitivity, resolution, and transparency, which is preferred in this respect.

[0063] The content of structural unit (Uα) relative to all structural units constituting polymer component (A) is preferably 16% by mass or more and less than 70% by mass. The content of structural unit (Uα) relative to all structural units constituting polymer component (A) is more preferably 17% by mass or more, further preferably 23% by mass or more, and particularly preferably 30% by mass or more. Furthermore, the content of structural unit (Uα) relative to all structural units constituting polymer component (A) is more preferably 67% by mass or less, further preferably 65% ​​by mass or less, and particularly preferably 60% by mass or less.

[0064] In the polymer component (A), the proportion of structural unit (U1) relative to the total amount of structural unit (Uα) is particularly preferably 28% by mass or more. Here, according to our research, the main chain of a polymer containing structural units derived from methacrylic acid compounds having monovalent cyclic hydrocarbon groups is prone to decomposition (depolymerization) due to heat, etc., and there is concern that the generation of gas caused by depolymerization may affect the performance of the element (e.g., the performance of the organic light-emitting layer, etc., in the case of organic EL elements). Furthermore, the side chains of polymers containing structural units derived from acrylic acid compounds having monovalent cyclic hydrocarbon groups are prone to decomposition due to heat, etc., and there is concern that the alcohol components generated by decomposition (e.g., cyclohexanol in the case of structural units derived from cyclohexyl acrylate) may affect the performance of the element, etc. Especially in recent years, there has been a demand for further high performance in the field of organic EL elements; to achieve this, it is necessary to develop an organic EL element that minimizes the generation of gas even under more demanding conditions.

[0065] In this regard, by setting the content ratio of structural unit (U1) to the total amount of structural unit (Uα) within the aforementioned range, the hydrophobicity of polymer component (A) can be sufficiently improved by introducing structural unit (Uα), while the generation of gas caused by polymer component (A) can be sufficiently reduced. From the viewpoint of minimizing gas generation, the content ratio of structural unit (U1) to the total amount of structural unit (Uα) is more preferably 28.5% by mass or more, more preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably 40% by mass or more. Furthermore, from the viewpoint of achieving good resolution and developability, the content ratio of structural unit (U1) to the total amount of structural unit (Uα) is more preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.

[0066] The polymer component (A) may also include structural units (Uα) that are different from structural units (Uα) (hereinafter also referred to as "other structural units"). Examples of other structural units include structural units having cyclic ether groups (hereinafter also referred to as "structural units (U3)") and structural units having acid groups (hereinafter also referred to as "structural units (U4)").

[0067] • Structural unit (U3)

[0068] By including structural unit (U3) in the polymer component (A), the resolution, adhesion of the hardened film, and chemical resistance of the film obtained using the polymer composition can be improved. Furthermore, the cyclic ether group present in the structural unit (U3) acts as a crosslinking group, enabling the formation of a hardened film that inhibits degradation over a long period. Examples of cyclic ether groups present in the structural unit (U3) include three- to eight-membered ring cyclic ether groups. Among these, oxetanyl group and oxetanyl group are preferred. In this specification, oxetanyl and oxetanyl are also referred to as "epoxy groups".

[0069] The structural unit (U3) is preferably a structural unit derived from an unsaturated monomer having a cyclic ether group, and more particularly preferably a structural unit represented by the following formula (3).

[0070] [Chemistry 3]

[0071]

[0072] (In equation (3), R) 5 R is a monovalent group with an epoxy group. 6 X is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 1 (For single-bond or divalent linkages)

[0073] In equation (3), R 5 Examples include oxacyclopropyl, oxacyclobutyl, 3,4-epoxycyclohexyl, and 3,4-epoxytricyclic [5.2.1.0]. 2,6 Decyl, 3-ethyloxetyl, etc. Among these, R is the most reactive. 5 Preferably, it is a monovalent group having an oxacyclopropyl group.

[0074] R 6 Preferably, it contains a hydrogen atom or a methyl group. As X 1 Divalent linkages, such as methylene, ethylene, 1,3-propanediyl, etc., can be listed.

[0075] Specific examples of monomers constituting the structural unit (U3) include: glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo(meth)acrylate [5.2.1.0]. 2,6 [Decayl ester; (meth)acrylate (3-methyloxetane-3-yl)methyl ester, (meth)acrylate (3-ethyloxetane-3-yl) ester, (meth)acrylate (oxetane-3-yl)methyl ester, (meth)acrylate (3-ethyloxetane-3-yl)methyl ester, etc.

[0076] In polymer component (A), the content of structural unit (U3) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to all structural units constituting polymer component (A). Furthermore, the content of structural unit (U3) is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less, relative to all structural units constituting polymer component (A). By setting the content of structural unit (U3) within the aforementioned range, the coating film exhibits better developability, while the heat resistance and chemical resistance of the obtained cured film are sufficiently improved; therefore, this is preferable.

[0077] • Structural unit (U4)

[0078] The polymer component (A) preferably contains a structural unit (U4). By including a structural unit (U4) in the polymer component (A), the coating containing the polymer composition exhibits good developability with alkaline developers, which is preferred in this respect. The structural unit (U4) is not particularly limited as long as it has an acid group, but is preferably selected from at least one group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units.

[0079] Specific examples of monomers constituting the structural unit (U4) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, succinic acid, and itaconic acid; monomers constituting sulfonic acid structural units such as vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, and (meth)acryloyloxyethylsulfonic acid; and monomers constituting phenolic hydroxyl groups such as 4-hydroxy-α-methylstyrene. Furthermore, "maleimide unit" refers to a monomeric unit derived from maleimide.

