Curing compositions, curing films and their applications, methods for manufacturing curing films, and polymers

Abstract

This invention provides a curable composition capable of producing films with low dielectric constant and good curability. A curable composition comprises (A) a compound having a group represented by formula (1) below; and (B) a solvent. In formula (1), R1 is a hydrogen atom or an acid-dissociable group. "*" indicates a bond.

Description

Technical Field

[0001] This invention relates to a curing composition, a curing film, a method for manufacturing the same, and a polymer. Prior Technology

[0002] Hardened films such as interlayer insulating films, spacers, and protective films in semiconductor devices or display devices are generally formed using hardening compositions. In recent years, with the increasing integration or miniaturization of semiconductor devices, a low dielectric constant is required as a characteristic of hardened films. To achieve this characteristic, various hardening compositions have been proposed (for example, see Patent Document 1).

[0003] Patent Document 1 discloses a composition comprising: a polymer component containing, in the same or different polymer molecules, structural units having an oxetyl group and structural units having an oxetyl group in a specific ratio; and a radiosensitive linear acid generator that produces an acid with a pKa of 4.0 or less. Patent Document 1 describes how, by using the composition, a hardened film with a low dielectric constant and high surface hardness and voltage retention rate can be obtained. [Existing Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2017-173376 Summary of the Invention

[0005] [The problem that the invention aims to solve]

[0006] With the increasing speed and capacity of communications, there is a desire for new materials that can achieve even lower dielectric constants in the hardened films of semiconductor devices. Therefore, the hardened films are required to have high hardenability and exhibit sufficiently low dielectric constants.

[0007] The present invention was made in view of the aforementioned issues, and its main objective is to provide a curable composition capable of producing films with low dielectric constant and good curability. [Methods for solving problems]

[0008] The inventors have discovered that the aforementioned problem can be solved by including a compound having a specific structure in the curing composition. Specifically, according to the present invention, the following curing compositions, curing films, methods for manufacturing the same, organic electroluminescence (EL) elements, liquid crystal display elements, semiconductor elements, printed circuit boards, and polymers are provided.

[0009] [1] A curable composition comprising (A) a compound having a base represented by the following formula (1); and (B) a solvent. [Chemistry 1] (In formula (1), R1 is a hydrogen atom or an acid dissociative group; "*" indicates a bond)

[0010] [2] A hardened film obtained using the hardening composition of [1]. [3] An organic electroluminescent element having the hardened film of [2]. [4] A liquid crystal display element having the hardened film of [2]. [5] A semiconductor element having the hardened film of [2]. [6] A printed substrate having the hardened film of [2].

[0011] [7] A method for manufacturing a hardened film, comprising the step of heating the hardening composition of [1]. [8] A method for manufacturing a hardened film includes: a step of forming a coating film using the hardening composition of [1]; a step of irradiating at least a portion of the coating film with radiation; a step of developing the irradiated coating film; and a step of heating the developed coating film. [9] A polymer having a base represented by the formula (1). [The effects of the invention]

[0012] The curable composition according to the present invention can produce films with low dielectric constant and good curability. Therefore, the curable composition of the present invention is preferably used in the formation of curable films in the manufacturing processes of organic EL elements or liquid crystal display elements, semiconductor elements, printed circuit boards, etc. Implementation

[0013] The following provides a detailed explanation of matters related to the implementation. Furthermore, in this specification, the numerical range indicated by "~" refers to the values ​​before and after the "~" as the lower and upper limits, respectively.

[0014] Hardening Compositions The curable composition disclosed herein (hereinafter also referred to as "the composition") is, for example, a resin composition for forming a curable film for semiconductor elements or liquid crystal display elements, organic EL elements, printed circuit boards, etc. The composition contains component (A) and component (B) as described below. (A) Components: Compounds having the base represented by the following formula (1) [Chemistry 2] (In formula (1), R1 is a hydrogen atom or an acid dissociative group; "*" indicates a bond) (B) Components: Solvent

[0015] The following describes each component contained in this composition, as well as other components formulated as needed. Furthermore, unless otherwise specified, each component may be used alone or in combination of two or more.

[0016] Here, in this specification, "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 that does not contain a ring structure in its main chain and is composed only of a chain structure. It 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. It does not need to consist solely of an alicyclic hydrocarbon structure; it may also include groups with a chain structure in a portion of it. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as its ring structure. It does not need to consist solely of an aromatic ring structure; it may also contain a chain structure or an alicyclic hydrocarbon structure in a portion of it. 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. "Structural unit" refers to the unit that mainly constitutes the main chain structure, and it means that the main chain structure contains at least two units.

[0017] <(A) Component: Compound (A)> This composition contains the compound represented by formula (1) (hereinafter also referred to as "compound (A)"). In formula (1), the acid-dissociable group represented by R1 is a group that substitutes for the polar hydrogen atom of the carboxyl group, and is a group that dissociates by the action of an acid.

[0018] When R1 is an acid-dissociable group, specific examples of the group "-COOR 1" include: the structure represented by formula (r-1) below, the acetal structure of a carboxylic acid, the ketal structure of a carboxylic acid, etc. Additionally, specific examples of the acid-dissociable group represented by R1 include the group represented by formula (r-2) below, hydroxymethyl, and the group represented by formula (r-1) below. [Chemistry 3] (In formula (r-1), R5, R6 and R7 are either (1) or (2) below; (1) R5, R6 and R7 are independently alkyl groups with 1 to 10 carbon atoms or monovalent alicyclic hydrocarbon groups with 3 to 20 carbon atoms; (2) R5 and R6 represent alicyclic hydrocarbon structures or cyclic ether structures with 4 to 20 carbon atoms that are bonded together with each other and together with the carbon atoms bonded to R5 and R6; R7 is an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms or an aryl group with 6 to 20 carbon atoms; "*" indicates a bond) [Chemistry 4] (In formula (r-2), R16, R17, and R18 are independently hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, monovalent alicyclic hydrocarbon groups, aryl groups, or -Si(R20)3, respectively; R20 is an alkyl group with 1 to 10 carbon atoms; multiple R20s may be the same or different from each other; R19 is a single bond or a divalent organogroup with 1 to 12 carbon atoms; "*" indicates a bond with the oxygen atom of the carbonyl group.)

[0019] Specific examples of the structure represented by formula (r-1) include: tert-butoxycarbonyl, 1-cyclopentylethoxycarbonyl, 1-cyclohexylethoxycarbonyl, 1-norbornylethoxycarbonyl, 1-phenylethoxycarbonyl, 1-(1-naphthyl)ethoxycarbonyl, 1-benzylethoxycarbonyl, 1-phenylethylethoxycarbonyl, etc.

[0020] Specific examples of acetal structures of carboxylic acids include: 1-methoxyethoxycarbonyl, 1-ethoxyethoxycarbonyl, 1-propoxyethoxycarbonyl, 1-butoxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 2-tetrahydropyranoxycarbonyl, 1-phenoxyethoxycarbonyl, 2-tetrahydrofuranoxycarbonyl, etc.

[0021] Specific examples of ketal ester structures of carboxylic acids include: 1-methyl-1-methoxyethoxycarbonyl, 1-methyl-1-ethoxyethoxycarbonyl, 1-methyl-1-propoxyethoxycarbonyl, 1-methyl-1-butoxyethoxycarbonyl, 1-methyl-1-cyclohexyloxyethoxycarbonyl, 2-(2-methyltetrahydrofuranyl)oxycarbonyl, 2-(2-methyltetrahydropyranyl)oxycarbonyl, 1-methoxycyclopentoxycarbonyl, 1-methoxycyclohexyloxycarbonyl, etc.

[0022] Specific examples of the groups represented by formula (r-2) include: trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, diethylisopropylsilyl, triisopropylsilyl, dimethylhexylsilyl, tert-butyldiphenylsilyl, dimethylphenylsilyl, tri(trimethylsilyl)silyl, 2-(trimethylsilyl)ethyl, 2-(trimethylsilyl)ethoxymethyl, 2-(trimethylsilyl)ethoxycarbonyl, etc.

[0023] When R 1 is an acid-dissociable group, in terms of the good dissociation brought about by the acid, the group "-COOR 1" is preferably the structure represented by the formula (r-1) or the acetal structure of the carboxylic acid.

[0024] Compound (A) may be a polymer component of this composition or a low-molecular-weight component formulated separately from the polymer component. Here, in this specification, "low-molecular-weight" refers to a compound that does not have repeating units, and preferably has a molecular weight of 1,000 or less, more preferably 800 or less. Furthermore, the low-molecular-weight component differs from the polymer component in that it does not have a molecular weight distribution.

[0025] In terms of achieving high radiation sensitivity and further improving the low dielectric constant and film curability, compound (A) is preferably a polymer (hereinafter also referred to as "polymer (A)") having the group represented by formula (1). Polymer (A) may have the group represented by formula (1) at the end of the polymer main chain or in the side chain of the polymer. Here, in this specification, the "main chain" of the polymer refers to the longest "stem" portion of the polymer's atomic chain. Furthermore, the "stem" portion is allowed to contain a ring structure. The "side chain" of the polymer refers to the portion that branches off from the "stem" of the polymer. In terms of being able to introduce multiple points along the polymer main chain and further improve the film curability, polymer (A) is preferably having the group represented by formula (1) in the side chain.

[0026] Regarding polymer (A) The main framework of polymer (A) is not particularly limited. Examples of polymer (A) include: (meth)acrylic acid polymers, styrene polymers, styrene-maleimide polymers, phenolic resins, phenolic varnish resins, triazine polymers, polycarbonate polymers, polyimide polymers, etc. Furthermore, in this specification, "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid".

[0027] In terms of improving the introduction efficiency of the base represented by formula (1) and forming a film with low dielectric constant and high curability, polymer (A) is preferably used having at least one of the group consisting of structural units represented by formula (2), formula (3), formula (4), formula (5), and formula (6).

