Radiation-sensitive composition for forming planarization films or partitions of organic EL elements, cured product, organic EL display element, and method for manufacturing the cured product.

Abstract

The present invention has been made in view of the above problems, and aims to provide a radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element that can form a cured product with excellent radiation sensitivity, melt flow resistance, light resistance (outgassing suppression), and chemical resistance. The present invention also aims to provide a cured product formed using the above radiation-sensitive composition, and an organic EL display element equipped with the above cured product. [Solution] The present invention relates to a radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element, comprising an alkali-soluble polymer (A) and a photoacid generator (B), wherein the alkali-soluble polymer (A) is a (meth)acrylic polymer or a polyimide polymer, and satisfies at least one of the following 1) and 2).

Description

[Technical Field]

[0001] The present invention relates to a radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element, a cured product, an organic EL display element, and a method for manufacturing the cured product. [Background technology]

[0002] The display element is provided with an insulating cured film, such as an interlayer insulating film that insulates the space between the wiring and the substrate, or between the wiring itself, as well as a planarizing film and partitions. Generally, the cured film is formed by exposing and developing a coating film made of a radiation-sensitive composition, followed by a heat treatment to thermally cure it.

[0003] In the cured film constituting such display elements, ultraviolet absorbers may be added from the viewpoint of light resistance. Examples of photosensitive compositions to which such ultraviolet absorbers have been added include a positive-type photosensitive paste containing an alkali-soluble resin, a photoacid generator, glass powder having a glass transition temperature in the range of 400 to 600°C, and an ultraviolet absorber (see, for example, Patent Document 1), and a positive-type photosensitive resin composition containing a siloxane copolymer, a 1,2-quinone diazide compound, a specific UV absorber, and a solvent (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2004-110019 [Patent Document 2] Special Publication No. 2022-551938 [Overview of the project] [Problems that the invention aims to solve]

[0005] Various display devices equipped with organic EL elements may be used outdoors depending on their application, and the planarization film and partitions used in the organic EL elements may be exposed to ultraviolet light. It has been found that exposure to ultraviolet light can cause outgassing of these planarization films and partitions, and that this outgassing can cause malfunctions such as wiring corrosion and reduced lifespan in the organic EL elements.

[0006] The present invention has been made in view of the above problems, and aims to provide a radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element that can form a cured product with excellent radiation sensitivity, melt flow resistance, light resistance (outgassing suppression), and chemical resistance. The present invention also aims to provide a cured product formed using the above radiation-sensitive composition, a method for producing the cured product, and an organic EL display element equipped with the above cured product. [Means for solving the problem]

[0007] According to the present invention, the following radiation-sensitive composition, cured product, organic EL display element, and method for manufacturing the cured product are provided.

[0008] In one embodiment, the present invention is Alkali-soluble polymer (A), Photoacid generator (B), A radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element, comprising: The alkali-soluble polymer (A) is a (meth)acrylic polymer or a polyimide polymer. This invention relates to a radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element, satisfying at least one of the following conditions 1) and 2). 1) The above composition is A UV absorber (C1) having a maximum absorption wavelength between 250 nm and 350 nm, and whose absorbance at 365 nm is 0.4 or less when the maximum absorbance between 250 nm and 350 nm is set to 1, and UV absorber precursor compound (C2) that exhibits UV absorption function upon heating or light irradiation. A compound (C) comprising one or more compounds selected from the group, 2) The alkali-soluble polymer (A) contains structural units (III) derived from an ultraviolet-absorbing compound (a) which has a maximum absorption wavelength between 250 nm and 350 nm and whose absorbance at 365 nm is 0.4 or less when the maximum absorbance between 250 nm and 350 nm is set to 1.

[0009] In another embodiment, the present invention is A step of forming a coating film using the above-mentioned radiation-sensitive composition, A step of irradiating at least a portion of the above coating film with radiation, The process of developing the above coating after irradiation with radiation, A step of heating the developed coating film, This relates to a method for producing a cured product, including the product itself.

[0010] In another embodiment, the present invention is The present invention relates to a cured product formed using the above-mentioned radiation-sensitive composition, and an organic EL display element comprising the above-mentioned cured product. [Effects of the Invention]

[0011] The radiation-sensitive composition of the present invention, by containing a specific compound (C) or a polymer having structural units derived from a specific ultraviolet-absorbing compound (a), can form a cured product with excellent radiation sensitivity, melt flow resistance, light resistance (outgassing suppression), and chemical resistance. Furthermore, the method for producing the cured product of the present invention, by using the above-mentioned radiation-sensitive composition, can form a cured product with excellent radiation sensitivity, melt flow resistance, light resistance (outgassing suppression), and chemical resistance. Moreover, the organic EL display element of the present invention is of high quality because it is equipped with the above-mentioned cured product. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0013] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the values ​​indicated before and after "~" as the lower and upper limits, respectively. "Structural unit" refers to a unit that mainly constitutes the main chain structure and is included in the main chain structure in pairs or more.

[0014] In this specification, "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Linear hydrocarbon group" means a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in its main chain and consists only of a linear structure. However, linear hydrocarbon groups may be saturated or unsaturated. "Alicyclic hydrocarbon group" means a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as its ring structure and does not contain an aromatic ring structure. However, an alicyclic hydrocarbon group does not need to consist only of the structure of an alicyclic hydrocarbon; it may also include a linear structure as part of it. "Aromatic hydrocarbon group" means a hydrocarbon group that contains an aromatic ring structure as its ring structure. However, an aromatic hydrocarbon group does not need to consist only of an aromatic ring structure; it may also include a linear structure or an alicyclic hydrocarbon structure as part of it. The ring structure of an alicyclic hydrocarbon group and an aromatic hydrocarbon group may have substituents consisting of hydrocarbon structures. "Cyclic hydrocarbon" includes alicyclic hydrocarbons and aromatic hydrocarbons.

[0015] In this specification, "(meth)acryloyl" encompasses "acryloyl" and "methacryloyl," and "(meth)acrylic" encompasses "acrylic" and "methacrylic." "(meth)acrylate" encompasses "acrylate" and "methacrylate."

[0016] ≪Radiation-sensitive composition≫ The radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element according to this embodiment (hereinafter also referred to as "this composition") is Alkali-soluble polymer (A), Photoacid generator (B), Includes, The alkali-soluble polymer (A) is a (meth)acrylic polymer or a polyimide polymer. At least one of the following conditions 1) and 2) must be satisfied. 1) The above composition is A UV absorber (C1) having a maximum absorption wavelength between 250 nm and 350 nm, and whose absorbance at 365 nm is 0.4 or less when the maximum absorbance between 250 nm and 350 nm is set to 1, and UV absorber precursor compound (C2) that exhibits UV absorption function upon heating or light irradiation. A compound (C) comprising one or more compounds selected from the group, 2) The alkali-soluble polymer (A) contains structural units (III) derived from an ultraviolet-absorbing compound (a) which has a maximum absorption wavelength between 250 nm and 350 nm and whose absorbance at 365 nm is 0.4 or less when the maximum absorbance between 250 nm and 350 nm is set to 1.

[0017] The maximum absorption wavelength and absorbance described above can be obtained by preparing a solution (0.1 g / L) of the ultraviolet absorber (C1) or ultraviolet-absorbing compound (a) and measuring it using an ultraviolet-visible near-infrared spectrophotometer (e.g., JASCO Corporation, V-670). The solvent for forming the solution of the ultraviolet absorber (C1) or ultraviolet-absorbing compound (a) is not particularly limited and any solvent in which the ultraviolet absorber (C1) or ultraviolet-absorbing compound (a) dissolves may be used, but acetonitrile, ethyl acetate, toluene, chloroform, and tetrahydrofuran are preferred. The maximum absorption wavelength and absorbance may be measured directly by placing the solution of the ultraviolet absorber (C1) or ultraviolet-absorbing compound (a) in a quartz cell, or the measurement may be taken on a coating film formed by coating and drying the solution on a glass substrate using spin coating or the like. In this case, a polymer such as polymethyl methacrylate, which does not absorb in the ultraviolet region, may be used in combination for coating film formation. Furthermore, having a maximum absorption wavelength between 250 nm and 350 nm means that in the absorption spectrum of the ultraviolet absorber (C1) or 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 may be further maximum absorption wavelengths in the range of less than 250 nm or greater than 350 nm.

[0018] The following describes each component contained in this composition, as well as any other components that may be added as needed. Unless otherwise specified, each component may be used alone or in combination of two or more components.

[0019] <Compound (C)> This composition comprises an ultraviolet absorber (C1) having a maximum absorption wavelength between 250 nm and 350 nm, and an absorbance of 0.4 or less at a wavelength of 365 nm when the maximum absorbance between 250 nm and 350 nm is set to 1, and UV absorber precursor compound (C2) that exhibits UV absorption function upon heating or light irradiation. It may include one or more compounds (C) selected from the group.

[0020] If this composition contains the above compound (C), the alkali-soluble polymer (A) described later may or may not contain structural unit (III).

[0021] The molecular weight of 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, and more preferably 1500 or less. Having the molecular weight of compound (C) within the above range is preferable because it allows compound (C) to remain in the cured product even during the heating process when forming the cured product, and the effect of adding compound (C) can be fully expressed.

[0022] (UV absorber (C1)) The above-mentioned ultraviolet absorber (C1) has a maximum absorption wavelength between 250 nm and 350 nm, and its absorbance at 365 nm is 0.4 or less, with the maximum absorbance between 250 nm and 350 nm being set to 1.

[0023] 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, and more preferably 0.25 or less. The lower limit is not particularly limited, and the lower the value, the better, usually around 0.01.

[0024] As long as the above ultraviolet absorber (C1) has the above wavelength and absorbance characteristics, its structure is not particularly limited. For example, it is preferably at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers represented by the following formula (1), triazine-based ultraviolet absorbers represented by the following formula (2), hydroxybenzophenone-based ultraviolet absorbers represented by the following formula (3), and cyanoacrylate-based ultraviolet absorbers represented by the following formula (4). More preferably, it is at least one ultraviolet absorber selected from the group consisting of triazine-based ultraviolet absorbers represented by the following formula (2), hydroxybenzophenone-based ultraviolet absorbers represented by the following formula (3), and cyanoacrylate-based ultraviolet absorbers represented by the following formula (4). [Chemical formula] (In the above formula (1), X , 22 , 22 , 23 , 21 , 23 , 21 , 23 , 21 , 22 is a hydroxyl group or an organic group having 1 to 20 carbon atoms. When there are a plurality of X 11 the plurality of X 11 are the same as or different from each other. X 12 is a halogen atom. When there are a plurality of X 12 the plurality of X 12 are the same as or different from each other. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3.) [Chemical formula] (In the above formula (2), X 21 , X 22 and X 23 are each independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. When there are a plurality of X 21 , X 22 , X 23 the plurality of X 21 , X 22 , X<​ [ka] (In the above formula (3), X 31 and X 32 Each of these is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. 31 , X 32 If there are multiple X 31 , X 32 They are either identical or different from one another. n6 and n7 are independent integers between 0 and 3, provided that n6 + n7 ≥ 1. [ka] (In the above formula (4), X 41 This refers to an organic group with 1 to 20 carbon atoms and a t-valent charge. t is an integer between 1 and 10. X 42 and X 43 Each of these is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. 42 , X 43 If there are multiple X 42 , X 43 They are either identical or different from one another. n8 and n9 are each independent integers between 0 and 3.