[0080] The polymer component (A) is preferably alkali-soluble. Therefore, to make the polymer component (A) alkali-soluble, it may contain a structural unit (U4). Specifically, in the polymer component (A), the content of the structural unit (U4) is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to all the structural units constituting the polymer component (A). Furthermore, the content of the structural unit (U4) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to all the structural units constituting the polymer component (A). In addition, the term "alkali-soluble" in this specification refers to the ability to dissolve or swell in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0081] Other structural units, besides those described above, may be derived from: alkyl methacrylate compounds such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate; dialkyl dicarboxylic acid ester compounds such as diethyl itaconic acid; aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene; conjugated diene compounds such as 1,3-butadiene and isoprene; nitrogen-containing vinyl compounds such as methacrylonitrile and methacrylamide; maleimide compounds other than monomers A1 and maleimides such as methylmaleimide and ethylmaleimide; and structural units derived from unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate. The proportion of structural units derived from these unsaturated monomers is preferably 30% by mass or less, more preferably 20% by mass or less, relative to all structural units constituting polymer component (A).

[0082] Polymer component (A) may contain only one structural unit (U1) or more than two. The same applies to structural units (U2) through (U4). Furthermore, the proportion of each structural unit is generally equivalent to the proportion of monomers used in the manufacture of the polymer. Polymer component (A) may contain one polymer or more polymers as long as it contains structural unit (U1). For example, when polymer component (A) contains structural units (U1), (U3), and (U4), the structural units (U1), (U3), and (U4) may be contained in the same polymer or in different polymers. Furthermore, polymer component (A) may also contain polymers that do not have any of the structural units (U1) through (U4).

[0083] Examples of forms in which the polymer component (A) is contained in the polymer composition include: [1] a polymer containing structural units (U1), (U2), (U3), and (U4) (hereinafter also referred to as "polymer P"); [2] a polymer containing structural units (U1), (U3), and (U4), as well as a polymer containing structural units (U2), (U3), and (U4); [3] a polymer containing structural units (U1), (U2), (U3), and (U1), etc. Of these, [1] is preferred in terms of reducing the number of constituent components of the polymer composition while simultaneously achieving the effects of the present invention. Polymer P is preferably an alkali-soluble resin.

[0084] In polymer component (A), the weight-average molecular weight (Mw) of the polystyrene obtained by gel permeation chromatography (GPC) is preferably 2000 or more. If Mw is 2000 or more, a hardened film with sufficiently high heat resistance or chemical resistance and good developability can be obtained, which is preferable in this respect. Mw is more preferably 5000 or more, even more preferably 8000 or more, and particularly preferably 10000 or more. Furthermore, from the viewpoint of achieving good film-forming properties, Mw is preferably 50000 or less, more preferably 30000 or less, and even more preferably 25000 or less.

[0085] In polymer component (A), the dispersion (Mw / Mn), expressed as the ratio of weight average molecular weight Mw to number average molecular weight Mn, is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. Furthermore, when polymer component (A) contains two or more polymers, it is preferable that the Mw and Mw / Mn of a mixture of the two or more polymers satisfy the aforementioned range.

[0086] The proportion of polymer component (A) relative to the total amount of solid components contained in the polymer composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. Furthermore, the proportion of polymer component (A) relative to the total amount of solid components contained in the polymer composition is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. By setting the proportion of polymer component (A) within the aforementioned range, a hardened film exhibiting sufficiently high heat resistance and chemical resistance, as well as good developability and transparency, can be obtained.

[0087] Furthermore, polymer component (A) can be manufactured, for example, using the unsaturated monomers that can be introduced into each structural unit, in the presence of a suitable solvent, a polymerization initiator, or the like, according to known methods such as free radical polymerization.

[0088] [Reaction initiator (B)]

[0089] The reaction initiator (B) is a component that generates active species such as free radicals or cations through light or heat. The reaction initiator (B) is formulated into the polymer composition as a component for initiating the polymerization reaction of a multifunctional polymerizable compound. Specifically, examples of reaction initiators (B) include, for instance, free radical polymerization initiators, cationic polymerization initiators, and other polymerization initiators.

[0090] There are no particular limitations on the free radical polymerization initiator, as long as it generates free radicals through light irradiation, heating, etc. Specific examples of free radical polymerization initiators include: photoradical polymerization initiators such as oxime ester compounds, benzyl ketone compounds, acylphosphine oxide compounds, biimidazole compounds, triazine compounds, benzoin compounds, and benzophenone compounds; and thermal free radical polymerization initiators such as peroxides and azo compounds. In terms of the ability to form fine patterns through exposure, photoradical polymerization initiators are preferred, and oxime ester compounds are more preferred.

[0091] Examples of oxime ester compounds include O-acyl oxime compounds. Specific examples of O-acyl oxime compounds include: 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 1-(9-ethyl-6-benzoyl-9.H.-carbazole-3-yl)-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, etc. Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), acetoketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), acetoketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), acetoketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl)methoxybenzoyl}-9.H.-carbazole-3-yl]-1-(O-acetyl oxime).

[0092] As oxime ester compounds, commercially available products such as NCI-831, NCI-930 (manufactured by ADEKA Corporation), DFI-020, DFI-091 (manufactured by Daitochemix Corporation), and Irgacure OXE01, OXE02, and OXE03 (manufactured by BASF) can also be used.

[0093] There are no particular limitations on cationic polymerization initiators, as long as they generate propionic acid or Lewis acid through light irradiation or heating. In terms of the ability to form fine patterns by exposure, cationic polymerization initiators are preferred, such as ionic photoacid-generating and nonionic photoacid-generating polymerization initiators.

[0094] Examples of photocationic polymerization initiators that generate ionic photoacids include: onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonylimide compounds, and diazomethane compounds. Examples of onium salt compounds include, for instance, aromatic sulfonium salts, aromatic monazonium salts, aromatic diazonium salts, aromatic ammonium salts, and (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe salts. Specific examples of such onium salt compounds include those with a cationic moiety consisting of an aromatic sulfonium, aromatic monazonium, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe cation, and an anionic moiety containing BF4. - PF6 - SbF6 - [BX4] - (where X is a phenyl group substituted with two or more fluorine or trifluoromethyl groups), or [PRf] 6- [Rf is a fluorinated alkyl group] of onium salts.

