Radiation-sensitive composition for forming planarization film or partition wall of organic EL element, cured product, organic EL display element, and method for producing cured product

Abstract

The invention provides a radiation-sensitive composition, a cured product, an organic EL display element, and a method for producing the cured product. The radiation-sensitive composition includes an alkali-soluble polymer (A) and a photoacid generator (B), and the alkali-soluble polymer (A) is a (meth) acrylic polymer or a polyimide polymer and satisfies at least one of 1) and 2). (1) The composition contains one or more compounds (C) selected from the group consisting of an ultraviolet light absorber (C1) and an ultraviolet light absorber precursor compound (C2), (C1) has a maximum absorption wavelength between 250 and 350 nm and an absorbance of 0.4 or less at a wavelength of 365 nm when the maximum absorption wavelength is 1, and (C2) exhibits an ultraviolet light absorption function by heating. (2) (A) contains a structural unit (III) derived from an ultraviolet-absorbing compound (a), and (a) has a maximum absorption wavelength between 250 and 350 nm and has an absorbance of 0.4 or less at a wavelength of 365 nm when the maximum absorption wavelength is 1.

Description

TECHNICAL FIELD

[0001] The present application relates to a radiation-sensitive composition for planarization film or barrier rib formation of an organic EL element, a hardened product, an organic EL display element, and a method for producing a hardened product. BACKGROUND

[0002] A display element is provided with an interlayer insulating film or a planarization film, a barrier rib, or the like, which insulates between a wiring and a substrate or between wirings. The hardened film is generally formed by performing a heating treatment and thermally hardening after performing an exposure and development treatment on a coating film formed from a radiation-sensitive composition.

[0003] In a hardened film constituting such a display element, an ultraviolet absorber is sometimes added from the viewpoint of light resistance. As a photosensitive composition to which such an ultraviolet absorber is added, a positive photosensitive paste including an alkali-soluble resin, a photoacid generator, a glass powder having a glass transition point in the range of 400 to 600°C, an ultraviolet absorber (for example, refer to Patent Document 1), or a positive photosensitive resin composition including a siloxane-based copolymer, a 1,2-quinonediazide compound, a specific ultraviolet (UV) absorber, a solvent (for example, refer to Patent Document 2) is known.

[0004] [Related Art Documents]

[0005] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Laid-Open No. 2004-110019

[0007] [Patent Document 2] Japanese Patent Laid-Open No. 2022-551938 SUMMARY

[0008] [Problems to be Solved by the Invention]

[0009] Various display devices including an organic electroluminescence (EL) element are sometimes used outdoors depending on their use, and a planarization film or a barrier rib used in the organic EL element is sometimes exposed to ultraviolet light. It is known that these planarization films or barrier ribs sometimes generate an outgassing gas due to exposure to ultraviolet light, and that adverse events such as corrosion of a wiring in the organic EL element and reduction in lifetime due to the generated outgassing gas occur.

[0010] The present application has been achieved in view of the above-described problems, and aims to provide a radiation-sensitive composition for planarization film or barrier wall formation of an organic EL element, which can form a hardened product excellent in radiation sensitivity, melt flow resistance, light resistance (exhaust gas inhibition), and chemical resistance. In addition, the present application also aims to provide a hardened product formed using the radiation-sensitive composition, a method for producing a hardened product, and an organic EL display element including the hardened product.

[0011] [Technical means for solving the problems]

[0012] According to the present application, the following radiation-sensitive composition, hardened product, organic EL display element, and method for producing a hardened product are provided.

[0013] The present application relates to a radiation-sensitive composition for planarization film or barrier wall formation of an organic EL element, which comprises, in one embodiment:

[0014] an alkali-soluble polymer (A), and

[0015] a photoacid generator (B), in the radiation-sensitive composition for planarization film or barrier wall formation of an organic EL element, the alkali-soluble polymer (A) is a (meth)acrylic polymer or a polyimide polymer, and

[0016] at least one of the following 1) and 2) is satisfied.

[0017] 1) the composition comprises one or more compounds (C) selected from the group consisting of an ultraviolet absorber (C1) and an ultraviolet absorber precursor compound (C2),

[0018] the ultraviolet absorber (C1) has an absorption maximum wavelength between 250 nm and 350 nm and has an absorbance at a wavelength of 365 nm of 0.4 or less when the maximum value of the absorbance between 250 nm and 350 nm is taken as 1,

[0019] the ultraviolet absorber precursor compound (C2) exhibits an ultraviolet absorption function by heating or light irradiation;

[0020] 2) the alkali-soluble polymer (A) contains a structural unit (III) derived from an ultraviolet absorbing compound (a) having an absorption maximum wavelength between 250 nm and 350 nm and having an absorbance at a wavelength of 365 nm of 0.4 or less when the maximum value of the absorbance between 250 nm and 350 nm is taken as 1.

[0021] The present application relates to a method for producing a hardened product, which comprises, in another embodiment:

[0022] a step of forming a coating film using the radiation-sensitive composition;

[0023] a step of irradiating at least a part of the coating film with radiation;

[0024] a step of developing the coating film after the radiation irradiation; and

[0025] a step of heating the developed coating film.

[0026] The present application relates to, in another embodiment, a hardened product formed using the radiation-sensitive composition, and an organic EL display element including the hardened product.

[0027] [Effects of the Invention]

[0028] The radiation-sensitive composition of the present application can form a hardened product excellent in radiation sensitivity, melt flow resistance, light resistance (outgas inhibition), and chemical resistance by containing a specific compound (C), or a polymer having a structural unit derived from a specific ultraviolet absorbing compound (a). In addition, the manufacturing method of the hardened product of the present application can form a hardened product excellent in radiation sensitivity, melt flow resistance, light resistance (outgas inhibition), and chemical resistance because the radiation-sensitive composition is used. Furthermore, the organic EL display element of the present application is high quality because it includes the hardened product. DETAILED DESCRIPTION

[0029] Hereinafter, the embodiments of the present application will be described in detail, but the present application is not limited to these embodiments.

[0030] Hereinafter, matters related to the embodiments will be described in detail. Furthermore, in the present specification, a numerical range written using "~" is meant to include the numerical values written before and after the "~" as lower limit values and upper limit values. The so-called "structural unit" means a unit mainly constituting a main chain structure, and means a unit including two or more units in at least the main chain structure.

[0031] In this specification, "hydrocarbon group" encompasses chain-like hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Chain-like hydrocarbon group" refers to a straight-chain hydrocarbon group or branched hydrocarbon group whose main chain consists only of chain structures and does not contain any ring structures. The chain-like hydrocarbon group can be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as its ring structure and does not contain any aromatic ring structures. The alicyclic hydrocarbon group does not necessarily need to consist solely of an alicyclic hydrocarbon structure; it may also include a group 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. The aromatic hydrocarbon group does not necessarily need to consist solely of an aromatic ring structure; it may also include 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" encompasses both alicyclic hydrocarbons and aromatic hydrocarbons.

[0032] In this specification, "(meth)acryloyl" means including both "acryloyl" and "methacryloyl", "(meth)acrylate" means including both "acrylate" and "methacrylate", and "(meth)acrylate" means including both "acrylate" and "methacrylate".

[0033] Radioactive linear compositions

[0034] The planarization film or isolation wall formation of the organic EL element in this embodiment comprises:

[0035] Alkali-soluble polymer (A), and

[0036] Photoacid generator (B),

[0037] The alkali-soluble polymer (A) is a (meth)acrylic acid polymer or a polyimide polymer, and

[0038] Satisfy at least one of 1) and 2) below.

[0039] 1) The composition comprises one or more compounds (C) selected from the group consisting of ultraviolet absorbers (C1) and ultraviolet absorber precursor compounds (C2).

[0040] The ultraviolet absorber (C1) has a maximum absorption wavelength between 250 nm and 350 nm, and when the maximum absorbance between 250 nm and 350 nm is set to 1, the absorbance at a wavelength of 365 nm is less than 0.4.

[0041] The UV absorber precursor compound (C2) exhibits UV absorption function upon heating or light irradiation;

[0042] 2) The alkali-soluble polymer (A) comprises a structural unit (III) derived from the ultraviolet-absorbing compound (a), which has a maximum absorption wavelength between 250 nm and 350 nm and an absorbance of less than 0.4 at a wavelength of 365 nm when the maximum absorbance between 250 nm and 350 nm is set to 1.

[0043] The maximum absorption wavelength and absorbance can be obtained by preparing a solution (0.1 g / L) of an ultraviolet absorber (C1) or an ultraviolet-absorbing compound (a) and measuring it using a UV-Vis-NIR spectrophotometer (e.g., Nippon Spectrophotometer, V-670). The solvent used to form the solution of the ultraviolet absorber (C1) or ultraviolet-absorbing compound (a) is not particularly limited, as long as it is a solvent that dissolves the ultraviolet absorber (C1) or ultraviolet-absorbing compound (a), preferably acetonitrile, ethyl acetate, toluene, chloroform, or tetrahydrofuran. The maximum absorption wavelength and absorbance can be measured directly by placing the solution of the ultraviolet absorber (C1) or ultraviolet-absorbing compound (a) in a quartz bath, or by coating the solution onto a glass substrate using spin coating or the like and drying it, and then measuring using the resulting coating. In this case, polymers such as polymethyl methacrylate, which do not absorb in the ultraviolet region, can also be used to form the coating. Furthermore, the term "having a maximum absorption wavelength between 250 nm and 350 nm" means that in the absorption spectrum of the ultraviolet absorber (C1) or the ultraviolet absorbing compound (a), there is at least one peak with a maximum absorption wavelength in the range of 250 nm to 350 nm. As long as there is at least one peak with a maximum absorption wavelength in the range of 250 nm to 350 nm, there can be further maximum absorption wavelengths in the range of less than 250 nm or more than 350 nm.

[0044] The following describes the components contained in this composition, as well as other components that may be formulated as needed. Furthermore, unless otherwise specified, each component may be used alone or in combination of two or more.

[0045] <Compound (C)>

[0046] This composition may contain one or more compounds (C) selected from the group consisting of ultraviolet absorbers (C1) and ultraviolet absorber precursor compounds (C2).

[0047] The ultraviolet absorber (C1) has a maximum absorption wavelength between 250 nm and 350 nm, and when the maximum absorbance between 250 nm and 350 nm is set to 1, the absorbance at a wavelength of 365 nm is less than 0.4.

[0048] The UV absorber precursor compound (C2) exhibits UV absorption function when heated or irradiated with light.

[0049] When the composition contains the compound (C), the alkali-soluble polymer (A) described later may or may not contain structural unit (III).

[0050] The molecular weight of the compound (C) is preferably 300 or more, more preferably 350 or more, even more preferably 400 or more, and particularly preferably 500 or more. Furthermore, the molecular weight is preferably 2000 or less, more preferably 1500 or less. Because the molecular weight of the compound (C) is within this range, even during the heating process when forming the hardened product, the compound (C) is easily retained in the hardened product, thus fully demonstrating the effect of adding the compound (C), and is therefore preferred.

[0051] (UV absorber (C1))

[0052] The ultraviolet absorber (C1) has a maximum absorption wavelength between 250 nm and 350 nm, and the absorbance at a wavelength of 365 nm is less than 0.4 when the maximum absorbance between 250 nm and 350 nm is set to 1.

[0053] When the maximum absorbance between wavelengths of 250 nm and 350 nm is set to 1, the absorbance at a wavelength of 365 nm is preferably 0.3 or less, more preferably 0.25 or less. There is no particular limitation on the lower limit, but a lower value is preferred; typically around 0.01.

[0054] The structure of the ultraviolet absorber (C1) is not particularly limited as long as it has the wavelength and absorbance characteristics. For example, it is preferably one or more ultraviolet absorbers selected from the group consisting of benzotriazole-based ultraviolet absorbers represented by formula (1), triazine-based ultraviolet absorbers represented by formula (2), hydroxybenzophenone-based ultraviolet absorbers represented by formula (3), and cyanoacrylate-based ultraviolet absorbers represented by formula (4). More preferably, it is one or more ultraviolet absorbers selected from the group consisting of triazine-based ultraviolet absorbers represented by formula (2), hydroxybenzophenone-based ultraviolet absorbers represented by formula (3), and cyanoacrylate-based ultraviolet absorbers represented by formula (4).