[0028] [Chemistry 5] (In formula (2), L1 is a single bond or a divalent linker; P1 is the base represented by formula (1); R11 is a monovalent hydrocarbon group or halogen atom with 1 to 5 carbon atoms; n is an integer from 0 to 4; m is an integer from 1 to 4; where n+m≦5)

[0029] [Chemistry 6] (In equation (3), L1 is a single bond or a divalent linker; P1 is the base represented by equation (1))

[0030] [Chemistry 7] (In formula (4), Ar 1 is a trivalent aromatic cyclic group or a heterocyclic group; L 1 is a single bond or a divalent linker; P 1 is the group represented by formula (1)) [Chemistry 8] (In formula (5), Ar2 is a divalent group with an aromatic ring or heterocyclic ring; Y1 and Y2 are independently oxygen atoms, sulfur atoms or -NH-, respectively; L1 is a single bond or a divalent linker; P1 is the group represented by formula (1))

[0031] [Chemistry 9] (In formula (6), X1 is a tetravalent group derived from a tetracarboxylic acid derivative; X2 is a divalent group derived from a diamine compound; L1 is a single bond or a divalent linkage group; P1 is the group represented by formula (1); R3 and R4 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

[0032] In the above formulas (2) to (6), the divalent linker represented by L1 can be listed as: -O-, -S-, -NH-, -CO-, -COO-, -OCO-, alkyl diesters with 1 to 10 carbon atoms, divalent groups formed by substituting any methylene group of alkyl diesters with 2 to 10 carbon atoms with -O-, -S-, -NH-, -CO-, -COO- or -OCO-, etc.

[0033] From the viewpoint of exhibiting high curability and obtaining a film with excellent heat resistance and solvent resistance, L1 is preferably a divalent group formed by -O-substitution of any methylene group of a single bond, an alkyldiyl group having 1 to 5 carbons, or an alkyldiyl group having 2 to 5 carbons; more preferably, a divalent group formed by -O-substitution of any methylene group of a single bond, an alkyldiyl group having 1 to 3 carbons, or an alkyldiyl group having 2 or 3 carbons; and even more preferably, an alkyldiyl group having 1 to 2 carbons. Furthermore, from the viewpoint of improving the efficiency of crosslinking by heating, L1 is preferably an alkyldiyl group having 1 or more carbons.

[0034] There is no particular limitation on the method for synthesizing polymer (A). Polymer (A) can be synthesized, for example, by any of the methods described in (i) to (iii) below, or by a combination thereof. (i) A method of polymerization using monomers having the base represented by the formula (1). (ii) A method for obtaining a polymer having a first functional group in the side chain, and then reacting the polymer with a reactive compound having a second functional group that reacts with the first functional group and a group represented by formula (1). (iii) A method for obtaining a polymer having acetylene groups on the side chain, reacting it with a metal compound to generate acetylene metal, and then reacting it with carbon dioxide.

[0035] Polymers having the structural unit represented by equation (2) As specific examples of the structural unit represented by the above formula (2) (hereinafter also referred to as "structural unit (U1)"), the structural units represented by each of the following formulas (2-1) to (2-11) can be listed. In the following formula (2-10), R 12 is a linear or branched alkyl group with 1 to 4 carbon atoms. [Chemistry 10]

[0036] When polymer (A) is a polymer having structural units (U1), the content of structural units (U1) in polymer (A) is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 5 mol% or more, relative to all structural units in polymer (A). Furthermore, the content of structural units (U1) is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, relative to all structural units in polymer (A). If the content of structural units (U1) is within the aforementioned range, high radiation sensitivity can be sufficiently satisfied, and the improvement effects of low dielectric constant and film curing properties can be enhanced; therefore, this is preferable.

[0037] Polymers having structural unit (U1) may also contain structural units (hereinafter also referred to as "other structural units (W1)") that do not have the base represented by formula (1). Examples of other structural units (W1) include: structural units derived from aromatic vinyl compounds, structural units derived from maleimine or N-substituted maleimine compounds, structural units having heterocyclic structures, structural units derived from alkyl methacrylates, structural units having alicyclic structures, structural units having aromatic ring structures, etc.

[0038] As aromatic vinyl compounds, there are no particular limitations, but examples include: styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tert-butoxystyrene, vinylbenzyl dimethylamine, (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, and other styrene-based compounds; vinylnaphthalene, divinylnaphthalene, and other vinylnaphthalene-based compounds; and heterocyclic vinyl compounds such as vinylpyridine. Among these, styrene-based compounds are preferred.

[0039] In a polymer having structural units (U1), the content of structural units derived from aromatic vinyl compounds is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to all structural units in the polymer. Furthermore, the content of structural units derived from aromatic vinyl compounds is preferably 95% by mass or less, more preferably 90% by mass or less, relative to all structural units in the polymer. If the content of structural units derived from aromatic vinyl compounds is within the aforementioned range, it is preferable to suppress the increase of dielectric constant, form a film with excellent heat resistance and solvent resistance, sufficiently satisfy high radiation sensitivity, and achieve a low dielectric constant.

[0040] As N-substituted maleimide compounds, examples include compounds in which the hydrogen atom bonded to the nitrogen atom of maleimide is replaced by a monovalent hydrocarbon group. Examples of such monovalent hydrocarbon groups include: monovalent chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups. Among these, N-substituted maleimide compounds are preferably those having a monovalent cyclic hydrocarbon group, and examples include compounds having an aromatic hydrocarbon group, or monovalent alicyclic hydrocarbon groups containing a monocyclic, bridged, or spirocyclic ring.

[0041] Specific examples of N-substituted maleimide compounds, as compounds having an alicyclic hydrocarbon group, include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, and N-norbornylmaleimide. Examples of compounds with aromatic hydrocarbon groups include N-tricyclodecylmaleimide, N-adamantylmaleimide, etc.; and N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. Regarding N-substituted maleimide compounds, these are preferably selected from at least one group consisting of N-cyclohexylmaleimide, N-(4-methylcyclohexyl)maleimide, N-phenylmaleimide and N-(4-methylphenyl)maleimide, more preferably at least any one of N-cyclohexylmaleimide and N-phenylmaleimide.

[0042] When the polymer having structural unit (U1) has structural units derived from maleimide or N-substituted maleimide compounds, from the viewpoint of achieving a good pattern shape, the content of structural units derived from maleimide or N-substituted maleimide compounds is preferably 1% by mass or more, more preferably 2% by mass or more, relative to all structural units possessed by the polymer. Furthermore, from the viewpoint of suppressing a decrease in developability, the content of structural units derived from maleimide or N-substituted maleimide compounds is preferably 40% by mass or less, more preferably 35% by mass or less, relative to all structural units possessed by the polymer.

[0043] In polymers having structural units (U1), a preferred example of a structural unit having a heterocyclic structure is the structural unit represented by the following formula (7). [Chemistry 11] (In formula (7), R8 is a monovalent group with a heterocyclic structure; RA is a hydrogen atom, methyl, hydroxymethyl, cyano or trifluoromethyl)

[0044] In formula (7), the ring portion of the heterocyclic structure of R8 can be directly bonded to the oxygen atom in formula (7), or it can be bonded via a divalent linker (e.g., an alkyl diester with 1 to 5 carbon atoms). The heterocyclic structure of R8 is more preferably a cyclic ether structure, a cyclic ester structure, a cyclic carbonate structure, a cyclic amide structure, or a cyclic amide imine structure, and is even more preferably a cyclic ether structure.

[0045] Regarding the provision of monoliths of structural units having heterocyclic structures, as compounds having cyclic ether structures, examples include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclic (meth)acrylate [5.2.1.0]. [2,6] Decyl acrylate, (3-methyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl) acrylate, (oxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl acrylate, (tetrahydrofuran-2-yl) acrylate, (tetrahydrofurfuryl) acrylate, (tetrahydropyranyl) acrylate, (5-ethyl-1,3-dioxane-5-yl)methyl acrylate, (1,3-dioxane-5-yl)methyl acrylate, (5-methyl-1,3-dioxane-5-yl) acrylate Oxycarbonyl-5-ylmethyl ester, (meth)acrylate (2-methyl-2-ethyl-1,3-dioxacyclopentan-4-yl) methyl ester, (meth)acrylate (2,2-dimethyl-1,3-dioxacyclopentan-4-yl) methyl ester, (meth)acrylate (2,2-dimethyl-1,3-dioxacyclopentan-4-yl) ethyl ester, 2-(meth)propenyloxymethyl-1,4,6-trioxaspiro[4.6]undecane, 2-(meth)propenyloxymethyl-1,4,6-trioxaspiro[4.4]nonane, 2-(meth)propenyloxymethyl-1,4,6-trioxaspiro[4.5]decane, etc.; Examples of compounds having a cyclic ester structure include (γ-butyrolactone-2-yl) acrylate, (γ-butyrolactone-2-yl) methyl acrylate, and (δ-valerolactone-2-yl) ethyl acrylate. Examples of compounds having a cyclic carbonate structure include glycerol carbonate (meth)acrylates, etc. Examples of compounds having a cyclic amide structure include (meth)acrylate (γ-lactam-2-yl) ester and (meth)acrylate (γ-lactam-2-yl) methyl ester. Examples of compounds having a cyclic acetylide structure include N-(meth)propenylideneoxyethylhexahydrophthalimide.

[0046] When the polymer having structural unit (U1) contains structural units having heterocyclic structures, the content of structural units having heterocyclic structures is preferably 1% by mass or more, more preferably 2% by mass or more, relative to all structural units of the polymer. Furthermore, the content of structural units having heterocyclic structures is preferably 40% by mass or less, more preferably 35% by mass or less, relative to all structural units of the polymer. By setting the content of structural units having heterocyclic structures within the aforementioned range, the sensitivity of this composition can be increased, and the pattern shape of the hardened film after development is good; this is preferable in this respect.

[0047] Structural units derived from alkyl methacrylates are introduced into polymers for purposes such as adjusting the glass transition temperature of the polymer. Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate.

