Radiation-sensitive composition, cured film and method for manufacturing the same, liquid crystal display device and organic EL display device

Abstract

To provide a radiation-sensitive composition that can form a film with excellent development adhesion and curing adhesion. [Solution] A radiation-sensitive composition comprising (A-2) a polymer containing a structural unit having an acid group, (B-2) a quinone diazide compound, (C-2) a solvent, and (E) a compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. A radiation-sensitive composition comprising (A-3-1) a polymer containing a structural unit having an acid group, (A-3-2) a polymerizable monomer, (B-3) a photopolymerization initiator, (C-3) a solvent, and (E) a compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group.

Description

[Technical Field]

[0001] The present invention relates to a radiation-sensitive composition, a cured film and a method for producing the same, a semiconductor element, and a display element. [Background technology]

[0002] Cured films (e.g., interlayer insulating films, spacers, protective films, etc.) in display devices such as liquid crystal displays and organic EL displays are generally formed using a radiation-sensitive composition containing polymer components and radiation-sensitive compounds (e.g., photoacid generators, photopolymerization initiators, etc.) (see, for example, Patent Documents 1 to 3). For example, a patterned cured film can be formed by irradiating and developing a coating film formed with a radiation-sensitive composition to form a pattern, and then performing a heat treatment to thermally cure it. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2017-107024 [Patent Document 2] International Publication No. 2011 / 065215 [Patent Document 3] Japanese Patent Publication No. 2003-5357 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] If the adhesion between the coating film and the substrate after irradiation is insufficient, the developer may seep in from the interface between the film and the substrate during the developing process, causing the film's pattern to peel off. In particular, in recent years, there has been a demand for even higher quality in display devices, and as patterns become finer to meet this demand, the film's pattern tends to peel off more easily during the developing process.

[0005] Furthermore, during the heat treatment for thermal curing, the film may peel off the substrate due to stress caused by film shrinkage during heating. From the viewpoint of suppressing a decrease in manufacturing yield, radiation-sensitive compositions are required to be less prone to peeling between the film and the substrate during the development process (i.e., have good development adhesion) and less prone to peeling off the film from the substrate during thermal curing (i.e., have good curing adhesion).

[0006] The present invention has been made in view of the above problems, and its main objective is to provide a radiation-sensitive composition that can form a film with excellent developability and curing adhesion. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by incorporating a specific compound into a radiation-sensitive composition. That is, the present invention provides the following radiation-sensitive composition, cured film and method for producing the same, semiconductor element and display element.

[0008] [1] (A-2) Polymers containing structural units having acid groups, (B-2) Quinone diazide compounds, (C-2) Solvent and, (E) A compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. A radiation-sensitive composition containing the following:

[0009] [2] (A-3-1) Polymers containing structural units having acid groups, (A-3-2) Polymerizable monomers, (B-3) Photopolymerization initiator, (C-3) Solvent and (E) A compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. A radiation-sensitive composition containing the following:

[0010] [3] A step of applying the radiation-sensitive composition described in [1] or [2] above onto a substrate, A step of removing the solvent from the coated radiation-sensitive composition, A step of irradiating the radiation-sensitive composition from which the solvent has been removed with radiation, A step of developing the radiation-sensitive composition that has been irradiated with the aforementioned radiation, The process of thermally curing the developed radiation-sensitive composition, A method for manufacturing a cured film, including [the specified element].

[0011] [4] A cured film formed using the radiation-sensitive composition of [1] or [2] above. [5] A liquid crystal display device comprising the cured film described in [4] above. [6] An organic EL display device comprising the cured film described in [4] above. [Effects of the Invention]

[0012] According to the radiation-sensitive composition of the present invention, by including a polymer component, a radiation-sensitive compound, and a solvent, along with a compound having a specific functional group and a cardo structure, it is possible to form a film with excellent developability and curing adhesion. [Modes for carrying out the invention]

[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, it 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, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, and it may also include those that have 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, it is not necessary to consist only of the structure of an aromatic ring, and it may also contain a linear structure or the structure of an alicyclic hydrocarbon 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 group" includes alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0015] In this specification, "(meth)acrylic" encompasses "acrylic" and "methacrylic." "(meth)acryloyl group" encompasses "acryloyl group" and "methacryloyl group." In this specification, "epoxy group" also refers to the oxyranyl group and the oxetanyl group.

[0016] 《Radiation sensitive composition》 The radiation-sensitive composition of this disclosure (hereinafter also referred to as "the Composition") is a resin composition comprising a polymer component, a solvent, and a cardo compound having a specific functional group. The Composition is used, for example, to form a cured film for a display device (such as a liquid crystal display device or an organic EL display device). Specifically, a cured film can be obtained by coating the Composition onto a substrate, removing the solvent, irradiating the solvent-free Composition with radiation, developing it with a developer, and then thermally curing it.

[0017] The following describes in detail the components contained in the first, second, and third compositions, which are specific embodiments of the present composition, as well as other components that may be added as needed. Unless otherwise specified, each component may be used alone or in combination of two or more. The first and second compositions are preferably used as positive-type resin compositions, and the third composition is preferably used as a negative-type resin composition.

[0018] [First composition] The first composition in this disclosure comprises the following components (A-1), (B-1), (C-1), and (E). (A-1) A polymer selected from the group consisting of polymers containing a structural unit having a group represented by the following formula (1) or an acid-dissociable group, and siloxane polymers; (B-1) Photoacid generator; (C-1) solvent; (E) Compounds having a cardi structure and at least one functional group (X) selected from the group consisting of alkoxysilyl groups, oxyranyl groups, oxetanyl groups, mercapto groups, (meth)acryloyl groups, vinyl groups, and amino groups (excluding compounds that are polymers containing a structural unit having a group represented by the following formula (1)). [ka] (In formula (1), R 1 , R 2 and R 3 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 1 , R 2 and R 3 At least one of these is an alkoxy group having 1 to 6 carbon atoms. (* indicates a bond.)