[0025] X in equation (1) above 11 Examples of organic groups having 1 to 20 carbon atoms include monovalent hydrocarbon groups having 1 to 20 carbon atoms, groups having a divalent heteroatom-containing group between carbon atoms or at the end of the carbon chain of the hydrocarbon group, groups in which some or all of the hydrogen atoms of the hydrocarbon group are replaced with a monovalent heteroatom-containing group, or combinations thereof.

[0026] Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms in the above-mentioned organic group include chain hydrocarbon groups having 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0027] Examples of monovalent linear hydrocarbon groups having 1 to 20 carbon atoms include monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, or monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and 1,1,3,3-tetramethylbutyl. Examples of monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.

[0028] Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include monocyclic or polycyclic saturated hydrocarbon groups, or monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic saturated hydrocarbon groups include bridged alicyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl groups. Examples of monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups. Examples of polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norborneyl, tricyclodecenyl, and tetracyclododecenyl groups. A bridged alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other are bonded together by a linking group containing one or more carbon atoms.

[0029] Examples of the above-mentioned monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xyl, naphthyl, and anthyl groups; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl groups.

[0030] Examples of heteroatoms that constitute the monovalent heteroatom-containing groups and divalent heteroatom-containing groups mentioned above include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, and halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0031] Examples of the monovalent heteroatom-containing groups mentioned above include hydroxyl groups, carboxyl groups, sulfanyl groups, cyano groups, nitro groups, halogen atoms, and the like.

[0032] Examples of the above-mentioned divalent heteroatom-containing groups include -CO-, -C(=O)O-, -CS-, -NH-, -O-, -S-, -SO-, -SO2-, or combinations thereof.

[0033] X in equation (1) above 12 Examples of halogen atoms in this context include fluorine, chlorine, bromine, and iodine atoms.

[0034] In formula (1) above, n1 is an integer between 1 and 3, preferably 1 or 2, and n2 is an integer between 0 and 3, preferably 0 or 1.

[0035] X in equation (2) above 21 , X 22 and X 23 As for organic groups with 1 to 20 carbon atoms in the above formula (1), X 11 Organic groups having 1 to 20 carbon atoms can be suitably used in X. 21 , X 22 and X 23 Preferably, the group is a hydroxyl group, a monovalent linear hydrocarbon group having 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.

[0036] In equation (2) above, n3, n4, and n5 are integers between 0 and 3, and it is preferable that n3+n4+n5≧1 and 6≧n3+n4+n5≧2.

[0037] X in equation (3) above 31 , X 32 As for organic groups with 1 to 20 carbon atoms in the above formula (1), X 11 Organic groups having 1 to 20 carbon atoms can be suitably used in X. 31 , X 32 Preferably, the group is a monovalent linear hydrocarbon group having 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, and more preferably an alkoxy group having 1 to 10 carbon atoms.

[0038] In equation (3) above, n6 and n7 are integers between 0 and 3, and n6 + n7 ≥ 1.

[0039] X in equation (4) above 42 and X 43 In this, the monovalent organic group having 1 to 20 carbon atoms is X in formula (1) above. 11 Organic groups having 1 to 20 carbon atoms can be suitably used in this material.

[0040] X in equation (4) above 41 As the t-valent organic group having 1 to 20 carbon atoms, a group obtained by removing (t-1) hydrogen atoms from the above-mentioned monovalent organic group having 1 to 20 carbon atoms can be suitably adopted. Among these, X 41 When t is 1, a monovalent linear hydrocarbon group having 1 to 20 carbon atoms is preferred, and a group having -CO-, -C(=O)O-, or -O- between carbon atoms or at the end of the carbon chain of the linear hydrocarbon group is preferred, with an alkyl group having 1 to 20 carbon atoms being more preferred.

[0041] In formula (4) above, n8 and n9 are integers between 0 and 3, and are preferably 0 or 1.

[0042] The above value of t is an integer between 1 and 10, and preferably an integer between 1 and 5.

[0043] In the compounds of formulas (1) to (4) above, the hydroxyl group or *-OR bonded to the benzene ring is t1(R t1 * represents an organic group having 1 to 20 carbon atoms, and * represents a bond with a benzene ring. The number of * groups is preferably 3 or less, and more preferably 2. Hydroxyl group or *-OR t1 If the number of elements increases, the maximum absorption wavelength and absorbance ratio may not be met, which is undesirable.

[0044] The following structures can be given as examples of the above-mentioned UV absorber (C1). [ka]

[0045] Commercially available UV absorbers (C1) can also be used, such as TINUVIN400, TINUVIN405, Ubinal 3039, and Ubinal 3030 from BASF Japan Ltd., and ADEKA LA-46 and ADEKA 1413 from ADEKA Corporation.

[0046] (UV absorber precursor compound (C2)) UV absorber precursor compounds (C2) are compounds that have relatively low UV absorption capacity under normal conditions, but exhibit UV absorption function upon heating or light irradiation. UV absorber precursor compounds are also called "UV absorber precursors" or "latent UV absorbers." When this composition contains UV absorber precursor compounds (C2), the UV absorption capacity of the UV absorber precursor compound (C2) is low during composition preparation, but UV absorption capacity is exhibited by carrying out heating or exposure processes in curing product manufacturing using the composition.

[0047] The above ultraviolet absorber precursor compound (C2) is preferably one or more compounds selected from the group consisting of the compound represented by the following formula (5), the compound represented by the following formula (5'), the compound represented by the following formula (6), and the compound represented by the following formula (7). [ka] (In equations (5), (5'), (6), and (7) above, R a1 and R a2 Each of these 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 leaving group. However, R a1 , R a2 At least one of them is -OQ. a1 , R a2 If multiple R a1 , R a2 They are either identical or different from one another. R a3 , R a4 , R a5 , R a6 , R a7 and R a8 Each of these is independently 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. a3 , R a4 , R a5 , R a6 , R a7 , R a8 If multiple R a3 , R a4 , R a5 , R a6 , R a7 , R a8 They are either identical or different from one another. m1 is an integer between 0 and 4, and m2 is an integer between 0 and 2. m3 and m4 are independent integers between 0 and 4. m5 is an integer between 0 and 3. m6 is an integer between 0 and 3, and m7 is an integer between 1 and 3, provided that m6 + m7 ≤ 3. L 2 This represents a single bond or a linking group with s1 valency. s1 represents an integer between 1 and 10.

[0048] The above R a1 , R a2 , R a3 , R a4 , R a5, R a6 , R a7 , R a8 As for organic groups with 1 to 40 carbon atoms in the above formula (1), X 11 In this material, organic groups with 1 to 20 carbon atoms can be suitably adopted, with the number of carbon atoms extended up to 40.

[0049] The above m1 is an integer between 0 and 4, preferably 0 or 1, and the above m2 is an integer between 0 and 2, preferably 0 or 1.

[0050] The above values ​​of m3 and m4 are integers between 0 and 4, and are preferably 0 or 1.

[0051] The above values ​​of m5 and m6 are integers between 0 and 3, and are preferably 0 or 1.

[0052] The above m7 is an integer from 1 to 3, and 2 or 3 is preferred.

[0053] The above s1 is an integer between 1 and 10, preferably between 1 and 5, and particularly preferably 1 or 2.

[0054] The above L 2 represents a single bond or an s1-valent linking group. When s1 is 2, a single bond or an alkanediyl group having 1 to 3 carbon atoms is preferred, and a methylene group is more preferred. When s1 is 3, an alkanetriyl group having 1 to 3 carbon atoms is preferred.

[0055] The above s1-valent linking group may be, for example, an s1-valent atom such as -O- (a divalent atom).

[0056] The compound represented by formula (5') is L 2 It has a structure in which s1 specific groups, as shown below, are bonded to it. These s1 specific groups may be the same or different from each other. [ka] (In the above formula, * represents L 2 (This represents a combination of two elements.)

[0057] The above R a1 and R a2 in which Q is a leaving group, and it is preferably a BOC group (t-butyloxycarbonyl group), a group represented by the following formula (8), a group represented by the following formula (9), or a group represented by the following formula (10), and more preferably a BOC group, a group represented by the following formula (8), or a group represented by the following formula (9).

Chemical formula

[0059] The above R 102 , R 103 The alkyl group having 1 to 10 carbon atoms in the above formula (1) is X 11 Among the alkyl groups having 1 to 20 carbon atoms, those with the corresponding number of carbon atoms can be suitably adopted.

[0060] The above n3 is an integer between 0 and 4, preferably 0 or 1.

[0061] n4 and n5 are integers between 0 and 5, preferably 0 or 1.

[0062] The above n11 is an integer between 0 and 5, and is preferably 1 or 2.

[0063] The above L 1 As the divalent linking group in this compound, alkanediyl groups such as methanediyl, ethanediyl, and 1,3-propanediyl are preferred.

[0064] The following structures can be cited as examples of the above-mentioned UV absorber precursor compound (C2). [ka]

[0065] [ka]

[0066] Furthermore, as the ultraviolet absorber precursor compound (C2), in addition to those mentioned above, compounds corresponding to formulas (5), (5'), (6), and (7) described in Japanese Patent No. 7393205 and Japanese Patent No. 7236386 can be suitably adopted.

[0067] As the above-mentioned UV absorber precursor compound (C2), those with model numbers assigned by the manufacturer can also be used. For example, GPA-1103, GPA-1104, GPA-1105, etc., manufactured by ADEKA Corporation, as described in Non-Patent Literature (Photopolymer Conference Newsletter, No. 84, p. 7, 2018), can be used.

[0068] If the composition contains compound (C), the lower limit of the content of compound (C) is preferably 0.1 parts by mass, more preferably 0.3 parts by mass, even more preferably 0.5 parts by mass, and particularly preferably 0.8 parts by mass, per 100 parts by mass of the alkali-soluble polymer (A). The upper limit of the content of compound (C) is preferably 30 parts by mass, more preferably 20 parts by mass, even more preferably 10 parts by mass, and particularly preferably 5 parts by mass, per 100 parts by mass of the alkali-soluble polymer (A). It is preferable to set the content of compound (C) within the above ranges from the viewpoint of light resistance (outgassing suppression).

[0069] <Alkali-soluble polymer (A)> The alkali-soluble polymer (A) is an aggregate of polymerization chains (hereinafter, this aggregate is also 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.