[0048] When a polymer having structural unit (U1) has structural units derived from alkyl (meth)acrylate, the content of structural units derived from alkyl (meth)acrylate relative to all structural units of the polymer can be set to, for example, 1% by mass or more. Furthermore, the content of structural units derived from alkyl (meth)acrylate relative to all structural units of the polymer is preferably 40% by mass or less, more preferably 30% by mass or less.

[0049] Examples of (meth)acrylates with an alicyclic structure include: cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decane-8-yl ester (meth)acrylate, tricyclo[5.2.1.0 2,5]decane-8-yloxyethyl ester (meth)acrylate, and isobornyl (meth)acrylate.

[0050] When a polymer having structural unit (U1) contains structural units derived from (meth)acrylates having an alicyclic structure, the content of structural units derived from (meth)acrylates having an alicyclic structure can be set to, for example, 1% by mass or more, relative to all structural units of the polymer. Furthermore, the content of structural units derived from (meth)acrylates having an alicyclic structure is preferably 30% by mass or less, more preferably 20% by mass or less, relative to all structural units of the polymer. By setting the content of structural units derived from (meth)acrylates having an alicyclic structure within the aforementioned range, a cured film with a well-patterned shape can be obtained.

[0051] Examples of (meth)acrylates having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate. When a polymer having structural unit (U1) contains structural units derived from (meth)acrylates having an aromatic ring structure, the content of structural units derived from (meth)acrylates having an aromatic ring structure relative to all structural units of the polymer can be, for example, set to 1% by mass or more. Furthermore, the content of structural units derived from (meth)acrylates having an aromatic ring structure relative to all structural units of the polymer is preferably 30% by mass or less, more preferably 20% by mass or less.

[0052] Other structural units (W1), besides those described above, may include: structural units derived from unsaturated monomers having an alcoholic hydroxyl group; structural units derived from monomers of unsaturated dialkyl dicarboxylic acid esters (e.g., diethyl itaconic acid), conjugated diene compounds (e.g., 1,3-butadiene, isoprene), nitrogen-containing vinyl compounds (e.g., (meth)acrylonitrile, (meth)acrylamide), vinyl chloride, vinylidene chloride, vinyl acetate, etc. The content of structural units derived from these monomers may be appropriately set according to each compound without impairing the effects of this disclosure.

[0053] Polymers having structural units (U1) can be manufactured, for example, using unsaturated monomers capable of incorporating structural units (U1), in a suitable solvent and in the presence of a polymerization initiator, according to known methods such as free radical polymerization. Examples of polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), and dimethyl 2,2'-azobis(isobutyric acid) ester. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the total monomer used in the reaction. Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably set to 0.1% to 60% by mass relative to the total amount of the reaction solution.

[0054] In polymerization, the reaction temperature is typically 30°C to 180°C. The reaction time varies depending on the type of polymerization initiator and monomer, or the reaction temperature, and is usually 0.5 hours to 10 hours. The polymer obtained through polymerization can be used in the preparation of curable compositions while dissolved in the reaction solution, or it can be used in the preparation of curable compositions after being separated from the reaction solution. There are no particular limitations on the method for separating the polymer; known methods can be used. Examples of methods for polymer separation include: injecting the reaction solution into a large volume of a poor solvent and drying the resulting precipitate under reduced pressure; and removing the precipitate by vacuum distillation using an evaporator.

[0055] Polymers having the structural unit represented by formula (3) As specific examples of the structural unit represented by the above formula (3) (hereinafter also referred to as "structural unit (U2)"), the structural units represented by each of the following formulas (3-1) to (3-9) can be listed. In the following formula (3-8), R 13 is a linear or branched alkyl group having 1 to 4 carbon atoms. [Chemistry 12]

[0056] When polymer (A) is a polymer having structural unit (U2), the content of structural unit (U2) in polymer (A) is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 5 mol% or more, relative to all structural units in polymer (A). Furthermore, the content of structural unit (U2) is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, relative to all structural units in polymer (A).

[0057] Polymers having structural unit (U2) may also contain structural units (hereinafter also referred to as "other structural units (W2)") that do not have the base represented by formula (1). Examples of other structural units (W2) include: structural units derived from aromatic vinyl compounds, structural units derived from maleimine or N-substituted maleimine compounds, structural units having heterocyclic structures, structural units derived from alkyl methacrylates, structural units derived from (meth)acrylates having alicyclic structures, structural units derived from (meth)acrylates having aromatic ring structures, etc. Specific examples of these include compounds identical to those exemplified as other structural units (W1).

[0058] Polymers having structural units (U2) can be manufactured, for example, using monomers capable of incorporating structural units (U2) and other monomers as needed, in a suitable solvent, in the presence of a polymerization initiator, according to known methods such as free radical polymerization. Details of the synthesis method can be followed in the same manner as for polymers having structural units (U1).

[0059] Polymers having the structural unit represented by equation (4) In the structural unit represented by formula (4) (hereinafter also referred to as "structural unit (U3)"), the aromatic ring group represented by Ar 1 is a group formed by removing three hydrogen atoms from the ring portion of an aromatic ring. The aromatic ring can be either a monocyclic or fused ring. Specific examples of aromatic rings constituting the aromatic ring group represented by Ar 1 include: benzene rings, naphthalene rings, anthracene rings, etc. Among these, the aromatic ring constituting the aromatic ring group represented by Ar 1 is preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring. The aromatic ring group represented by Ar 1 may have substituents in the ring portion. Examples of such substituents include: alkyl groups having 1 to 5 carbon atoms, halogen atoms, hydroxyl groups, etc.

[0060] The heterocyclic group represented by Ar 1 is preferably a group formed by removing three hydrogen atoms from the ring portion of an aromatic heterocycle. Examples of such aromatic heterocycles include: nitrogen-containing aromatic heterocycles such as pyrrole, pyridine, pyridazine, pyrimidine, quinoline, isoquinoline, carbazole, and acridine; oxygen-containing aromatic heterocycles such as furan and dibenzofuran; and sulfur-containing aromatic heterocycles such as thiophene. The heterocyclic group represented by Ar 1 may have substituents in the ring portion. Examples of such substituents include: alkyl groups having 1 to 5 carbon atoms, halogen atoms, and hydroxyl groups.

[0061] In terms of the ability to fully obtain improved radiation sensitivity, low dielectric constant of the film, and improved hardening properties, or in terms of the ease of obtaining the compound, Ar 1 is particularly preferably a benzene ring.

[0062] Specific examples of the structural unit (U3) can be listed, for example, the structural units represented by each of the following formulas (4-1) to (4-9). In the following formulas (4-1) to (4-9), R 14 is a straight-chain or branched alkyl group having 1 to 4 carbon atoms. R 15 is a hydrogen atom or a methyl group. [Chemistry 13]

[0063] When polymer (A) is a polymer having structural unit (U3), the content of structural unit (U3) in polymer (A) is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 5 mol% or more, relative to all structural units in polymer (A). Furthermore, the content of structural unit (U3) is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, relative to all structural units in polymer (A). With the content of structural unit (U3) within the aforementioned range, high radiation sensitivity can be sufficiently satisfied, and the improvement effects of low dielectric constant and film hardening properties are enhanced; therefore, this is preferable.

[0064] Polymers having structural unit (U3) can be obtained, for example, by a method comprising: reacting phenols (e.g., phenol, cresol, etc.) with aldehydes (e.g., formaldehyde, paraformaldehyde, etc.) to obtain a polymer (phenolic varnish resin); reacting the obtained polymer with a reactive compound having an acetylene group to obtain a polymer having an acetylene group in the side chain; and reacting the polymer having an acetylene group in the side chain with a metal compound to convert it into acetylene metal, followed by a reaction with carbon dioxide.

[0065] Regarding the reaction between phenols and aldehydes, examples include heating phenols and aldehydes in an organic solvent in the presence of a catalyst at 50°C to 200°C. The reaction ratio of phenols to aldehydes is not particularly limited; for example, 0.3 to 1 mol of aldehydes can be used relative to 1 mol of phenols.

[0066] Examples of catalysts include: organic acids, phosphoric acid, organophosphonic acid, transition metal salts, and basic catalysts. Examples of organic acids include: acetic acid, oxalic acid, formic acid, and lactic acid. Examples of organophosphonic acids include: ethylenediaminetetramethylenephosphonic acid and ethylenediaminedimethylenephosphonic acid. Examples of transition metal catalysts include: inorganic salts and organic acid salts of transition metals such as titanium, iron, zinc, nickel, cobalt, and copper. Examples of basic catalysts include: sodium hydroxide, lithium hydroxide, potassium hydroxide, triethylamine, and sodium carbonate. Examples of organic solvents include: alcohols, ketones, esters, and ethers.

[0067] As a reactive compound having an acetylene group, there is no particular limitation as long as it is a compound having a functional group (equivalent to a second functional group) that reacts with the hydroxyl group (equivalent to the first functional group) of the polymer and an acetylene group. Examples of such reactive compounds include epoxides, halides, and isocyanate compounds having an acetylene group. Examples of such metal compounds include salts (nitrates, sulfates, etc.) or halides (silver iodide, copper iodide, etc.) of metals such as lithium, sodium, potassium, copper, silver, and gold. The content of the group represented by formula (1) in the polymer having the structural unit (U3) can be adjusted to a desired value by adjusting the conversion rate of the carboxyl group.

[0068] In the polymer having structural unit (U3), the content of structural unit (U3) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, relative to all structural units contained in polymer (A). Furthermore, the content of structural unit (U3) is preferably 95 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, relative to all structural units contained in polymer (A).

[0069] Furthermore, polymers having the structural unit (U3) can also be obtained, for example, by polymerizing phenols with acetylene groups, reacting the acetylene groups of the resulting polymer with a metal compound, and then reacting it with carbon dioxide. Alternatively, polymers having the structural unit (U3) can also be obtained by reacting polymers with acetylene groups on their side chains with carbon dioxide in the presence of silver iodide and cesium carbonate.