[0019] <Polymer components> The first composition contains, as a polymer component, at least one polymer selected from the group consisting of a polymer containing a structural unit having a group represented by the above formula (1) or an acid dissociable group and a siloxane polymer (also referred to as “(A-1) polymer”). Specific examples of the polymer component contained in the first composition include a polymer containing a structural unit (I-1) having a group represented by the above formula (1) (hereinafter also referred to as “polymer (a1-1)”), a polymer containing a structural unit (I-2) having an acid dissociable group (hereinafter also referred to as “polymer (a1-2)”), and a siloxane polymer.

[0020] 〔Regarding polymer (a1-1)〕 Polymer (a1-1) is a polymer containing a structural unit (I-1) having a group represented by the above formula (1). In the above formula (1), R 1 ~R 3 Examples of the alkoxy group having 1 to 6 carbon atoms represented by include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group. Among these, the alkoxy group represented by R 1 ~R 3 preferably has 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group. In particular, when the group represented by the above formula (1) is bonded to an aromatic ring group, the alkoxy group represented by R 1 ~R 3 is preferably a methoxy group. When the group represented by the above formula (1) is bonded to a chain hydrocarbon group, the alkoxy group represented by R 1 ~R<00000`14>is preferably an ethoxy group.

[0021] <` R 1 ~R 3 The alkyl group having 1 to 10 carbon atoms represented by may be either linear or branched. Examples of the alkyl group represented by R 1 ~R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these, R 1 ~R 3The alkyl group represented is preferably a methyl group, an ethyl group, or a propyl group.

[0022] R 1 ~R 3 One of the groups represented is an alkoxy group having 1 to 6 carbon atoms. The remaining 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, more preferably a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0023] From the viewpoint of obtaining a cured film with excellent heat resistance by forming a cross-linked structure, R 1 ~R 3 Preferably, two or more of these are alkoxy groups having 1 to 6 carbon atoms, and it is particularly preferable that all of them are alkoxy groups having 1 to 6 carbon atoms.

[0024] In structural unit (I-1), the group represented by formula (1) is preferably bonded to an aromatic ring group or a linear hydrocarbon group. In this specification, "aromatic ring group" means a group obtained by removing n (n is an integer) hydrogen atoms from the ring portion of an aromatic ring. Examples of such aromatic rings include benzene rings, naphthalene rings, and anthracene rings. These rings may have substituents such as alkyl groups. Examples of linear hydrocarbon groups to which the group represented by formula (1) is bonded include alkanediyl groups and alkenediyl groups.

[0025] The group represented by formula (1) above is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. Specifically, structural unit (I-1) preferably has at least one selected from the group consisting of the group represented by formula (3-1), the group represented by formula (3-2), and the group represented by formula (3-3). [ka] (In equations (3-1), (3-2), and (3-3), A 1and A 2 Each of these is independently a halogen atom, a hydroxyl group, a C1-C6 alkyl group, or a C1-C6 alkoxy group. n1 is an integer from 0 to 4. n2 is an integer from 0 to 6. However, if n1 is 2 or greater, multiple A 1 These are either the same group or different groups. If n2 is 2 or more, there are multiple A 2 These are either identical or different groups. 6 This is an alkanediyl group. 1 , R 2 and R 3 This is equivalent to equation (1) above. "*" indicates a bonding operation.

[0026] In equations (3-1) and (3-2) above, A 1 and A 2 Examples of alkoxy groups having 1 to 6 carbon atoms and alkyl groups having 1 to 6 carbon atoms are given by R in formula (1) above. 1 ~R 3 Similar groups to those exemplified above can be cited. Groups that bond to aromatic rings "-SiR 1 R 2 R 3 The position of " is A 1 and A 2 It can be in any position with respect to the other groups except for . For example, in the case of formula (3-1) above, "-SiR 1 R 2 R 3 The position of " can be the ortho, meta, or para position, and is preferably the para position. n1 is preferably 0 or 1, and more preferably 0. n2 is preferably 0 to 2, and more preferably 0.

[0027] In the above equation (3-3), R 6 It is preferable that it is linear. From the viewpoint of increasing the heat resistance of the resulting cured film, R 6 The carbon atoms preferably have 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

[0028] In order to improve the heat resistance, chemical resistance, and hardness of the cured film, it is preferable that the structural unit (I-1) has at least one selected from the group consisting of the group represented by formula (3-1) and the group represented by formula (3-2) among the above formulas (3-1) to (3-3). In addition, the aromatic ring may have the group "-SiR 1 R 2 R 3 When the group is directly bonded, it becomes possible to stabilize the silanol group that is generated in the presence of water. This is preferable because it allows for higher solubility of the exposed area in the alkaline developer and enables the formation of a good pattern. Among these, structural unit (I-1) is particularly preferably a structural unit having a group represented by the above formula (3-1).

[0029] The structural unit (I-1) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as an "unsaturated monomer"). Specifically, it is preferably at least one selected from the group consisting of the structural unit represented by the following formula (4-1) and the structural unit represented by the following formula (4-2). [ka] (In equations (4-1) and (4-2), R A R is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. 7 and R 8 Each of these is independently a divalent aromatic ring group or a chain-like hydrocarbon group. 1 , R 2 and R 3 This is equivalent to equation (1) above.

[0030] In equations (4-1) and (4-2) above, R 7 , R 8 The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalylene 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.

[0031] In terms of obtaining a cured film with higher heat resistance, chemical resistance, and hardness, and in terms of increasing the solubility of the exposed area in alkaline developing solution, R 7 , R 8 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.

[0032] Specific examples of structural units represented by formula (4-1) above include the structural units represented by formulas (4-1-1) and (4-1-2) below. Specific examples of structural units represented by formula (4-2) above include the structural units represented by formulas (4-2-1) and (4-2-2) below. [ka] (In equations (4-1-1), (4-1-2), (4-2-1), and (4-2-2), R 11 and R 12 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 13 n3 is an integer between 1 and 4 carbon atoms, an alkyl group between 1 and 4 carbon atoms, an alkoxy group between 1 and 4 carbon atoms, or a hydroxyl group. 1 , A 2 n1 and n2 are equivalent to equations (3-1) and (3-2) above. A This is equivalent to equations (4-1) and (4-2) above.