[0095] Examples of nonionic photoacid-generating photocationic polymerization initiators include: nitrobenzyl ester, sulfonic acid derivatives, phosphate esters, phenol sulfonates, diazonaquinone, and N-hydroxyimide phosphonates.

[0096] The proportion of reaction initiator (B) relative to 100 parts by mass of polymer component (A) (the total amount of two or more reaction initiators (B) if two or more are present) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. Furthermore, the proportion of reaction initiator (B) relative to 100 parts by mass of polymer component (A) is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and even more preferably 15 parts by mass or less. By setting the proportion of reaction initiator (B) within the aforementioned range, the effect of reduced pattern-forming ability caused by uneven exposure can be minimized when exposing the coating film formed using the polymer composition. In addition, a cured film with better developability, excellent curing properties, and superior transparency can be formed, which is preferable in this respect.

[0097] [Multifunctional polymeric compound (C)]

[0098] The polyfunctional polymerizable compound (C) is a compound having two or more polymerizable groups. The polymerizable groups are preferably groups containing carbon-carbon unsaturated double bonds, such as vinyl groups, (meth)acryloyl groups, etc. The polyfunctional polymerizable compound (C) preferably has 2 to 10 polymerizable groups, more preferably 2 to 6.

[0099] Regarding high reactivity to light and heat, the polyfunctional polymerizable compound (C) is preferably a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups. Specific examples of polyfunctional (meth)acrylates include: polyfunctional (meth)acrylates of alkyl glycols or polyalkylene glycols such as ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, and 1,9-nonanediol dimethacrylate; polyfunctional (meth)acrylates of monocyclic alkylene glycols or polycyclic alkylene glycols such as cyclohexanediethanol dimethacrylate and tricyclodecanediethanol dimethacrylate; polyfunctional (meth)acrylates of trivalent or higher polyols such as trimethylolpropane poly(meth)acrylate, di-trimethylolpropane poly(meth)acrylate, pentaerythritol poly(meth)acrylate, and dipentaerythritol poly(meth)acrylate; and pentaerythritol epoxides (Alkylene... AO-modified or succinic acid-modified polyfunctional (meth)acrylates, including AO-modified polyfunctional (meth)acrylates such as trimethylolpropane (AOP), dipentaerythritol (AOP), pentaerythritol (Trimethylolpropane), and dipentaerythritol (Pentaerythritol) (Texamethacrylate), succinic acid-modified pentaerythritol (Texamethacrylate), and succinic acid-modified dipentaerythritol (Texamethacrylate); ethoxylated isocyanurate tri(meth)acrylate, ε-caprolactone-modified tri-(2-(meth)acryloyloxyethyl)isocyanurate, and tri(2-(meth)acryloyloxyethyl)phosphate. Furthermore, in this specification, "AO modification" refers to ethylene oxide (EO) modification and propylene oxide (PO) modification, among other epoxide modifications.

[0100] The proportion of the multifunctional polymeric compound (C) relative to 100 parts by mass of polymer component (A) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more. Furthermore, the proportion of the multifunctional polymeric compound (C) relative to 100 parts by mass of polymer component (A) is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less. Setting the proportion of the multifunctional polymeric compound (C) to 20 parts by mass or more improves the heat resistance and chemical resistance of the cured film obtained using the polymer composition, which is preferable in this respect. Furthermore, setting the proportion of the multifunctional polymeric compound (C) to 200 parts by mass or less is preferable in terms of ensuring sufficient developability and effectively reducing exposure unevenness.

[0101] [Other ingredients]

[0102] In addition to the polymer component (A), reaction initiator (B), and multifunctional polymerizable compound (C) disclosed herein, the polymer composition may also contain other components as shown below.

[0103] • Sealing agent (D)

[0104] Adhesion enhancer (D) is a component that improves the adhesion between the hardened film obtained using the polymer composition and the underlying layer (e.g., substrate). Preferably, adhesion enhancer (D) is a silane coupling agent (hereinafter also referred to as "functional silane coupling agent") having reactive functional groups such as carboxyl, (meth)acryloyl, vinyl, isocyanate, or oxacyclopropyl groups. Examples of functional silane coupling agents include: trimethoxysilylbenzoic acid, (meth)acryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-((meth)acryloyloxy)ethyl phosphate. The proportion of the bonding agent (D) relative to 100 parts by mass of polymer component (A) is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, and even more preferably 0.5 parts by mass to 4 parts by mass.

[0105] • Polymerization inhibitor (E)

[0106] Polymerization inhibitor (E) is a component that improves the storage stability of polymer compositions. Examples of polymerization inhibitors (E) include sulfur compounds, quinones (e.g., benzoquinone), hydroquinones (e.g., hydroquinone, 2,5-di-tert-butylhydroquinone), polyoxyethylene compounds (e.g., p-methoxyphenol), amine compounds (e.g., N,N-diethylhydroxylamine), and nitrosamine compounds (e.g., N-nitroso-N-phenylhydroxylamine aluminum). The content of polymerization inhibitor (E) relative to 100 parts by weight of polymer component (A) is preferably 0.01 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight, and even more preferably 0.01 to 0.2 parts by weight.

[0107] Solvent (F)

[0108] The polymer composition disclosed herein is a liquid composition comprising a polymer component (A), a reaction initiator (B), a multifunctional polymerizable compound (C), and other components formulated as needed, preferably dissolved or dispersed in a solvent. The solvent (F) used is preferably an organic solvent that dissolves the components and does not react with them.

[0109] Specific examples of solvents (F) include: alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Among these, esters are preferred as solvents (F).

[0110] In addition to the above, the polymer compositions disclosed herein may also contain other components such as antioxidants, surfactants, and chain transfer agents. The proportions of these components may be appropriately selected based on the individual components, without compromising the effectiveness of the present disclosure.