[0070] Polymers having the structural unit represented by equation (5) In the structural unit represented by formula (5) (hereinafter also referred to as "structural unit (U4)"), the group represented by Ar2 is preferably a group that is bonded to Y1 or Y2 in formula (5) using the same or different aromatic rings or heterocycles. When Ar2 is a group having an aromatic ring, specific examples of the aromatic ring include benzene rings, naphthalene rings, biphenyl rings, etc., preferably benzene rings or biphenyl rings. When Ar2 is a group having a heterocycle, the heterocycle is preferably an aromatic heterocycle, for example, pyrrole rings, pyridine rings, pyridazine rings, pyrimidine rings, etc. The aromatic ring and heterocycle of Ar2 may have substituents in the ring portion. Examples of substituents include alkyl groups having 1 to 5 carbon atoms, phenyl groups, halogen atoms, etc.

[0071] Ar 2 is preferably derived from bisphenols, dithiols, or diamines. Examples of bisphenols include bisphenol A, bisphenol B, bisphenol E, bisphenol F, and bisphenol P. Examples of dithiols include 1,6-naphthalenedithiol, 1,5-naphthalenedithiol, 1,3-benzenedithiol, and bis(4-mercaptophenyl)sulfide. Examples of diamines include diaminodiphenyl ether, 9,9-bis(4-aminophenol)fluorene, 2,2-bis(4-aminophenol)hexafluoropropane, and 2,2-bis(trifluoromethyl)benzidine.

[0072] As a specific example of structural unit (U4), the structural units represented by equations (5-1) to (5-10) can be listed below. [Chemistry 14] [Chemistry 15]

[0073] When polymer (A) is a polymer having structural unit (U4), the content of structural unit (U4) in polymer (A) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all structural units in polymer (A).

[0074] Polymers having structural unit (U4) can be obtained, for example, by a method comprising: reacting a bisphenol with a halogenated cyanurate (preferably a chlorocyanurate) having an acetylene group to obtain a polymer having an acetylene group in the side chain; and reacting the polymer having an acetylene group in the side chain with a metal compound to convert it into acetylene metal, followed by reacting it with carbon dioxide. Alternatively, polymers having structural unit (U4) can also be obtained by reacting a polymer having an acetylene group in the side chain with carbon dioxide in the presence of silver iodide and cesium carbonate.

[0075] Regarding the reaction between bisphenols and halocyanurates, methods such as polycondensation of bisphenols and halocyanurates in an aqueous sodium hydroxide solution can be cited. The reaction ratio of bisphenols to halocyanurates is not particularly limited; for example, 0.5 to 1.5 mol of halocyanurates can be used relative to 1 mol of bisphenols. The preferred reaction temperature for polymerization is -10°C to 50°C, more preferably -5°C to 30°C. The preferred reaction time is 0.5 to 24 hours.

[0076] Subsequently, the metal compound is reacted with a polymer having acetylene groups in the side chains obtained through the aforementioned polycondensation to generate acetylene metal, which is then reacted with carbon dioxide. This yields a polymer (triazine polymer) having the group represented by formula (1) in the side chains (more specifically, R1 is a hydrogen atom group). The details of the reaction can be carried out in the same manner as for polymers having structural unit (U3). The content of the group represented by formula (1) in the polymer can be adjusted to a desired value by adjusting the conversion rate of the carboxyl groups.

[0077] In a polymer having a structural unit (U4), the content of the structural unit (U4) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, relative to all the structural units of the polymer (A).

[0078] Polymers having the structural unit represented by equation (6) In the case where polymer (A) is a polymer having the structural unit represented by the formula (6) (hereinafter also referred to as "structural unit (U5)"), the polymer can be obtained, for example, by a method comprising: obtaining a polymer selected from the group consisting of polyamides, polyamide esters and polyimides (hereinafter also referred to as "polyimide polymers") by polycondensation of a tetracarboxylic acid derivative with a diamine compound containing a diamine having an ethynyl group; and reacting the obtained polyimide polymer (i.e., a polyimide polymer having an ethynyl group in the side chain) with a metal compound, followed by a reaction with carbon dioxide.

[0079] When synthesizing polymers having a structural unit (U5), the tetracarboxylic acid derivative used can be suitably selected from compounds known as tetracarboxylic acid derivatives for the synthesis of polyimide polymers. Here, in this specification, "tetracarboxylic acid derivative" means including tetracarboxylic dianhydrides, tetracarboxylic acid diesters, and tetracarboxylic acid diester dihalides.

[0080] As diamines having an ethynyl group, examples include compounds represented by each of the formulas (6-1) to (6-4). [Chemistry 16]

[0081] When synthesizing polymers having the structural unit (U5), other diamines may also be used as diamine compounds in conjunction with diamines having an ethynyl group. There are no particular limitations on the other diamines; suitable compounds may be selected from those known as diamine compounds for the synthesis of polyimide polymers (e.g., aliphatic diamines, alicyclic diamines, aromatic diamines, etc.).

[0082] From the viewpoint of fully satisfying high radiation sensitivity and fully obtaining the effect of improving the dielectric constant and film hardening properties when synthesizing polymers having structural units (U5), the proportion of diamines with ethynyl groups used is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 30 mol% or more, relative to the total amount of diamine compounds used to synthesize the polymer.

[0083] Polyimide polymers can be obtained by reacting a tetracarboxylic acid derivative with a diamine compound and, if desired, a molecular weight modifier (e.g., anhydride, monoamine compound, etc.). During the synthesis reaction, the preferred ratio of the tetracarboxylic acid derivative to the diamine compound is 0.7 to 1.2 mol of anhydride or carboxyl group in the tetracarboxylic acid derivative relative to the amino group of the diamine compound.

[0084] The synthesis reaction of polyimide polymers is preferably carried out in an organic solvent. The preferred reaction temperature is -20°C to 150°C, and the preferred reaction time is 0.1 hours to 24 hours. Examples of organic solvents used in the reaction include: aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The amount of organic solvent used is preferably 0.1% to 50% by mass of the total amount of the tetracarboxylic dianhydride and diamine compound relative to the total amount of the reaction solution.

[0085] Polyimides can be obtained, for example, by dehydrating and ring-closing polyamide and then amide-imidizing it. The dehydration and ring-closing of polyamide can be carried out, for example, by adding a dehydrating agent (e.g., acetic anhydride, etc.) and a dehydration and ring-closing catalyst (e.g., tertiary amine, etc.) to a polymer solution obtained by dissolving polyamide in an organic solvent, and heating as needed.

[0086] Subsequently, the polyimide polymer with acetylene groups on its side chains is reacted with a metal compound to generate acetylene metal, which is then reacted with carbon dioxide. Alternatively, the polyimide polymer with acetylene groups on its side chains is reacted with carbon dioxide in the presence of silver iodide and cesium carbonate, thereby obtaining a polymer having structural unit (U5). This yields a polyimide polymer having the group represented by formula (1) on its side chains (more specifically, R1 is a hydrogen atom group). The details of the reaction can be carried out in the same manner as for the polymer having structural unit (U3). The content of the group represented by formula (1) in the polyimide polymer can be adjusted by changing the conversion rate of the carboxyl group.

[0087] In a polymer having structural unit (U5), in terms of satisfying high radiation sensitivity and sufficiently improving low dielectric constant and film curability, the content of structural unit (U5) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, relative to all structural units of polymer (A).

[0088] Regarding polymer (A), the weight-average molecular weight (Mw) of polystyrene obtained by gel permeation chromatography (GPC) is preferably 1,000 or more. If Mw is 1,000 or more, a hardened film with sufficiently high heat resistance and good developability can be obtained, which is preferable in this respect. Mw is more preferably 2,000 or more, and even more preferably 3,500 or more. Furthermore, from the viewpoint of achieving good film-forming properties, Mw is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 70,000 or less.

[0089] Furthermore, the molecular weight distribution (Mw / Mn) represented by 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.

[0090] Furthermore, when a low-molecular-weight component is formulated into this composition as compound (A), compound (A) may be contained in the composition as a crosslinking agent. In this case, the polymeric component formulated into the composition together with compound (A) is not particularly limited. Examples of such polymeric components include (meth)acrylic polymers, styrene polymers, styrene-maleimide polymers, phenolic resins, phenolic varnish resins, triazine polymers, polycarbonate polymers, and polyimide polymers.

[0091] <(B) Component: Solvent> This composition is preferably a liquid composition formed by dissolving or dispersing component (A) and other components formulated as needed in a solvent. The solvent is preferably an organic solvent that dissolves each component in the composition and does not react with any of the components.

[0092] Specific examples of solvents 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, ethylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; acetamides 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, the solvent is preferably at least one selected from the group consisting of ethers and esters, more preferably at least one selected from the group consisting of ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates.

[0093] <Other Ingredients> In addition to components (A) and (B) described above, this composition may also contain other components (hereinafter also referred to as "other components").

[0094] (C) Composition: Radiosensitive linear compound While this composition can form a hardened film by including compound (A), it may also contain a radiosensitive linear compound as a photosensitizer along with component (A). By including the radiosensitive linear compound in this composition, irradiating the composition with radiation (visible light, ultraviolet light, far ultraviolet light, etc.) can form positive or negative patterns. Examples of radiosensitive linear compounds include photoacid generators, free radical polymerization initiators, and photobase generators. Among these, at least one selected from the group consisting of quinone diazide compounds, photoacid generators, and free radical polymerization initiators is preferably used as the radiosensitive linear compound.

[0095] Here, when using a photoacid generator or a photoalkali generator as a radiosensitive linear compound, positive or negative patterns can be formed by changing the solubility of the exposed portion relative to the developer. Alternatively, when the photoacid generator or photoalkali generator functions as a curing catalyst, the solubility of the exposed portion relative to the developer decreases as curing is promoted, thereby forming a negative pattern. On the other hand, when using a free radical polymerization initiator as a radiosensitive linear compound, for example, curing of the exposed portion can be promoted by reacting with compounds having vinyl or (meth)acrylic groups, reducing the solubility of the exposed portion relative to the developer, thereby forming a negative pattern.