[0055] [Chemistry 1]

[0056]

[0057] (in the above formula (1),

[0058] X 11 It is a hydroxyl group or an organic group having 1 to 20 carbon atoms; in the presence of multiple X groups 11 In the case of multiple X 11 They are the same or different;

[0059] X 12 It is a halogen atom; in the presence of multiple X atoms 12 In the case of multiple X 12 They are the same or different;

[0060] n1 is an integer from 1 to 3;

[0061] (n2 is an integer from 0 to 3)

[0062] [Chemistry 2]

[0063]

[0064] (in the above formula (2),

[0065] X 21 X 22 and X 23 Each is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms; in the presence of multiple X groups 21 X 22 X 23 In the case of multiple X 21 X 22 X 23 They are either the same as or different from each other;

[0066] n3, n4, and n5 are independent integers from 0 to 3; where n3 + n4 + n5 ≥ 1.

[0067] [Chemistry 3]

[0068]

[0069] (in the above formula (3),

[0070] X 31 and X 32 Each is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms; in the presence of multiple X groups 31 X 32 In this case,

[0071] Multiple X 31 X 32 They are either the same as or different from each other;

[0072] n6 and n7 are independent integers from 0 to 3; where n6 + n7 ≥ 1.

[0073] [Chemistry 4]

[0074]

[0075] (in the above formula (4),

[0076] X 41 It is an organogroup with 1 to 20 carbon atoms and a t-valence.

[0077] t is an integer from 1 to 10;

[0078] X 42 and X 43 Each is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms; in the presence of multiple X groups 42 X 43 In this case,

[0079] Multiple X 42 X 43 They are either the same as or different from each other;

[0080] n8 and n9 are independent integers from 0 to 3.

[0081] X as in equation (1) 11 Organic groups with 1 to 20 carbon atoms, for example, include: monovalent hydrocarbon groups with 1 to 20 carbon atoms, groups having divalent heteroatoms between carbon atoms or at the end of the carbon chain of the hydrocarbon group, groups formed by substituting some or all of the hydrogen atoms of the hydrocarbon group with a monovalent heteroatom group, or combinations thereof.

[0082] Examples of monovalent hydrocarbon groups with 1 to 20 carbon atoms in the organic group include: chain hydrocarbon groups with 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups with 3 to 20 carbon atoms, and monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms.

[0083] Examples of monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include monovalent straight-chain or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, and monovalent straight-chain or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of monovalent straight-chain or branched saturated hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and 1,1,3,3-tetramethylbutyl. Examples of monovalent straight-chain or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as vinyl, propynyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.

[0084] Examples of monovalent alicyclic hydrocarbon groups with 3 to 20 carbon atoms include monocyclic or polycyclic saturated hydrocarbon groups and monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cycloalkyl groups. Examples of polycyclic saturated hydrocarbon groups include norbornyl, adamantyl, tricyclic decyl, tetracyclic dodecyl, and other bridged alicyclic hydrocarbon groups. Examples of monocyclic unsaturated hydrocarbon groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and other monocyclic cycloalkenyl groups. Examples of polycyclic unsaturated hydrocarbon groups include norbornyl, tricyclic decenyl, tetracyclic dodecenyl, and other polycyclic cycloalkenyl groups. Furthermore, a bridged alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group in which two non-adjacent carbon atoms constituting the alicyclic ring are bonded by a linker group containing one or more carbon atoms.

[0085] Examples of monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms include: aryl groups such as phenyl, tolyl group, xylyl group, naphthyl group, and anthryl group; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl group.

[0086] Examples of heteroatoms constituting the monovalent or divalent heteroatom-containing bases include: oxygen, nitrogen, sulfur, phosphorus, silicon, and halogen atoms. Examples of halogen atoms include: fluorine, chlorine, bromine, and iodine atoms.

[0087] Examples of monovalent heteroatom-containing groups include: hydroxyl, carboxyl, sulfanyl, cyano, nitro, halogen atoms, etc.

[0088] Examples of divalent heteroatom-containing bases include: -CO-, -C(=O)O-, -CS-, -NH-, -O-, -S-, -SO-, -SO2-, or combinations thereof.

[0089] X as in equation (1) 12 Halogen atoms in the atom can be listed as: fluorine atom, chlorine atom, bromine atom, and iodine atom.

[0090] In the formula (1), n1 is an integer from 1 to 3, preferably 1 or 2, and n2 is an integer from 0 to 3, preferably 0 or 1.

[0091] X as in equation (2) 21 X 22 and X 23The organic group with 1 to 20 carbon atoms in it can preferably be X of the formula (1). 11 Organogroups with 1 to 20 carbon atoms. As X 21 X 22 and X 23 Preferably, it is a hydroxyl group, a monovalent chain hydrocarbon group with 1 to 20 carbon atoms, or a group having -CO-, -C(=O)O-, or -O- between carbon atoms or at the end of the carbon chain of the chain hydrocarbon group.

[0092] In the formula (2), n3, n4 and n5 are integers from 0 to 3, preferably n3+n4+n5≧1 and 6≧n3+n4+n5≧2.

[0093] X, as in equation (3) 31 X 32 The organic group with 1 to 20 carbon atoms in it can preferably be X of the formula (1). 11 Organogroups with 1 to 20 carbon atoms. As X 31 X 32 Preferably, it is a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, or a group having -CO-, -C(=O)O-, or -O- at the carbon-carbon interval or carbon chain end of the chain hydrocarbon group, more preferably an alkoxy group having 1 to 10 carbon atoms.

[0094] In the above formula (3), n6 and n7 are integers from 0 to 3, and n6+n7≧1.

[0095] X, as in equation (4) 42 and X 43 The monovalent organic group with 1 to 20 carbon atoms in it can preferably be X of the formula (1). 11 Organic groups with 1 to 20 carbon atoms.

[0096] X, as in equation (4) 41 The t-valent organic groups with 1 to 20 carbon atoms are preferably derived by removing (t-1) hydrogen atoms from the monovalent organic groups with 1 to 20 carbon atoms. Among these, X is... 41 When t is 1, it is preferably a monovalent chain hydrocarbon group with 1 to 20 carbon atoms, or a group having -CO-, -C(=O)O-, or -O- between carbon atoms or at the end of the carbon chain of the chain hydrocarbon group, and more preferably an alkyl group with 1 to 20 carbon atoms.

[0097] In the formula (4), n8 and n9 are integers from 0 to 3, preferably 0 or 1.

[0098] The t is an integer from 1 to 10, preferably an integer from 1 to 5.

[0099] In the compounds of formulas (1) to (4), the hydroxyl group or *-OR bonded to the benzene ringt1 (R t1 The number of organic groups (representing 1 to 20 carbon atoms, with * indicating a bond to the benzene ring) is preferably 3 or less, more preferably 2. If the hydroxyl group or *-OR t1 If the quantity increases, it may not meet the maximum absorption wavelength or absorbance ratio, and therefore is not preferred.

[0100] The following structures can be listed as ultraviolet absorbers (C1).

[0101] [Chemistry 5]

[0102]

[0103] As the ultraviolet absorber (C1), commercially available products may also be used, such as TINUVIN 400, TINUVIN 405, Uvinul 3039, Uvinul 3030 manufactured by BASF Japan, and Adekastab LA-46, Adekastab 1413 manufactured by ADEKA.

[0104] (UV absorber precursor compound (C2))

[0105] The UV absorber precursor compound (C2) is a compound that has relatively low UV absorption capacity under normal conditions, but exhibits its function as a UV absorber through heating or light irradiation. UV absorber precursor compounds are also referred to as "UV absorber precursors" or "latent UV absorbers." In the case where this composition contains the UV absorber precursor compound (C2), the UV absorption capacity of the UV absorber precursor compound (C2) is low when the composition is made, but UV absorption capacity can be exhibited by performing a heating or exposure process when manufacturing a hardened object using the composition.

[0106] The ultraviolet absorber precursor compound (C2) is preferably one or more compounds selected from the group consisting of the compound represented by formula (5), the compound represented by formula (5'), the compound represented by formula (6), and the compound represented by formula (7).

[0107] [Chemistry 6]

[0108]

[0109] (in the above equations (5), (5'), (6), and (7),)

[0110] R a1 and Ra2 Each group is independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an organic group having 1 to 40 carbon atoms, or -OQ; Q is a detachable group; wherein, R a1 R a2 At least one of them is -OQ; when there are multiple R a1 R a2 In the case of multiple R a1 R a2 They are either the same as or different from each other;

[0111] R a3 R a4 R a5 R a6 R a7 and R a8 Each group can be independently a halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, or an organic group having 1 to 40 carbon atoms; in the presence of multiple R groups a3 R a4 R a5 R a6 R a7 R a8 In the case of multiple R a3 R a4 R a5 R a6 R a7 R a8 They are either the same as or different from each other;

[0112] m1 is an integer from 0 to 4, and m2 is an integer from 0 to 2;

[0113] m3 and m4 are independent integers from 0 to 4;

[0114] m5 is an integer from 0 to 3;

[0115] m6 is an integer from 0 to 3, and m7 is an integer from 1 to 3; where m6 + m7 ≦ 3;

[0116] L 2 Indicates an atom or linker with a single bond or s1 valence;

[0117] s1 represents an integer from 1 to 10.

[0118] As the R a1 R a2 R a3 R a4 R a5 R a6 R a7 R a8 The organic group with 1 to 40 carbon atoms in the formula (1) can preferably be the X group of the formula (1). 11The carbon number of organic groups with carbon numbers from 1 to 20 is expanded to 40.

[0119] The m1 is an integer from 0 to 4, preferably 0 or 1; the m2 is an integer from 0 to 2, preferably 0 or 1; the m3 and m4 are integers from 0 to 4, preferably 0 or 1.

[0120] The m5 and m6 are integers from 0 to 3, preferably 0 or 1.

[0121] The m7 is an integer from 1 to 3, preferably 2 or 3.

[0122] The s1 is an integer from 1 to 10, preferably an integer from 1 to 5, and particularly preferably 1 or 2.

[0123] The L 2 This indicates a single bond, an s1-valent atom, or an s1-valent linker. When s1 is 2, it is preferably a single bond or an alkyl dienyllium with 1 to 3 carbon atoms, more preferably a methylene group. When s1 is 3, it is preferably an alkyl triyl group with 1 to 3 carbon atoms.

[0124] The compound represented by formula (5') has the property of L 2 The structure has s1 specific bases as shown below as bonded to the top. The s1 specific bases may be the same as or different from each other.

[0125] [Chemistry 7]

[0126]

[0127] (In the formula, * indicates that it is related to L) 2 (the bond)

[0128] The R a1 and R a2 Q in the formula is a detachable group, preferably a BOC group (tert-butyloxycarbonyl group), a group represented by formula (8) below, a group represented by formula (9) below, a group represented by formula (10) below, and more preferably a BOC group, a group represented by formula (8) below, or a group represented by formula (9) below.

[0129] [Chemistry 8]

[0130]

[0131] (In the above equations (8), (9), and (10),

[0132] R 81 R 91 R 92 and R 101Each group can be independently a halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, or an organic group having 1 to 40 carbon atoms; in the presence of multiple R groups 81 R 91 R 92 R 101 In the case of multiple R 81 R 91 R 92 R 101 They are either the same as or different from each other;

[0133] R 82 It can be a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an organic group having 1 to 40 carbon atoms; two Rs 82 They are either the same as or different from each other;

[0134] n3 is an integer from 0 to 4;

[0135] n4, n5, and n11 are each an independent integer from 0 to 5;

[0136] L 1 It is a single-bond or divalent linker;

[0137] R 102 and R 103 Each is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

[0138] n12 and n13 are each independently 0 or 1; where n12 + n13 ≥ 1;

[0139] * indicates a bond with an oxygen atom.

[0140] As the R 81 R 91 R 92 R 101 R 82 The organic group with 1 to 40 carbon atoms in the formula (1) can preferably be the X group of the formula (1). 11 The carbon number of organic groups with carbon numbers from 1 to 20 is expanded to 40.

[0141] As the R 102 R 103 The alkyl group having 1 to 10 carbon atoms can preferably be X of formula (1). 11 The group with the corresponding number of carbons in the alkyl group having 1 to 20 carbons.

[0142] The n3 is an integer from 0 to 4, preferably 0 or 1.

[0143] n4 and n5 are integers from 0 to 5, preferably 0 or 1.

[0144] The n11 is an integer from 0 to 5, preferably 1 or 2.

[0145] As the L 1 The divalent linker in it is preferably a alkyl group such as methanediyl, ethanediyl, or 1,3-propanediyl.

[0146] The following structures can be listed as precursor compounds (C2) for the ultraviolet absorber.