[0111] When the polymer composition is a liquid composition, its solids concentration (the proportion of the total mass of the components in the polymer composition excluding the solvent to the total mass of the polymer composition) is appropriately selected considering viscosity, volatility, etc., and is preferably in the range of 5% to 60% by mass. If the solids concentration is 5% by mass or more, the film thickness of the coating can be sufficiently ensured when the polymer composition is coated onto the substrate. Furthermore, if the solids concentration is 60% by mass or less, the film thickness will not be excessive, thereby moderately increasing the viscosity of the polymer composition and ensuring good coatability. The solids concentration of the polymer composition is more preferably 10% to 55% by mass, and more preferably 15% to 50% by mass.

[0112] <Curing film and its manufacturing method>

[0113] The hardened film disclosed herein is formed from a polymer composition prepared in the manner described. According to the polymer composition, a hardened film with reduced gas generation and excellent heat resistance and transparency can be obtained. Therefore, the hardened film is useful as an insulating film for organic EL elements. Specifically, in organic EL elements, the hardened film can be used as a planarization film to flatten the surface unevenness caused by thin-film transistors (TFTs), an interlayer insulating film to insulate wiring, an isolation wall and accumulation layer defining the area where the light-emitting layer is formed, a protective film to protect TFTs, a separator, an adhesive layer for color filters, etc. Compared with existing organic EL elements that, for example, use polyimide materials as materials for isolation walls, accumulation layers, planarization films, etc., the hardened film can achieve cost reduction, which is significant in this respect. Furthermore, in this specification, "isolation wall" refers to a component used to distinguish colors, such as a color conversion layer using filters or quantum dots, and "accumulation layer" refers to a component that distinguishes the light-emitting layer.

[0114] In manufacturing the hardened film, a negative-type hardened film can be formed by irradiation with radiation such as ultraviolet light, far ultraviolet light, or visible light, using a radioactive linear curing composition as the polymeric composition. The hardened film can be manufactured, for example, by a method including steps 1 to 4 below.

[0115] (Step 1) Step of forming a coating film on a substrate using the polymeric composition.

[0116] (Step 2) A step of exposing at least a portion of the coating.

[0117] (Step 3) The process of developing the coating.

[0118] (Step 4) The process of heating the developed coating.

[0119] The following is a detailed description of each process.

[0120] [Process 1: Membrane Formation Process]

[0121] In this process, a polymer composition is coated onto the surface on which the film is to be formed (hereinafter also referred to as the "film-forming surface"). Preferably, the solvent is removed by heat treatment (pre-baking), thereby forming a coating on the film-forming surface. The material of the film-forming surface is not particularly limited and is appropriately selected depending on the application of the hardened film. For example, in the case of a planarization film application, the polymer composition is coated onto a substrate on which switching elements such as TFTs are provided to form a coating. For example, a glass substrate or a resin substrate is used as the substrate. In the case of an isolation wall and accumulation layer application, the polymer composition is coated onto a planarization film on which electrodes are formed to form a coating. For example, metals or alloys, or inorganic conductive materials (ITO, etc.) are used as electrodes.

[0122] Examples of coating methods for polymer compositions include spraying, roller coating, spin coating, stencil coating, bar coating, and inkjet coating. Spin coating, stencil coating, or bar coating are preferred among these methods. Pre-baking conditions vary depending on the type and proportion of each component in the polymer composition, and for example, are carried out at 60°C to 130°C for 0.5 to 10 minutes. The film thickness formed (i.e., the film thickness after pre-baking) is preferably 1.0 μm to 12.0 μm.

[0123] [Process 2: Exposure Process]

[0124] In this process, at least a portion of the coating film formed in step 1 is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a patterned hardened film can be formed. Examples of radiation include ultraviolet light, far ultraviolet light, visible light, X-rays, and charged particle beams such as electron beams. Ultraviolet light is preferred among these, such as gamma rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The exposure dose of the radiation is preferably 0.1 J / m². 2 ~20,000 J / m 2 .

[0125] [Process 3: Developing Process]

[0126] In this process, the coating film irradiated with radiation is developed. Specifically, the coating film irradiated with radiation in step 2 is subjected to negative development using a developing solution to remove the non-irradiated portions of the radiation. Examples of developing solutions include aqueous solutions of alkalis (alkaline compounds). Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and the alkali exemplified in paragraph

[0127] of Japanese Patent Application Publication No. 2016-145913. The alkali concentration of the aqueous solution is preferably 0.1% to 5.0% by mass from the viewpoint of obtaining adequate developability.

[0127] Examples of suitable development methods include liquid coating, immersion, shaking immersion, and spraying. The development time varies depending on the type and proportion of each component in the polymer composition, and is, for example, 30 to 120 seconds. Furthermore, it is preferable to perform a rinsing treatment with running water after the development process on the patterned coating.

[0128] [Process 4: Heating Process]

[0129] In this process, the developed coating is heated (post-baking). Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120°C to 250°C. Furthermore, if heating is performed on a hot plate, the heating time is 5 minutes to 40 minutes; if heating is performed in an oven, the heating time is 10 minutes to 80 minutes. By performing this process as described above, a hardened film with the target pattern can be formed on the substrate.

[0130] The hardened film obtained through the process is formed using the polymer composition, thus reducing gas escape generation even under stringent conditions. Specifically, it is preferable that the amount of gas escape generated during the period of holding at 230°C for 15 minutes after heating from room temperature to 230°C at a heating rate of 10°C / min is less than 100 ng / cm³. 2 The more preferred escaping gas volume under the aforementioned conditions is 80 ng / cm³. 2 The preferred value is 70 ng / cm³. 2 The following is particularly preferred: less than 50 ng / cm 2 Furthermore, the details of the method for measuring the escape volume are as described in the examples below.