[0096] [quinone diazide compounds] Quinone diazide compounds are compounds that produce carboxylic acids upon irradiation with radiation. Examples of quinone diazide compounds include condensates of phenolic or alcoholic compounds (hereinafter also referred to as "cores") with o-naphthoquinone diazide compounds. Among these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the core and an o-naphthoquinone diazide compound. Specific examples of cores include the compounds described in paragraphs 0065 to 0070 of Japanese Patent Application Publication No. 2014-186300.

[0097] Specific examples of quinone diazide compounds include compounds containing phenolic hydroxyl groups selected from 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and ester compounds with 1,2-naphthoquinone diazide-4-sulfonyl chloride or 1,2-naphthoquinone diazide-5-sulfonyl chloride.

[0098] When using a quinone diazide compound as a radiosensitive linear compound, the content of the quinone diazide compound in this composition is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the polymer component. Furthermore, the content of the quinone diazide compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the polymer component. Setting the content of the quinone diazide compound to 2 parts by mass or more allows for sufficient generation of carboxylic acids by irradiating the composition with radiation, thus significantly increasing the difference in solubility between the irradiated and unirradiated portions of the developer. This allows for good patterning. Additionally, increasing the amount of carboxylic acids participating in the reaction with the polymer component ensures adequate heat resistance and solvent resistance. On the other hand, setting the content of the quinone diazide compound to 50 parts by mass or less significantly reduces the amount of unreacted quinone diazide compound after exposure, suppressing the decrease in developability caused by the residue of quinone diazide compound, which is preferable in this respect.

[0099] [Photoacid generator] Photoacid generators are any compounds that generate acid in response to radiation (i.e., radiosensitive acid generators), and there are no particular limitations. Examples of photoacid generators include: oxime sulfonates, onium salts, sulfonimides, halogenated compounds, diazomethane compounds, sulfonates, and carboxylic acid esters.

[0100] Specific examples of oxime sulfonate compounds, onium salts, sulfonamide compounds, halogenated compounds, diazomethane compounds, sulfonate compounds, and carboxylic acid ester compounds include compounds described in paragraphs 0078 to 0106 of Japanese Patent Application Publication No. 2014-157252 and compounds described in International Publication No. 2016 / 124493. As a photoacid generator, from the viewpoint of radiation sensitivity, at least one selected from the group consisting of oxime sulfonate compounds and sulfonamide compounds is preferably used.

[0101] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (8). [Chemistry 17] (In formula (8), R9 is a monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted by a substituent; "*" indicates a bond)

[0102] In formula (8), the monovalent hydrocarbon group of R9 can be, for example, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 4 to 12 carbon atoms, or an aryl group with 6 to 20 carbon atoms. The substituent can be, for example, an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, a side oxygen group, or a halogen atom.

[0103] Examples of oxime sulfonate compounds include: (5-propylsulfoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, [2-[2-(4-methylphenylsulfoxyimino)]-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile, 2-(octylsulfoxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493, etc. Commercially available oxime sulfonate compounds include Irgacure PAG121 manufactured by BASF.

[0104] Examples of sulfonamide compounds include: N-(trifluoromethylsulfonoxy)succinimide, N-(camphorsulfonoxy)succinimide, N-(4-methylphenylsulfonoxy)succinimide, N-(2-trifluoromethylphenylsulfonoxy)succinimide, N-(4-fluorophenylsulfonoxy)succinimide, N-(trifluoromethylsulfonoxy)phthalimide, N-(camphorsulfonoxy)phthalimide, etc. N-(2-trifluoromethylphenylsulfonyl)phthalimide, N-(2-fluorophenylsulfonyl)phthalimide, N-(trifluoromethylsulfonyl)diphenylmaleimide, N-(camphorsulfonyl)diphenylmaleimide, N-(4-methylphenylsulfonyl)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalenedimethimide.

[0105] When using a photoacid generator as a radiosensitive linear compound, the content of the photoacid generator in the composition 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, relative to 100 parts by mass of the polymer component. Furthermore, the content of the photoacid generator is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the polymer component. Setting the content of the photoacid generator to 1 part by mass or more allows for good patterning and sufficiently ensures heat resistance and solvent resistance, which is preferable in this respect. Additionally, setting the content of the photoacid generator to 50 parts by mass or less sufficiently reduces the amount of unreacted photoacid generator after exposure, suppressing the decrease in developability caused by the residue of the photoacid generator, which is preferable in this respect.

[0106] [Free radical polymerization initiator] Free radical polymerization initiators are compounds that can sense radiation and generate free radicals, thus initiating polymerization (i.e., radiosensitive linear free radical polymerization initiators). There are no particular limitations on free radical polymerization initiators; examples include O-acetyl oxime compounds, acetophenone compounds, and biimidazole compounds.

[0107] Examples of O-acetylated oxime compounds include: 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)], 1,2-octanedione 1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), and acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetylated) Oxime), 1-(9-ethyl-6-benzoyl-9H-carbazole-3-yl)-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazole-3-yl]-ethyl Alkyl-1-one oxime-O-benzoate, acetone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetylgoxime), acetone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetylgoxime), acetone -1-〔9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl〕-1-(O-acetylgoxime), acetone-1-〔9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxane ...

[0108] Examples of acetophenone compounds include, for example, α-aminoketone compounds and α-hydroxyketone compounds. Specific examples of these include, for α-aminoketone compounds, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one. Examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, and 1-hydroxycyclohexylphenyl ketone.

[0109] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. Among these, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferred.

[0110] Regarding free radical polymerization initiators, O-acyloxime compounds are preferably used. When using a free radical polymerization initiator as a radiosensitive linear compound, the content of the free radical polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the polymer component contained in the composition. Furthermore, the content of the free radical polymerization initiator is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the polymer component. By setting the content of the free radical polymerization initiator within the aforementioned range, good curing properties, etc., can be achieved.

[0111] (D) Ingredients: Sealing aid Adhesion enhancers are components that improve the adhesion between the cured film formed using the curing composition and the substrate. As adhesion enhancers, functionalized silane coupling agents having reactive functional groups are preferably used. Examples of reactive functional groups in functionalized silane coupling agents include: carboxyl groups, (meth)acrylic groups, epoxy groups, vinyl groups, isocyanate groups, etc.

[0112] Specific examples of functional coupling agents include: trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)propenyloxypropyltrimethoxysilane, 3-(meth)propenyloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanopropyltriethoxysilane, etc.

[0113] When a bonding agent is incorporated into the composition, the content of the bonding agent is preferably 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the polymer component incorporated into the composition.

[0114] (E) Components: Cross-linked compounds Crosslinking compounds typically have multiple crosslinking groups within a single molecule. Furthermore, the crosslinking compound does not contain compound (A). Examples of crosslinking groups found in crosslinking compounds include vinyl, (meth)acrylic, and hydroxymethylphenyl groups. Among these, vinyl and (meth)acrylic groups are preferred. By using a compound having two or more such crosslinking groups in conjunction with a free radical polymerization initiator, the curing of the exposed portion can be promoted, and negative patterns can be formed efficiently.

[0115] As a crosslinking compound, polyfunctional (meth)acrylates are preferably used, such as difunctional (meth)acrylates and trifunctional or higher (meth)acrylates. Specific examples of these include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, and 1,9-nonanediol dimethacrylate.

[0116] Examples of trifunctional or higher (meth)acrylates include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloxyethyl)phosphate, succinic acid modified pentaerythritol tri(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, carboxyl-containing polyacid-modified (meth)acrylate oligomers, and other polyfunctional carbamate acrylate compounds obtained by reacting compounds having straight-chain alkylene and alicyclic structures and having two or more isocyanate groups with compounds having one or more hydroxyl groups and having three, four or five (meth)acryloxy groups.

[0117] The crosslinking compound may also be a polymer (except for polymer (A)). Examples of such polymers include polymers that contain structural units having (meth)acrylic or vinyl groups and do not have the group represented by formula (1).

[0118] When a crosslinking compound is incorporated into this composition, the content of the crosslinking compound is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, relative to 100 parts by mass of the polymer component incorporated into the composition. Furthermore, the content of the crosslinking compound is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, relative to 100 parts by mass of the polymer component. By setting the content of the crosslinking compound in this composition to the aforementioned range, the heat resistance or chemical resistance of the obtained cured film can be improved more effectively.

[0119] Other components, besides those described above, may include, for example, acid diffusion control agents, dehydrating agents (e.g., orthoester compounds), surfactants (fluorinated surfactants, silicone surfactants, nonionic surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, etc. The proportions of these components can be appropriately selected based on the individual components without compromising the effectiveness of this disclosure.

[0120] The concentration of solids in this composition (the proportion of the total mass of the curing composition, excluding the solvent, relative to the total mass of the curing composition) can be appropriately selected considering factors such as viscosity and volatility. The concentration of solids in the curing composition is preferably in the range of 5% to 60% by mass. If the concentration of solids is 5% by mass or more, sufficient film thickness can be ensured when the curing composition is coated onto a substrate. Furthermore, if the concentration of solids is 60% by mass or less, the film thickness will not be excessive, thereby moderately increasing the viscosity of the curing composition and ensuring good coatability. The concentration of solids in the curing composition is more preferably 10% to 55% by mass, and more preferably 12% to 50% by mass.

[0121] Hardened films and their manufacturing methods The hardened film disclosed herein is formed from a hardenable composition prepared in the manner described. This composition exhibits high radiation sensitivity and excellent photolithography properties. Furthermore, the film formed using this composition has a low dielectric constant and excellent hardening properties. Therefore, this composition is preferably used, for example, as a forming material for interlayer insulating films, planarization films, spacers, protective films, colored patterned films for color filters, isolation walls, and banks.

[0122] This composition allows for the formation of positive or negative hardened films, depending on the type of radiosensitive linear compound incorporated into it. The hardened film can be manufactured using this composition, for example, by a method comprising steps 1 through 4 below. (Step 1) The step of forming a coating film using a curing composition. (Step 2) The step of irradiating at least a portion of the coating with radiation. (Step 3) The step of developing the coating that has been irradiated with radiation. (Step 4) Heating the developed coating. The following is a detailed explanation of each step.