[0033] Specific examples of monomers constituting structural unit (I-1) include compounds having the group represented by formula (3-1) above, such as styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc. Compounds having the group represented by the above formula (3-2) include trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloxynaphthyltrimethoxysilane, etc. Examples of compounds having the group represented by the above formula (3-3) include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and 4-(meth)acryloxybutyltrimethoxysilane, respectively.

[0034] The content of structural unit (I-1) in polymer (a1-1) is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer (a1-1). Furthermore, the content of structural unit (I-1) is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 45% by mass or less, relative to the total structural units constituting polymer (a1-1). Setting the content of structural unit (I-1) within the above range is preferable because it allows for sufficiently high heat resistance and chemical resistance of the resulting cured film, enables high sensitivity, and allows the coating film to exhibit better resolution.

[0035] If the polymer component contained in the first composition contains polymer (a1-1), the polymer component may further contain structural units other than structural unit (I-1) (hereinafter also referred to as "other structural units (1)"). Examples of other structural units (1) include structural units having a crosslinkable group (II-1), structural units having an acid group (III-1), and the like. Other structural units (1) may be introduced into the same polymer as polymer (a1-1) having structural unit (I-1), or they may be introduced as structural units of a polymer different from polymer (a1-1), or they may be introduced into both polymer (a1-1) and a polymer different from polymer (a1-1).

[0036] • Structural unit (II-1) The polymer component containing structural unit (II-1) is preferable because it can further enhance the resolution, developability, and curing adhesion of the film, and because it can form a cured film with high chemical resistance that can suppress degradation over a long period of time. The crosslinkable group is not particularly limited as long as it is a group that undergoes a curing reaction by heat treatment, but oxyranyl group, oxetanyl group, and "-NH-CH2-OR" are preferred because they have high thermosetting properties. 10 The base represented by " (where R 10 At least one selected from the group consisting of a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an ethylenically unsaturated group is preferred. Among these, oxyranyl group, oxetanyl group, and "-NH-CH2-OR 10 At least one selected from the group consisting of groups represented by " is preferred, and epoxy groups are particularly preferred.

[0037] (Structural unit containing epoxy groups) When the crosslinking group is an epoxy group, the structural unit (II-1) is preferably a structural unit derived from an unsaturated monomer having an epoxy group. Specifically, this includes at least one selected from the group consisting of the structural unit represented by the following formula (5-1) and the structural unit represented by the following formula (5-2). [ka] (In equations (5-1) and (5-2), R 20 R is a monovalent group having an oxyranyl group or an oxetanyl group. A X is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. 1 (This is a single bond or a divalent linking group.)

[0038] In equations (5-1) and (5-2) above, R 20 Examples include oxyranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl groups and 3-ethyloxetanyl groups.

[0039] X 1 Examples of divalent linking groups include methylene groups, ethylene groups, alkanediyl groups such as 1,3-propanediyl groups, and divalent groups in which any methylene group of an alkanediyl group is replaced by an oxygen atom.

[0040] Specific examples of monomers having an epoxy group include 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, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, etc.

[0041] ("-NH-CH2-OR 10 (A structural unit having a group represented by ") The crosslinking group is “-NH-CH2-OR 10 If the group is represented by ", it is preferable in that thermal curing can be carried out under mild conditions. Here, R 10 The monovalent saturated aliphatic hydrocarbon group represented by may be linear or cyclic. 10 From the viewpoint of ease of crosslinking reaction, alkyl groups or cycloalkyl groups having 1 to 7 carbon atoms are preferred, linear or branched alkyl groups having 1 to 7 carbon atoms are more preferred, and linear or branched alkyl groups having 1 to 4 carbon atoms are even more preferred.

[0042] The crosslinking group is “-NH-CH2-OR 10 If the group is represented as ", the structural unit (II-1) is "-NH-CH2-OR 10It is preferable that the structural unit is derived from an unsaturated monomer having a group represented by ". Specifically, a structural unit represented by the following formula (6-1) is an example. [ka] (In formula (6-1), R 10 R is a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group. A (This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group.)

[0043] (Structural units containing ethylenically unsaturated groups) When the crosslinkable group is an ethylenically unsaturated group, the structural unit (II-2) preferably has an ethylenically unsaturated group in its side chain, and more preferably has a side chain structure with 3 to 20 carbon atoms having an ethylenically unsaturated group at its terminal. Specifically, a structural unit represented by the following formula (7-1) can be cited. [ka] (In formula (7-1), X 3 R is a divalent linking group with 1 to 12 carbon atoms. 11 R is a hydrogen atom or a methyl group. A This is equivalent to equation (6-1) above.

[0044] In the above equation (7-1), X 3 Examples of divalent linking groups represented by the above formula (7-1) include divalent hydrocarbon groups having 1 to 12 carbon atoms, divalent groups in which any methylene group in a divalent hydrocarbon group is replaced with -O-, -COO-, -OCO-, -NHCO-, -CONH-, -OCONH-, or -NHCOO- (hereinafter also referred to as "divalent heteroatom-containing groups"), and divalent groups in which any hydrogen atom in a divalent hydrocarbon group or a divalent heteroatom-containing group is replaced with a hydroxyl group, a carboxyl group, etc. 3 -C(=CH2)-R 11 The side chain represented by preferably has a (meth)acryloyl group at its terminus.

[0045] When the polymer (a1-1) has structural units (II-1), the content of structural units (II-1) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting the polymer (a1-1). Furthermore, the content of structural units (II-1) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting the polymer (a1-1). Setting the content of structural units (II-1) within the above range is preferable because it allows for the formation of a coating film exhibiting good developability and resolution, and also allows for sufficiently high curing adhesion, heat resistance, and chemical resistance in the resulting cured film.

[0046] If polymer (a1-1) substantially does not contain structural unit (II-1), the first composition preferably contains a polymer different from polymer (a1-1) that contains structural unit (II-1) but substantially does not contain structural unit (I-1) (hereinafter also referred to as "polymer (b1-1)") together with polymer (a1-1). In this specification, "substantially does not contain" a certain structural unit means that the content of that structural unit is less than 1% by mass relative to the total structural units constituting the polymer, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less.