[0070] By using either a (meth)acrylic polymer (A1) or a polyimide polymer (A2) as the alkali-soluble polymer (A) mentioned above, excellent chemical resistance can be achieved. Among these, the (meth)acrylic polymer (A1) is preferred. Polymers (A1) and (A2) will be described below.

[0071] ((meth)acrylic polymer (A1)) As polymer (A1), a (meth)acrylic polymer containing structural unit (I) having an acid group is preferred. Polymer (A1) may also contain structural unit (III) derived from the ultraviolet-absorbing compound (a). Furthermore, polymer (A1) may contain structural units other than structural unit (I) and structural unit (III) mentioned above. The following describes each structural unit included in polymer (A1).

[0072] [Structural Unit (I)] By including a structural unit (I) having an acidic group in the polymer (A1), the solubility (alkali solubility) of the polymer (A1) in an alkaline developer can be increased, and the curing reactivity can be enhanced.

[0073] Structural unit (I) is not particularly limited as long as it has an acid group, but it is preferably at least one selected from the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units. In this specification, "phenolic hydroxyl group" means a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, anthracene ring, etc.).

[0074] Structural unit (I) is preferably a structural unit derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having an acid group include: Examples of monomers constituting structural units having a carboxyl group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Examples of monomers constituting structural units having a sulfonic acid group include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, etc. Examples of monomers constituting structural units having phenolic hydroxyl groups include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acrylate, etc. Each of these can be listed.

[0075] Furthermore, maleimide can be used as the monomer constituting the structural unit (I).

[0076] Among these, monomers constituting structural units having a carboxyl group and monomers constituting structural units having a phenolic hydroxyl group are preferred, and (meth)acrylic acid and p-isopropenylphenol are more preferred.

[0077] The base polymer may contain one or more structural units (I) in combination.

[0078] When polymer (A) contains structural unit (I), the lower limit of the content of structural unit (I) (or the total content if multiple types are included) is preferably 3% by mass, more preferably 5% by mass, and even more preferably 10% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 50% by mass, more preferably 40% by mass, even more preferably 30% by mass, and particularly preferably 25% by mass. Setting the content of structural unit (I) within the above range is preferable because it allows for good solubility in alkaline developing solutions.

[0079] [Structural Units (II)] Polymer (A1) may contain structural units (II) having one or more groups selected from the group consisting of oxetanyl groups and oxyranyl groups. Polymer (A1) containing structural units (II) is preferable because it allows for the formation of cured products with excellent melt flow resistance and chemical resistance. Polymer (A1) containing structural units (II) is also preferable because it can further improve the resolution and adhesion of the film. Furthermore, the oxetanyl and oxyranyl groups act as crosslinking groups, allowing for the formation of a pattern (cured product) with high heat resistance and suppressed degradation over a long period of time. Structural units (II) are preferably structural units derived from unsaturated monomers having oxetanyl or oxyranyl groups, and specifically, are preferably structural units represented by the following formula (a1). [ka] (In formula (a1), R 21 This is a monovalent group having an oxyranyl group or an oxetanyl group. R α This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X 1 (This is a single bond or a divalent linking group.)

[0080] In the above equation (a1), R 21 Examples include oxyranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl groups, 3-methyloxetanyl groups, and 3-ethyloxetanyl groups.

[0081] X 1 As the divalent linking group, alkanediyl groups such as methanediyl, ethanediyl, and 1,3-propanediyl are preferred.

[0082] Specific examples of monomers that give structural unit (II) represented by the above formula (a1) include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate.

[0083] Among these, glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate are preferred.

[0084] The base polymer may contain one or more structural units (II) in combination.

[0085] When polymer (A) contains structural unit (II), the lower limit of the content of structural unit (II) (total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, even more preferably 20% by mass, and particularly preferably 30% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. Setting the content of structural unit (II) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured product to have sufficiently high heat resistance and chemical resistance.

[0086] [Structural Unit (III)] Structural unit (III) is derived from ultraviolet-absorbing compound (a) which has a maximum absorption wavelength between 250 nm and 350 nm and whose absorbance at a wavelength of 365 nm is 0.4 or less, with the maximum absorbance between 250 nm and 350 nm being set to 1.

[0087] If the polymer (A1) contains structural unit (III) derived from the ultraviolet-absorbing compound (a), the composition may or may not contain the compound (C).

[0088] When the maximum absorbance of the ultraviolet-absorbing compound (a) between wavelengths of 250 nm and 350 nm is set to 1, the absorbance at a wavelength of 365 nm is 0.4 or less, preferably 0.38 or less, and more preferably 0.35 or less. The lower limit is not particularly limited, and the lower the value, the better, and is usually around 0.01.

[0089] The above ultraviolet-absorbing compound (a) is not particularly limited as long as it satisfies the above absorbance conditions, but it is preferably one or more compounds selected from the group consisting of the compound represented by the following formula (1'), the compound represented by the following formula (2'), the compound represented by the following formula (3'), and the compound represented by the following formula (4'), and the compound represented by the following formula (1') is more preferred. [ka] (In the above equation (1'), X 11’ X is a hydroxyl group or an organic group having 1 to 20 carbon atoms. 11’ If there are multiple X 11’ They are either identical or different from each other. 11’ At least one of them has a polymerizable group. X 12 n1 and n2 are equivalent to those in equation (1) above. [ka] (In the above equation (2'), X 21’ , X 22’ and X 23’ Each of these is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. 21’ , X 22’ , X 23’ If there are multiple X 21’ , X 22’ , X 23’ Each is either identical or different from the others. 21’ , X 22’ , X 23’ At least one of them has a polymerizable group. n3, n4, and n5 are equivalent to those in equation (2) above. [ka] (In the above equation (3'), X 31’ and X 32’ Each of these is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. 31’ , X32’ If there are multiple X 31’ , X 32’ Each is either identical or different from the others. 31’ , X 32’ At least one of them has a polymerizable group. n6 and n7 are equivalent to those in equation (3) above. [ka] (In the above equation (4'), X 41’ It is a monovalent organic group having 1 to 20 carbon atoms. X 42’ and X 43’ Each of these is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. 42’ , X 43’ If there are multiple X 42’ , X 43’ Each is either identical or different from the others. 42’ , X 43’ At least one of them has a polymerizable group. n8' and n9' are independent integers between 0 and 3, provided that n8' + n9' ≥ 1.

[0090] X in equation (1') above 11’ As for organic groups with 1 to 20 carbon atoms in the above formula (1), X 11 Organic groups having 1 to 20 carbon atoms can be suitably used in this. Among these, X 11’ Preferably, the group is a monovalent linear hydrocarbon group having 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.

[0091] X in equation (1') above 11’At least one of the groups has a polymerizable group. Examples of polymerizable groups include (meth)acryloyl group, styryl group, maleimide group, vinyl group, vinyl ether group, allyl group, and ethynyl group. Among these, (meth)acryloyl group, vinyl group, or allyl group is preferred, and (meth)acryloyl group is more preferred. The number of polymerizable groups in formula (1') is not particularly limited, but 1 to 4 is preferred, and 1 to 2 is more preferred.

[0092] X in equation (2') above 21’ , X 22’ , X 23’ , X in the above equation (3') 31’ , X 32’ , X in the above equation (4') 41’ , X 42’ , X 43’ As for organic groups with 1 to 20 carbon atoms in the above formula (1), X 11 Organic groups having 1 to 20 carbon atoms can be suitably used in this material.

[0093] X in equation (2') above 21’ , X 22’ , X 23’ , X in the above equation (3') 31’ , X 32’ , X in the above equation (4') 42’ , X 43’ The polymerizable group that it may have is X of formula (1') above. 11’ Polymerizable groups can be suitably adopted in this material.

[0094] In equation (4') above, n8' and n9' are integers between 0 and 3, and n8' + n9' ≥ 1.

[0095] The following structure can be given as an example of the above-mentioned ultraviolet-absorbing compound (a). [ka] (R above) a (This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group.)

[0096] As the above-mentioned ultraviolet-absorbing compound (a), commercially available products can also be used, for example, RUVA-93 (2-(2-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole) manufactured by Otsuka Chemical Co., Ltd.

[0097] The base polymer may contain one or more structural units (III) in combination.

[0098] When polymer (A) contains structural unit (III), the lower limit of the content of structural unit (III) (or the total content if multiple types are included) is preferably 0.5% by mass, and more preferably 0.8% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 30% by mass, more preferably 20% by mass, even more preferably 10% by mass, and particularly preferably 5% by mass. Setting the content of structural unit (III) within the above range is preferable from the viewpoint of light resistance (outgassing suppression).

[0099] [Structural Units (IV)] The polymer (A1) described above may further contain structural units (IV) derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic rings, aromatic vinyl compounds, N-substituted maleimide compounds, heterocyclic vinyl compounds, conjugated dienes, nitrogen-containing vinyl compounds, and unsaturated dialkyl dicarboxylic acid compounds. Introducing these structural units (IV) into the polymer is preferable because it allows for adjusting the glass transition temperature of the polymer (A1) components and improving the pattern morphology of the resulting cured product.

[0100] Examples of the alkyl (meth)acrylate esters mentioned above include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

[0101] Examples of (meth)acrylic acid esters having the above alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and tricyclo(meth)acrylate. 2,6 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.0 2,5 Examples include decane-8-yloxyethyl and isobornyl (meth)acrylate.

[0102] Examples of (meth)acrylic acid esters having the above aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0103] Examples of the above aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, and the like.

[0104] Examples of the above 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, and N-naphthylmaleimide.

[0105] Examples of vinyl compounds having the above heterocyclic structure include, excluding those corresponding to structural unit (VI) below, tetrahydrofuranylmethyl (meth)acrylate, tetrahydropyranylmethyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 5-methyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (meth)acrylate (γ-butyrolactone-2-yl), (meth)acrylate glycerin carbonate, (meth)acrylate (γ-lactam-2-yl), and N-(meth)acryloxyethylhexahydrophthalimide.

[0106] Examples of the above-mentioned conjugated diene compounds include 1,3-butadiene and isoprene; examples of the above-mentioned nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; and examples of the above-mentioned unsaturated dicarboxylate dialkyl ester compounds include diethyl itaconate. In addition to the above, other monomers constituting the structural units include, for example, vinyl chloride, vinylidene chloride, and vinyl acetate.

[0107] The monomer that gives the above structural unit (IV) preferably includes 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.

[0108] The base polymer may contain one or more structural units (IV).

[0109] When polymer (A) contains structural unit (IV), the lower limit of the content of structural unit (IV) (or the total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, even more preferably 20% by mass, and particularly preferably 30% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 60% by mass, and more preferably 50% by mass. Setting the content of structural unit (IV) within the above range is preferable because it allows the glass transition temperature of polymer (A1) to be raised to a moderate level.