[0147] [Chemistry 9]

[0148]

[0149] [Chemistry 10]

[0150]

[0151] In addition, as a precursor compound for ultraviolet absorber (C2), besides those described above, a compound that conforms to formulas (5), (5'), (6), and (7) from the compounds described in Japanese Patent No. 7393205 and Japanese Patent No. 7236386 may preferably be used.

[0152] As the precursor compound (C2) for the ultraviolet absorber, a compound with a designation given by the manufacturer may also be used, such as GPA-1103, GPA-1104, GPA-1105, etc., manufactured by ADEKA (stock) as described in non-patent literature (Photopolymer Symposium, Newsletter, No. 84, p. 7, 2018).

[0153] When the composition contains the compound (C), the lower limit of the content of compound (C) relative to 100 parts by mass of the alkali-soluble polymer (A) is preferably 0.1 parts by mass, more preferably 0.3 parts by mass, further preferably 0.5 parts by mass, and particularly preferably 0.8 parts by mass. The upper limit of the content of compound (C) relative to 100 parts by mass of the alkali-soluble polymer (A) is preferably 30 parts by mass, more preferably 20 parts by mass, further preferably 10 parts by mass, and particularly preferably 5 parts by mass. From the viewpoint of lightfastness (escape gas suppression), it is preferable to set the content of compound (C) within the aforementioned range.

[0154] <Alkali-soluble polymer (A)>

[0155] The alkali-soluble polymer (A) is an aggregate of polymeric chains (hereinafter, the aggregate will also be referred to as the "base polymer"). The alkali-soluble polymer (A) is preferably a polymer having acidic groups such as carboxyl groups. Here, "alkali-soluble polymer" refers to a polymer that can dissolve or swell in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C.

[0156] By using a (meth)acrylic polymer (A1) or a polyimide polymer (A2) as the alkali-soluble polymer (A), excellent chemical resistance is achieved. Among these, the (meth)acrylic polymer (A1) is preferred. Polymers (A1) and (A2) will be described below.

[0157] ((Meth)acrylic polymer (A1))

[0158] The polymer (A1) is preferably a (meth)acrylic acid polymer containing a structural unit (I) having an acid group. The polymer (A1) may contain a structural unit (III) derived from an ultraviolet-absorbing compound (a). Alternatively, the polymer (A1) may also contain structural units other than the aforementioned structural units (I) and (III). The structural units contained in the polymer (A1) will be described below.

[0159] [Structural Unit (I)]

[0160] By including structural units (I) with acid groups in the polymer (A1), the solubility (alkali solubility) of the polymer (A1) relative to alkaline developing solutions or the curing reactivity can be improved.

[0161] The structural unit (I) is not particularly limited as long as it has an acid group, but is preferably selected from at least one of the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units. Furthermore, in this specification, "phenolic hydroxyl group" refers to a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0162] Structural unit (I) is preferably derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having acid groups are provided below.

[0163] Examples of monocarboxylic acids that constitute structural units with carboxyl groups include: (meth)acrylic acid, crotonic acid, 4-vinylbenzoic acid, and other unsaturated monocarboxylic acids; maleic acid, fumaric acid, citraconic acid, succinic acid, itaconic acid, and other unsaturated dicarboxylic acids.

[0164] Examples of monoisocyanates that constitute structural units having sulfonic acid groups include: vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, etc.

[0165] Examples of monomorphs that constitute structural units with phenolic hydroxyl groups include: 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, and hydroxyphenyl(meth)acrylate.

[0166] In addition, maleimide can also be used as a monolith that constitutes structural unit (I).

[0167] Among these, the preferred ones are monoforms constituting structural units having carboxyl groups or structural units constituting phenolic hydroxyl groups, and more preferably (meth)acrylic acid or p-isopropenylphenol.

[0168] The basic polymer may contain one structural unit (I) or a combination of two or more.

[0169] When polymer (A) contains structural unit (I), the lower limit of the content ratio of structural unit (I) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 3% by mass, more preferably 5% by mass, and even more preferably 10% by mass. Furthermore, the upper limit of the content ratio is preferably 50% by mass, more preferably 40% by mass, even more preferably 30% by mass, and particularly preferably 25% by mass. By setting the content ratio of structural unit (I) within the aforementioned range, good solubility in alkaline developing solutions is imparted, and therefore preferred.

[0170] [Structural Unit (II)]

[0171] The polymer (A1) may contain a structural unit (II) having one or more groups selected from the group consisting of oxetanyl and oxiranyl. It is preferred that the polymer (A1) contains a polymer including structural unit (II) to form a hardened material with excellent melt flow resistance and chemical resistance. Furthermore, it is preferred that the polymer (A1) contains structural unit (II) to further improve the resolution or adhesion of the film. Additionally, by having oxetanyl or oxiranyl act as a crosslinking group, a pattern (hardened material) with high heat resistance and inhibited degradation over a long period can be formed. The structural unit (II) is preferably a structural unit derived from an unsaturated monomer having oxetanyl or oxiranyl, and more specifically, preferably a structural unit represented by the following formula (a1).

[0172] [Chemistry 11]

[0173]

[0174] (in formula (a1),

[0175] R 21 It is a monovalent group having an oxetine propyl or oxetine butyl group;

[0176] R α It can be a hydrogen atom, methyl group, hydroxymethyl group, cyano group, or trifluoromethyl group;

[0177] X 1 (For single-bond or divalent linkages)

[0178] In the above equation (a1), R is... 21 Examples include: oxetyl propyl, oxetyl butyl, 3,4-epoxycyclohexyl, 3,4-epoxytricyclic [5.2.1.0] 2,6 Decyl, 3-methyloxetyl, 3-ethyloxetyl, etc.

[0179] As X 1 The divalent linker is preferably a dialkyl group such as methanediyl, ethanediyl, or 1,3-propanediyl.

[0180] Specific examples of providing a monolithic form of structural unit (II) represented by formula (a1) include, for example: glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo (meth)acrylate [5.2.1.0]. 2 ,6[Decayl acrylate, (3-methyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl) acrylate, (oxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl acrylate, etc.]

[0181] Among these, glycidyl methacrylate and 3,4-epoxycyclohexyl methacrylate are preferred.

[0182] The base polymer may contain one structural unit (II) or a combination of two or more.

[0183] When polymer (A) contains structural unit (II), the lower limit of the content ratio of structural unit (II) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 5% by mass, more preferably 10% by mass, further preferably 20% by mass, and particularly preferably 30% by mass. Furthermore, the upper limit of the content ratio is preferably 90% by mass, more preferably 85% by mass, and further preferably 80% by mass. By setting the content ratio of structural unit (II) within the aforementioned range, the coating film exhibits better resolution, and the heat resistance and chemical resistance of the obtained cured product can be sufficiently improved, which is preferable in these respects.

[0184] [Structural Unit (III)]

[0185] Structural unit (III) is a structural unit derived from ultraviolet-absorbing compound (a), which has a maximum absorption wavelength between 250 nm and 350 nm and an absorbance of less than 0.4 at a wavelength of 365 nm when the maximum absorbance between 250 nm and 350 nm is set to 1.

[0186] When the polymer (A1) contains a structural unit (III) derived from the ultraviolet-absorbing compound (a), the composition may or may not contain the compound (C).

[0187] The absorbance of the ultraviolet-absorbing compound (a) at a wavelength of 365 nm, with the maximum absorbance between 250 nm and 350 nm set to 1, is 0.4 or less, preferably 0.38 or less, and more preferably 0.35 or less. There is no particular limitation on the lower limit, but a lower value is preferred; typically, it is around 0.01.

[0188] As for the ultraviolet-absorbing compound (a), there is no particular limitation as long as the absorbance condition is met. For example, it is preferably one or more compounds selected from the group consisting of the compound represented by formula (1'), the compound represented by formula (2'), the compound represented by formula (3'), and the compound represented by formula (4'), and more preferably the compound represented by formula (1').

[0189] [Chemistry 12]

[0190]

[0191] (in the above formula (1'),

[0192] X 11' It is a hydroxyl group or an organic group having 1 to 20 carbon atoms; in the presence of multiple X groups 11' In the case of multiple X 11' They are the same or different; X 11' At least one of them has a polymerizable group;

[0193] X 12 n1, n2 have the same meaning as in equation (1).

[0194] [Chemistry 13]

[0195]

[0196] (in the above formula (2'),

[0197] X 21' X 22' and X 23' Each is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms; in the presence of multiple X groups 21' X 22' X 23' In the case of multiple X 21' X 22' X 23' They are either the same or different from each other; X 21' X 22' X 23' At least one of them has a polymerizable group;

[0198] n3, n4, n5 have the same meaning as in equation (2).

[0199] [Chemistry 14]

[0200]

[0201] (in the above formula (3'),

[0202] X 31' and X32' Each is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms; in the presence of multiple X groups 31' X 32' In the case of multiple X 31' X 32' They are either the same or different from each other; X 31' X 32' At least one of them has a polymerizable group;

[0203] n6 and n7 have the same meaning as in equation (3).

[0204] [Chemistry 15]

[0205]

[0206] (in the above equation (4'),

[0207] X 41' It is a monovalent organic group with 1 to 20 carbon atoms;

[0208] X 42' and X 43' Each is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms; in the presence of multiple X groups 42' X 43' In the case of multiple X 42' X 43' They are either the same or different from each other; X 42' X 43' At least one of them has a polymerizable group;

[0209] n8' and n9' are independent integers from 0 to 3; where n8'+n9'≧1)

[0210] X as in equation (1') 11' The organic group with 1 to 20 carbon atoms in it can preferably be X of the formula (1). 11 Organic groups containing 1 to 20 carbon atoms. Among these, X... 11' Preferably, it is a monovalent chain hydrocarbon group with 1 to 20 carbon atoms, or a group having -CO-, -C(=O)O-, or -O- at the carbon-carbon intervals or carbon chain ends of the chain hydrocarbon group.

[0211] X of equation (1') 11' At least one of them has a polymerizable group. Examples of polymerizable groups include (meth)acryloyl, styrene, maleimide, vinyl, vinyl ether, allyl, ethynyl, etc. Among these, (meth)acryloyl, vinyl, or allyl is preferred, and (meth)acryloyl is more preferred. The number of polymerizable groups in the stated formula (1') is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 2.

[0212] X as in equation (2') 21' X 22' X 23' X of equation (3') 31' X 32' X of equation (4') 41' X 42' X 43' The organic group with 1 to 20 carbon atoms in it can preferably be X of the formula (1). 11 Organic groups with 1 to 20 carbon atoms.

[0213] X as in equation (2') 21' X 22' X 23' X of the above formula (3') 31' X 32' X of equation (4') 42' X 43' The polymerizable groups that can be present can preferably be X of formula (1'). 11' Polymer groups in.

[0214] In the above equation (4'), n8' and n9' are integers from 0 to 3, and n8'+n9'≧1.

[0215] The following structures can be listed as examples of the ultraviolet-absorbing compound (a).

[0216] [Chemistry 16]

[0217]

[0218] (the R) a (e.g., hydrogen atom, methyl, hydroxymethyl, cyano, or trifluoromethyl)

[0219] As the ultraviolet-absorbing compound (a), commercially available products may also be used, such as RUVA-93 (2-(2-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole) manufactured by Otsuka Chemicals, Ltd.

[0220] The basic polymer may contain one structural unit (III) or a combination of two or more.

[0221] When polymer (A) contains structural unit (III), the lower limit of the content ratio of structural unit (III) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 0.5% by mass, more preferably 0.8% by mass. Furthermore, the upper limit of the content ratio is preferably 30% by mass, more preferably 20% by mass, further preferably 10% by mass, and particularly preferably 5% by mass. From the viewpoint of lightfastness (escape gas suppression), it is preferable to set the content ratio of structural unit (III) within the aforementioned range.

[0222] [Structural Unit (IV)]

[0223] The polymer (A1) may further comprise structural units (IV) derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, aromatic vinyl compounds, N-substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, and dialkyl dicarboxylic acid esters. By incorporating these structural units (IV) into the polymer, the glass transition temperature of the polymer (A1) composition can be adjusted, improving the patternability of the resulting cured material, which is preferred in this respect.

[0224] Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate.

[0225] Examples of (meth)acrylates having an alicyclic structure include: cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, and tricyclo(meth)acrylate [5.2.1.0]. 2,6 ] Decane-8-yl ester, (meth)acrylate tricyclic [5.2.1.0] 2,5 Decane-8-yloxyethyl ester, isobornyl acrylate, etc.