[0131] <Organic EL Components>

[0132] The organic EL element disclosed herein has a hardened film formed using the polymer composition. Examples of the organic EL element include display elements and lighting elements. In organic EL display elements and organic EL lighting elements, the hardened film may be, for example, at least one selected from the group consisting of planarization films, interlayer insulating films, insulating walls, accumulation layers, separators, protective films, and adhesive layers for color filters.

[0133] The specific implementation of the organic EL element will be described with appropriate use of the accompanying drawings. One embodiment of the organic EL element 10 is... Figure 1 The organic EL element 10 is shown as a top-emitting type. The organic EL element 10 is an active matrix type having multiple pixels formed in a matrix shape. The organic EL element 10 includes a support substrate 11, a pair of electrodes including a pixel electrode 12 and a counter electrode 13, an organic light-emitting layer 14, and a sealing substrate 15.

[0134] In the top-emitting organic EL element 10, the supporting substrate 11 is not particularly limited, and can be made of glass materials such as alkali-free glass, or transparent substrates made of resin materials such as polyethylene terephthalate, polyethylene naphthalate, and polyimide. A thin-film transistor (TFT) 16 is formed on the supporting substrate 11 for each pixel. The TFT 16 can be a bottom-gate type with a gate insulating film and a semiconductor layer sequentially formed on the gate electrode, or a top-gate type with a gate insulating film and a gate electrode sequentially formed on the semiconductor layer.

[0135] A planarization film 17 is disposed on the support substrate 11. The planarization film 17 is an insulating film and is formed on the entire surface of the support substrate 11 in such a way as to cover the TFT 16. By forming the planarization film 17 on the support substrate 11, the surface unevenness generated by the TFT 16 is planarized. A pixel electrode 12, serving as an anode, is formed on the planarization film 17.

[0136] The pixel electrode 12 is formed of a conductive material. In the case of a top-emitting organic EL element 10, the pixel electrode 12 is required to be light-reflective. The conductive material constituting the light-reflective electrode is preferably Al (aluminum), APC alloy (an alloy of silver, palladium, and copper), ARA alloy (an alloy of silver, rubidium, and gold), MoCr alloy (an alloy of molybdenum and chromium), NiCr alloy (an alloy of nickel and chromium), or a laminate of these metals with a highly transparent electrode (e.g., indium tin oxide (ITO)). The pixel electrode 12 is electrically connected to the TFT 16 via a via 18 formed in the planarization film 17.

[0137] The opposing electrode 13 is positioned opposite to the pixel electrode 12. The opposing electrode 13 is formed of a conductive material and functions as a common electrode for all pixels. In the case of a top-emitting organic EL element 10, the opposing electrode 13 is required to be transparent. The conductive material constituting the transparent electrode is preferably ITO, indium zinc oxide (IZO), or tin oxide.

[0138] An organic light-emitting layer 14 is disposed between the pixel electrode 12 and the opposing electrode 13. Specifically, a partition wall 19 protruding from the film surface is formed on the planarization film 17. The partition wall 19 is arranged to cover the outer periphery of each pixel electrode 12, dividing the plurality of pixel electrodes 12 respectively. A recess 21 is formed in the region surrounded by the partition wall 19, and an organic light-emitting layer 14 is disposed on the pixel electrode 12 in each recess 21. The organic light-emitting layer 14 is a layer containing an organic light-emitting material that performs electroluminescence. The organic light-emitting material can be a low molecular weight compound or a polymer. In addition, the organic light-emitting layer 14 may also include a plurality of thin film layers comprising, together with the light-emitting layer, at least one of a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.

[0139] In the organic EL element 10, at least one of the planarization film 17 and the isolation wall 19 is formed using the aforementioned polymer composition. For example, when using a negative-type radiosensitive linear polymer composition as the polymer composition to form the planarization film 17, firstly, the polymer composition is coated on the TFT 16 side of the support substrate 11 having the TFT 16, preferably by pre-baking, thereby forming a coating on the support substrate 11. Next, the coating is irradiated with radiation using a necessary interferometric mask, resulting in a curing reaction of a multifunctional polymeric compound (C) in the exposed portion. After exposure, the planarization film 17 can be formed by performing a development process and a post-baking process.

[0140] The same applies to the formation of the isolation wall 19. First, a negative-type radiosensitive linear polymer composition is coated onto the electrode formation surface of the planarization film 17 where the pixel electrode 12 is formed, preferably after pre-baking, thereby forming a coating film. Next, the coating film is irradiated with radiation through a mask having a pattern corresponding to the shape of the isolation wall 19. Then, by performing a development process and a post-baking process, the isolation wall 19 and the recess 21 can be formed on the planarization film 17 where the pixel electrode 12 is formed. An organic light-emitting layer 14 is formed in the recess 21 formed in this manner, for example by inkjet printing. In the planarization film 17, the opposing electrode 13 and the passivation film 22 are sequentially stacked on the formation surface of the organic light-emitting layer 14.

[0141] The sealing substrate 15 is disposed at a predetermined interval from the surface of the support substrate 11, facing the surface in which the organic light-emitting layer 14 is disposed. The sealing substrate 15 is formed of an insulating material with high light transmittance, such as a glass substrate including an alkali-free glass substrate; or a transparent resin substrate such as polyethylene terephthalate, polyethylene naphthalate, or polyimide. The outer peripheral end of the sealing substrate 15 is bonded to the support substrate 11 using a sealant. Thus, a sealing layer 23 is formed in the space surrounded by the support substrate 11, the sealing substrate 15, and the sealant.

[0142] The sealing layer 23 is, for example, an inert gas layer filled with nitrogen or the like, or a filler layer formed of an adhesive or the like. Furthermore, a black matrix 24 and a color filter 25 are disposed on the surface of the sealing substrate 15 on the side of the sealing layer 23. White light emitted from the organic light-emitting layer 14 of each pixel becomes colored light selected by the color filter 25 and is transmitted through the sealing substrate 15.