[0110] [Structural Unit (V)] The polymer (A1) described above may further contain structural units (V) having a cyclic ether structure and methylene groups bonded to carbon atoms constituting the cyclic ether structure in its main chain. Introducing structural units (V) into the polymer is preferable because it can improve the bending resistance of the resulting cured product.

[0111] The cyclic ether structure of structural unit (V) preferably has 5 or 6 ring members, specifically a tetrahydrofuran ring structure or a tetrahydropyran ring structure. Structural unit (V) may have a substructure in which a cyclic ether structure and a methylene group bonded to the carbon atoms constituting the cyclic ether structure are introduced into the polymer main chain. A preferred specific example is a structural unit (V) having one or two methylene groups constituting the polymer main chain, where the main chain portion of the polymer constituting structural unit (V) is a repeating unit of a structure consisting of a cyclic ether structure and one or two methylene groups. The cyclic ether structure of structural unit (V) may have substituents on the ring portion.

[0112] More specifically, the structural unit (V) is preferably a structural unit represented by the following formula (v). [ka] (In formula (v), R A1 This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R A2 is a hydrogen atom or -COOR A3 That is. R A3 This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. a is either 0 or 1.

[0113] In the above equation (v), R A1 or R A2 As a monovalent hydrocarbon group having 1 to 30 carbon atoms represented by the above formula (1), X 11 In this material, a monovalent hydrocarbon group with 1 to 20 carbon atoms can be suitably adopted, with the number of carbon atoms extended up to 30.

[0114] Among these, R A1 or R A2 Preferably, these are a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.

[0115] Specific examples of structural units (V) include the structural units represented by equations (v-1) to (v-11) below. [ka]

[0116] For example, the structural unit represented by formula (v) can be introduced into the polymer by polymerization using a diene compound represented by formula (v1) as a monomer. Preferred specific examples of the diene compound include methyl 2-(allyloxymethyl)(meth)acrylate, ethyl 2-(allyloxymethyl)(meth)acrylate, and n-propyl 2-(allyloxymethyl)(meth)acrylate. [ka] (In formula (v1), R A1 and R A2 This is equivalent to equation (v) above.

[0117] The base polymer may contain one or more structural units (V).

[0118] When polymer (A) contains structural units (V), the lower limit of the content of structural units (V) (or the total content if multiple types are included) is preferably 1% by mass, more preferably 5% by mass, and even more preferably 8% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. By setting the content of structural units (V) within the above range, it is possible to obtain a cured product with superior bending resistance, which is preferable. Furthermore, it is possible to suppress the melting of the composition and the resulting pattern collapse when heated at a relatively high temperature (post-bake) during film formation.

[0119] [Structural Unit (VI)] In the case of the radiation-sensitive composition of the present invention being a chemically amplified composition, it is preferable from the viewpoint of forming a coating film with excellent developability that the polymer (A1) further comprises a structural unit (VI) having one or more groups selected from the group consisting of a group represented by the following formula (vi) and an acid-dissociable group. [ka] (In formula (vi), R B1 , R B2 and R B3 Each of these 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. However, R B1 , R B2 and R B3 At least one of them is an alkoxy group having 1 to 6 carbon atoms. The asterisk (*) indicates a bonding operation.

[0120] R B1 ~R B3 Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, and tert-butoxy groups. Of these, R B1 ~R B3 The alkoxy group is preferably a methoxy group or an ethoxy group.

[0121] R B1 ~R B3 The C1-C10 alkyl group may be linear or branched. Examples of C1-C10 alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and tert-butyl groups. Of these, methyl, ethyl, or propyl groups are preferred.

[0122] From the viewpoint of obtaining a cured product with excellent heat resistance by forming a cross-linked structure, and from the viewpoint of improving the storage stability of the radiation-sensitive composition, R B1 ~R B3Preferably, at least one of them is an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all are alkoxy groups.

[0123] Among the above, R B1 The group is preferably 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 group or an ethoxy group. B2 and R B3 The group is preferably 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, and more preferably a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0124] The structural unit (VI) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as "unsaturated monomer"), and more specifically, it is preferably at least one selected from the group consisting of the structural unit represented by the following formula (vi-1) and the structural unit represented by the following formula (vi-2). [ka] (In equations (vi-1) and (vi-2), R β1 This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R B21 and R B22 Each of these is independently a divalent aromatic ring group or a chain-like hydrocarbon group. R B1 , R B2 and R B3 This is equivalent to equation (vi) above.

[0125] In equations (vi-1) and (vi-2) above, R B21 , R B22The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalenediyl group. The divalent chain hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.

[0126] In terms of obtaining patterns (cured products) with higher heat resistance and hardness, and increasing the solubility of the exposed areas in alkaline developing solutions, R B21 , R B22 Among the above, it is preferable that it be a divalent aromatic ring group, and particularly preferable that it be a substituted or unsubstituted phenylene group.

[0127] Specific examples of monomers constituting structural unit (VI) include, for example, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethyldimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc.; trimethoxy(4-vinyl naphthyl Examples include (4-)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloxynaphthyltrimethoxysilane, etc.; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, etc.

[0128] The above-mentioned "acid-dissociable group" refers to a group in which a hydrogen atom in an acidic functional group, such as a phenolic hydroxyl group, carboxyl group, or sulfonic acid group, has been substituted, and which dissociates upon the action of an acid. For example, the acid generated from a photoacid generator upon exposure dissociates the acid-dissociable group, generating a carboxyl group, etc. This creates a difference in solubility in the developer between the exposed and unexposed areas of the coating film, enabling pattern formation.

[0129] The above acid-dissociable group is preferably a group represented by the following formula (vi-3) or a group represented by the following formula (vi-4). [ka] (In formula (vi-3), R B4 and R B5 Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which at least some of the hydrogen atoms of the hydrocarbon group are substituted with a hydroxyl group, a halogen atom, or a cyano group. However, R B4 and R B5 It is impossible for both to be hydrogen atoms. R B6 This refers to a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom or a sulfur atom between carbon atoms or at the end of the bond of this hydrocarbon group, or a group in which at least some of the hydrogen atoms of these groups are substituted with a hydroxyl group, a halogen atom, or a cyano group. R B7 It is a carbon atom or a silicon atom. In formula (vi-4), R B8 ~R B14 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. m is either 1 or 2. If m is 2, there are multiple R B11 and R B12 These may be the same or different. In equations (vi-3) and (vi-4), "*" indicates the site of joining.

[0130] R B4 ~RB6 As the hydrocarbon group having 1 to 30 carbon atoms in the above formula (1), the group obtained by extending the number of carbon atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms in X in the above formula (1) to 30 can be preferably adopted. 11

[0131] R in the above formula (vi-3) B4 ~R B6 As each of them, an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, an alkyl group having 1 to 10 carbon atoms is further preferable, and an alkyl group having 1 to 5 carbon atoms is particularly preferable.

[0132] R B8 ~R B14 As the hydrocarbon group having 1 to 12 carbon atoms of R~R, the group corresponding to 1 to 12 carbon atoms among the hydrocarbon groups having 1 to 30 carbon atoms of the above R~R can be preferably adopted. B4 ~R B6

[0133] As the structural unit having the above acid dissociable group, for example, the structural units represented by the following formulas (vi-3-1) and (vi-4-1) are preferable.

Chemical formula

[0134] In the above formulas (vi-3-1) and (vi-4-1), m1 is 0 or 1. R is synonymous with R in the above formulas (vi-1) and (vi-2). R~R is synonymous with R~R in the above formulas (vi-3) and (vi-4). β1 β1 B4 ~R B14 B4 ~R B14

[0135] L in the above formulas (vi-3-1) and (vi-4-1), L B1 B2 are each independently a single bond or a divalent linking group.

[0136] The above L B1 ​B2 Examples of divalent linking groups in this compound include alkanediyl groups, cycloalkanediyl groups, alkenediyl groups, and arenediyl groups.

[0137] Examples of monomers that give rise to the structural unit represented by the above formula (vi-4-1) include tetrahydrofurfuryl (meth)acrylate and tetrahydrofuranyl (meth)acrylate.

[0138] The base polymer may contain one or more structural units (VI) in combination.

[0139] When polymer (A) contains structural unit (VI), the lower limit of the content of structural unit (VI) (or the total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 12% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass. Setting the content of structural unit (VI) within the above range is preferable in that the coating film exhibits better resolution.

[0140] (Method for synthesizing polymer (A1)) Polymer (A1) can be produced, for example, by using an unsaturated monomer into which each of the above-mentioned structural units can be introduced, in a suitable solvent in the presence of a polymerization initiator, according to known methods such as radical polymerization.

[0141] Examples of polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl. The amount of polymerization initiator used is preferably 0.01 to 30 parts by mass per 100 parts by mass of the total amount of monomers used in the reaction.

[0142] Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1 to 60% by mass of the total amount of the reaction solution.

[0143] 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 and the reaction temperature, but is usually 0.5 to 10 hours. The polymer obtained by the polymerization reaction may be used in the preparation of the radiation-sensitive composition while still dissolved in the reaction solution, or it may be isolated from the reaction solution before being used in the preparation of the radiation-sensitive composition. The polymer can be isolated by known isolation methods, such as pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator.

[0144] The weight-average molecular weight (Mw) of the polymer contained in polymer (A1), measured by gel permeation chromatography (GPC) on a polystyrene basis, is preferably 2,000 or more. An Mw of 2,000 or more is preferable because it allows for the production of a cured product with sufficiently high heat resistance and chemical resistance, as well as good developability. The Mw of the polymer is more preferably 5,000 or more, even more preferably 6,000 or more, and particularly preferably 7,000 or more. Furthermore, from the viewpoint of improving film-forming properties, the Mw is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 15,000 or less.

[0145] Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight Mw to number-average molecular weight Mn, is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. When the base polymer consists of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above ranges.

[0146] (Polyimide polymer (A2)) The polyimide polymer (A2) is a polycondensate of a tetracarboxylic dianhydride and a diamine compound, and has an imide ring structure.

[0147] 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. An imidization rate within the above range is preferable because it results in less outgassing from the cured product obtained using this composition and allows for the production of a cured product with good surface flatness. Furthermore, the solubility of the polyimide polymer (A2) in alkaline developers is not excessively high, allowing for a radiation-sensitive composition exhibiting good resolution. From the viewpoint of ease of synthesis, an imidization rate of 99% or less is preferred, and 95% or less is more preferred. The imidization rate is expressed as a percentage of the ratio of the number of imid ring structures to the total number of amic acid structures and imid ring structures in the polyimide.

[0148] Polyimide polymers (A2) can be obtained by synthesizing polyamic acid by reacting a tetracarboxylic dianhydride with a diamine compound, and then imidizing the polyamic acid by dehydration and cyclization.

[0149] (Tetracarboxylic acid dianhydride) Examples of tetracarboxylic dianhydrides that constitute the polyimide polymer (A2) include aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides.