[0226] Examples of (meth)acrylates having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0227] Examples of such aromatic vinyl compounds 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, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, etc.

[0228] Examples of the N-substituted maleimide compounds include: N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc.

[0229] Examples of vinyl compounds having heterocyclic structures, other than those conforming to structural unit (VI) below, include: tetrahydrofuranyl methyl (meth)acrylate, tetrahydropyranyl methyl (meth)acrylate, 5-ethyl-1,3-dioxane-5-yl methyl (meth)acrylate, 5-methyl-1,3-dioxane-5-yl methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxane-4-yl)methyl (meth)acrylate, 2-(meth)acryloyloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl) acrylate, glyceryl carbonate (meth)acrylate, (γ-lactam-2-yl) acrylate, N-(meth)acryloyloxyethylhexahydrophthalimide, etc.

[0230] Examples of conjugated diene compounds include 1,3-butadiene and isoprene; examples of nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; and examples of unsaturated dialkyl dicarboxylic acid esters include diethyl itaconic acid. In addition to the aforementioned examples, other monomers constituting the structural unit include, for example, vinyl chloride, vinylidene chloride, and vinyl acetate.

[0231] As a monolithic entity providing the structural unit (IV), it is preferably composed of at least one selected from the group consisting of alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, N-substituted maleimide compounds, and vinyl compounds having a heterocyclic structure.

[0232] The base polymer may contain one structural unit (IV) or a combination of two or more.

[0233] When the polymer (A) contains structural units (IV), the lower limit of the content ratio of structural units (IV) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 5% by mass, more preferably 10% by mass, further preferably 20% by mass, and particularly preferably 30% by mass. Furthermore, the upper limit of the content ratio is preferably 60% by mass, more preferably 50% by mass. By setting the content ratio of structural units (IV) within the aforementioned range, the glass transition temperature of the polymer (A1) can be moderately increased, which is preferable in this respect.

[0234] [Structural Unit (V)]

[0235] The polymer (A1) may further comprise a structural unit (V) having a cyclic ether structure in the main chain and a methylene group bonded to the carbon atoms constituting the cyclic ether structure. Introducing the structural unit (V) into the polymer can improve the flexural strength of the resulting cured material, which is preferred in this respect.

[0236] The cyclic ether structure of the structural unit (V) preferably has 5 or 6 ring elements; specifically, tetrahydrofuran ring structures or tetrahydropyran ring structures are examples. The structural unit (V) only needs to have a cyclic ether structure and a methylene group bonded to the carbon atom constituting the cyclic ether structure to be incorporated into a portion of the polymer backbone. As a preferred example, repeating units with the following structure can be listed: the structural unit (V) has one or two methylene groups constituting the polymer backbone in each structural unit (V), and the main chain portion of the polymer formed by the structural unit (V) includes a cyclic ether structure and one or two methylene groups. Furthermore, the cyclic ether structure of the structural unit (V) may also have substituents in the ring portion.

[0237] More specifically, the structural unit (V) is preferably the structural unit represented by the following formula (v).

[0238] [Chemistry 17]

[0239]

[0240] (in formula (v),

[0241] R A1 It consists of hydrogen atoms or a monovalent hydrocarbon group having 1 to 30 carbon atoms;

[0242] R A2 For hydrogen atoms or -COOR A3 ;R A3 It consists of hydrogen atoms or a monovalent hydrocarbon group having 1 to 30 carbon atoms;

[0243] (a is 0 or 1)

[0244] In the above equation (v), R is... A1 or R A2 The monovalent hydrocarbon group representing 1 to 30 carbon atoms can preferably be represented by X of formula (1). 11 The carbon number of monovalent hydrocarbon groups with 1 to 20 carbons is expanded to 30.

[0245] Among these, as R A1 or R A2 Preferably, they are hydrogen atoms or monovalent hydrocarbon groups having 1 to 10 carbon atoms, and more preferably, they are straight-chain or branched alkyl groups having hydrogen atoms or 1 to 10 carbon atoms.

[0246] As specific examples of structural units (V), the structural units represented by the following equations (v-1) to (v-11) can be listed respectively.

[0247] [Chemistry 18]

[0248]

[0249] Furthermore, for example, by using a diene compound represented by formula (v1) as a monomer in the polymerization, the structural unit represented by formula (v) can be introduced into the polymer. Preferred specific examples of such diene compounds include: methyl 2-(allyloxymethyl)(meth)acrylate, ethyl 2-(allyloxymethyl)(meth)acrylate, n-propyl 2-(allyloxymethyl)(meth)acrylate, etc.

[0250] [Chemistry 19]

[0251]

[0252] (In formula (v1), R) A1 and R A2 (This has the same meaning as the aforementioned formula (v))

[0253] The base polymer may contain one structural unit (V) or a combination of two or more.

[0254] When the polymer (A) contains structural units (V), the lower limit of the content ratio of structural units (V) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 1% by mass, more preferably 5% by mass, and even more preferably 8% by mass. Furthermore, the upper limit of the content ratio is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. By setting the content ratio of structural units (V) within the aforementioned range, a cured product with superior flexural strength can be obtained, which is therefore preferred. Additionally, it can suppress the possibility of pattern collapse caused by melting of the composition during heating (post-baking) at relatively high temperatures during film formation.

[0255] [Structural Unit (VI)]

[0256] In the case that the radiosensitive linear composition of the present invention is a chemically amplified composition, when the polymer (A1) further comprises a structural unit (VI) having one or more groups selected from the group consisting of groups represented by the following formula (vi) and acid-dissociable groups, a coating film with excellent development adhesion can be formed, which is preferred from the aforementioned point of view.

[0257] [Chemistry 20]

[0258]

[0259] (in formula (vi),

[0260] R B1 R B2 and R B3 Each of the following is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group; wherein, R B1 R B2 and R B3 At least one of them is an alkoxy group having 1 to 6 carbon atoms;

[0261] "*" indicates a bond.

[0262] As R B1 ~R B3 Alkoxy groups with 1 to 6 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc. Among these, R... B1 ~R B3 The alkoxy group is preferably methoxy or ethoxy.

[0263] R B1 ~R B3The alkyl group having 1 to 10 carbon atoms can be either straight-chain or branched. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Among these, methyl, ethyl, or propyl is preferred.

[0264] From the perspective of obtaining a hardened material with excellent heat resistance by forming a cross-linked structure, and from the perspective of improving the storage stability of radiosensitive linear compositions, R B1 ~R B3 At least one of them is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all of them are alkoxy groups.

[0265] In the above, R B1 Preferably, it is an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and even more preferably a methoxy or ethoxy group. B2 and R B3 Preferably, it is a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, an alkyl group with 1 to 10 carbon atoms, or a phenyl group; more preferably, it is a hydroxyl group, an alkoxy group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms.

[0266] The structural unit (VI) is preferably a structural unit derived from a monolith having polymeric carbon-carbon unsaturated bonds (hereinafter also referred to as "unsaturated monolith"), and more specifically, preferably at least one selected from the group consisting of the structural units represented by the following formula (vi-1) and the structural units represented by the following formula (vi-2).

[0267] [Chemistry 21]

[0268]

[0269] In equations (vi-1) and (vi-2),

[0270] R β1 It can be a hydrogen atom, methyl group, hydroxymethyl group, cyano group, or trifluoromethyl group;

[0271] R B21 and R B22 Each can be independently a divalent aromatic cyclic group or a chain hydrocarbon group;

[0272] R B1 R B2 and R B3 (This has the same meaning as the aforementioned formula (vi))

[0273] In equations (vi-1) and (vi-2), R B21 R B22The divalent aromatic cyclic group is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthyl group. The divalent chain hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

[0274] In terms of obtaining patterns (hardened materials) with higher heat resistance and hardness, and in terms of improving the solubility of the exposed part relative to alkaline developer, R B21 R B22 Preferably, it is a divalent aromatic cyclic group, and particularly preferably a substituted or unsubstituted phenylene group.

[0275] Specific examples of monomorphs constituting structural unit (VI) include: styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloyloxyphenyltrimethoxysilane, (meth)acryloyloxyphenyltriethoxysilane, (meth)acryloyloxyphenylmethyldimethoxysilane, (meth)acryloyloxyphenylethyldiethoxysilane, etc.; trimethoxy(4- Vinylnaphthyl silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloyloxynaphthyltrimethoxysilane, etc.; 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 4-(meth)acryloyloxybutyltrimethoxysilane, etc.

[0276] The term "acid-dissociable group" refers to a group formed by substituting hydrogen atoms in acidic functional groups such as phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups, and specifically, a group that dissociates under the action of an acid. For example, exposure to light can cause the acid-dissociable group to dissociate, producing a carboxyl group, etc., due to the acid generated by the photoacid generator. This creates a difference in solubility relative to the developer between the exposed and unexposed areas of the coating, thereby enabling pattern formation.

[0277] The acid dissociative group is preferably the group represented by formula (vi-3) or the group represented by formula (vi-4).

[0278] [Chemistry 22]

[0279]

[0280] (in equation (vi-3),

[0281] R B4 and R B5Each group is independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which at least a portion of the hydrogen atoms of the hydrocarbon group is substituted by a hydroxyl group, a halogen atom, or a cyano group; wherein, R is absent. B4 and R B5 The case where all atoms are hydrogen atoms;

[0282] R B6 It is a hydrocarbon group having 1 to 30 carbon atoms, a group having an oxygen atom or a sulfur atom at the carbon-carbon inter-carbon or bond side end of the hydrocarbon group, or a group having at least a portion of the hydrogen atoms of these groups substituted by a hydroxyl group, a halogen atom or a cyano group.

[0283] R B7 It consists of carbon atoms or silicon atoms;

[0284] In equation (vi-4),

[0285] R B8 ~R B14 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms;

[0286] m is 1 or 2; when m is 2, multiple R B11 and R B12 They can be the same or different;

[0287] In equations (vi-3) and (vi-4), "*" indicates the location where the bonding occurs.

[0288] As R B4 ~R B6 Hydrocarbon groups with 1 to 30 carbon atoms, preferably X of formula (1) 11 The carbon number of monovalent hydrocarbon groups with 1 to 20 carbons is expanded to 30.

[0289] R as in equation (vi-3) B4 ~R B6 Each of the alkyl groups is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

[0290] As R B8 ~R B14 The hydrocarbon group having 1 to 12 carbon atoms can preferably be the R group. B4 ~R B6 The group corresponding to carbon number 1 to 12 in hydrocarbon groups with carbon number 1 to 30.

[0291] As a structural unit having the acid dissociative group, the structural unit represented by the following formulas (vi-3-1) and (vi-4-1) is preferred, for example.

[0292] [Chemistry 23]

[0293]

[0294] In equations (vi-3-1) and (vi-4-1), m1 is either 0 or 1. R β1 R in equations (vi-1) and (vi-2) β1 They have the same meaning. R B4 ~R B14 R in equations (vi-3) and (vi-4) B4 ~R B14 They have the same meaning.

[0295] In equations (vi-3-1) and (vi-4-1), L B1 L B2 They are independent single-bond and divalent linkage groups, respectively.

[0296] As the L B1 L B2 Divalent linkages in alkyl groups can be listed as: alkyldiyl, cycloalkyldiyl, alkenyl, and aryldiyl.

[0297] Examples of monotonous entities that provide the structural unit represented by formula (vi-4-1) include tetrahydrofurfuryl methacrylate and tetrahydrofuran methacrylate.

[0298] The base polymer may contain one structural unit (VI) or a combination of two or more.

[0299] When the polymer (A) contains structural unit (VI), the lower limit of the content ratio of structural unit (VI) (the total content ratio when multiple structural units are included) relative to all structural units constituting the base polymer is preferably 5% by mass, more preferably 10% by mass, and even more preferably 12% by mass. Furthermore, the upper limit of the content ratio is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass. By setting the content ratio of structural unit (VI) within the aforementioned range, the coating film exhibits better resolution, which is preferable in this respect.

[0300] (Synthesis method of polymer (A1))

[0301] The polymer (A1) can be manufactured, for example, using an unsaturated monomer capable of incorporating the structural units, in a suitable solvent, in the presence of a polymerization initiator, by known methods such as free radical polymerization.

[0302] 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 preferred proportion of the polymerization initiator is 0.01 to 30 parts by mass relative to 100 parts by mass of the total monomer used in the reaction.

[0303] Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably set to be 0.1% to 60% by mass of the total amount of the monomers used in the reaction relative to the total amount of the reaction solution.