[0047] The content of structural unit (II-1) in polymer (b1-1) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer (b1-1). Furthermore, the content of structural unit (II-1) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer (b1-1).

[0048] When the first composition contains polymer (a1-1) and polymer (b1-1), the ratio of polymer (a1-1) to polymer (b1-1) is preferably, by mass ratio, polymer (a1-1):polymer (b1-1) = 95:5 to 5:95, more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.

[0049] • Structural unit (III-1) The polymer (a1-1) preferably further contains a structural unit (III-1) having an acid group. The structural unit (III-1) can enhance the solubility (alkali solubility) of the polymer (a1-1) in an alkaline developer or enhance its curing reactivity. In this specification, "alkali solubility" means dissolving in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0050] Structural unit (III-1) is not particularly limited as long as it has an acid group. Preferred examples of structural unit (III-1) include structural units having a carboxyl group, structural units having a phenolic hydroxyl group, structural units having a sulfonic acid group, structural units having a sulfonamide group, structural units having a phosphonic acid group, maleimide units, etc. Among these, at least one selected from the group consisting of structural units having a carboxyl group, structural units having a phenolic hydroxyl group, structural units having a sulfonic acid group, and maleimide units is preferred, and at least one selected from the group consisting of structural units having a carboxyl group, structural units having a phenolic hydroxyl group, and maleimide units is more preferred. In this specification, "phenolic hydroxyl group" means a hydroxyl group directly bonded to an aromatic ring (e.g., a benzene ring, naphthalene ring, anthracene ring, etc.).

[0051] The structural unit (III-1) is preferably a structural unit derived from an unsaturated monomer having an acidic group. Examples of unsaturated monomers having an acidic group include styrene compounds, vinyl compounds, (meth)acrylic compounds, maleimide compounds, and the like.

[0052] Specific examples of unsaturated monomers having an acid group include, as unsaturated monomers constituting a structural unit having a carboxyl group, 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; as unsaturated monomers constituting a structural unit having a sulfonic acid group, unsaturated monomers such as vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, and (meth)acryloyloxyethylsulfonic acid; and as unsaturated monomers constituting a structural unit having a phenolic hydroxyl group, unsaturated monomers such as 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, and hydroxyphenyl(meth)acrylate. Maleimide can also be used as the monomer constituting structural unit (III-1).

[0053] When the polymer (a1-1) contains structural unit (III-1), the content of structural unit (III-1) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total structural units constituting the polymer (a1-1), from the viewpoint of imparting good solubility to the alkaline developer. On the other hand, if the content of structural unit (III-1) is too high, the difference in solubility to the alkaline developer between the exposed and unexposed areas becomes small, and it may become difficult to obtain a good pattern shape. From this viewpoint, the content of structural unit (III-1) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting the polymer (a1-1).

[0054] If polymer (a1-1) substantially does not contain structural unit (III-1), it is preferable that the composition contains a polymer different from polymer (a1-1) that contains structural unit (III-1) but substantially does not contain structural unit (I-1) (hereinafter also referred to as "polymer (b1-2)") together with polymer (a1-1). As polymer (b1-2), a polymer having a carboxyl group in its side chain can be preferably used.

[0055] Specific examples of polymers having carboxyl groups in their side chains include (meth)acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, carboxyl group-containing acidic cellulose derivatives, and acid anhydride adducts of hydroxyl group-containing polymers.

[0056] From the viewpoint of providing good solubility in alkaline developer, the content of structural unit (III-1) in polymer (b1-2) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer (b1-2). Furthermore, the content of structural unit (III-1) is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, relative to the total structural units constituting polymer (b1-2).

[0057] When the first composition contains polymer (a1-1) and polymer (b1-2), the ratio of polymer (a1-1) to polymer (b1-2) is preferably, by mass ratio, polymer (a1-1):polymer (b1-2) = 95:5 to 5:95, more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.

[0058] Other monomers constituting structural unit (1) include at least one 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 dicarboxylate compounds. By introducing structural units derived from these monomers into the polymer, the glass transition temperature of the polymer components can be adjusted, or the pattern shape and chemical resistance of the resulting cured film can be further improved.

[0059] Specific examples of the above monomers include, as (meth)acrylic acid alkyl esters, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc.; As (meth)acrylic acid esters having an alicyclic structure, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 decane-8-yl, tricyclo[5.2.1.0 2,5 decane-8-yloxyethyl, isobornyl (meth)acrylate, etc.; As (meth)acrylic acid esters having an aromatic ring structure, phenyl (meth)acrylate, benzyl (meth)acrylate, etc.; As aromatic vinyl compounds, 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, etc.; Examples of N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. Examples of vinyl compounds having a heterocyclic structure include tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (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, (γ-butyrolactone-2-yl) (meth)acrylate, glycerin carbonate (meth)acrylate, (γ-lactam-2-yl) (meth)acrylate, N-(meth)acryloxyethylhexahydrophthalimide, etc. Examples of conjugated diene compounds include 1,3-butadiene and isoprene; Examples of nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; Examples of unsaturated dicarboxylate dialkyl ester compounds include diethyl itaconate, etc. In addition to the above, other monomers that constitute structural unit (1) include vinyl chloride, vinylidene chloride, vinyl acetate, etc.

[0060] As monomers constituting other structural units (1), at least one selected from the group consisting of aromatic vinyl compounds and (meth)acrylic acid esters having an alicyclic structure can be preferably used from the viewpoint of electrical properties. Preferred specific examples include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, hydroxystyrene, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and benzyl (meth)acrylate.

[0061] Furthermore, as monomers constituting other structural units (1), alkyl (meth)acrylates can be preferably used from the viewpoint of improving adhesion to the substrate. Preferred specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate, with methyl (meth)acrylate being the most preferred. The polymer component may further have structural units having an oxazoline group as other structural units.

[0062] If the polymer (a1-1) has structural units other than structural units (II-1) and structural units (III-1) (hereinafter also referred to as "other structural units (IV-1)"), the content of other structural units (IV-1) is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total structural units constituting the polymer (a1-1). Furthermore, the content of other structural units (IV-1) is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total structural units constituting the polymer (a1-1).