[0150] Herein, in this specification, "aliphatic tetracarboxylic dianhydride" means a tetracarboxylic dianhydride in which the two acid anhydride groups (-CO-O-CO-) of the tetracarboxylic dianhydride are bonded to a linear or cyclic aliphatic group. That is, an aliphatic tetracarboxylic dianhydride may be a linear tetracarboxylic dianhydride in which the two acid anhydride groups of the tetracarboxylic dianhydride are bonded to a linear structure, or it may be an alicyclic tetracarboxylic dianhydride in which the two acid anhydride groups of the tetracarboxylic dianhydride are bonded to the same or different aliphatic rings, or one of the two acid anhydride groups is bonded to an aliphatic ring and the other is bonded to a linear structure. In addition, an aliphatic tetracarboxylic dianhydride may have an aromatic ring structure insofar as the two acid anhydride groups of the tetracarboxylic dianhydride are bonded to a linear or cyclic aliphatic group. "Aromatic tetracarboxylic dianhydride" means a tetracarboxylic dianhydride in which one or more of the two acid anhydride groups of the tetracarboxylic dianhydride are bonded to an aromatic ring. In aromatic tetracarboxylic dianhydrides, when two acid anhydride groups are both bonded to an aromatic ring, the two acid anhydride groups may be bonded to the same aromatic ring or to different aromatic rings.

[0151] 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-tricarboxycyclopentylacetic acid dianhydride, and 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3 Examples include -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-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, and 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride. Examples of aromatic tetracarboxylic acid dianhydrides include pyromellitic acid dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-carbonyldiphthalic acid anhydride, 4,4'-oxydiphthalic acid anhydride, and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride. Among these, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, and 4,4'-oxydiphthalic anhydride are preferred.

[0152] For the polyimide polymer (A2), the content of structural units derived from aliphatic tetracarboxylic dianhydride is 60 mol% or more relative to the total amount of structural units derived from tetracarboxylic dianhydride in the polyimide polymer (A2). If the content of structural units derived from aliphatic tetracarboxylic dianhydride is less than 60 mol%, the solubility of the polyimide polymer (A2) in the solvent is insufficient, and the coatability of the composition and the surface flatness of the cured product obtained from the composition tend to be poor. In addition, the solubility of tetracarboxylic dianhydride in the polymerization solvent is insufficient, resulting in a low monomer concentration in the polymerization solvent, which tends to lead to poor productivity of the polyimide polymer (A2). From this viewpoint, the content of structural units derived from aliphatic tetracarboxylic dianhydride is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, relative to the total amount of structural units derived from tetracarboxylic dianhydride in the polyimide polymer (A2).

[0153] (Diamine compounds) Examples of diamine compounds that constitute polyimide polymers (A2) include aliphatic diamines and aromatic diamines.

[0154] Here, in this specification, the "aliphatic diamine" refers to a diamine compound in which the two primary amino groups (-NH2) possessed by the diamine compound are bonded to a linear or cyclic aliphatic group. That is, the aliphatic diamine may be a linear diamine in which the two primary amino groups possessed by the diamine compound are bonded to a linear structure, or the two primary amino groups possessed by the diamine compound are bonded to the same or different aliphatic rings, or a cycloaliphatic diamine in which one of the two primary amino groups is bonded to an aliphatic ring and the other is bonded to a linear structure. Incidentally, the aliphatic diamine may have an aromatic ring structure as long as the two primary amino groups possessed by the diamine compound are bonded to a linear or cyclic aliphatic group. The "aromatic diamine" refers to a diamine compound in which at least one of the two primary amino groups possessed by the diamine compound is bonded to an aromatic ring. In the aromatic diamine, when the two primary amino groups are both bonded to an aromatic ring, the two primary amino groups may be bonded to the same aromatic ring or different aromatic rings.

[0155] [Specific diamine] The diamine constituting the polyimide-based polymer (A2) preferably has at least one functional group (hereinafter also referred to as "functional group (F1)") selected from the group consisting of a phenolic hydroxyl group, a carboxy group, a thiophenol group, and a sulfo group (-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 an alkaline developer and high transparency of the cured product, the phenolic hydroxyl group is preferable among the above functional groups (F1).

[0156] The molecular weight of the specific diamine is not particularly limited. In terms of high solubility in the polymerization solvent and the ability to achieve a high monomer concentration in the polymerization solvent, the molecular weight of the specific diamine is preferably 300 or higher, more preferably 350 or higher, even more preferably 450 or higher, and particularly preferably 500 or higher. Furthermore, from the viewpoint of improving the coatability of the composition and the surface flatness of the cured product obtained from this composition, the molecular weight of the specific diamine is preferably 850 or lower, and more preferably 750 or lower.

[0157] In terms of high solubility in polymerization solvents and, consequently, the ability to increase the polyimide concentration in the reaction solution obtained by polymerization, it is preferable that the specific diamine has at least one substructure selected from the group consisting of a fluorene ring structure, an indene ring structure, an indan ring structure, a lactone ring structure, a steroid structure, and an alkyl halide structure. Among these, diamines having a fluorene ring structure are preferred due to their high solubility in polymerization solvents.

[0158] From the viewpoint of ensuring solubility in the polymerization solvent while improving the surface flatness of the cured product obtained from this composition, the specific diamine is preferably an aromatic diamine. Specific examples of the specific diamine include compounds represented by the following formulas (A2-1) to (A2-7). [ka]

[0159] [Other diamines] The diamine compound constituting the polyimide polymer (A2) may consist solely of a specific diamine, or it may be a combination of a specific diamine and a diamine without a functional group (F1) (hereinafter also referred to as "other diamines"). Examples of other diamines include aliphatic diamines, aromatic diamines, and diaminoorganosiloxanes. Examples of aliphatic diamines include linear diamines and alicyclic diamines.

[0160] Other specific examples of diamines include, as chain-like diamines, metaxylylenediamine and hexamethylenediamine. Examples of alicyclic diamines include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine). Examples of aromatic diamines include 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-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, and 1,3 -Bis(4-aminophenoxy)propane, 1,6-bis(4-aminophenoxy)hexane, 6,6'-(pentamethylenedioxy)bis(3-aminopyridine), N,N'-di(5-amino-2-pyridyl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, bis[2-(4-aminophenyl)ethyl]hexanediic acid, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenethylurea, 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'-(phenylenediisopropylidene)bisaniline, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 3,6-diamino Cryzine, N4,N4'-bis(4-aminophenyl)-N4,N4'-dimethylbenzidine, N,N'-bis(5-aminopyridine-2-yl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholestanyloxy-2,Examples include 4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholestanil 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanostanil 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-diaminobenzoate=5ξ-cholestane-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 diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and 1,3-bis(4-anilino)tetramethyldisiloxane.

[0161] For the polyimide polymer (A2), the content 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 content of structural units derived from a specific diamine is less than 30 mol%, the solubility of the polyimide polymer (A2) in the alkaline developer is insufficient, and the resolution tends to be poor. Furthermore, from the viewpoint of suppressing excessive solubility in the developer of unexposed areas and maintaining good resolution of this composition, the content of structural units derived from a specific diamine is preferably 99 mol% or less, and more preferably 95 mol% or less, relative to the total amount of structural units derived from the diamine compound in the polyimide polymer (A2).

[0162] Polyimide polymers (A2) can be obtained by dehydrating and cyclizing polyamic acid to imidize it. The method for synthesizing polyamic acid is not particularly limited, but for example, the method described in Japanese Patent Application Publication No. 2023-177343 can be suitably employed.

[0163] The weight-average molecular weight (Mw) of the polyimide polymer (A2), measured by gel permeation chromatography (GPC), is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number-average molecular weight (Mn) measured by GPC, is preferably 5 or less, and more preferably 4 or less.

[0164] The content of polymer (A) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, based on the total amount of solids contained in the radiation-sensitive composition. Furthermore, the content of polymer (A) is preferably 95% by mass or less, and more preferably 90% by mass or less, based on the total amount of solids contained in the radiation-sensitive composition. Setting the content of polymer (A) within the above range is preferable because it allows for the production of a cured product that exhibits sufficiently high chemical resistance, as well as good developability and transparency.

[0165] <Photoacid Generator (B)> This composition contains a photoacid generator (B) together with the polymer (A) described above. 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, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, etc. Of these, quinone diazide compounds and oxime sulfonate compounds are preferred due to their high radiation sensitivity.

[0166] (Quinone diazide compounds) Quinone diazide compounds are compounds that generate carboxylic acids upon irradiation with radiation. Examples of quinone diazide compounds include condensates of phenolic compounds or alcoholic compounds (hereinafter also referred to as "parent compounds") and orthonaphthoquinone diazide compounds. Of these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the parent compound and an orthonaphthoquinone diazide compound. Specific examples of parent compounds include, for example, the compounds described in paragraphs

[0065] to

[0070] of Japanese Patent Publication No. 2014-186300.

[0167] Specific examples of quinone diazide compounds include 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, and 1,4-bis[1-(4-hydroxyphenyl)-1-methyl Examples of ester compounds include those of a phenolic hydroxyl group-containing compound selected from ethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and 1,2-naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, a condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinone diazide-5-sulfonic acid chloride is preferred as the quinone diazide compound.

[0168] These quinone diazide compounds may be used individually or in combination of two or more.

[0169] (Oxime sulfonate compounds) The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (t). [ka] (In formula (t), R 40 This refers to a monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with substituents. The asterisk (*) indicates a bonding operation.

[0170] In the above equation (t), R 40 Examples of monovalent hydrocarbon groups include C1-C20 alkyl groups, C4-C12 cycloalkyl groups, and C6-C20 aryl groups. Examples of substituents include C1-C5 alkyl groups, C1-C5 alkoxy groups, oxo groups, and halogen atoms.

[0171] Examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (2-[2-(4-methylphenylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493. Examples of commercially available oximesulfonate compounds include Irgacure PAG121 from BASF.

[0172] (Sulfonimide compounds) Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphasulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphasulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphasulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide.

[0173] Specific examples of the above-mentioned onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds include, for example, the compounds described in paragraphs

[0078] to

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

[0174] The above-mentioned photoacid generator (B) may be used alone or in combination of two or more types. The lower limit of the photoacid generator content is preferably 0.01 parts by mass, more preferably 0.1 parts by mass, and even more preferably 1 part by mass, per 100 parts by mass of polymer (A) incorporated into this composition. The upper limit of the photoacid generator (B) content is preferably 50 parts by mass, more preferably 40 parts by mass, and even more preferably 30 parts by mass, per 100 parts by mass of polymer (A) incorporated into this composition. A photoacid generator (B) content of 0.01 parts by mass or more is preferable because it allows for good patterning and ensures sufficient heat resistance. Furthermore, a photoacid generator (B) content of 50 parts by mass or less is preferable because it sufficiently reduces the amount of unreacted photoacid generator (B) after exposure, thereby suppressing a decrease in developability due to residual photoacid generator (B).