[0304] 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 directly in the reaction solution for the preparation of radiosensitive linear compositions, or it can be used after separation from the reaction solution. Polymer separation can be carried out using known methods such as injecting the reaction solution into a large volume of undesirable solvent and drying the resulting precipitate under reduced pressure, or removing the precipitate by vacuum distillation using an evaporator.

[0305] The weight-average molecular weight (Mw) of the polymer contained in polymer (A1), calculated from polystyrene by gel permeation chromatography (GPC), is preferably 2,000 or more. A Mw of 2,000 or more is preferable in terms of obtaining a cured product with sufficiently high heat resistance or chemical resistance and good developability. A Mw of 5,000 or more is more preferable, even more preferable to 6,000 or more, and particularly preferable to 7,000 or more. Furthermore, from the viewpoint of good film-forming properties, a Mw of 50,000 or less is preferable, more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 15,000 or less.

[0306] 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. In addition, when the base polymer comprises two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer respectively satisfy the aforementioned range.

[0307] (Polyimide polymer (A2))

[0308] Polyimide polymers (A2) are condensation polymers of tetracarboxylic dianhydrides and diamine compounds, and have an imide ring structure.

[0309] The imidization rate of the polyimide polymer (A2) is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. If the imidization rate is within this range, the amount of escaping gas from the cured product obtained using this composition is low, resulting in a cured product with good surface flatness, which is therefore preferred. Furthermore, the solubility of the polyimide polymer (A2) in alkaline developing solution does not become excessively high, allowing for the preparation of a radiosensitive linear composition exhibiting good resolution. From the viewpoint of ease of synthesis, the imidization rate is preferably 99% or less, more preferably 95% or less. Moreover, the imidization rate is expressed as a percentage, representing the proportion of the number of imide ring structures relative to the total number of ammonium acid structures and imide ring structures in the polyimide.

[0310] Polyimide polymers (A2) can be obtained by reacting tetracarboxylic dianhydride with a diamine compound to synthesize polyamic acid, followed by dehydration, ring closure, and imidization of the polyamic acid.

[0311] (Tetracarboxylic acid dianhydride)

[0312] Examples of tetracarboxylic dianhydrides that constitute polyimide polymers (A2) include aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides.

[0313] In this specification, "aliphatic tetracarboxylic dianhydride" refers to a tetracarboxylic dianhydride in which the two anhydride groups (-CO-O-CO-) are bonded to a chain-like or cyclic aliphatic group. That is, an aliphatic tetracarboxylic dianhydride can be a chain-like tetracarboxylic dianhydride in which the two anhydride groups are bonded to a chain structure; it can also be an alicyclic tetracarboxylic dianhydride in which the two anhydride groups are bonded to the same or different aliphatic rings; or it can be an alicyclic tetracarboxylic dianhydride in which one of the two anhydride groups is bonded to an aliphatic ring and the other to a chain structure. Furthermore, as long as the two anhydride groups of the tetracarboxylic dianhydride are bonded to a chain-like or cyclic aliphatic group, the aliphatic tetracarboxylic dianhydride can also have an aromatic ring structure. "Aromatic tetracarboxylic dianhydride" refers to a tetracarboxylic dianhydride in which one or more of the two anhydride groups are bonded to an aromatic ring. In aromatic tetracarboxylic dianhydrides, when both anhydride groups are bonded to aromatic rings, the two anhydride groups can be bonded to the same aromatic ring or to different aromatic rings.

[0314] Specific examples of tetracarboxylic dianhydrides constituting polyimide polymers (A2) include, as chain-like tetracarboxylic dianhydrides, 1,2,3,4-butanetetracarboxylic dianhydride and ethylenediaminetetraacetic acid dianhydride. Examples of alicyclic tetracarboxylic dianhydrides include: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxylated cyclopentylacetic acid dianhydride, and 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan- Examples of aromatic tetracarboxylic dianhydrides include: 1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxylic bicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornene-2:3,5:6-dianhydride, etc. Examples of aromatic tetracarboxylic dianhydrides include: pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)phthalic anhydride, ethylene glycol bis(p-phenylene)tricarboxylic anhydride ester, 4,4'-carbonyl phthalic anhydride, 4,4'-oxyphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, etc. Among these, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,4,6,8-tetracarboxylic bicyclo[3.3.0]octane-2:4,6:8-dianhydride, and 4,4'-oxydiphthalic anhydride are preferred.

[0315] Regarding the polyimide polymer (A2), the proportion of aliphatic tetracarboxylic dianhydride-derived structural units in the polyimide polymer (A2) is 60 mol% or more, relative to the total amount of tetracarboxylic dianhydride-derived structural units. If the proportion of aliphatic tetracarboxylic dianhydride-derived structural units is less than 60 mol%, the polyimide polymer (A2) has insufficient solubility in the solvent, tending to result in poor coatability of the composition and poor surface flatness of the cured product obtained from the composition. Furthermore, insufficient solubility of tetracarboxylic dianhydride in the polymerization solvent leads to a lower monomer concentration in the polymerization solvent, resulting in poor productivity of the polyimide polymer (A2). From this perspective, the proportion of aliphatic tetracarboxylic dianhydride-derived structural units in the polyimide polymer (A2) is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more.

[0316] (Diamine compounds)

[0317] Examples of diamine compounds that constitute polyimide polymers (A2) include aliphatic diamines and aromatic diamines.

[0318] In this specification, "aliphatic diamine" refers to a diamine compound in which two primary amino groups (-NH2) are bonded to a chain-like or cyclic aliphatic group. That is, an aliphatic diamine can be a chain-like diamine formed by the two primary amino groups of a diamine compound bonded to a chain structure, or an alicyclic diamine formed by the two primary amino groups of a diamine compound bonded to the same or different aliphatic rings, or an alicyclic diamine formed by one of the two primary amino groups of a diamine compound bonded to an aliphatic ring and the other to a chain structure. Furthermore, as long as the two primary amino groups of a diamine compound are bonded to a chain-like or cyclic aliphatic group, the aliphatic diamine may also have an aromatic ring structure. "Aromatic diamine" refers to a diamine compound in which one or more of the two primary amino groups of a diamine compound are bonded to an aromatic ring. In aromatic diamines, when both primary amino groups are bonded to aromatic rings, the two primary amino groups may be bonded to the same aromatic ring or to different aromatic rings.

[0319] [Specific diamine]

[0320] The diamine constituting the polyimide polymer (A2) preferably has at least one functional group (hereinafter also referred to as "functional group F1") selected from the group consisting of phenolic hydroxyl, carboxyl, thiophenol, and sulfonyl (-SO3H) (hereinafter also referred to as "specific diamine"). The number of functional groups (F1) possessed by the specific diamine is not particularly limited. The number of functional groups (F1) possessed by the specific diamine is preferably 1 to 6, more preferably 2 to 4. In terms of high solubility in alkaline developing solutions and high transparency of the cured product, the functional group (F1) is preferably a phenolic hydroxyl group.

[0321] The molecular weight of the specific diamine is not particularly limited. However, regarding its high solubility in the polymerization solvent and its ability to increase the monomer concentration in the solvent, the molecular weight of the specific diamine is preferably 300 or more, more preferably 350 or more, further preferably 450 or more, and particularly preferably 500 or more. Furthermore, from the viewpoint of improving the coatability of the composition and the surface flatness of the cured product obtained from the composition, the molecular weight of the specific diamine is preferably 850 or less, more preferably 750 or less.

[0322] Regarding the aspect that high solubility in the polymerization solvent can increase the concentration of polyimide in the reaction solution obtained by polymerization, the specific diamine is preferably having at least one partial structure selected from the group consisting of fluorene ring structure, indene ring structure, indene ring structure, lactone ring structure, steroidal structure, and halogenated alkyl structure. Among them, diamines having a fluorene ring structure are preferred due to their high solubility in the polymerization solvent.

[0323] From the viewpoint of ensuring solubility in the polymerization solvent and simultaneously achieving good surface flatness of the hardened product obtained from this composition, the specific diamine is preferably an aromatic diamine. Specific examples of the specific diamine include compounds represented by each of the following formulas (A2-1) to (A2-7).

[0324] [Chemistry 24]

[0325]

[0326] [Other diamines]

[0327] The diamine compound constituting the polyimide polymer (A2) may be a specific diamine, or it may combine a specific diamine with a diamine that does not have a functional group (F1) (hereinafter also referred to as "other diamines"). Examples of other diamines include: aliphatic diamines, aromatic diamines, and diamino organosiloxanes. Examples of aliphatic diamines include chain diamines and alicyclic diamines.

[0328] Specific examples of other diamines include, as chain diamines, m-phenylenediamine, hexamethylenediamine, etc. As alicyclic diamines, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc. As aromatic diamines, 1,1-bis(4-aminophenyl)cyclopentane, 1,1-bis(4-aminophenyl)cyclohexane, 1,1-bis(4-aminophenyl)cycloheptane, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4-aminophenyl-4-aminobenzoic acid ester, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,6-bis(4-aminophenoxy)hexane, 6,6'-(pentamethylenedioxy)cyclohexane, etc. bis(3-aminopyridine), N,N'-di(5-amino-2-pyridyl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, bis[2-(4-aminophenyl)ethyl]adipic acid, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylethyl urea, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4, 4'-(phenylene diisopropylidene)bisaniline, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 3,6-diaminoacridine, N4,N4'-bis(4-aminophenyl)-N4,N4'-dimethylbenzidine, N,N'-bis(5-aminopyridin-2-yl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholesterylalkyloxy-3,5-diaminobenzene, cholesterolyl 3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid

[0329] =5ξ-cholestan-3-yl, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, etc. Examples of diamino organosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and 1,3-bis(4-anilino)tetramethyldisiloxane.

[0330] Regarding the polyimide polymer (A2), the proportion of structural units derived from a specific diamine is preferably 30 mol% or more, relative to the total amount of structural units derived from the diamine compound in the polyimide polymer (A2). If the proportion of structural units derived from the specific diamine is less than 30 mol%, the polyimide polymer (A2) has insufficient solubility in the alkaline developer, tending to have poor resolution. Furthermore, from the viewpoint of preventing the unexposed portion from becoming too soluble in the developer and maintaining good resolution of the composition, the proportion of structural units derived from the specific diamine is preferably 99 mol% or less, more preferably 95 mol% or less, relative to the total amount of structural units derived from the diamine compound in the polyimide polymer (A2).

[0331] Polyimide polymers (A2) can be obtained by dehydrating and ring-closing polyamic acid and then imidizing it. There are no particular limitations on the synthesis method of polyamic acid; for example, the method described in Japanese Patent Application Publication No. 2023-177343 is preferred.

[0332] The polyimide polymer (A2) having a polystyrene-converted weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is preferably 1,000 or more and 500,000 or less, more preferably 2,000 or more and 300,000 or less. Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the polystyrene-converted number average molecular weight (Mn) determined by GPC, is preferably 5 or less, more preferably 4 or less.

[0333] The proportion of polymer (A) relative to the total amount of solid components contained in the radiosensitive linear composition is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. Furthermore, the proportion of polymer (A) relative to the total amount of solid components contained in the radiosensitive linear composition is preferably 95% by mass or less, more preferably 90% by mass or less. By setting the proportion of polymer (A) within the aforementioned range, a cured product exhibiting sufficiently high chemical resistance and good developability and transparency can be obtained, which is preferable in these respects.

[0334] <Photoacid Generator (B)>

[0335] This composition contains the polymer (A) and a photoacid generator (B). A positive pattern can be formed by irradiating this composition with radiation (visible light, ultraviolet light, far ultraviolet light, etc.). The photoacid generator (B) can be any compound that generates acid upon irradiation with radiation, such as quinone diazide compounds, oxime sulfonate compounds, onium salts, sulfonylimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylic acid ester compounds, etc. Among these, quinone diazide compounds and oxime sulfonate compounds are preferred in terms of high radiation sensitivity.

[0336] (quinone diazide compound)

[0337] Quinone diazide compounds are compounds that produce carboxylic acids through 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 with 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.

[0338] 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-[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. Among these, the preferred condensate of 4,4'-[1-[4-[1-[4-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinone diazide-5-sulfonyl chloride is the quinone diazide-5-sulfonyl chloride.

[0339] These quinone diazide compounds can be used alone or in combination of two or more.

[0340] (oxime sulfonate compounds)

[0341] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (t).

[0342] [Chemistry 25]

[0343]

[0344] (in formula (t),

[0345] R 40 It 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;

[0346] "*" indicates a bond.