[0143] Another embodiment of the organic EL element 10 is Figure 2 The organic EL element shown is a bottom-emitting structure. Furthermore, in the following... Figure 2 In the explanation, regarding the relationship with Figure 1 Similar points, references Figure 1 The explanation, and in conjunction with Figure 1 The explanation will focus on the differences.

[0144] exist Figure 2 In the organic EL element 10 shown, a TFT 16 and a color filter 25 are disposed on a support substrate 11. A pair of electrodes, including a pixel electrode 12 and a counter electrode 13, and an organic light-emitting layer 14 disposed between the pair of electrodes are disposed on a planarization film 17. When the organic EL element 10 is a bottom-emitting structure, the support substrate 11 and the pixel electrode 12 are required to be transparent, and the counter electrode 13 is required to be reflective. Examples of transparent substrate materials, transparent conductive materials, and reflective conductive materials can be listed. Figure 1 The material is illustrated in the example. White light emitted from the organic light-emitting layer 14 of each pixel becomes colored light selected by the color filter 25 and is transmitted through the support substrate 11.

[0145] [Example]

[0146] The present invention will be further described in detail below based on embodiments, but the present invention is not limited to these embodiments. Unless otherwise specified, "parts" in the following description of embodiments, etc., refers to "parts by mass". The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the polymer were determined by the following methods.

[0147] [Methods for determining Mw, Mn, and Mw / Mn]

[0148] The Mw and Mn of the polymer were determined using gel permeation chromatography (GPC) with two G2000HXL columns, one G3000HXL column, and one G4000HXL column from Tosoh under the analytical conditions described below. The dispersity (Mw / Mn) was calculated based on the Mw and Mn determination results.

[0149] (Analysis conditions)

[0150] Dissolution solvent: tetrahydrofuran

[0151] Flow rate: 1.0 mL / min

[0152] Sample concentration: 1.0% by mass

[0153] Sample injection volume: 100 μL

[0154] Column temperature: 40℃

[0155] Detector: Differential refractometer

[0156] Standard material: Monodisperse polystyrene

[0157] Synthesis of Alkali-Soluble Resins

[0158] [Synthesis example 1]

[0159] In a flask equipped with a cooling tube and a stirrer, 10 parts of 2,2'-azobis-(2,4-dimethylpentanonitrile) and 200 parts of methyl 3-methoxypropionate were added. Next, 10 parts of methacrylic acid, 35 parts of methyl 3,4-epoxycyclohexyl methacrylate, 25 parts of cyclohexyl acrylate, 25 parts of N-cyclohexylmaleimide, and 5 parts of methyl methacrylate were added. After nitrogen purging, stirring was started slowly. The temperature of the solution was raised to 75°C and maintained at this temperature for 5 hours, thereby obtaining a solution containing an alkali-soluble resin (hereinafter referred to as "resin (A-1)"). The resulting resin solution had a solids content of 34.2% by mass, a Mw of 12,000 for resin (A-1), and an Mw / Mn ratio of 2.0.

[0160] [Synthesis Example 2 to Synthesis Example 12]

[0161] Using the components shown in Table 1 in the specified types and amounts as monomers, the same procedure as in Synthesis Example 1 was followed to obtain solutions containing resins (A-2) to (A-20). The results are shown in Table 1.

[0162] [Table 1]

[0163]

[0164] In Table 1, the abbreviations for monomers are as follows.

[0165] (a1)N-Cyclohexylmaleimide

[0166] (a2)N-Phenylanimide

[0167] (a3) Cyclohexyl acrylate

[0168] (a4) Tricyclic acrylic acid [5.2.1.0] 2,6 ] Decane-8-yl ester

[0169] (a5) Benzyl acrylate

[0170] (a6) Phenyl acrylate

[0171] (a7) 3,4-Epoxycyclohexyl methacrylate

[0172] (a8) Acrylic acid 3,4-epoxy tricyclic [5.2.1.0] 2,6 ] Decyl ester

[0173] (a9) Glycidyl methacrylate

[0174] (a10) Methyl methacrylate (3-ethyloxetane-3-yl)

[0175] (a11) Methacrylic acid

[0176] (a12)4-hydroxy-α-methylstyrene

[0177] (a13) Maleimide

[0178] (a14) Methyl methacrylate

[0179] (a15) Styrene

[0180] <Preparation of Radiosensitive Linear Resin Composition>

[0181] [Example 1]

[0182] In a solution containing resin (A-1), in an amount equivalent to 100 parts (solid component) of resin (A-1), 4 parts of "NCI-930" (ADEKA) as a reaction initiator and 5 parts of "Irgacure OXE01" (BASF) were mixed, along with 50 parts of "KAYARAD DPHA" (Nippon Kayaku Co., Ltd.) as a multifunctional polymerizable compound, and methacryloyloxypropyltrimethoxysilane (Toray Industries Co., Ltd.). A resin composition (S-1) was prepared by dissolving 3 parts of Dow Corning's "XIAMETER (R) OFS-6030 Silane (SILANE)" and 0.1 parts of 2,5-di-tert-butylhydroquinone (Wako Pure Chemical Industries, Ltd.) in a mixed solvent of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate (mass ratio of 50:50) to achieve a solid content concentration of 30% by mass, and then filtering the mixture through a membrane filter with a pore size of 0.2 μm.

[0183] [Examples 2 to 19 and Comparative Examples 1 to 4]

[0184] Regarding the alkali-soluble resin, reaction initiator, and multifunctional polymerizable compound, the types and amounts of each component shown in Tables 2 and 3 were used. Except for these, the procedures were performed in the same manner as in Example 1 to prepare resin compositions (S-2) to (S-10) and resin compositions (CS-1) to (CS-3). In Comparative Example 4, a photosensitive composition containing polyimide (“DL1000” manufactured by Toray Industries, Inc.) was used as the resin composition (CS-4).