[0123] [Step 1: Coating Step] In this step, the curable 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. For example, in the case of forming an interlayer insulating film, the curable composition is coated onto a substrate on which switching elements such as thin-film transistors (TFTs) are provided to form a coating. As the substrate, for example, a glass substrate, a silicon substrate, or a resin substrate can be used. A metal thin film, depending on the application, may also be formed on the surface of the substrate on which the coating is formed, and various surface treatments such as hexamethyldisilazane (HMDS) treatment may be performed.

[0124] Examples of coating methods for the curing composition include spraying, roller coating, spin coating, slot die coating, rod coating, and inkjet coating. Among these methods, spin coating, slot die coating, or rod coating are preferred. Pre-baking conditions vary depending on the type and proportion of each component in the curing composition, and for example, are performed 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 0.1 μm to 12 μm. For the curing composition coated on the film-forming surface, vacuum drying (VCD) can also be performed before pre-baking.

[0125] [Step 2: Exposure Step] In this step, at least a portion of the coating film formed in step 1 is irradiated with radiation. At this time, the coating film is irradiated with radiation through a photomask with a predetermined pattern, thereby forming a patterned hardened film. 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, for example, gamma rays (wavelength 436 nm) or i-rays (wavelength 365 nm) or gamma rays, h-rays, and i-rays (wavelengths 436 nm, 405 nm, and 365 nm). The exposure dose of the radiation is preferably 0.1 J / m² to 20,000 J / m².

[0126] [Step 3: Development Step] In this step, the coating film irradiated with radiation in step 2 is developed. When performing positive development (removing the irradiated portion by developing with a developing solution) or negative development (removing the non-irradiated portion by developing with a developing solution) on the coating film irradiated with radiation in step 2, the developing solution may include, for example, an aqueous solution of an alkali (alkaline compound). Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and [the paragraph in Japanese Patent Application Publication No. 2016-145913].

[0127] The alkali exemplified herein. From the viewpoint of obtaining adequate developability, the alkali concentration of the aqueous solution is preferably 0.1% to 5% by mass.

[0127] Suitable development methods include liquid coating, immersion, shaking immersion, and spraying. The development time also varies depending on the composition of the composition, for example, from 30 to 120 seconds. Furthermore, it is preferable to perform a rinsing treatment with running water after the development step on the patterned coating.

[0128] [Step 4: Heating Step] In this step, the developed coating from step 3 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. For example, when heating on a hot plate, the heating time is 5 to 40 minutes; when heating in an oven, the heating time is 10 to 80 minutes. Performing this as described above, a hardened film with a target pattern can be formed on the substrate. The shape of the pattern in the hardened film is not particularly limited; examples include line and space patterns, dot patterns, hole patterns, and grid patterns.

[0129] Furthermore, it is believed that the residual carboxyl groups in the obtained hardened film are the main reason for the increased dielectric constant of the hardened film. In this regard, it is believed that when the hardened film is formed by a curing composition containing compound (A), the solubility of the film relative to the developer is increased by the carboxyl groups during development. On the other hand, the carboxyl groups are removed by heating (more specifically, post-baking) during the formation of the hardened film, and the unsaturated bonds after removal contribute to the cross-linking reaction, thereby forming a film with good photolithographic properties, low dielectric constant and excellent curing properties.

[0130] Semiconductor Components and Printed Substrates The semiconductor device disclosed herein includes a hardened film formed using the curing composition. The hardened film is preferably an interlayer insulating film that insulates the wirings within the semiconductor device. The semiconductor device of this disclosure can be manufactured using known methods. Additionally, the printed circuit board of this disclosure includes a hardened film formed using the curing composition. The printed circuit board can be a printed wiring board with conductor wiring (before mounting) or a printed circuit board with electronic components mounted. Furthermore, the printed circuit board of this disclosure can include the semiconductor device of this disclosure, thereby including the hardened film formed using the curing composition.

[0131] Display Components The display element disclosed herein includes a hardened film formed using the curing composition. Furthermore, the display element of this disclosure includes the semiconductor element of this disclosure, thereby including the hardened film formed using the curing composition. Additionally, the display element of this disclosure may also include a planarization film formed on a TFT substrate as the hardened film formed using the curing composition. Examples of display elements include liquid crystal display elements and organic electroluminescence (EL) display elements. [Example]

[0132] The present invention will be specifically described below through examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" and "%" in the examples and comparative examples are quality standards.

[0133] In this embodiment, each measurement is performed using the following method. (Nuclear Magnetic Resonance (NMR)) was measured using a 400 MHz proton NMR spectrometer manufactured by Nippon Spectrophotometer. For the sample, it was suitable to solidify it by reprecipitation, vacuum dry it, and then dissolve it in dimethyl sulfoxide (DMSO-d7) for analysis. (Weight average molecular weight) is the converted value of polystyrene determined by gel permeation chromatography under the following conditions. Tube column: Manufactured by Tosoh (stock), TSKgelGRCXLII Solvent: Tetrahydrofuran Temperature: 40℃ Pressure: 68 kgf / cm² (Acid value) was determined using an automatic potentiometric titration apparatus (AT-510) manufactured by Kyoto Electronics Industry Co., Ltd., and titrated with 0.1 mol / L ethanol-based KOH.

[0134] 1. Synthesis of monomers [Synthesis example 1] Compound (2M-1) was synthesized as per procedure 1. 30.48 g of copper iodide, 22.12 g of potassium carbonate, and 59.08 g of tetrabutylammonium iodide were added to a 500 mL three-necked flask containing a reflux tube, a nitrogen inlet tube, and a thermometer. The mixture was then subjected to three separate nitrogen purgings. Next, 120 mL of dehydrated acetonitrile, 39.9 mL of tert-butyl propargylate, and 22.5 mL of 4-vinylbenzyl chloride were added using a syringe. The mixture was stirred at 40 °C for 10 hours. After the reaction was complete, 800 mL of ethyl acetate was added. The mixture was then washed four times with 400 mL of saturated ammonium chloride aqueous solution and three times with 200 mL of water. The mixture was then dried over magnesium sulfate and concentrated. Next, the compound (2M-1) was purified, concentrated, and vacuum dried using a silica column (eluent: hexane 100 → hexane: ethyl acetate = 90:10 (vol / vol)) to obtain 32 g of a pale orange viscous liquid. [Chemistry 18]

[0135] [Synthesis example 2] To a 1 L three-necked flask containing a dropping funnel, a nitrogen inlet tube, and a thermometer, 35.0 g of propargyl acid, 500 mL of dichloromethane, and 0.65 g of p-toluenesulfonic acid pyridinium salt were added, and the mixture was cooled to below 5°C in an ice bath. Next, 46.0 g of 2,3-dihydrofuran was slowly added dropwise, and the mixture was brought back to room temperature and stirred for 24 hours. After the reaction was complete, the mixture was washed three times with a saturated sodium bicarbonate aqueous solution and three times with water. The organic layer was then dried with magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 73.5 g of compound (2M-2-1). [Chemistry 19]

[0136] [Synthesis example 3] Compound (2M-2) was synthesized as per procedure 3. 30.48 g of copper iodide, 22.12 g of potassium carbonate, and 59.08 g of tetrabutylammonium iodide were added to a 500 mL three-necked flask containing a nitrogen inlet tube, a cooling tube, and a thermometer. The mixture was then subjected to three separate nitrogen purgings. Next, 120 mL of dehydrated acetonitrile, 48.8 g of compound (2M-2-1), and 22.5 mL of 4-vinylbenzyl chloride were added using a syringe. The mixture was stirred at 40 °C for 10 hours. After the reaction was complete, 800 mL of ethyl acetate was added. The mixture was then washed four times with 400 mL of saturated ammonium chloride aqueous solution and three times with 200 mL of water. The mixture was then dried over magnesium sulfate and concentrated. Next, the compound (2M-2) was purified, concentrated, and vacuum dried by a silicon dioxide column (eluent: hexane 100 → hexane: ethyl acetate = 90:10 (vol / vol)) to obtain 35 g of a pale orange viscous liquid. [Chemistry 20]

[0137] [Synthesis example 4] The synthesis of the HB catalyst was carried out according to *Organic Letters*, Vol. 8, No. 19, pp. 4315-4318. 18.4 g of norbornene, 200 mL of 1,2-dichloroethane, and 12.6 g of tert-butyl propynate were added to a 1 L three-necked flask containing a nitrogen inlet tube, a reflux tube, and a thermometer. Then, 3.4 g of the HB catalyst was added, and the reaction was carried out at 55 °C for 20 hours. After the reaction was completed, the mixture was concentrated and passed through a silicon dioxide column (expanding solvent: hexane 100 to hexane:ethyl acetate = 80:20) to obtain 15 g of the target compound (compound (3M-1)) as a brown oil. [Chemistry 21]

[0138] 2. Polymer Manufacturing [Synthesis Example 5] To a 200 mL three-necked flask including a reflux tube, a nitrogen inlet tube, and a thermometer, 30 g (60 parts by mass) of compound (2M-1), 20 g (40 parts by mass) of styrene, 125 g of propylene glycol monomethyl ether, and 4.0 g (8 parts by mass) of 2,2'-azobis(2,4-dimethylpentanonitrile) were added, and nitrogen bubbling was performed for 30 minutes. The mixture was then heated to 80 °C and stirred for 4 hours to obtain a polymer solution. Next, the polymer solution was injected into 1.5 L of methanol, the resulting precipitate was recovered by filtration, and the solution was vacuum dried to obtain 45 g of polymer powder. Then, to a 1 L round-bottom flask including a nitrogen inlet tube, 45 g of the obtained polymer powder, 200 mL of dichloromethane, and 100 mL of trifluoroacetic acid were added, and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the solution was concentrated and dried. Then, 180 mL of propylene glycol monomethyl ether was used for two solvent replacements to obtain 128 g of a polymer (2P-1) solution with a solid content of 30%. The Mw of the polymer (2P-1) was 8,000. [Chemistry 22]

[0139] [Synthetic Examples 6-9 and Comparative Synthetic Examples 1-3] Polymerization and deprotection were performed in the same manner as in Synthesis Example 5, using the compositions shown in Table 1. However, polymer (2P-5) was not deprotected (for chemical amplification). Furthermore, the polymerization of Comparative Synthesis Examples 1 to 3 was compared using the compositions shown in Table 1.