[0347] In the above equation (t), R is... 40 Monovalent hydrocarbon groups, for example, include alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 4 to 12 carbon atoms, and aryl groups with 6 to 20 carbon atoms. Substituents, for example, include alkyl groups with 1 to 5 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, side oxygen groups, and halogen atoms.

[0348] Examples of oxime sulfonate compounds include: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (2-[2-(4-methylphenylsulfonyloxyimino)-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493, etc. Commercially available oxime sulfonate compounds include BASF's Irgacure PAG121.

[0349] (sulfonamide compounds)

[0350] If sulfonylimide compounds are to be exemplified, the following can be listed: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphor... (Sulfoyloxy) phthalimide, N-(2-trifluoromethylphenylsulfonyloxy) phthalimide, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy) diphenylmaleimide, N-(camphorsulfonyloxy) diphenylmaleimide, (4-methylphenylsulfonyloxy) diphenylmaleimide, trifluoromethanesulfonic acid-1,8-naphthalenediamide.

[0351] Specific examples of the onium salts, halogenated compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylic acid ester compounds include, for example, the compounds described in paragraphs

[0078] to

[0106] of Japanese Patent Application Publication No. 2014-157252, and the compounds described in International Publication No. 2016 / 124493.

[0352] The photoacid generator (B) can be used alone or in combination with two or more. The lower limit of the photoacid generator content relative to 100 parts by weight of polymer (A) incorporated into the composition is preferably 0.01 parts by weight, more preferably 0.1 parts by weight, and even more preferably 1 part by weight. Furthermore, the upper limit of the photoacid generator (B) content relative to 100 parts by weight of polymer (A) incorporated into the composition is preferably 50 parts by weight, more preferably 40 parts by weight, and even more preferably 30 parts by weight. Setting the photoacid generator (B) content to 0.01 parts by weight or more allows for good patterning and ensures sufficient heat resistance, which is preferable in this respect. Additionally, setting the photoacid generator (B) content to 50 parts by weight or less allows for a sufficient reduction in the amount of unreacted photoacid generator (B) after exposure, suppressing the decrease in developability caused by the residue of photoacid generator (B), which is preferable in this respect.

[0353] When using a quinone diazide compound as the photoacid generator (B), the lower limit of the content of the quinone diazide compound relative to 100 parts by mass of polymer (A) formulated into the composition is preferably 1 part by mass, more preferably 10 parts by mass, and even more preferably 15 parts by mass. Furthermore, the upper limit of the content of the quinone diazide compound relative to 100 parts by mass of polymer (A) formulated into the composition is preferably 50 parts by mass, more preferably 30 parts by mass. Setting the content of the quinone diazide compound to 1 part by mass or more allows for sufficient generation of carboxylic acids through irradiation of the composition, significantly increasing the difference in solubility between the irradiated and unirradiated portions relative to the developing solution, thus enabling good patterning; this is preferable in this respect. Additionally, increasing the amount of carboxylic acid participating in the reaction with the polymer components sufficiently ensures heat resistance and chemical resistance; this is also preferable in this respect. On the other hand, by setting the content of quinone diazide compound to 50 parts by mass or less, the amount of quinone diazide compound that does not react after exposure can be sufficiently reduced, and the reduction in developability caused by the residue of quinone diazide compound can be suppressed, which is preferred in this respect.

[0354] When using a compound other than a quinone diazide compound as the photoacid generator (B), the lower limit of its content relative to 100 parts by weight of polymer (A) formulated into the composition is preferably 0.1 parts by weight, more preferably 0.3 parts by weight, and even more preferably 0.5 parts by weight. Furthermore, the upper limit of its content relative to 100 parts by weight of polymer (A) formulated into the composition is preferably 5 parts by weight, more preferably 3 parts by weight.

[0355] <Solvent (E)>

[0356] The radiosensitive linear composition disclosed herein is a liquid composition in which other components, such as polymer (A), photoacid generator (B), and compound (C), are preferably dissolved or dispersed in a solvent (E). The solvent used is preferably an organic solvent that dissolves each component incorporated into the radiosensitive linear composition and does not react with any of the components.

[0357] There are no particular limitations on the solvent (E), and examples include: alcohol solvents, ether solvents, ester solvents, ketone solvents, amide solvents, etc. Solvent (E) can be used alone or in combination of two or more.

[0358] Examples of alcohol solvents include: methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, diacetone alcohol, and other alkyl alcohols; and benzyl alcohol and other aromatic alcohols.

[0359] Examples of ether solvents include: diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and other ethylene glycol monoalkyl ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and other propylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and other diethylene glycol monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and other diethylene glycol dialkyl ethers; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and other dipropylene glycol monoalkyl ethers, etc.

[0360] Examples of ester-based solvents include: ethyl acetate, isopropyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and other carboxylic acid esters; propylene glycol diacetate and other polyol carboxylic acid ester solvents; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other polyol partial ether carboxylic acid ester solvents; and lactone solvents such as γ-butyrolactone and valerolactone.

[0361] Examples of ketone solvents include: acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, etc.

[0362] Among these, ether-based solvents and ester-based solvents are preferred, more preferably ester-based solvents, and even more preferably polyol partial ether carboxylic acid ester solvents. Furthermore, among the ether-based and ester-based solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl lactate, and methyl 3-methoxypropionate are preferred.

[0363] The content of solvent (E) in this composition is not particularly limited, but it is preferably adjusted so that the concentration of the solid components (components other than solvent (E)) in this composition is within the following range. As a lower limit for the concentration of the solid components in this composition, 5% by mass is preferred, more preferably 8% by mass, and even more preferably 15% by mass. On the other hand, as an upper limit for the concentration of the solid components, 60% by mass is preferred, more preferably 40% by mass, and even more preferably 30% by mass. If the concentration of the solid components in the radiosensitive linear composition is 5% by mass or more, the film thickness can be sufficiently ensured when the radiosensitive linear composition is coated onto the substrate, which is preferable in this respect. Furthermore, if the concentration of the solid components is 60% by mass or less, the film thickness will not become excessive, thereby moderately improving the viscosity of the radiosensitive linear composition and ensuring good coatability, which is preferable in this respect.

[0364] <Other Ingredients>

[0365] In addition to the polymer (A), photoacid generator (B), compound (C), and solvent (E) described herein, the radiosensitive linear composition may also contain other components (hereinafter also referred to as "other components"). Examples of other components include, for instance, bonding aids (functional silane coupling agents, etc.), surfactants, polymerization inhibitors, antioxidants, chain transfer agents, etc. The formulation ratios of these components can be suitably selected according to each component without impairing the effects of this disclosure.

[0366] The radiosensitive linear composition disclosed herein, by comprising a polymer (A), a photoacid generator (B), and satisfying at least one of 1) or 2), exhibits excellent radiation sensitivity, melt flow resistance, lightfastness (escape gas suppression), and chemical resistance. Such a radiosensitive linear composition disclosed herein is useful as a radiosensitive linear composition for organic EL display elements.

[0367] Methods for manufacturing hardened materials

[0368] The method for manufacturing the hardened material in this embodiment includes:

[0369] (Step 1) Step of forming a coating film using a radioactive linear composition;

[0370] (Step 2) The step of irradiating at least a portion of the coating with radiation;

[0371] (Step 3) The step of developing the coating after radiation irradiation; and

[0372] (Step 4) The step of heating the developed coating.

[0373] The following is a detailed description of each process.

[0374] <Process 1: Coating Formation Process>

[0375] In this process, a linearly induced radiation composition is applied to the surface on which the coating will be formed (hereinafter also referred to as the "coating surface"), preferably by heat treatment (pre-baking) to remove the solvent and form a coating on the coating surface. The material of the coating surface is not particularly limited. For example, when using a linearly induced radiation composition to form a planarization film, the linearly induced radiation composition is applied to a substrate on which switching elements such as thin-film transistors (TFTs) are disposed to form the coating. For example, a glass substrate or a resin substrate can be used as the substrate.

[0376] Examples of coating methods for the radiosensitive linear composition include spraying, roller coating, spin coating, slot die coating, bar coating, and inkjet coating. Spin coating, slot die coating, or bar coating are preferred. Pre-baking conditions vary depending on the type and proportion of each component in the radiosensitive linear 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 1 μm to 12 μm.

[0377] <Process 2: Exposure Process>

[0378] In this process, 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 mask having a predetermined pattern, thereby forming a patterned hardened film (e.g., an interlayer insulating 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, such as gamma rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The exposure dose of the radiation is preferably 0.1 J / m². 2 ~20,000 J / m 2 .

[0379] <Process 3: Development Process>

[0380] In this process, the coating film irradiated with radiation in step 2 is developed. Specifically, the coating film irradiated with radiation in step 2 is subjected to positive development using a developing solution to remove the irradiated portion. An aqueous solution of an alkali (alkaline compound) can be used as the developing solution. Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and the alkali exemplified in paragraph

[0127] of Japanese Patent Application Publication No. 2016-145913. The alkali concentration of the aqueous solution is preferably 0.1% to 5.0% by mass from the viewpoint of obtaining adequate developability. 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 seconds to 120 seconds. Furthermore, it is preferable to perform a rinsing treatment with running water after the development process.

[0381] <Process 4: Heating Process>

[0382] In this process, the coating film developed in step 3 is subjected to a heating treatment (post-baking). This causes a curing reaction in the film, resulting in a cured film exhibiting good chemical resistance. Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120°C to 250°C. Furthermore, for example, when heating is performed on a hot plate, the heating time is 5 minutes to 40 minutes, and when heating is performed in an oven, the heating time is 10 minutes to 80 minutes. By performing this process as described above, a cured film with a target pattern can be formed on the substrate.

[0383] Furthermore, a post-exposure step may also be included between steps 3 and 4. By irradiating the developed coating with radiation, a hardened film with excellent melt flow resistance or transparency during the heating process can be formed. Examples of radiation include ultraviolet light, far ultraviolet light, visible light, X-rays, and charged particle beams such as electron beams. Among these, ultraviolet light is preferred, such as gamma rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The exposure dose of the radiation is preferably 0.1 J / m. 2 ~20,000 J / m 2 .

[0384] Hardened materials

[0385] The cured material disclosed herein is formed using the aforementioned radiosensitive linear composition. The radiosensitive linear composition of this disclosure has high radiation sensitivity, and after patterning, it can suppress melt flow caused by heat, and also exhibits good light resistance (escape gas suppression) and chemical resistance. Therefore, the cured material is useful for forming planarization films or isolation walls in organic EL elements. Specifically, in organic EL elements, the cured material can be used as a planarization film to flatten surface irregularities caused by thin-film transistors (TFTs), an isolation wall used for color differentiation in color conversion layers using quantum dots, and an isolation wall to differentiate areas where a light-emitting layer is formed. Furthermore, the cured material can also be used as an interlayer insulating film to insulate between wirings, a protective film to protect TFTs, a spacer, a color filter, etc.

[0386] Organic EL Display Components

[0387] The organic EL (electroluminescent) display element disclosed herein includes a hardened film formed using the aforementioned radiometric linear composition. The organic EL display element of this disclosure can be effectively applied to a variety of uses, such as as a display device for: clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (PDAs), digital cameras, mobile phones, smartphones, various monitors, LCD televisions, information displays, etc.

[0388] [Example]

[0389] The present invention will now be specifically described through examples, but the present invention is not limited to these examples. Furthermore, unless otherwise specified, "parts" and "%" in the examples and comparative examples refer to quality standards.

[0390] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)]

[0391] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were determined by the following methods.

[0392] • Determination method: Gel permeation chromatography (GPC)

[0393] • Device: HLC-8420GPC manufactured by Tosoh Corporation

[0394] • Mobile phase: Tetrahydrofuran

[0395] (When the polymer is polyimide or polyamic acid ester, dimethylformamide is used as the mobile phase.)

[0396] • Column temperature: 40℃

[0397] • Flow rate: 1.0 mL / min

[0398] • Sample concentration: 1.0% by mass

[0399] • Sample injection volume: 100 μL

[0400] • Detector: Differential refractometer

[0401] • Standard reference material: Monodisperse polystyrene

[0402] [Determination of the maximum absorption wavelength and absorbance of compound (C) or ultraviolet-absorbing compound (a)]

[0403] The following values ​​were used: acetonitrile solutions of compound (C) or ultraviolet-absorbing compound (a) at a concentration of 0.1 g / L were prepared and measured using a UV-Vis-NIR spectrophotometer (Japan Spectrophotometer, V-670).