[0175] When a quinone diazide compound is used as the photoacid generator (B) described above, the lower limit of the quinone diazide compound content is preferably 1 part by mass, more preferably 10 parts by mass, and even more preferably 15 parts by mass, per 100 parts by mass of polymer (A) incorporated into the composition. The upper limit of the quinone diazide compound content is preferably 50 parts by mass, and more preferably 30 parts by mass, per 100 parts by mass of polymer (A) incorporated into the composition. A quinone diazide compound content of 1 part by mass or more is preferable because sufficient carboxylic acid is generated upon irradiation of the composition with radiation, allowing for a sufficiently large difference in solubility between the irradiated and unirradiated portions in the developer, and enabling good patterning. It is also preferable because it allows for a larger amount of carboxylic acid involved in the reaction with the polymer components, ensuring sufficient heat resistance and chemical resistance. On the other hand, by limiting the quinone diazide compound content to 50 parts by mass or less, the amount of unreacted quinone diazide compound after exposure can be sufficiently reduced, which is preferable in that it can suppress the decrease in developability due to residual quinone diazide compound.

[0176] When using a photoacid generator (B) other than a quinone diazide compound, the lower limit of the content is preferably 0.1 parts by mass, more preferably 0.3 parts by mass, and even more preferably 0.5 parts by mass, per 100 parts by mass of polymer (A) incorporated into this composition. The upper limit of the content is preferably 5 parts by mass, and more preferably 3 parts by mass, per 100 parts by mass of polymer (A) incorporated into this composition.

[0177] <Solvent (E)> The radiation-sensitive composition of this disclosure is a liquid composition in which a polymer (A), a photoacid generator (B), and other components, such as a compound (C), which may be added as needed, are dissolved or dispersed in a solvent (E). The solvent used is preferably an organic solvent that dissolves each component of the radiation-sensitive composition and does not react with each component.

[0178] The solvent (E) is not particularly limited and can include, for example, alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, etc. Solvent (E) may be used alone or in combination of two or more types.

[0179] Examples of alcohol-based solvents include methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, alkyl alcohols such as diacetone alcohol, and aromatic alcohols such as benzyl alcohol.

[0180] Examples of ether-based solvents include ethylene glycol monoalkyl ethers such as diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; and dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.

[0181] Examples of ester solvents include carboxylic acid esters such as ethyl acetate, i-propyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; polyhydric alcohol carboxylate solvents such as propylene glycol diacetate; polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; and lactone solvents such as γ-butyrolactone and valerolactone.

[0182] Examples of ketone-based solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0183] Among these, ether-based solvents and ester-based solvents are preferred, ester-based solvents are more preferred, and polyhydric alcohol partial ether carboxylate-based solvents are even more preferred. Furthermore, among the ether-based solvents 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.

[0184] The content of solvent (E) in this composition is not particularly limited, but it is preferable that the concentration of solids (components other than solvent (E)) in this composition be adjusted to be within the following ranges. The lower limit of the solids concentration in this composition is preferably 5% by mass, more preferably 8% by mass, and still more preferably 15% by mass. On the other hand, the upper limit of the solids concentration is preferably 60% by mass, more preferably 40% by mass, and still more preferably 30% by mass. A solids concentration of 5% by mass or more in the radiation-sensitive composition is preferable because it ensures a sufficient film thickness when the radiation-sensitive composition is applied to a substrate. Furthermore, a solids concentration of 60% by mass or less is preferable because it prevents the film thickness from becoming excessively large, and allows for a moderately high viscosity of the radiation-sensitive composition, ensuring good coatability.

[0185] <Other ingredients> The radiation-sensitive composition of this disclosure may further contain, in addition to the polymer (A), photoacid generator (B), compound (C), and solvent (E) described above, other components (hereinafter also referred to as "other components"). Examples of other components include adhesion aids (such as functional silane coupling agents), surfactants, polymerization inhibitors, antioxidants, and chain transfer agents. The proportions of these components are appropriately selected according to each component, within a range that does not impair the effects of this disclosure.

[0186] The radiation-sensitive composition of this disclosure comprises a polymer (A) and a photoacid generator (B), and by satisfying at least one of the above conditions 1) or 2), it can exhibit excellent radiation sensitivity, melt flow resistance, light resistance (outgassing suppression), and chemical resistance. Such a radiation-sensitive composition of this disclosure is useful as a radiation-sensitive composition for organic EL display elements.

[0187] ≪Method for manufacturing hardened products≫ The method for manufacturing the cured product according to this embodiment is as follows: (Step 1) A step of forming a coating film using a radiation-sensitive composition, (Step 2) A step of irradiating at least a portion of the above coating film with radiation, (Step 3) A step of developing the above coating film after irradiation with radiation, (Step 4) The process includes heating the developed coating film.

[0188] The following provides a detailed explanation of each step.

[0189] <Process 1: Paint film formation process> In this process, a radiation-sensitive composition is applied to the surface on which the coating film will be formed (hereinafter also referred to as the "film-forming surface"), and preferably a heat treatment (pre-bake) is performed to remove the solvent and form a coating film on the film-forming surface. The material of the film-forming surface is not particularly limited. For example, when forming a planarization film using a radiation-sensitive composition, the radiation-sensitive composition is applied to a substrate on which switching elements such as TFTs are provided, and a coating film is formed. As the substrate, for example, a glass substrate or a resin substrate can be used.

[0190] Methods for applying the radiation-sensitive composition include, for example, spray coating, roll coating, spin coating, slit die coating, bar coating, and inkjet coating. Among these, spin coating, slit die coating, or bar coating are preferred. Pre-baking conditions vary depending on the type and proportion of each component in the radiation-sensitive composition, but for example, 60 to 130°C for 0.5 to 10 minutes is preferred. The thickness of the formed coating film (i.e., the film thickness after pre-baking) is preferably 1 to 12 μm.

[0191] <Step 2: Exposure Process> In this step, at least a portion of the coating film formed in step 1 is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured film with a pattern (e.g., an interlayer insulating film) can be formed. Examples of radiation include charged particle beams such as ultraviolet light, far ultraviolet light, visible light, X-rays, and electron beams. Among these, ultraviolet light is preferred, for example, g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m². 2 It is preferable.

[0192] <Process 3: Development process> In this step, the coating film irradiated with radiation in step 2 is developed. Specifically, the coating film irradiated with radiation in step 2 is developed with a developer to remove the irradiated portion, performing positive-type development. Examples of the developer include aqueous solutions of alkali (basic compounds). Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and alkalis exemplified in paragraph

[0127] of Japanese Patent Publication No. 2016-145913. From the viewpoint of obtaining appropriate developability, the alkali concentration in the aqueous alkali solution is preferably 0.1 to 5.0% by mass. Appropriate development methods include the liquid-filling method, dipping method, agitation immersion method, and shower method. The development time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. After the development step, it is preferable to rinse the patterned coating film with running water.

[0193] <Step 4: Heating step> In this step, the coating developed in step 3 is subjected to a heating process (post-bake). This allows the hardening reaction of the film to proceed, resulting in a cured film exhibiting good chemical resistance. Post-bake can be performed using a heating device such as an oven or a hot plate. Regarding the post-bake conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when heating on a hot plate, and 10 to 80 minutes when heating in an oven. In this way, a cured film having the desired pattern can be formed on the substrate.

[0194] Furthermore, a post-exposure step may be included between steps 3 and 4 described above. By irradiating the developed coating with radiation, a cured film with excellent melt flow resistance and transparency during the heating process can be formed. Examples of radiation include charged particle beams such as ultraviolet light, far ultraviolet light, visible light, X-rays, and electron beams. Among these, ultraviolet light is preferred, for example, g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m 2 It is preferable.

[0195] ≪Cured product≫ The cured product of this disclosure is formed using the above-mentioned radiation-sensitive composition. The radiation-sensitive composition of this disclosure has high radiation sensitivity, can suppress thermal melt flow after patterning, and has good light resistance (outgassing suppression) and chemical resistance. Therefore, the cured product is useful for forming planarization films or partitions in organic EL elements. Specifically, the cured product can be used in organic EL elements as a planarization film to flatten surface irregularities caused by thin-film transistors (TFTs), partitions used for color separation in color conversion layers using quantum dots, and partitions to demarcate regions for forming the light-emitting layer. The cured product can also be used as an interlayer insulating film to insulate between wiring, a protective film to protect TFTs, a spacer, a color filter, etc.

[0196] ≪Organic EL Display Element≫ The organic EL (electroluminescent) display element of this disclosure comprises a cured film formed using the above-mentioned radiation-sensitive composition. The organic EL display element of this disclosure can be effectively applied to a variety of uses, and can be used as various display devices such as watches, portable game consoles, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays. [Examples]

[0197] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are based on mass unless otherwise specified.

[0198] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were measured by the following method. • Measurement method: Gel permeation chromatography (GPC) method • Equipment: HLC-8420GPC manufactured by Tosoh Corporation • Mobile phase: tetrahydrofuran (If the polymer is a polyimide or polyamic acid ester, use dimethylformamide as the mobile phase.) Column temperature: 40°C ·Flow rate: 1.0mL / min • Sample concentration: 1.0% by mass • Sample injection volume: 100 μL • Detector: Differential refractometer • Standard material: Monodisperse polystyrene

[0199] [Measurement of maximum absorption wavelength and absorbance of compound (C) or UV-absorbing compound (a)] A 0.1 g / L acetonitrile solution of compound (C) or ultraviolet-absorbing compound (a) was prepared, and the values ​​measured using a UV-Vis-Near-Infrared spectrophotometer (JASCO Corporation, V-670) were used.

[0200] <Synthesis of polymer (A)> [Synthesis Example A-1] Synthesis of (meth)acrylic polymer (A1-1) Thirteen parts of 2,2'-azimonos(isobutyrate)dimethyl and 200 parts of diethylene glycol ethyl methyl ether were charged into a flask equipped with a condenser and a stirrer. Subsequently, 13 parts of methacrylic acid, 20 parts of 3,4-epoxycyclohexylmethyl methacrylate, 20 parts of glycidyl methacrylate, and 47 parts of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 80°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A1-1). The solid content concentration of this 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.

[0201] [Synthesis Examples A-2 to A-6] Synthesis of polymers (A1-2) to (A1-6) A polymer solution containing polymers (A1-2) to (A1-6) having the same solid content concentration, molecular weight, and molecular weight distribution as polymer (A1-1) was obtained using the same method as in Synthesis Example A-1, except that the components used were of the types and amounts (parts by mass) shown in Table 1. In Table 1 below, "-" indicates that the corresponding component was not used. The same applies to subsequent tables.