[0063] Polymer (a1-1) 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, etc., according to a known method such as radical polymerization. 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. Examples of polymerization solvents include alcohols, ethers, ketones, esters, hydrocarbons, etc. 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 reaction solution.

[0064] 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.

[0065] For polymer (a1-1), the weight-average molecular weight (Mw) in polystyrene terms, determined by gel permeation chromatography (GPC), is preferably 3,000 or more. An Mw of 3,000 or more is preferable because it allows for the production of a cured film with sufficiently high heat resistance and chemical resistance, as well as good developability. More preferably, Mw is 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 formation, 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.

[0066] Furthermore, for polymer (a1-1), the molecular weight distribution (Mw / Mn), which is expressed as the ratio of the weight-average molecular weight (Mw) to the 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.

[0067] Preferred embodiments of the polymer component included in the first composition, when the first composition includes polymer (a1-1) as a polymer component, are shown below. However, the first composition containing polymer (a1-1) is not limited to the embodiments shown below. <1A> An embodiment in which the polymer (a1-1) further comprises structural unit (II-1) and structural unit (III-1), and also comprises one or more other structural units (IV-1). <2A> An embodiment comprising polymer (a1-1) and polymer (b1-1) or polymer (b1-2). However, polymer (a1-1) further comprises structural unit (III-1) and one or more other structural units (IV-1), and substantially does not contain structural unit (II-1), and polymer (b1-1) or polymer (b1-2) comprises structural unit (II-1), structural unit (III-1), and one or more other structural units (IV-1), and substantially does not contain structural unit (I-1). <3A> An embodiment further comprising a polymer (a1-1) and a polymer substantially free of structural units (I-1) and (II-1). <4A> An embodiment consisting of two or more combinations of the embodiments described in <1A> to <3A> above.

[0068] The embodiment of <1A> described above is particularly preferred because it can obtain the effect of improving developability and curing adhesion while minimizing the number of components constituting the first composition.

[0069] [Regarding polymerization (a1-2)] Polymer (a1-2) is a polymer containing structural unit (I-2) having an acid-dissociable group. The acid-dissociable group is a group that substitutes a hydrogen atom in acidic groups such as carboxyl groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, and sulfo groups, and dissociates upon the action of an acid. In this composition containing polymer (a1-2), the acid-dissociable group is removed by the acid generated when the composition is irradiated with radiation, resulting in the formation of acidic groups. This makes it possible to change the solubility of the polymer component in the developer and obtain a cured film with a pattern formed on it.

[0070] In particular, structural unit (I-2) is preferably a structural unit in which an acid-dissociable group is removed by the action of an acid to produce a carboxyl group (hereinafter also referred to as "structural unit (I-2-1)"), or a structural unit in which an acid-dissociable group is removed by the action of an acid to produce a phenolic hydroxyl group (hereinafter also referred to as "structural unit (I-2-2)").

[0071] • Regarding structural units (I-2-1) Structural units (I-2-1) include structural units derived from protected unsaturated carboxylic acids. The unsaturated carboxylic acids used are not particularly limited, but examples include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, and unsaturated polycarboxylic acids.

[0072] Specific examples of these include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, (meth)acrylic acid-2-carboxyethyl ester, and 4-vinylbenzoic acid. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, and citraconic acid. Examples of unsaturated anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of unsaturated polycarboxylic acids include ω-carboxypolycaprolactone mono(meth)acrylate.

[0073] Examples of the acid dissociable group contained in the structural unit (I-2-1) include an acetal-based functional group, a tertiary alkyl group, a tertiary alkyl carbonate group, etc. Among these, an acetal-based functional group is preferable in terms of being easily dissociated by an acid.

[0074] When the acid dissociable group is an acetal-based functional group, the structural unit (I-2-1) preferably has an acetal ester structure of a carboxylic acid as a protected carboxy group, and specifically, preferably has a group represented by the following formula (X-1).

Chemical formula

[0075] The alkyl group having 1 to 12 carbon atoms represented by R 31 , R 32 and R 33 may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 4. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc. can be mentioned.

[0076] R 31, R 32 and R 33 Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, represented by R, include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, isobornyl, and adamantyl groups. 32 and R 33 Examples of aralkyl groups with 7 to 20 carbon atoms represented by this formula include phenylmethyl group, phenylethyl group, and methylphenylmethyl group.

[0077] R 32 and R 33 The cyclic ether structure formed by combining these elements preferably has five or more ring members. Specifically, examples include tetrahydrofuran ring structures and tetrahydropyran ring structures.

[0078] In terms of being easily dissociated by acid, R 31 The group is preferably a hydrogen atom, a methyl group, or an ethyl group, with a hydrogen atom being more preferred.

[0079] Specific examples of the acetal ester structure of the carboxylic acid represented by the above formula (X-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-propoxyethoxycarbonyl group, 1-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, and 1-phenylmethoxyethoxycarbonyl group.

[0080] Among the above, the structural unit (I-2-1) is preferably the structural unit represented by the following formula (Y-1) and the structural unit represented by formula (Y-2). [ka] (In formula (Y-1), R 30 X is a hydrogen atom or a methyl group. 30 R is a single bond or an arylene group. 40 R is a hydrogen atom or an alkyl group.41 and R 42 Each of these is independently an alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. [ka] (In formula (Y-2), R 30 X is a hydrogen atom or a methyl group. 31 R is a single bond or an arylene group. 43 ~R 49 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. k is either 1 or 2.

[0081] A preferred example of a structural unit (I-2-1) is the structural unit represented by the following formula. In the formula, R 30 This is either a hydrogen atom or a methyl group. [ka]

[0082] • Regarding structural units (I-2-2) The structural unit (I-2-2) is not particularly limited, as long as it has a protected phenolic hydroxyl group. In particular, from the viewpoint of the sensitivity of this composition, structural units derived from hydroxystyrene or its derivatives and structural units derived from (meth)acrylic compounds having a hydroxybenzene structure are preferred.