[0404] <Synthesis of Polymer (A)>

[0405] [Synthetic Example A-1] Synthesis of (meth)acrylic polymer (A1-1)

[0406] 13 parts of 2,2'-azobis(isobutyrate) dimethyl ester and 200 parts of diethylene glycol ethyl methyl ether were charged into a flask including a cooling tube and a stirrer. Then, 13 parts of methacrylic acid, 20 parts of 3,4-epoxycyclohexyl methacrylate, 20 parts of glycidyl methacrylate, and 47 parts of methyl methacrylate were added. After nitrogen purging, the temperature of the solution was raised to 80°C while slowly stirring, and this temperature was maintained for 5 hours, thereby obtaining a polymer solution containing polymer (A1-1). The solid content concentration of the polymer solution was 34.5% by mass, the Mw of polymer (A1-1) was 9,500, and the molecular weight distribution (Mw / Mn) was 2.3.

[0407] Synthesis Examples A-2 to A-6: Synthesis of Polymers (A1-2) to (A1-6)

[0408] In addition to using the types and proportions (parts by mass) of each component shown in Table 1, polymer solutions containing polymers (A1-2) to (A1-6) having the same solid component concentration, molecular weight, and molecular weight distribution as polymer (A1-1) were obtained using the same method as in Synthesis Example A-1. Furthermore, in Table 1 below, "-" indicates that the corresponding component was not used. The same applies to the following tables.

[0409] The monomers used in the synthesis of polymers (A1-1) to (A1-6) are as follows.

[0410] (Provide a single volume of structural unit (I))

[0411] MA: Methacrylic acid

[0412] •PIPE: p-Isopropylenephenol

[0413] (Provide a single volume of structural unit (II))

[0414] ECHMA: 3,4-epoxycyclohexyl methyl methacrylate

[0415] GMA: Glycidyl methacrylate

[0416] (Provide a single volume of structural unit (III))

[0417] ·RUVA-93: 2-(2-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.)

[0418] (Provide a single volume of structural unit (IV))

[0419] CHMA: Cyclohexyl methacrylate

[0420] CHMI: N-Cyclohexylmaleimide

[0421] MMA: Methyl methacrylate

[0422] (Provide a single volume of structural unit (V))

[0423] ·AOMA: Methyl 2-(allyloxymethyl)acrylate (manufactured by Nippon Shokubai Co., Ltd.)

[0424] (Provide a single volume of structural unit (VI))

[0425] MATHF: Tetrahydrofuranyl methacrylate

[0426] [Table 1]

[0427]

[0428] [Synthesis Examples A-7 and A-8] Synthesis of polyimide polymers (A2-1) and (A2-2)

[0429] The synthesis was carried out in the same manner as in Synthesis Examples 2 and 3 disclosed in Japanese Patent Application Publication No. 2023-177343, to obtain a γ-butyrolactone (GBL) solution containing 25% by mass of polymers (A2-1) and (A2-2). Table 2 below shows the amounts, molecular weights, and imidization rates of the raw materials used in polymers (A2-1) and (A2-2). The imidization rate was determined by the following method.

[0430] <Imidification rate of polyimide>

[0431] The polyimide solution was added to pure water, and the resulting precipitate was dried under reduced pressure at room temperature. It was then dissolved in deuterated dimethyl sulfoxide, and proton NMR spectroscopy was performed at room temperature using tetramethylsilane as a reference. 1H-nuclear magnetic resonance, 1 H-NMR) determination. Based on the obtained 1 The H-NMR spectrum was used to determine the imidization rate (%) using the following formula (1).

[0432] Imidification rate (%) = (1-(β) 1 / (β 2 ×α)))×100(1)

[0433] (In equation (1), β) 1 It is the peak area of ​​protons originating from NH groups that appears near a chemical shift of 10 ppm, β 2 It originates from the peak area of ​​other protons, and α is the ratio of the number of other protons to the number of NH groups in the polymer precursor (polyamic acid).

[0434] [Table 2]

[0435]

[0436] The structures of the compounds used in Table 2 are shown below.

[0437] [Chemistry 26]

[0438]

[0439] [Synthetic Example A-9] Synthesis of Polyamate (A2-3)

[0440] The synthesis was carried out in the same manner as in Synthesis Example 14 of Japanese Patent Application Publication No. 2023-177343 to obtain polyamic acid ester (polymer (A2-3)) powder. The raw materials used in the synthesis were (DA-2) / (DA-3) / (AN-3) / (MA-1).

[0441] = 80 / 5 / 100 / 30 (molar parts). The structures of (DA-2), (DA-3), and (MA-1) are as described above. The structure of (AN-3) is as follows.

[0442] [Chemistry 27]

[0443]

[0444] [Synthetic Example AC-1] Synthesis of Polysiloxane (AC-1)

[0445] The synthesis was carried out in the same manner as in Synthesis Example 1 of Japanese Patent Publication No. 2022-551938, and a propylene glycol monomethyl ether acetate (PGMEA) solution containing 40% by mass of polysiloxane (SI-1) (polymer (AC-1)) was obtained.

[0446] [Synthetic Examples C-1 and C-2] Synthesis of UV absorber precursor compounds (C-6) and (C-7)

[0447] According to Examples 5 and 16 of Japanese Patent No. 7393205, UV absorber precursor compound (C-6) and UV absorber precursor compound (C-7) (compounds I-1-35 and I-1-47 of Japanese Patent No. 7393205) were synthesized.

[0448] Synthesis of [Synthetic Examples C-3, C-4, C-5, C-6, C-7] Precursor compounds for ultraviolet absorbers (C-9), (C-10), (C-11), (C-12), and (C-13)

[0449] According to Manufacturing Examples A1-1, 2-1, 3-1, 3-2, and 3-3 of Japanese Patent No. 7236386, UV absorber precursor compounds (C-9), (C-10), (C-11), (C-12), and (C-13) were synthesized (compounds A1-1, A2-1, A3-1, A3-2, and A3-3 of Japanese Patent No. 7236386).

[0450] <Preparation of Radiosensitive Linear Compositions>

[0451] The following shows the polymer (A), photoacid generator (B), compound (C), and solvent (E) used in the preparation of the radiosensitive linear composition.

[0452] Polymer (A)

[0453] • A1-1 to A1-6: Polymers (A1-1) to (A1-6) synthesized in Synthetic Examples A-1 to A-6

[0454] • A2-1~A2-3: Polymers (A2-1) to (A2-3) synthesized in Synthetic Examples A-7 to A-9

[0455] • AC-1: The polymer synthesized in synthesis example AC-1 (AC-1)

[0456] Photoacid Generator (B)

[0457] B-1: A condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazido-5-sulfonyl chloride (2.0 mol).

[0458] • B-2: Irgacure PAG121 (manufactured by BASF)

[0459] Compound (C)

[0460] •C-1: TINUVIN 400 (manufactured by BASF Japan), molecular weight: 647

[0461] • C-2: Tinuvin 405 (manufactured by BASF Japan), molecular weight: 583.8

[0462] • C-3: Adekastab LA-46 (manufactured by ADEKA), molecular weight: 512

[0463] • C-4: Uvinul 3039 (manufactured by BASF Japan), molecular weight: 361

[0464] • C-5: Adekastab 1413 (manufactured by ADEKA (stock)), molecular weight: 326

[0465] • C-6: Compound (C-6) synthesized in Synthesis Example C-1 (Compound I-1-35 of Japanese Patent No. 7393205), molecular weight: 517.7

[0466] • C-7: Compound (C-7) synthesized in Synthetic Example C-2 (Compound I-1-47 of Japanese Patent No. 7393205), molecular weight: 646.7

[0467] • C-8: RUVA-93: 2-(2-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.), molecular weight: 320.3

[0468] • C-9: Compound (C-9) synthesized in Synthesis Example C-3 (Compound A1-1 of Japanese Patent No. 7236386), molecular weight 859.1

[0469] • C-10: Compound (C-10) synthesized in Synthesis Example C-4 (Compound A2-1 of Japanese Patent No. 7236386), molecular weight 474.5

[0470] • C-11: Compound (C-11) synthesized in Synthesis Example C-5 (Compound A3-1 of Japanese Patent No. 7236386), molecular weight 1000.3

[0471] • C-12: Compound (C-11) synthesized in Synthesis Example C-6 (Compound A3-2 of Japanese Patent No. 7236386), molecular weight 868.0

[0472] • C-13: Compound (C-11) synthesized in Synthesis Example C-7 (Compound A3-3 of Japanese Patent No. 7236386), molecular weight 611.7

[0473] •C'-1: TINUVIN 460 (manufactured by BASF Japan), molecular weight: 630

[0474] • C'-2: Uvinul 3050 (manufactured by BASF Japan), molecular weight: 246

[0475] • C'-3: SEESORB 107 (manufactured by SHIPRO KASEI), molecular weight: 274

[0476] • C'-4: TINUVIN PS (manufactured by BASF Japan), molecular weight: 267

[0477] • C'-5: TINUVIN 234 (manufactured by BASF Japan), molecular weight: 448

[0478] Solvent (E)

[0479] E-1: Diethylene glycol methyl ethyl ether (EDM)

[0480] E-2: Propylene glycol monomethyl ether (PGME)

[0481] E-3: Propylene glycol monomethyl ether acetate (PGMEA)

[0482] E-4: γ-Butyrolactone (GBL)

[0483] E-5: Ethyl lactate (EL)

[0484] <Preparation of Radiosensitive Linear Compositions>

[0485] [Example 1]

[0486] In a polymer solution containing polymer (A1-1), 20 parts of photoacid generator (B-1) and 1 part of compound (C-1) are mixed in an amount equivalent to 100 parts (solid component) of polymer (A1-1). Solvents (E-1), (E-2), and (E-3) are added to achieve a final solid component concentration of 20% by mass. The solvents in the radiosensitive linear composition are added in a ratio of (E-1):(E-2):(E-3) = 50% by mass:25% by mass:25% by mass. The mixture is then filtered using a 0.2 μm membrane filter to prepare the radiosensitive linear composition.

[0487] [Examples 2-26, Comparative Examples 1-12]

[0488] Except for the types and proportions (parts by mass) of each component shown in Table 3, the radiosensitive linear compositions of Examples 2 to 26 and Comparative Examples 1 to 12 were prepared by the same method as in Example 1. Furthermore, when polyimide and polyamic acid ester were used as polymers, solvent (E-4) and solvent (E-5) were used in a ratio of 60% by mass:40% by mass; when polysiloxane was used as a polymer, only solvent (E-3) was used as the solvent.

[0489] [Table 3]

[0490]

[0491] <Evaluation>

[0492] Hardened films were formed from the radiosensitive linear compositions of Examples 1 to 26 and Comparative Examples 1 to 12, and the following items were evaluated using the methods described below. The evaluation results are shown in Table 4.

[0493] <Radiation Sensitivity>

[0494] Hexamethyl disilazane (HMDS) was coated onto a 6-inch glass wafer using a spin coater and heated at 60°C for 1 minute (HMDS treatment). Using a spin coater, various radiosensitive linear compositions prepared as described were coated onto the HMDS-treated wafer. The spin coater rotation speed was adjusted to achieve a post-baked film thickness of 2.0 μm. After drying at 30 Pa for 1 second in a small vacuum drying apparatus, a pre-baking at 100°C for 2 minutes was performed to form a coating with a thickness of 3.0 μm. Subsequently, the coating was exposed using an exposure machine (using a Canon MPA-600FA: ultra-high pressure mercury lamp) with varying exposure levels, through a mask with a 10 μm × 10 μm rectangular exposure area. Afterward, development was performed using a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23°C using the overlay method. The development time was set to 80 seconds. Next, the wafer is rinsed with ultrapure water for one minute, followed by drying, thereby forming a pattern on the HMDS-treated wafer. The entire coating surface is then subjected to a 300 mJ / cm² spray. 2 The wafer was exposed to light by heating it in a clean oven at 250°C for 60 minutes and then baking it to obtain a hardened film. The exposure required to form a 10μm × 10μm pattern during development was investigated. The lower the exposure, the better the radiation sensitivity was considered.

[0495] (Evaluation Criteria)

[0496] AA: less than 90 mJ / cm 2

[0497] A: 90mJ / cm 2 Above and below 120 mJ / cm 2

[0498] B: 120mJ / cm 2 Above and below 150 mJ / cm 2

[0499] C: 150mJ / cm 2 above

[0500] <Mel flow resistance>

[0501] The rectangular aperture cross-sectional shape of the coating, resolved at the optimal exposure, was observed using a scanning electron microscope. Tangents were drawn to the coating pattern at the endpoints where it meets the substrate, and the angle between the tangents and the substrate surface was calculated. A higher angle indicates better melt flow resistance even after heating to 250°C.