[0202] The monomers used in the synthesis of the above polymers (A1-1) to (A1-6) are as follows. (Monomers that give structural units (I)) • MA: Methacrylic acid • PIPE: p-isopropenylphenol

[0203] (Monomers that give structural unit (II)) ECHMA: 3,4-Epoxycyclohexylmethyl methacrylate GMA: Glycidyl methacrylate

[0204] (Monomers that give structural unit (III)) RUVA-93: 2-(2-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.)

[0205] (Monomers that give structural unit (IV)) • CHMA: Cyclohexyl methacrylate • CHMI:N-cyclohexylmaleimide • MMA: Methyl methacrylate

[0206] (Monomers that give structural units (V)) • AOMA: 2-(allyloxymethyl)methyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)

[0207] (Monomers that give structural units (VI)) • MATHF: 2-tetrahydrofuranyl methacrylate

[0208] [Table 1]

[0209] [Synthesis Examples A-7, A-8] Synthesis of polyimide polymers (A2-1) and (A2-2) The polymers (A2-1) and (A2-2) were synthesized in the same manner as in Synthesis Examples 2 and 3 of Japanese Patent Publication No. 2023-177343 to obtain a γ-butyrolactone (GBL) solution containing 25% by mass of each polymer. The amount of raw materials used, molecular weight, and imidization rate for polymers (A2-1) and (A2-2) are shown in Table 2 below. The imidization rate was measured by the following method.

[0210] <Imidification rate of polyimides> A polyimide solution was added to pure water, and the resulting precipitate was thoroughly dried under reduced pressure at room temperature. Then it was dissolved in deuterated dimethyl sulfoxide, with tetramethylsilane as the reference substance, at room temperature. 1 1H-NMR measurements were performed. 1 The imidization rate (%) was determined from the 1H-NMR spectrum using the following formula (1). Imidization rate (%) = (1 - (β) 1 / ( β 2 ×α)))×100 (1) (In formula (1), β 1 This represents the peak area originating from the proton of the NH group, appearing around a chemical shift of 10 ppm, and β 2 α represents the peak area derived from other protons, and α is the ratio of other protons to one proton of the NH group in the polymer precursor (polyamic acid). [Table 2]

[0211] The structures of the compounds used in Table 2 above are shown below. [ka]

[0212] [Synthesis Example A-9] Synthesis of polyamic acid esters (A2-3) The polyamic acid ester (polymer (A2-3)) powder was obtained by synthesis in the same manner as in Synthesis Example 14 of Japanese Patent Publication No. 2023-177343. The raw materials used in the synthesis were (DA-2) / (DA-3) / (AN-3) / (MA-1) = 80 / 5 / 100 / 30 (moles). The structures of (DA-2), (DA-3), and (MA-1) are as described above. The structure of (AN-3) is as follows. [ka]

[0213] [Synthesis Example AC-1] Synthesis of polysiloxane (AC-1) The polysiloxane (SI-1) (polymer (AC-1)) was synthesized in the same manner as in Synthesis Example 1 of Japanese Patent Publication No. 2022-551938 to obtain a propylene glycol monomethyl ether acetate (PGMEA) solution containing 40% by mass of polysiloxane (SI-1) (polymer (AC-1)).

[0214] [Synthesis Examples C-1, C-2] Synthesis of UV absorber precursor compounds (C-6) and (C-7) UV absorber precursor compounds (C-6) and (C-7) were synthesized according to Examples 5 and 16 of Japanese Patent No. 7393205 (compounds I-1-35 and I-1-47 of Japanese Patent No. 7393205).

[0215] [Synthesis Examples C-3, C-4, C-5, C-6, C-7] Synthesis of UV absorber precursor compounds (C-9), (C-10), (C-11), (C-12), (C-13) The ultraviolet absorber precursor compounds (C-9), (C-10), (C-11), (C-12), and (C-13) were synthesized according to production examples A1-1, 2-1, 3-1, 3-2, and 3-3 of Japanese Patent No. 7236386 (compounds A1-1, A2-1, A3-1, A3-2, and A3-3 of Japanese Patent No. 7236386).

[0216] <Preparation of radiation-sensitive composition> The polymer (A), photoacid generator (B), compound (C), and solvent (E) used in the preparation of the radiation-sensitive composition are shown below.

[0217] ≪Potassium polymerization (A)≫ • A1-1~A1-6: Polymers synthesized using synthesis examples A1-1~A1-6 (A1-1)~(A1-6) • A2-1~A2-3: Polymers synthesized in synthesis examples A-7~A-9 (A2-1)~(A2-3) • AC-1: Synthesis Example - Polymer synthesized with AC-1 (AC-1)

[0218] ≪Photoacid Generator (B)≫ · B-1: Condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) • B-2: Irgacure PAG121 (made by BASF)

[0219] ≪Compound (C)≫ • C-1: TINUVIN 400 (manufactured by BASF Japan Ltd.), Molecular weight: 647 • C-2: TINUVIN 405 (manufactured by BASF Japan Ltd.), Molecular weight: 583.8 • C-3: ADEKA stab LA-46 (manufactured by ADEKA Corporation), molecular weight: 512 • C-4: Ubinal 3039 (manufactured by BASF Japan Ltd.), Molecular weight: 361 • C-5: ADEKA Stab 1413 (manufactured by ADEKA Corporation), Molecular weight: 326 • C-6: Compound synthesized in synthesis example C-1 (C-6) (compound I-1-35 in patent No. 7393205), molecular weight: 517.7 • C-7: Compound synthesized in synthesis example C-2 (C-7) (compound I-1-47 in Japanese Patent No. 7393205), molecular weight: 646.7 C-8:RUVA-93:2-(2-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.), molecular weight: 320.3 • C-9: Compound synthesized in synthesis example C-3 (C-9) (compound A1-1 in patent No. 7236386), molecular weight 859.1 • C-10: Compound synthesized in synthesis example C-4 (C-10) (compound A2-1 in patent No. 7236386), molecular weight 474.5 • C-11: Compound synthesized in synthesis example C-5 (C-11) (compound A3-1 in patent No. 7236386), molecular weight 1000.3 • C-12: Compound synthesized in synthesis example C-6 (C-11) (compound A3-2 in patent No. 7236386), molecular weight 868.0 • C-13: Compound synthesized in synthesis example C-7 (C-11) (compound A3-3 in patent No. 7236386), molecular weight 611.7 • C'-1: TINUVIN 460 (manufactured by BASF Japan Ltd.), Molecular weight: 630 C'-2: Ubinal 3050 (manufactured by BASF Japan Ltd.), molecular weight: 246 • C'-3: SEESORB 107 (manufactured by Cipro Chemical Co., Ltd.), Molecular weight: 274 C'-4: TINUVIN PS (manufactured by BASF Japan Ltd.), molecular weight: 267 • C'-5: TINUVIN 234 (manufactured by BASF Japan Ltd.), Molecular weight: 448

[0220] ≪Solvent (E)≫ • E-1: Diethylene glycol methyl ethyl ether (EDM) • E-2: Propylene glycol monomethyl ether (PGME) • E-3: Propylene glycol monomethyl ether acetate (PGMEA) • E-4: γ-Butyrolactone (GBL) • E-5: Ethyl lactate (EL)

[0221] <Preparation of radiation-sensitive composition> [Example 1] To a polymer solution containing polymer (A1-1), 20 parts of photoacid generator (B-1) and 1 part of compound (C-1) were mixed in an amount equivalent to 100 parts (solids) of polymer (A-1). Solvents (E-1), (E-2), and (E-3) were then added to achieve a final solids concentration of 20% by mass. The ratio of solvents in the radiation-sensitive composition was (E-1):(E-2):(E-3) = 50:25:25% by mass. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare the radiation-sensitive composition.

[0222] [Examples 2-26, Comparative Examples 1-12] Radiation-sensitive compositions for Examples 2-26 and Comparative Examples 1-12 were prepared using the same method as in Example 1, except that the components used were of the types and amounts (parts by mass) shown in Table 3. When polyimide or polyamic acid ester was used as the polymer, solvents (E-4) and (E-5) were used in a ratio of 60:40% by mass, and when polysiloxane was used as the polymer, only solvent (E-3) was used as the solvent.

[0223] [Table 3]

[0224] <Rating> Cured films were formed from the radiation-sensitive compositions of Examples 1-26 and Comparative Examples 1-12, and the following items were evaluated using the method described below. The evaluation results are shown in Table 4.

[0225] <Radiation sensitivity> Hexamethyldisilazane (HMDS) was applied to a 6-inch glass wafer using a spinner and heated at 60°C for 1 minute (HMDS treatment). Each of the radiation-sensitive compositions prepared as described above was then applied to the HMDS-treated wafer using a spinner. The spin rate was adjusted to achieve a post-baking film thickness of 2.0 μm. Subsequently, a 3.0 μm thick coating film was formed by drying at 30 Pa for 1 second in a small vacuum drying apparatus, followed by pre-baking at 100°C for 2 minutes. Next, the coating film was exposed using an exposure machine (Canon's "MPA-600FA": using an ultra-high pressure mercury lamp) with varying exposure levels through a mask having a 10 μm × 10 μm rectangular exposure area. Finally, development was performed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23°C using the liquid-fill method. The development time was 80 seconds. Next, the wafer was rinsed with ultrapure water for 1 minute, and then dried to form a pattern on the HMDS-treated wafer. 300 mJ / cm² was applied to the entire surface of the coating. 2 The wafer was exposed to light, and then post-baked in a clean oven at 250°C for 60 minutes to obtain a cured film. The amount of exposure required to form a 10 μm × 10 μm pattern during development was investigated. A smaller exposure amount indicates better radiation sensitivity. (Evaluation Criteria) AA: 90 mJ / cm 2 less than A: 90 mJ / cm 2 More than 120mJ / cm 2 less than B: 120 mJ / cm 2 More than 150mJ / cm 2 less than C: 150 mJ / cm 2 That's all.

[0226] <Meltflow Resistance> The rectangular hole cross-sectional shape of the coating film resolved at the optimal exposure level described above was observed using a scanning electron microscope. A tangent line was drawn to the coating film pattern at the endpoint where the coating film pattern contacts the substrate, and the angle between the tangent line and the substrate surface was calculated. A higher angle indicates that the coating film maintains good melt flow resistance even after heating at 250°C. (Evaluation Criteria) A: 60° or higher B: 40° to less than 60° C: Less than 40°

[0227] <Lightfastness> Except for skipping the exposure step using a mask, the same process as described above for <radiation sensitivity> was followed to prepare post-baked substrates with a radiation-sensitive composition. A 1cm square of the substrate was irradiated with a xenon lamp for 72 hours. (Tabletop xenon tester: ATLAS, SUNTEST CPS+, illuminance: 765W / m²) 2 A temperature of 50°C was used. Outgassing measurements were performed by heating the substrate to 150°C using a TDS (manufactured by Denshi Kagaku Co., Ltd.) and holding it for 5 minutes. The total amount of outgassing was calculated from the sum of the peak intensities of each component of the mass spectrometry, and the light resistance was evaluated according to the following criteria. (Evaluation Criteria) A: The relative value when the total outgassing volume of Comparative Example 1 is set to 100% is less than 50%. B: The relative value when the total outgassing volume of Comparative Example 1 is set to 100% is 50% or more and less than 70%. C: The relative value when the total outgassing volume of Comparative Example 1 is set to 100% is 70% or more.