[0140] [Table 1] Synthesis example polymer components Compound 1 Compound 2 Compound 3 Compound 4 type content (parts by weight) type content (parts by weight) type content (parts by weight) type content (parts by weight) Synthesis example 5 2P-1 2M-1 60.0 N-1 40.0 - - - - Synthesis example 6 2P-2 3M-1 48.6 N-3 39.5 N-1 11.9 - - Synthesis Example 7 2P-3 2M-1 44.8 N-1 25.7 N-2 5.3 N-4 24.2 Synthesis example 8 2P-4 2M-1 52.4 N-5 47.6 - - - - Synthesis example 9 2P-5 2M-2 52.6 N-1 47.4 - - - - Comparative Synthesis Example 1 2P-6 N-2 26.2 N-1 73.8 - - - - Comparative Synthesis Example 2 2P-7 N-2 13.4 N-1 40.7 N-4 45.9 - - Comparative Synthesis Example 3 2P-8 N-2 11.3 N-1 3.4 N-5 43.3 N-6 50.0

[0141] The details of the abbreviations of the compounds in Table 1 are as follows. N-1: Styrene N-2: Methacrylic acid N-3:N-Phenylamimine N-4: 3,4-Epoxycyclohexyl methyl methacrylate N-5: Dicyclopentyl methacrylate N-6: Glycidyl methacrylate

[0142] [Synthesis Example 10] Synthesis of polymer (4P-1-1) 100 parts of phenol, 100 parts of propylene glycol monomethyl ether acetate, and 50 parts of paraformaldehyde were charged into a reaction apparatus including a condenser, thermometer, and stirrer. 2 parts of oxalic acid were added, and the mixture was heated to 120°C while undergoing dehydration. After reacting for 5 hours, a polymer (4P-1-1) with the following structural unit was obtained. The weight-average molecular weight (Mw) of the obtained polymer (4P-1-1) was 7,000. [Chemistry 23]

[0143] [Synthesis Example 11] Synthesis of polymer (4P-1-2) 10.7 g of polymer (4P-1-1), 27.6 g of potassium carbonate, and 100 mL of N,N-dimethylacetamide were added to a 300 mL three-necked flask containing a reflux tube, thermometer, and nitrogen inlet tube. The mixture was stirred at room temperature for 30 minutes. Then, 23.8 g of propargyl bromide was added, and the reaction was carried out at 50 °C for 6 hours. After the reaction was complete, 500 mL of ethyl acetate was added, and the mixture was washed three times with water. The organic layer was then concentrated to 100 mL. The precipitate formed by injecting 1 L of methanol was recovered by filtration and dried to obtain 13.1 g of polymer (4P-1-2). [Chemistry 24]

[0144] [Synthesis Example 12] Synthesis of polymer (4P-1) 13.1 g of polymer (4P-1-2), 450 mL of N,N-dimethylformamide, 0.20 g of silver iodide, and 16.5 g of cesium carbonate were added to a 300 mL three-necked flask containing a thermometer and a nitrogen inlet tube. Carbon dioxide was then introduced. A balloon displaced by carbon dioxide was then attached, and the mixture was stirred at room temperature for 20 hours. After the reaction was complete, the precipitate formed by adding 4 L of water was filtered, washed with water and methanol, and then dried under vacuum to obtain 13.6 g of polymer (4P-1). The conversion rate of carboxylic acid, determined by potassium hydroxide titration, was 30%. The Mw of polymer (4P-1) was 7,500. [Chemistry 25]

[0145] [Synthesis Example 13] Synthesis of compound (5P-1-1) The compound (5P-1-1) was synthesized according to the method described in Soft Matter, 2009, Volume 5, page 1863. [Chemistry 26]

[0146] [Synthesis Example 14] Synthesis of polymer (5P-1-2) To a 500 mL three-necked flask equipped with a mechanical stirrer, nitrogen inlet tube, and thermometer, 22.9 g of bisphenol A, 8.4 g of sodium hydroxide, 72 mL of water, 20.4 g of compound (5P-1-1), 150 mL of chloroform, and 0.4 g of octadecyltrimethylammonium chloride were added. The mixture was cooled to below 10 °C and stirred vigorously for 2 hours. After the reaction was complete, the product was reprecipitated in 1 L of methanol, then recovered by filtration and dried under vacuum to obtain 32.3 g of a white powder of polymer (5P-1-2). Mw: 18,000. [Chemistry 27]

[0147] [Synthesis Example 15] Synthesis of polymer (5P-1) To a 300 mL three-necked flask containing a thermometer and a nitrogen inlet tube, 32.3 g of polymer (5P-1-2), 450 mL of N,N-dimethylformamide, 0.528 g of silver iodide, and 44.0 g of cesium carbonate were added, followed by the introduction of carbon dioxide. A balloon displaced by carbon dioxide was then installed, and the mixture was stirred at room temperature for 20 hours. After the reaction was complete, the precipitate formed by adding 4 L of water was filtered, washed with water and methanol, and then dried under vacuum to obtain 29.0 g of polymer (5P-1). The conversion rate of carboxylic acid, determined by potassium hydroxide titration, was 90%. The Mw of polymer (5P-1) was 18,100. [Chemistry 28]

[0148] [Synthesis Example 16] Synthesis of compound (6P-1-3) 44.4 g of compound (6P-1-1), 200 mL of tetrahydrofuran, 0.79 g of pyridine, and methanol were added to a 500 mL three-necked flask containing a nitrogen inlet tube and a thermometer. The reaction was carried out at room temperature for 2 hours, followed by a reaction at 60 °C for 8 hours. After the reaction was completed, 51 g of compound (6P-1-2) was obtained by concentration under reduced pressure and vacuum drying. Then, 200 mL of heptane was added, and the mixture was heated to 75 °C. Next, 29.9 g of thionyl chloride was slowly added over 20 minutes, and the reaction was carried out at 75 °C for 3 hours. After the reaction was completed, excess thionyl chloride was removed by concentration under reduced pressure, followed by the addition of 200 mL of heptane to remove the insoluble components. The resulting filtrate was concentrated under reduced pressure and vacuum dried to obtain 50 g of compound (6P-1-3). [Chemistry 29]

[0149] [Synthesis Example 17] Synthesis of polymer (6P-1-5) To a 300 mL three-necked flask containing a nitrogen inlet tube, a thermometer, and a stirrer, 10.5 g of compound (6P-1-3), 77.8 g of N-methyl-2-pyrrolidone, 3.2 g of compound (6P-1-4), and 1.0 g of triethylamine were added, and the mixture was cooled to below 10°C in an ice bath. Then, 16.6 g of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride was added, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the mixture was reprecipitated twice with methanol, and the resulting precipitate was dried to obtain 9.9 g of polymer (6P-1-5) with a Mw of 33,000. [Chemistry 30]

[0150] [Synthesis Example 18] Synthesis of polymer (6P-1) To a 300 mL three-necked flask containing a thermometer and a nitrogen inlet tube, 8.7 g of polymer (6P-1-5), 200 mL of N,N-dimethylformamide, 0.80 g of silver iodide, and 29.3 g of cesium carbonate were added, followed by the introduction of carbon dioxide. A balloon purging with carbon dioxide was then installed, and the mixture was stirred at room temperature for 48 hours. After the reaction was complete, the precipitate formed by adding 4 L of water was filtered, washed with water and methanol, and then dried under vacuum to obtain 8.5 g of polymer (6P-1). The conversion rate of carboxylic acid, determined by potassium hydroxide titration, was 50%. [Chemistry 31]

[0151] <Preparation of Radiation-Inducing Linear Resin Compositions> The following shows the components used in the preparation of the radiosensitive linear resin composition. [A] Polymer Polymer (2P-1) ~ Polymer (2P-8), Polymer (4P-1), Polymer (5P-1), Polymer (6P-1) [B]Photosensitive agent A condensate of B-1:4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mole) and 1,2-naphthoquinone diazido-5-sulfonyl chloride (2.0 mole). B-2: Irgacure PAG121 (manufactured by BASF) B-3: Irgacure OXE01 (manufactured by BASF) [C] Additives C-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) [D] Sealing aid D-1:3-glycidoxypropyltrimethoxysilane [E] solvent E-1: Diethylene glycol ethyl methyl ether E-2: γ-Butyrolactone E-3: Ethyl lactate

[0152] [Example 1] A radiosensitive linear resin composition was prepared by dissolving 20 parts by mass of photosensitizer (B-1) and 5 parts by mass of bonding agent (D-1) in solvent (E-1) at a solid content of 20% by mass relative to 100 parts by mass of polymer (2P-1) (solid component). The mixture was then filtered using a membrane filter with a pore size of 0.2 μm.

[0153] [Examples 2-8, Comparative Examples 1-3] Except for using the components of the types shown in Table 2 below, the radiosensitive linear resin compositions of Examples 2 to 8 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1. Furthermore, in Table 2, the mass ratio of [E] solvent indicates the proportion of each compound used in the preparation of the radiosensitive linear resin composition relative to the total amount of [E] solvent.