[0083] The acid-dissociable group possessed by structural unit (I-2-2) is not particularly limited, but from the viewpoint of the sensitivity, pattern shape, and storage stability of this composition, acetal-based functional groups are preferred. Examples of acetal-based functional groups that can be used in structural unit (I-2-2) are the same as those that can be used in structural unit (I-2-1). Among them, "-OC(R 31 )(R 32 )(OR 33 )" (However, R 31 , R 32 and R 33It is preferable that the group is a phenolic hydroxyl group protected by a group represented by formula (X-1), which is synonymous with formula (X-1). In this case, the protected phenolic hydroxyl group contained in structural unit (I-2-2) can be represented by the following formula (Z-1). [ka] (In formula (Z-1), Ar 1 R is an arylene group. 31 , R 32 and R 33 This is equivalent to equation (X-1). "*" represents a bond.

[0084] The structural unit (I-2-2) contains "-C(R 31 )(R 32 )(OR 33 Preferred specific examples of the group represented by ) include 1-alkoxyalkyl groups and 1-arylalkoxyalkyl groups, and specifically, for example, 1-ethoxyethyl group, 1-methoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-(2-cyclohexylethoxy)ethyl group, 1-benzyloxyethyl group, etc.

[0085] A preferred example of a structural unit (I-2-2) is the structural unit represented by the following formula. In the formula, R 30 This is either a hydrogen atom or a methyl group. [ka]

[0086] The content of structural unit (I-2) in polymer (a1-2) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total structural units constituting polymer (a1-2). Furthermore, the content of structural unit (I-2) is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less, relative to the total structural units constituting polymer (a1-2). Setting the content of structural unit (I-2) within the above range is preferable in that it is possible to increase the sensitivity of the first composition and the coating film exhibits better resolution.

[0087] If the first composition contains polymer (a1-2) as a polymer component, the polymer component may further contain structural units other than structural unit (I-2) (hereinafter also referred to as "other structural units (2)"). Examples of other structural units (2) include structural units having a crosslinkable group (II-2), structural units having an acid group (III-2), etc. Other structural units (2) may be introduced into the same polymer as polymer (a1-2) having structural unit (I-2), may be introduced as structural units of a polymer different from polymer (a1-2), or may be introduced into both polymer (a1-2) and a polymer different from polymer (a1-2).

[0088] • Structural units (II-2) The crosslinkable group of structural unit (II-2) is not particularly limited, as long as it is a group that undergoes a hardening reaction by heat treatment. Among those with high thermosetting properties, oxyranyl group, oxetanyl group, and "-NH-CH2-OR 10 The base represented by " (where R 10 Preferably, at least one selected from the group consisting of a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an ethylenically unsaturated group. Specific examples and preferred examples of structural unit (II-2) are the same as those shown in the description of structural unit (II-1).

[0089] When polymer (a1-2) contains structural unit (II-2), the content of structural unit (II-2) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer (a1-2). Furthermore, the content of structural unit (II-2) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer (a1-2).

[0090] If polymer (a1-2) substantially does not contain structural unit (II-2), the first composition preferably contains a polymer different from polymer (a1-2) that contains structural unit (II-2) but substantially does not contain structural unit (I-2) (hereinafter also referred to as "polymer (b1-3)") together with polymer (a1-2).

[0091] The content of structural unit (II-2) in polymer (b1-3) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer (b1-3). Furthermore, the content of structural unit (II-2) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer (b1-3).

[0092] When this composition contains polymer (a1-2) and polymer (b1-3), the ratio of polymer (a1-2) to polymer (b1-3) is preferably, by mass ratio, polymer (a1-2):polymer (b1-3) = 95:5 to 5:95, more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.

[0093] • Structural units (III-2) It is preferable that the polymer (a1-2) further contains structural unit (III-2) having an acid group, as this can improve solubility in alkaline developers and enhance curing reactivity. Specific examples and preferred examples of structural unit (III-2) are the same as those shown in the description of structural unit (III-1).

[0094] When polymer (a1-2) contains structural unit (III-2), the content of structural unit (III-2) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer (a1-2), from the viewpoint of providing good solubility in alkaline developer. Furthermore, the content of structural unit (III-2) is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, relative to the total structural units constituting polymer (a1-2).

[0095] If polymer (a1-2) substantially does not contain structural unit (III-2), it is preferable that the composition also contains polymer (b1-4), which is a polymer different from polymer (a1-2) and substantially does not contain structural unit (I-2) (hereinafter also referred to as "polymer (b1-4)"). As polymer (b1-4), polymers having carboxyl groups in their side chains can be preferably used, and the description of polymer (b1-2) applies to specific examples thereof.

[0096] From the viewpoint of providing good solubility in alkaline developer, the content of structural unit (III-2) in polymer (b1-4) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer (b1-4). Furthermore, the content of structural unit (III-2) is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, relative to the total structural units constituting polymer (b1-4).

[0097] When the composition contains polymer (a1-2) and polymer (b1-4), the ratio of polymer (a1-2) to polymer (b1-4) is preferably, by mass ratio, polymer (a1-2):polymer (b1-4) = 95:5 to 5:95, more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.

[0098] Furthermore, if the first composition includes polymer (a1-2) as a polymer component, other structural units (2) that the polymer component may contain include the structural units exemplified as other structural units (1).

[0099] If the polymer (a1-2) contains structural units other than structural units (II-2) and structural units (III-2) (hereinafter also referred to as "other structural units (IV-2)"), the content of other structural units (IV-2) is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total structural units constituting the polymer (a1-2). Furthermore, the content of other structural units (VI-2) is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total structural units constituting the polymer (a1-2).

[0100] Polymers (a1-2) can be produced, for example, by using unsaturated monomers to which each of the above-mentioned structural units can be introduced, in a suitable solvent, in the presence of a polymerization initiator, etc., according to known methods such as radical polymerization. The details of the polymerization method are the same as for polymer (a1-1).

[0101] For polymers (a1-2), the weight-average molecular weight (Mw) in polystyrene terms, calculated by GPC, is preferably 1,000 or more. More preferably, Mw is 2,000 or more, and even more preferably 5,000 or more. Furthermore, from the viewpoint of improving film-forming properties, Mw is preferably 200,000 or less, and more preferably 50,000 or less.

[0102] Furthermore, for polymers (a1-2), the molecular weight distribution (Mw / Mn), which is expressed as the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is preferably 5.0 or less, and more preferably 3.0 or less.