[0228] <Chemical resistance> A 6-inch silicon wafer was used, and a cured film was fabricated on the wafer in the same manner as described above for <Radiation Sensitivity>, except that exposure via a mask was skipped. The wafer was immersed in N-300 resist stripping solution (Nagase ChemteX) heated to 60°C for 6 minutes, and after immersion, the coating was rinsed with ultrapure water for 5 seconds and dried. The film thickness of the cured film before and after treatment was measured using an optical interferometer film thickness measuring device (SCREEN Holdings Co., Ltd., VM-2210). The stripping solution swelling rate (%) was calculated according to the following formula. Furthermore, the wafer was heated in a clean oven at 230°C for 15 minutes, and the stripping solution elution rate (%) was calculated according to the following formula. Stripping solution swelling rate (%)=(P / Q-1)×100 (In the formula, P represents the residual film thickness after immersion (μm), and Q represents the residual film thickness before immersion (μm).) Stripping solution elution rate (%) = (1 - R / Q) × 100 (In the formula, R represents the residual film thickness after heating (μm), and Q represents the residual film thickness before immersion (μm).) (Evaluation Criteria) A: Swelling rate less than 4% and dissolution rate less than 1% B: Swelling rate of 4% or more but less than 6%, and dissolution rate of less than 1%. C: Swelling rate of 6% or more, or dissolution rate of 1% or more

[0229] <Bending resistance> A radiation-sensitive composition was applied to a polyimide film substrate using a spinner, similar to the <radiation sensitivity> method described above, and a coating film was formed by vacuum drying and pre-baking. Next, development was performed using a developer (2.38% by mass aqueous solution of tetramethylammonium hydroxide) at 23°C for 80 seconds, followed by rinsing with ultrapure water for 1 minute. The entire surface of the resulting coating film was exposed to 300 mJ / cm² using an exposure machine (Canon's "MPA-600FA": using an ultra-high pressure mercury lamp). 2 A cured film was formed on the substrate by GHI-ray exposure and post-baking in a clean oven at 250°C for 60 minutes. The spin coating speed was adjusted so that the post-baking film thickness was 3.0 μm. The resulting cured film-coated substrate was cut to a size of 50 mm x 50 mm. Next, with the side where the cured film was formed facing outwards, the cured film-coated substrate was bent so that the polyimide film substrates were in contact with each other, and held in that position for 10 minutes. After 10 minutes, the bent cured film-coated substrate was opened, and the bent portion of the cured film surface was observed using an optical microscope. The bending resistance (resistance to bending) was evaluated based on the change in appearance. (Evaluation Criteria) A: There are no cracks in the hardened film. B: There are cracks in part of the hardened film.

[0230] [Table 4]

[0231] As shown in Table 4, each of the radiation-sensitive compositions in Examples 1 to 26 exhibited good practical properties in terms of radiation sensitivity, melt flow resistance, light resistance (outgassing), chemical resistance, and bending resistance, demonstrating a good balance of various properties. In contrast, Comparative Examples 1 to 12 received a "C" rating in at least one of these properties, and all were inferior to Examples 1 to 26.

Claims

1. Alkali-soluble polymer (A), Photoacid generator (B), A radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element, comprising: The alkali-soluble polymer (A) is a (meth)acrylic polymer or a polyimide polymer. A radiation-sensitive composition for forming a planarization film or partition wall of an organic EL element, satisfying at least one of the following conditions 1) and 2). 1) The above composition is A UV absorber (C1) having a maximum absorption wavelength between 250 nm and 350 nm, and whose absorbance at 365 nm is 0.4 or less when the maximum absorbance between 250 nm and 350 nm is set to 1, and UV absorber precursor compound (C2) that exhibits UV absorption function upon heating or light irradiation. A compound (C) comprising one or more compounds selected from the group, 2) The alkali-soluble polymer (A) contains structural units (III) derived from an ultraviolet-absorbing compound (a) which has a maximum absorption wavelength between 250 nm and 350 nm and whose absorbance at a wavelength of 365 nm is 0.4 or less, with the maximum absorbance between 250 nm and 350 nm being set to 1.

2. The radiation-sensitive composition according to claim 1, wherein the molecular weight of compound (C) is 300 or more.

3. The radiation-sensitive composition according to claim 1, wherein the ultraviolet absorber (C1) is one or more ultraviolet absorbers selected from the group consisting of a benzotriazole ultraviolet absorber represented by the following formula (1), a triazine ultraviolet absorber represented by the following formula (2), a hydroxybenzophenone ultraviolet absorber represented by the following formula (3), and a cyanoacrylate ultraviolet absorber represented by the following formula (4). 【Chemistry 1】 (In the above formula (1), X １１ X is a hydroxyl group or an organic group having 1 to 20 carbon atoms. １１ If there are multiple X １１ They are either identical or different from one another. X １２ X is a halogen atom. １２ If there are multiple X １２ They are either identical or different from one another. n1 is an integer between 1 and 3. n² is an integer between 0 and 3. 【Chemistry 2】 (In the above formula (2), X ２１ 、 X ２２ and X ２３ are each independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. X ２１ 、 X ２２ 、 X ２３ When there are a plurality of X ２１ 、 X ２２ 、 X ２３ they may be the same as or different from each other. n3, n4, and n5 are each independent integers between 0 and 3, provided that n3 + n4 + n5 ≥ 1. 【Transformation 3】 (In the above formula (3), X ３１ and X ３２ Each of these is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. ３１ , X ３２ If there are multiple X ３１ , X ３２ They are either identical or different from one another. n6 and n7 are independent integers between 0 and 3, provided that n6 + n7 ≥ 1. 【Chemistry 4】 (In the above formula (4), X ４１ This refers to an organic group with 1 to 20 carbon atoms and a t-valence. t is an integer between 1 and 5. X ４２ and X ４３ Each of these is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. ４２ , X ４３ If there are multiple X ４２ , X ４３ They are either identical or different from one another. n8 and n9 are each independent integers between 0 and 3.

4. The radiation-sensitive composition according to claim 1, wherein the above-mentioned 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). 【Transformation 5】 (In the above equations (5), (5'), (6), and (7), R ａ１ and R ａ２ Each of these 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 -O-Q. Q is a leaving group. However, R ａ１ , R ａ２ At least one of them is -O-Q. ａ１ , R ａ２ If multiple R ａ１ , R ａ２ They are either identical or different from one another. R ａ３ , R ａ４ , R ａ５ , R ａ６ , R ａ７ and R ａ８ Each of these is independently 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. ａ３ , R ａ４ , R ａ５ , R ａ６ , R ａ７ , R ａ８ If multiple R ａ３ , R ａ４ , R ａ５ , R ａ６ , R ａ７ , R ａ８ They are either identical or different from one another. m1 is an integer between 0 and 4, and m2 is an integer between 0 and 2. m3 and m4 are each independent integers between 0 and 4. m5 is an integer between 0 and 3. m6 is an integer between 0 and 3, and m7 is an integer between 1 and 3, provided that m6 + m7 ≤ 3. L ２ This represents a single bond or a s1-valent linking group. s1 represents an integer between 1 and 10.

5. The radiation-sensitive composition according to claim 4, wherein the leaving group represented by Q is a t-butyloxycarbonyl group, a group represented by the following formula (8), or a group represented by the following formula (9). 【Transformation 6】 (In the above equations (8) and (9), R ８１ , R ９１ , and R ９２ Each of these is independently 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. ８１ , R ９１ , R ９２ If multiple R ８１ , R ９１ , R ９２ They are either identical or different from one another. R ８２ R is a hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, or organic group having 1 to 40 carbon atoms. ８２ They are either identical or different from one another. n3 is an integer between 0 and 4. n4 and n5 are each independent integers between 0 and 5. * indicates a bond with an oxygen atom.

6. The radiation-sensitive composition according to 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'). 【Transformation 7】 (In the above formula (1'), X １１’ X is a hydroxyl group or an organic group having 1 to 20 carbon atoms. １１’ If there are multiple X １１’ They are either identical or different from each other. １１’ At least one of them has a polymerizable group. X １２ n1 and n2 are equivalent to those in equation (1) above. 【Transformation 8】 (In the above equation (2'), X ２１’ , X ２２’ and X ２３’ Each of these is independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. ２１’ , X ２２’ , X ２３’ If there are multiple X ２１’ , X ２２’ , X ２３’ Each is either identical or different from the others. ２１’ , X ２２’ , X ２３’ At least one of them has a polymerizable group. n3, n4, and n5 are equivalent to those in equation (2) above. 【Chemistry 9】 (In the above formula (3'), X ３１’ and X ３２’ is each independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. X ３１’ , X ３２’ When there are a plurality of X ３１’ , X ３２’ are each the same as or different from one another. X ３１’ , X ３２’ At least one of them has a polymerizable group. n6 and n7 are equivalent to those in equation (3) above. 【Chemistry 10】 (In the above formula (4'), X ４１’ It is a monovalent organic group having 1 to 20 carbon atoms. X ４２’ and X ４３’ are each independently a hydroxyl group or an organic group having 1 to 20 carbon atoms. X ４２’ and X ４３’ When there are a plurality of X ４２’ and X ４３’ are each the same as or different from one another. X ４２’ and X ４３’ at least one of which has a polymerizable group. n8' and n9' are independent integers between 0 and 3, provided that n8' + n9' ≥ 1.

7. The radiation-sensitive composition according to claim 1, wherein the alkali-soluble polymer (A) has an acidic group.

8. The radiation-sensitive composition according to claim 1, wherein the alkali-soluble polymer (A) has a crosslinkable group.

9. The above radiation-sensitive composition contains the above compound (C), The radiation-sensitive composition according to claim 1, wherein the content of the above compound (C) is 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the above alkali-soluble polymer (A).

10. The alkali-soluble polymer (A) described above contains the structural unit (III), The radiation-sensitive composition according to claim 1, wherein the content of structural unit (III) in the total structural units constituting the polymer (A) is 0.5% by mass or more and 30% by mass or less.

11. A step of forming a coating film using the radiation-sensitive composition described in any one of claims 1 to 10, A step of irradiating at least a portion of the above coating film with radiation, The process of developing the above coating after irradiation with radiation, A step of heating the developed coating film, A method for producing a cured product, including the following:

12. A cured product formed using the radiation-sensitive composition according to any one of claims 1 to 10.

13. The cured product according to claim 12, which is a planarized film or a partition wall.

14. An organic EL display element comprising the cured product described in claim 13.

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