[0154] [Table 2] [A] Polymer [B]Photosensitive agent [C] Additives [D] Sealing aid [E] solvent type Quality type Quality type Quality type Quality type mass ratio type mass ratio Example 1 2P-1 100 B-1 20 D-1 5 E-1 100 Example 2 2P-2 100 B-1 30 D-1 5 E-1 100 Example 3 4P-1 100 B-1 20 D-1 5 E-1 100 Example 4 5P-1 100 B-1 20 D-1 5 E-1 100 Example 5 2P-3 100 B-1 30 D-1 5 E-1 100 Example 6 2P-4 100 B-2 15 C-1 50 D-1 5 E-1 100 Example 7 2P-5 100 B-3 1 D-1 5 E-1 100 Example 8 6P-1 100 B-1 20 D-1 5 E-2 50 E-3 50 Comparative Example 1 2P-6 100 B-1 20 D-1 5 E-1 100 Comparative Example 2 2P-7 100 B-1 30 D-1 5 E-1 100 Comparative Example 3 2P-8 100 B-1 20 D-1 5 E-1 100

[0155] Evaluation of Radiosensitive Linear Resin Compositions The radiosensitive linear resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3 were used to evaluate the following items using the methods described below. The evaluation results are shown in Table 3.

[0156] [Evaluation of Radiation Sensitivity] The radiosensitive linear resin composition shown in Table 2 was coated onto a silicon substrate using a spinner, and then pre-baked at 90°C on a heated plate for 2 minutes to form a coating with a thickness of 3.0 μm. Next, using an exposure machine (Canon MPA-600FA (ghi-ray mixing)), with a photomask containing a 10 μm linear and spatial pattern as a variable, the coating was irradiated with radiation. Then, it was developed for 60 seconds in a 2.38% (w / w) tetramethylammonium hydroxide aqueous solution at 23°C using a liquid-coating method. Following this, it was rinsed with ultrapure water for 1 minute and then dried to form the pattern. At this point, the required exposure amount for complete dissolution of the 10 μm spatial pattern was investigated. The exposure value is set to "◎" if it is less than 150 mJ / cm2, "○" if it is between 150 mJ / cm2 and 200 mJ / cm2, "△" if it is more than 200 mJ / cm2 but less than 300 mJ / cm2, and "×" if it is more than 300 mJ / cm2.

[0157] Fabrication of substrates for evaluating electrical properties Using the radiosensitive linear resin compositions shown in Table 2, each substrate was coated with an indium tin oxide (ITO) film onto a glass substrate using a spin coater at a thickness of 3 μm. The substrate was then pre-baked at 90°C for 2 minutes on a heated plate to evaporate organic solvents and form the coating. Subsequently, a portion of the end of the substrate coated with the radiosensitive linear resin composition was wiped away with acetone to expose the ITO substrate, serving as the electrode removal point for electrical property measurements. The entire surface of the substrate was irradiated with 300 mJ / cm² light using a proximity exposure machine (Canon's MA-1200 "ghi-ray mixing"). The substrate was then cured by heating (post-baking) at 230°C for 30 minutes, thereby forming an insulating film on the ITO substrate.

[0158] [Determination of dielectric constant] On the insulating film of each electrical characteristic evaluation substrate manufactured by the method described in "Fabrication of Substrate for Electrical Characteristic Evaluation", an Al (aluminum) electrode for measuring electrostatic capacitance is fabricated using a vacuum evaporation apparatus (JEOL VACUUM EVAPORATOR JEE-420). Then, electrode connection wires are soldered to the pre-exposed ITO portion, and these wires and the Al electrode fabricated using the vacuum evaporation apparatus are connected to the positive and negative terminals of an inductance-capacitance-resistance (LCR) meter (HEWLETT PACKARD 4284A PRECISION LCR METER), respectively. The electrostatic capacitance C of the insulating film is measured under an applied voltage of 100 mV and a frequency of 10 kHz. The measured electrostatic capacitance C, the area S (m²) of the Al electrode, and the film thickness d (m) of the hardened film are substituted into the following formula to calculate the value of the dielectric constant ε. Dielectric constant ε = electrostatic capacitance C × film thickness d (m) ÷ electrode area S (m²)

[0159] [Evaluation of the dielectric constant of the hardened film] The dielectric constant ε of the hardened film, determined using the method described in [Determination of Dielectric Constant] for the radiosensitive linear resin compositions shown in Table 2, is used as an indicator of low dielectric constant. A dielectric constant ε less than 2.8 is marked with "◎", a dielectric constant ε of 2.8 or higher but less than 3.0 is marked with "○", a dielectric constant ε of 3.0 or higher but less than 3.5 is marked with "△", and a dielectric constant ε of 3.5 or higher is marked with "×".

[0160] [Evaluation of membrane hardening properties] The curing properties of the film were evaluated based on its solubility upon contact with the stripping solution. A radiosensitive linear resin composition was coated onto a silicon substrate using a spinner, followed by pre-baking at 90°C on a heated plate for 2 minutes to form a 3.0 μm thick coating. Subsequently, the entire surface of the substrate was irradiated with 300 mJ / cm² light using a proximity exposure machine (Canon's MA-1200 (ghi-ray mixing)), and then calcined in an oven at 230°C for 30 minutes to form a cured film. This film was then immersed in N-methyl-2-pyrrolidone solvent at 40°C for 6 minutes, followed by rinsing with ultrapure water for 1 minute, and then calcined again in an oven at 230°C for 15 minutes. Cases where the film thickness did not change before immersion and after calcination were marked as "○", while cases where the film thickness changed were marked as "×". The film thickness was measured at 25°C using an optical interferometric film thickness measuring device (Lambda Ace VM-1010).

[0161] [Table 3] Radiation sensitivity Dielectric constant membrane hardening properties Example 1 ○ ◎ ○ Example 2 ○ ○ ○ Example 3 ○ ◎ ○ Example 4 ○ ○ ○ Example 5 ○ ○ ○ Example 6 ◎ ○ ○ Example 7 ◎ ◎ ○ Example 8 ○ ○ ○ Comparative Example 1 ○ △ × Comparative Example 2 × △ ○ Comparative Example 3 ○ × ○

[0162] As shown in Table 3, the radiation-sensitive linear resin compositions of Examples 1 to 8 all exhibit good practical properties such as radiation sensitivity, dielectric constant, and film curability. In contrast, Comparative Example 1, which uses a polymer (2P-6) with a carboxyl group introduced via methacrylic acid to replace the group represented by formula (1), was evaluated as having a dielectric constant of "△" and a film curability of "×". Furthermore, Comparative Example 2, which uses a polymer (2P-7) formed by introducing epoxy groups into the side chain of polymer (2P-6), showed improved film curability, but its radiation sensitivity was "×". Comparative Example 3, which uses a polymer (2P-8) formed by replacing a portion of the styrene in polymer (2P-7) with dicyclopentyl methacrylate, was evaluated as having good radiation sensitivity, but its dielectric constant was "×".

[0163] Based on the above results, it is clear that compound (A) can effectively improve radiation sensitivity, reduce dielectric constant, and improve film curability.

Claims

1. A curable composition comprising (A) a compound having a group represented by formula (1) below; and (B) a solvent, wherein the (A) component has at least one structural unit selected from the group consisting of a structural unit represented by formula (2), a structural unit represented by formula (3), a structural unit represented by formula (4), and a structural unit represented by formula (5); in formula (1), R1 is a hydrogen atom or an acid-dissociable group; "*" represents a bond; in formula (2), L1 is a single bond or a divalent bond; P1 is a group represented by formula (1); R11 is a monovalent hydrocarbon group or a halogen atom having 1 to 5 carbon atoms; n is an integer from 0 to 4; m is an integer from 1 to 4; wherein, Satisfying n+m≦5, in formula (3), L1 is a single bond or a divalent linkage group; P1 is the group represented by formula (1); in formula (4), Ar1 is a trivalent aromatic ring group or a heterocyclic group; L1 is a single bond or a divalent linkage group; P1 is the group represented by formula (1); in formula (5), Ar2 is a divalent group with an aromatic ring or a heterocyclic ring; Y1 and Y2 are independently oxygen atoms, sulfur atoms or -NH- respectively; L1 is a single bond or a divalent linkage group; P1 is the group represented by formula (1).

2. The curable composition as claimed in claim 1, wherein component (A) is a polymer.

3. The curable composition as claimed in claim 1, wherein the (A) component is a polymer having a group represented by formula (1) in the side chain.

4. The curable composition as claimed in any one of claims 1 to 3, wherein the (A) component is a polymer with a weight average molecular weight of 1,000 to 200,000.

5. The curing composition as described in any one of claims 1 to 3 further comprises (C) component: a radiosensitive linear compound.

6. The curable composition as claimed in claim 5, wherein the component (C) is at least one selected from the group consisting of quinone diazide compounds, photoacid generators and free radical polymerization initiators.

7. A curing film obtained using a curing composition as described in any one of claims 1 to 6.

8. An organic electroluminescent element having a hardened film as described in claim 7.

9. A liquid crystal display element having a hardened film as described in claim 7.

10. A semiconductor element having a hardened film as described in claim 7.

11. A printed circuit board having a hardened film as described in claim 7.

12. A method for manufacturing a hardened film, comprising the step of heating a hardening composition as described in any one of claims 1 to 6.

13. A method for manufacturing a hardened film, comprising: The step of forming a coating film using a curing composition as described in any one of claims 1 to 6; The steps of irradiating at least a portion of the coating with radiation; developing the irradiated coating; and heating the developed coating.

14. A polymer having a group represented by the following formula (1); and at least one structural unit selected from the group consisting of the following formula (2), the following formula (3), the following formula (4), and the following formula (5); in formula (1), R1 is a hydrogen atom or an acid-dissociable group; "*" represents a bond; in formula (2), L1 is a single bond or a divalent bond; P1 is the group represented by the formula (1); R11 is a monovalent hydrocarbon group or a halogen atom having 1 to 5 carbon atoms; n is an integer from 0 to 4; m is an integer from 1 to 4; wherein, Satisfying n+m≦5, in formula (3), L1 is a single bond or a divalent linkage group; P1 is the group represented by formula (1); in formula (4), Ar1 is a trivalent aromatic ring group or a heterocyclic group; L1 is a single bond or a divalent linkage group; P1 is the group represented by formula (1); in formula (5), Ar2 is a divalent group with an aromatic ring or a heterocyclic ring; Y1 and Y2 are independently oxygen atoms, sulfur atoms or -NH- respectively; L1 is a single bond or a divalent linkage group; P1 is the group represented by formula (1).