[0185] The meanings of the symbols in Tables 2 and 3 are as follows.

[0186] Alkali-soluble resins

[0187] A-1 to A-20: Resins synthesized in Synthetic Examples 1 to 20 respectively

[0188] • Reaction initiator

[0189] B-1: ADEKA's "NCI-930"

[0190] B-2: 1,2-Octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)] (BASF's "Irgacure OXE01")

[0191] Multifunctional polymeric compounds

[0192] C-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA from Nippon Kayaku Co., Ltd.)

[0193] C-2: 1,9-Nonadiol diacrylate

[0194] (Light Acrylate 1,9ND-A from Kyoei Chemical Co., Ltd.)

[0195] <Evaluation>

[0196] The resin compositions obtained in the examples and comparative examples were used to form insulating films, and the following methods were used to evaluate low gas escape, linearity, negative radiation sensitivity, negative resolution, development adhesion, light transmittance, and heat resistance and light transmittance. The evaluation results are shown in Tables 2 and 3.

[0197] [Low escape velocity]

[0198] After applying the resin compositions obtained in the examples and comparative examples onto a silicon substrate using a spinner, the substrate was pre-baked on a hot plate at 90°C for 2 minutes to form a coating. Subsequently, an exposure machine (Canon's "PLA-501F": using an ultra-high pressure mercury lamp) was used at 200 J / m². 2 The coating was exposed to a specific exposure level. Subsequently, a 2.38% (w / w) tetramethylammonium hydroxide aqueous solution (developer) was used for development at 25°C using the overlay method. The development time was 100 seconds. After development, the coating was rinsed with ultrapure water for 1 minute and then dried. The silicon substrate was then heated at 230°C for 30 minutes in a clean oven to obtain an insulating film with a thickness of 2.0 μm.

[0199] A silicon substrate with an insulating film was cut into 1cm × 5cm wafers. Four of these wafers were analyzed using a silicon wafer analyzer (Japan Analysis Industries Co., Ltd.'s "Heating Desorption Unit JTD-505" and Shimadzu Corporation's "Gas Chromatograph Mass Analyzer GCMS-QP2010 Plus"). The temperature was increased to 230°C at a rate of 10°C / min. The amount of alcohol gas released (ng / cm³) after holding at this temperature for 15 minutes was calculated. 2 The evaluation of escape volume is based on the following criteria.

[0200] (Evaluation Criteria)

[0201] A: Less than 50ng / cm 2

[0202] B: 50ng / cm 2 Above but less than 100 ng / cm 2

[0203] C: 100ng / cm 2 above

[0204] [Matching Lines]

[0205] The same procedures as those used in forming the insulating film during the "low fumes" evaluation were performed to obtain a silicon substrate with an insulating film thickness of 4.0 μm. ITO wiring (50 μm wide) was formed on the insulating film using a sputtering apparatus (Ulvac "SH-550-C12" target), followed by annealing at 230°C for 30 minutes. The thickness of the ITO wiring was measured using a surface roughness gauge α-stepper. Visually inspect the obtained ITO wiring board for cracks to evaluate the heat resistance of the insulating film (especially the coefficient of linear expansion, referred to as "line of distribution"). The evaluation of the line of distribution is based on the following criteria.

[0206] (Evaluation Criteria)

[0207] A: No cracks were generated.

[0208] B: Cracks have formed.

[0209] [Negative Radiation Sensitivity]

[0210] The resin compositions obtained in the examples and comparative examples were coated onto a glass substrate (Corning 7059) using a spinner, and then pre-baked on a hot plate at 90°C for 2 minutes to form a coating with a thickness of 4.0 μm. Subsequently, the coating was exposed using an exposure machine (Canon PLA-501F: using an ultra-high pressure mercury lamp) with varying exposure levels, separated by a pattern mask having multiple rectangular light-blocking portions (10 μm × 10 μm). Development was then performed at 25°C using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer) via a liquid-coating method. The development time was 100 seconds. After development, the coating was rinsed with ultrapure water for 1 minute to dry and form a pattern on the glass substrate. The glass substrate was then heated in a clean oven at 230°C for 30 minutes to obtain an insulating film with through-holes.

[0211] Regarding the film thickness of the insulating film formed using resin compositions (S-1) to (S-19) and resin compositions (CS-1) to (CS-3), the exposure amount that is 85% or more, expressed by the following formula (1), is used as the sensitivity, and the radiation sensitivity is evaluated according to the following criteria.

[0212] Residual film rate (%) = (film thickness after development / film thickness before development) × 100…(1)

[0213] Regarding the resin composition (CS-4), a patterned mask with a rectangular transmission portion (10μm×10μm) was used. Otherwise, the same operation was performed to determine the exposure amount required to form a through-hole by exposing the patterned mask to the exposure, which was then used as the sensitivity. The sensitivity was evaluated according to the following criteria.

[0214] (Evaluation Criteria)

[0215] A: Less than 200J / m 2

[0216] B: 200J / m 2 Above but less than 400 J / m 2

[0217] C: 400J / m 2 above

[0218] [Negative Analytical Properties]

[0219] Set the exposure to 200 J / m 2 In addition, an insulating film with through-holes is formed in the same manner as for the evaluation of "negative radiation sensitivity". Resolution is evaluated by observing the minimum diameter of the through-holes in the insulating film using an optical microscope. Resolution is evaluated according to the following criteria.

[0220] (Evaluation Criteria)

[0221] A: The minimum diameter of the through hole is 10μm or more.

[0222] B: The minimum diameter of the through hole is 8μm or more but less than 10μm.

[0223] C: The minimum diameter of the through hole is 5μm or more but less than 8μm.