[0103] Preferred embodiments of the polymer component included in the first composition, when the first composition includes polymer (a1-2) as a polymer component, are shown below. However, the first composition including polymer (a1-2) is not limited to the embodiments shown below. <1B> An embodiment in which the polymer (a1-2) further comprises structural units (II-2) and structural units (III-2), and also comprises one or more other structural units (IV-2). <2B> An embodiment comprising polymer (a1-2) and polymer (b1-3) or polymer (b1-4). However, polymer (a1-2) further comprises structural unit (III-2) and one or more other structural units (IV-2), and substantially does not contain structural unit (II-2), and polymer (b1-3) or polymer (b1-4) comprises structural unit (II-2), structural unit (III-2), and one or more other structural units (IV-2), and substantially does not contain structural unit (I-2). <3B> An embodiment further comprising a polymer (a1-2) and a polymer substantially free of structural units (I-2) and (II-2). <4B> An embodiment consisting of two or more combinations of the embodiments described in <1B> to <3B> above.

[0104] The embodiment <1B> described above is particularly preferred because it allows for improved development adhesion and curing adhesion while minimizing the number of components constituting the first composition.

[0105] [About siloxane polymers] When the first composition contains a siloxane polymer as a polymer component, irradiating the first composition with radiation allows the acid generated from the photoacid generator by the radiation irradiation to act as a catalyst, promoting the self-crosslinking of the siloxane polymer and thereby forming a cured film.

[0106] The siloxane polymer is not particularly limited as long as it can form a cured film by hydrolysis condensation. Preferably, the siloxane polymer is a polymer obtained by hydrolyzing a hydrolyzable silane compound represented by the following formula (6). (R 21 ) r Si(OR 22 ) 4-r …(6) (In formula (6), R 21It is a non-hydrolyzable monovalent group. 22 is an alkyl group having 1 to 4 carbon atoms. r is an integer from 0 to 3. However, if r is 2 or 3, multiple R in the formula. 21 These are either the same group or different groups. When r is between 0 and 2, there are multiple R in the formula. 22 These are either identical or different groups.

[0107] R 21 Examples include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, groups having a (meth)acryloyl group, and groups having an epoxy group. R 22 Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, etc. Among these, R is chosen because of its high hydrolysis properties. 22 A methyl group or an ethyl group is preferred. r is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0108] Specific examples of monomers constituting siloxane polymers include silane compounds having four hydrolyzable groups, such as tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabendyloxysilane, and tetra-n-propoxysilane; Examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc. Examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane; Examples of silane compounds having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane, respectively.

[0109] Siloxane polymers can be obtained by hydrolyzing and condensing one or more of the above hydrolyzable silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis and condensation reaction, the proportion of water used depends on the hydrolyzable group (-OR) of the hydrolyzable silane compound. 22 The amount of water is preferably 0.1 to 3 moles, more preferably 0.2 to 2 moles, and even more preferably 0.5 to 1.5 moles, per 1 mole of the total amount of ). By using such an amount of water, the reaction rate of hydrolysis condensation can be optimized.

[0110] Examples of catalysts used in hydrolysis-condensation reactions include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and is set appropriately, but is preferably 0.0001 to 0.2 moles, and more preferably 0.0005 to 0.1 moles, per mole of hydrolyzable silane compound.

[0111] Examples of organic solvents used in the above hydrolysis-condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Of these, it is preferable to use an organic solvent that is water-insoluble or poorly water-soluble. Examples include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid ester compounds. The proportion of organic solvent used is preferably 10 to 10,000 parts by mass, and more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the total hydrolyzable silane compounds used in the reaction.

[0112] During the hydrolysis-condensation reaction, the reaction temperature is preferably 130°C or lower, and more preferably 40-100°C. The reaction time is preferably 0.5-24 hours, and more preferably 1-12 hours. During the reaction, the mixture may be stirred or kept under reflux. After the hydrolysis-condensation reaction, a dehydrating agent may be added to the reaction solution, and then water and the resulting alcohol may be removed from the reaction system by evaporation.

[0113] The siloxane polymer contained in the first composition preferably has a weight-average molecular weight (Mw) of 500 or more in terms of polystyrene, calculated by GPC. An Mw of 500 or more is preferable because it allows for the production of a cured film with sufficiently high heat resistance and solvent resistance, as well as good developability. More preferably, Mw is 1000 or more. Furthermore, from the viewpoint of improving film formation and suppressing a decrease in radiation sensitivity, Mw is preferably 10000 or less, and more preferably 5000 or less.

[0114] Furthermore, for the polysiloxane polymer, the molecular weight distribution (Mw / Mn) is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0115] In the first composition, the content of the (A-1) polymer is preferably 20% 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 first composition. Furthermore, the content of the (A-1) polymer is preferably 99% by mass or less, and more preferably 90% by mass or less, based on the total amount of solids contained in the first composition. By setting the content of the (A-1) polymer within the above range, a cured film can be obtained that exhibits sufficiently high heat resistance and chemical resistance, as well as good developability and transparency.

[0116] <(B-1) Photoacid Generator> The first composition contains a photoacid generator as a radiation-sensitive compound. The photoacid generator included in the first composition (hereinafter also simply referred to as "photoacid generator") is preferably a compound that reacts to active light with a wavelength of 300 nm or more (preferably 300-450 nm) and generates acid. When using a photoacid generator that does not directly react to active light with a wavelength of 300 nm or more, it may be used in combination with a sensitizer to react to active light with a wavelength of 300 nm or more and generate acid.

[0117] As the photoacid generator, a compound that generates an acid with an acid dissociation constant (pKa) of 4 or less can be preferably used. The acid dissociation constant of the acid generated by the photoacid generator is more preferably 3 or less, and even more preferably 2 or less.

[0118] Specific examples of photoacid generators include, for example, oximesulfonate compounds, onium salts (sulfonium salts, iodonium salts, quaternary ammonium salts, etc.), sulfonimide compounds, halogen-containing compounds (trichloromethyl-s-triazine compounds, etc.), diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and the like.