[0502] (Evaluation Criteria)

[0503] A: Above 60°

[0504] B: 40° or higher and less than 60°

[0505] C: Less than 40°

[0506] <Lightfastness>

[0507] Except for skipping the exposure using a mask, a post-baked substrate of the radiosensitive linear composite film was prepared by performing the same process as described in the <Radiation Sensitivity> procedure. The substrate, cut to 1 cm square, was then irradiated for 72 hours using a xenon lamp. A benchtop xenon testing machine (ATLAS, SUNTEST CPS+) was used, with an illuminance of 765 W / m². 2 Temperature: 50°C. The substrate was heated to 150°C using a TDS (Electronic Science & Manufacturing Co., Ltd.) instrument, and the escape gas was measured after holding for 5 minutes. The total amount of escape gas was calculated based on the sum of the peak intensities of each component in the mass analysis, and lightfastness was evaluated according to the following criteria.

[0508] (Evaluation Criteria)

[0509] A: When the total amount of escaped gas in Comparative Example 1 is set to 100%, the relative value is less than 50%.

[0510] B: When the total amount of escaped gas in Comparative Example 1 is set to 100%, the relative value is 50% or more and less than 70%.

[0511] C: The relative value when the total amount of escaped gas in Comparative Example 1 is set to 100% is 70% or more.

[0512] <Chemical Tolerance>

[0513] The wafer was set to a 6-inch silicon wafer, and a hardening film was fabricated on the wafer in the same manner as described in the <Radiation Sensitivity> section, except that the exposure of the interposer mask was skipped. The wafer was immersed in resist stripping solution N-300 (NagaseChemteX) heated to 60°C for 6 minutes, followed by a 5-second water rinse with ultrapure water to allow it to dry. The film thickness of the hardened film before and after treatment was measured using an optical interferometer film thickness measuring device (SCREEN Holdings, VM-2210). The stripping solution swelling rate (%) was calculated according to the following formula. Furthermore, the wafer was heated at 230°C in a cleaning oven for 15 minutes, and the stripping solution dissolution rate (%) was calculated using the following formula.

[0514] Swelling rate of stripping fluid (%) = (P / Q-1) × 100

[0515] (In the formula, P represents the residual film after impregnation (μm), and Q represents the residual film before impregnation (μm))

[0516] Stripping solution dissolution rate (%) = (1 - R / Q) × 100

[0517] (In the formula, R represents the residual film after heating (μm), and Q represents the residual film before impregnation (μm))

[0518] (Evaluation Criteria)

[0519] A: Swelling rate less than 4% and dissolution rate less than 1%.

[0520] B: Swelling rate of 4% or higher but less than 6%, and dissolution rate of less than 1%.

[0521] C: Swelling rate of 6% or higher, or dissolution rate of 1% or higher.

[0522] <Bending resistance>

[0523] On a polyimide film substrate, similar to the <radiation sensitivity> description, a radiosensitive composition is coated using a spin coater, followed by vacuum drying and pre-baking to form a coating. Subsequently, development is performed at 23°C for 80 seconds using a developer (2.38% by mass aqueous solution of tetramethylammonium hydroxide), followed by rinsing with ultrapure water for 1 minute. Exposure is then performed using an exposure machine (using a Canon MPA-600FA: ultra-high pressure mercury lamp) at 300 mJ / cm². 2 The obtained coating was subjected to GHI radiation and then baked in a clean oven at 250°C for 60 minutes to form a hardened film on the substrate. The spin coating speed was then adjusted to achieve a final film thickness of 3.0 μm after baking.

[0524] The obtained substrate with the hardened film was cut into dimensions of 50mm x 50mm. Next, with the side with the hardened film facing outwards, the substrate with the hardened film was held in a bent state for 10 minutes with the polyimide film substrates joined together. After 10 minutes from the start of bending, the bent substrate with the hardened film was opened, and the bent portion on the surface of the hardened film was observed using an optical microscope. The bending resistance was evaluated based on the changes in appearance.

[0525] (Evaluation Criteria)

[0526] A: The hardened film has no cracks.

[0527] B: Part of the hardened film has cracks.

[0528] [Table 4]

[0529]

[0530] As shown in Table 4, the radiation-sensitive linear compositions of Examples 1 to 26 exhibited good practical properties in terms of radiation sensitivity, melt flow resistance, light resistance (escape gases), chemical resistance, and flexural resistance, achieving a balance among various properties. In contrast, Comparative Examples 1 to 12 received a "C" rating for each property, indicating they were all inferior to those of Examples 1 to 26.

Claims

1. A radiation-sensitive composition for forming a planarization film or a barrier rib of an organic electroluminescent element, comprising: an alkali-soluble polymer (A), and a photo-acid generator (B), wherein the alkali-soluble polymer (A) is a (meth)acrylic polymer or a polyimide polymer in the radiation-sensitive composition for forming a planarization film or a barrier rib of an organic electroluminescent element, and at least one of the following 1) and 2) is satisfied, 1) the composition contains one or more compounds (C) selected from the group consisting of an ultraviolet absorber (C1) and an ultraviolet absorber precursor compound (C2), 2) the alkali-soluble polymer (A) contains a structural unit (III) derived from an ultraviolet-absorbing compound (a) having an absorption maximum wavelength between 250 nm and 350 nm and an absorbance at 365 nm of 0.4 or less when the maximum value of the absorbance between 250 nm and 350 nm is taken as 1, wherein the compound (C) has a molecular weight of 300 or more, the ultraviolet absorber (C1) is one or more ultraviolet absorbers selected from the group consisting of a benzotriazole-based ultraviolet absorber represented by the following formula (1), a triazine-based ultraviolet absorber represented by the following formula (2), a hydroxybenzophenone-based ultraviolet absorber represented by the following formula (3), and a cyanoacrylate-based ultraviolet absorber represented by the following formula (4), in the formula (1), n1 is an integer of 1 to 3, n2 is an integer of 0 to 3, in the formula (2), n3, n4, and n5 are each independently an integer of 0 to 3, and n3 + n4 + n5 ≧ 1, in the formula (3), n6 and n7 are each independently an integer of 0 to 3, and n6 + n7 ≧ 1, in the formula (4), t is an integer of 1 to 5, n8 and n9 are each independently an integer of 0 to 3, and the ultraviolet absorber precursor compound (C2) is one or more compounds selected from the group consisting of a compound represented by the following formula (5), a compound represented by the following formula (5'), a compound represented by the following formula (6), and a compound represented by the following formula (7), in the formula (5), formula (5'), formula (6), and formula (7), m1 is an integer of 0 to 4, m2 is an integer of 0 to 2, m3 and m4 are each independently an integer of 0 to 4, m5 is an integer of 0 to 3, m6 is an integer of 0 to 3, m7 is an integer of 1 to 3, and m6 + m7 ≦ 3, s1 represents an integer of 1 to 10, and the leaving group represented by Q is a tert-butyloxycarbonyl group, a group represented by the following formula (8), or a group represented by the following formula (9). ​ ​ ​ ​ ​ ​ ​ ​ 2. The radiochromic composition of claim 1, wherein, ​ 3. The radio-sensitive composition according to claim 1, wherein, ​ ​ X 11 is a hydroxyl group or an organic group having a carbon number of 1 to 20; in the case where a plurality of X 11 are present, the plurality of X 11 are the same or different from each other; X 12 is a halogen atom; in case a plurality of X 12 are present, the plurality of X 12 are the same or different from each other; ​ ​ ​ X 21 , X 22 , and X 23 are each independently a hydroxyl group or an organic group having a carbon number of 1 to 20; in the case where a plurality of X 21 , X 22 , X 23 are present, the plurality of X 21 , X 22 , X 23 are each the same or different from each other; ​ ​ X 31 and X 32 are each independently hydroxyl or an organic group having a carbon number of 1 to 20; in the case where a plurality of X 31 , X 32 are present, the plurality of X 31 , X 32 are each the same or different from each other; ​ ​ X 41 R1is a t-valent organic group having a carbon number of 1 to 20; ​ X 42 and X 43 are each independently hydroxyl or an organic group having a carbon number of 1 to 20; in the case where a plurality of X 42 , X 43 are present, the plurality of X 42 , X 43 are each the same or different from each other; ​ 4. The radio-sensitive composition according to claim 1, wherein, ​ ​ R a1 and R a2 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an organic group having a carbon number of 1 to 40, or -O-Q; Q is a leaving group; wherein at least one of R a1 and R a2 is -O-Q; in the case where a plurality of R a1 and R a2 are present, the plurality of R a1 and R a2 are each the same or different from each other; R a3 , R a4 , R a5 , R a6 , R a7 , and R a8 are each independently a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an organic group having a carbon number of 1 to 40; in the case where a plurality of R a3 , R a4 , R a5 , R a6 , R a7 , R a8 are present, the plurality of R a3 , R a4 , R a5 , R a6 , R a7 , and R a8 are each the same or different from each other; ​ ​ ​ ​ L 2 represents a single bond or an s1-valent atom or linking group; ​ 5. The radio-sensitive composition according to claim 4, wherein, ​ in the formula (8), the formula (9), R 81 , R 91 , and R 92 are each independently a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an organic group having a carbon number of 1 to 40; in the case where a plurality of R 81 , R 91 , R 92 exist, the plurality of R 81 , R 91 , and R 92 are each the same or different from each other; R 82 is a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an organic group having a carbon number of 1 to 40; two R 82 are each independently the same or different; n3 is an integer of 0 to 4; n4 and n5 are each independently an integer of 0 to 5; * represents a bond with an oxygen atom.

6. The radiochromic composition of claim 1, wherein, The ultraviolet-absorbing compound (a) is one or more compounds selected from the group consisting of a compound represented by the following formula (1'), a compound represented by the following formula (2'), a compound represented by the following formula (3'), and a compound represented by the following formula (4'), in the formula (1'), X 11' is a hydroxyl group or an organic group having a carbon number of 1 to 20; in the case where a plurality of X 11' are present, the plurality of X 11' are the same or different from each other; at least one of X 11' has a polymerizable group; X 12 n1, n2 and n2 have the same meaning as in the formula (1) in the formula (2'), X 21' , X 22' , and X 23' are each independently a hydroxyl group or an organic group having a carbon number of 1 to 20; in the case where a plurality of X 21' , X 22' , and X 23' are present, the plurality of X 21' , X 22' , and X 23' are each the same or different from each other; at least one of X 21' , X 22' , and X 23' has a polymerizable group; n3, n4, n5 and the formula (2) have the same meaning in the formula (3'), X 31' and X 32' are each independently a hydroxyl group or an organic group having a carbon number of 1 to 20; in the case where a plurality of X 31' , X 32' are present, the plurality of X 31' , X 32' are each the same or different from each other; at least one of X 31' , X 32' has a polymerizable group; n6, n7 and the formula (3) have the same meaning in the formula (4'), X 41' a monovalent organic group having a carbon number of 1 to 20; X 42' and X 43' are each independently a hydroxyl group or an organic group having a carbon number of 1 to 20; in the case where a plurality of X 42' , X 43' are present, the plurality of X 42' , X 43' are each the same or different from each other; at least one of X 42' , X 43' has a polymerizable group; n8' and n9' are each independently an integer of 0 to 3; wherein n8' + n9' ≥ 1.

7. The radiochromic composition of claim 1, wherein, The base-soluble polymer (A) has an acid group.

8. The radiochromic composition of claim 1, wherein, The base-soluble polymer (A) has a cross-linkable group.

9. The radiochromic composition of claim 1, wherein, The radio-sensitizing composition contains the compound (C), The content of the compound (C) is 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the base-soluble polymer (A).

10. The radiochromic composition of claim 1, wherein, The base-soluble polymer (A) contains the structural unit (III), The content ratio of the structural unit (III) in all the structural units constituting the polymer (A) is 0.5% by mass or more and 30% by mass or less.

11. A method for producing a hardened product, comprising: a step of forming a coating film using the radio-sensitizing composition according to any one of claims 1 to 10; a step of irradiating a radio ray to at least a part of the coating film; a step of developing the coating film after the radio ray irradiation; and a step of heating the developed coating film.

12. A hardened product formed using the radio-sensitizing composition according to any one of claims 1 to 10.

13. The hardened product according to claim 12, which is a planarization film or a spacer.

14. An organic electroluminescent display element comprising the hardened product according to claim 13.

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