[0224] [Developable Adhesion]

[0225] A mask with a line-to-space ratio (L / S) of 1:1 (the space width is the same size as the linewidth of 5μm to 40μm) was used, and the exposure was set to 200J / m. 2 In addition, an insulating film is formed in the same manner as for evaluating radiation sensitivity. Regarding the insulating film, the minimum width of the lines remaining after development without being peeled off is observed using an optical microscope, and the adhesion of the developed film is evaluated according to the following criteria.

[0226] (Evaluation Criteria)

[0227] A: Minimum width is less than 10μm

[0228] B: Minimum width is 10μm or more but less than 30μm

[0229] C: Minimum width is 30μm or more

[0230] [Light transmittance and heat resistance]

[0231] The resin compositions obtained in the examples and comparative examples were applied to a glass substrate (Corning 7059) using a swivel, and then pre-baked on a hot plate at 90°C for 2 minutes to form a coating. Subsequently, an exposure machine (Canon PLA-501F: using an ultra-high pressure mercury lamp) was used with an exposure dose of 200 J / m². 2The coating was then exposed to light. Subsequently, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer) was used, and development was performed at 25°C using the overlay method. The development time was 100 seconds. The film was then heated at 230°C for 30 minutes in a clean oven to obtain a hardened film A with a thickness of 3.0 μm. The hardened film A was then heated at 230°C for 5 hours in a clean oven to obtain a hardened film B.

[0232] For each glass substrate with a hardened film, after the formation of hardened film A and hardened film B, the transmittance (light transmittance) in the wavelength range of 400 nm to 800 nm was measured using a spectrophotometer (Hitachi, Ltd.'s "150-20 type dual-beam"), and the lowest transmittance value in the wavelength range of 400 nm to 800 nm was evaluated. Furthermore, the measured value of hardened film A was set as the "lowest transmittance," and the measured value of hardened film B was set as the "lowest heat-resistant transmittance." The lowest transmittance and the lowest heat-resistant transmittance are shown in Tables 2 and 3.

[0233] [Table 2]

[0234] Table 2: Evaluation

[0235]

[0236] [Table 3]

[0237] Table 3: Evaluation

[0238]

[0239] As shown in Tables 2 and 3, the cured films of Examples 1 to 19 exhibited low gas leakage and excellent conformation, radiation sensitivity, resolution, development adhesion, light transmittance, and heat resistance light transmittance. In contrast, the cured films of Comparative Examples 1 and 2, which used polymers containing 40% by mass of structural unit (U2) and 15% by mass of structural unit (U1), showed good radiation sensitivity, resolution, and development adhesion, but had high gas leakage and poor conformation compared to the Examples. The cured film of Comparative Example 3, which used a polymer without structural unit (U1), had poor conformation, resolution, and development adhesion. The cured film of Comparative Example 4, which contained polyimide as a resin, had low gas leakage and good conformation, but its radiation sensitivity, resolution, and development adhesion were worse than the Examples. Furthermore, the minimum light transmittance and minimum heat resistance light transmittance of the cured film of Comparative Example 4 were both low, at 80% and 60% respectively, indicating poorer light transmittance and heat resistance light transmittance compared to the Examples.

[0240] These results demonstrate that the polymer composition according to the present invention can provide a curing film with excellent properties such as low gas escape, linearity (low thermal expansion coefficient), radiation sensitivity, resolution, development adhesion, light transmittance, and heat resistance and light transmittance (transparency after heat application). Therefore, the curing film of the present invention is particularly suitable as a planarization film, interlayer insulating film, separator, or accumulation layer in organic EL elements.

Claims

1. A polymer composition comprising: Polymer component (A); Reaction initiator (B); and Multifunctional polymeric compound (C), and The polymer component (A) comprises a structural unit (Uα) derived from at least one selected from the group consisting of N-substituted maleimide compounds having a monovalent cyclic hydrocarbon group and (meth)acrylic acid compounds having a monovalent cyclic hydrocarbon group, wherein the polymer component (A) comprises a structural unit (U1) derived from the N-substituted maleimide compound and a structural unit (U2) derived from an acrylic acid compound having a monovalent cyclic hydrocarbon group. The structural unit (Uα) comprises 28% by mass or more of the structural unit (U1) relative to the total amount of the structural unit (Uα) contained in the polymer component (A). The content of the structural unit (U2) is 5% by mass or more and 28% by mass or less, relative to all the structural units constituting the polymer component (A).

2. The polymer composition according to claim 1, wherein the polymer component (A) comprises more than 15% by mass and less than 35% by mass of the structural unit (U1) relative to all the structural units constituting the polymer component (A).

3. The polymer composition according to claim 1 or 2, used in an organic electroluminescent element.

4. The polymer composition according to claim 1 or 2, wherein the polymer component (A) has a weight average molecular weight of 10,000 or more.

5. The polymer composition according to claim 1 or 2, wherein the polymer component (A) further comprises a structural unit (U3) having a cyclic ether group.

6. The polymer composition according to claim 1 or 2, wherein the polymer component (A) is alkali-soluble.

7. The polymer composition according to claim 1 or 2, wherein the polymer component (A) further comprises at least one structural unit selected from the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units.

8. The polymer composition according to claim 1 or 2, wherein the N-substituted maleimide compound has a monovalent cyclic hydrocarbon group that is a monovalent alicyclic hydrocarbon group having a monocyclic, bridging, or spirocyclic ring, or a monovalent aromatic hydrocarbon group.

9. The polymer composition according to claim 1 or 2, used to form a planarization film, a barrier wall, or a cumulative layer.

10. A hardened film formed using a polymer composition as described in any one of claims 1 to 9.

11. The hardened membrane according to claim 10, wherein the amount of gas escape generated during the period of holding at 230°C for 15 minutes after heating from room temperature to 230°C at a heating rate of 10°C / min is less than 100 ng / cm³. 2 .

12. The hardened film according to claim 10 or 11, used in an organic electroluminescent display element or an organic electroluminescent lighting element.

13. An organic electroluminescent element comprising a hardened film as described in any one of claims 10 to 12.

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