[0119] Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds include 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. From the viewpoint of radiation sensitivity, it is preferable to use at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds as the photoacid generator, with oxime sulfonate compounds being particularly preferred.

[0120] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (7). [ka] (In formula (7), R 23 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 replaced by substituents. (* indicates a bond.)

[0121] In equation (7) above, R 23 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.

[0122] Preferred specific examples of compounds having a sulfonate group represented by formula (7) above include compounds represented by formulas (7-1) to (7-3) below. [ka] (In formula (7-1), R 51 X is a substituted or unsubstituted monovalent hydrocarbon group. 51 is an alkyl group, alkoxy group, or halogen atom. m1 is an integer from 0 to 3. If m1 is 2 or 3, there are multiple X 51 They are the same or different. In formula (7-2), R 52 X is a substituted or unsubstituted monovalent hydrocarbon group. 52 is an alkyl group, alkoxy group, or halogen atom. m2 is an integer from 0 to 3. If m2 is 2 or 3, there are multiple X 52 They are the same or different. In formula (7-3), R 53 R is a hydrogen atom, alkyl group, alkenyl group, alkoxy group, aryl group, heteroaryl group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, or cyano group. 54 X is a substituted or unsubstituted monovalent hydrocarbon group. 53 -O-, -S-, -NR 59 -or -C(R 59 )(R 60 )- is. R59 and R 60 Each of these is independently a hydrogen atom or a monovalent hydrocarbon group. 55 ~R 58 Each of these is independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, an arylcarbonyl group, an amino group, an amide group, a sulfo group, or a cyano group. However, R 55 ~R 58 Two adjacent groups may be bonded together to form a ring.

[0123] Specific 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.

[0124] Specific 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, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide.

[0125] In the first composition, the content of the photoacid generator is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, per 100 parts by mass of the (A-1) polymer contained in the first composition. Furthermore, the content of the photoacid generator is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the polymer component contained in the first composition.

[0126] If the content of the photoacid generator is 0.1 parts by mass or more, sufficient acid is generated by irradiation with radiation, and the difference in solubility between the irradiated and unirradiated areas in the alkaline solution can be sufficiently large. This allows for good patterning. In addition, the amount of acid involved in the reaction with the polymer component can be increased, and sufficient heat resistance and solvent resistance can be ensured. On the other hand, if the content of the photoacid generator is 20 parts by mass or less, the amount of unreacted photoacid generator after exposure can be sufficiently reduced, which is preferable in that it suppresses the decrease in developability due to residual photoacid generator.

[0127] <(C-1) Solvent> The first composition contains a solvent. Preferably, the first composition is a liquid composition in which a polymer component, (B-1) photoacid generator, (E) compound, and optionally added components are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each component incorporated into the first composition and does not react with each component.

[0128] Specific examples of solvents include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, dimethyl glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

[0129] Of these, the solvent preferably includes at least one selected from the group consisting of ethers and esters, and more preferably at least one selected from the group consisting of ethylene glycol alkyl ether acetate, diethylene glycols, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate.

[0130] In the first composition, the solvent content (total amount if two or more solvents are included) is preferably 50 to 95 parts by mass, and more preferably 60 to 90 parts by mass, per 100 parts by mass of all components of the first composition.

[0131] <(E) Compound> The first composition contains a compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxyranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group (hereinafter also simply referred to as "cardi compound").

[0132] The cardi structure has a first ring structure, a second ring structure, and a third ring structure, in which the second and third ring structures are directly bonded to the same carbon atom contained in the ring skeleton of the first ring structure. Specifically, the cardi structure can be represented by the following formula (10). [ka] (In formula (10), A 10 is, A 11 and A 12 It is a cyclic group formed together with the carbon atom to which it is bonded. 11 and A 12 These are each independently divalent cyclic groups. (* represents a bond.)

[0133] In the above formula (10), A 11 and A 12 The divalent cyclic group represented by may be either an alicyclic group or an aromatic group. An alicyclic group is a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aliphatic hydrocarbon ring, and may be either a monocyclic hydrocarbon group or a polycyclic hydrocarbon group. When the divalent alicyclic group is a polycyclic hydrocarbon group, the polycyclic hydrocarbon group may be either a bridged alicyclic hydrocarbon group or a condensed alicyclic hydrocarbon group, and may also be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. A condensed alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group in which multiple alicyclics share an edge (a bond between two adjacent carbon atoms).

[0134] Specific examples of monocyclic alicyclic hydrocarbon groups include saturated hydrocarbon groups such as cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, and cyclooctanediyl; and unsaturated hydrocarbon groups such as cyclopentenediyl, cyclohexenediyl, cycloheptenediyl, cyclooctenediyl, cyclopentadienediyl, and cyclohexadienediyl. Specific examples of polycyclic alicyclic hydrocarbon groups include bridged alicyclic saturated hydrocarbon groups such as bicyclo[2.2.1]heptane-2,2-diyl (norbornane-2,2-diyl), bicyclo[2.2.2]octane-2,2-diyl, and tricyclo[3.3.1.1 3,7 Examples of condensed alicyclic hydrocarbon groups include the decane-2,2-diyl group (adamantane-2,2-diyl group), and the decahydronaphthalenediyl group.

[0135] A divalent aromatic ring group is a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aromatic ring, and may be monocyclic or polycyclic. If the divalent aromatic ring group is a polycyclic hydrocarbon group, the polycyclic hydrocarbon group may be either a bridged aromatic hydrocarbon group or a condensed aromatic hydrocarbon group.

[0136] Specific examples of monocyclic aromatic hydrocarbon groups include the phenylene group. Polycyclic aromatic hydrocarbon groups are preferably condensed aromatic ring hydrocarbon groups, such as the naphthalylene group, anthracenediyl group, fluo-orangeyl group, and phenalendiyl group.

[0137] When a divalent alicyclic group or aromatic ring group has substituents on its ring portion, examples of such substituents include alkyl groups having 1 to 6 carbon atoms, halogen atoms, cyano groups, and the like.

[0138] A 11 and A 12 The divalent cyclic group represented by is preferably a divalent aromatic ring group, and particularly preferably a substituted or unsubstituted phenylene group.

[0139] A 10 is, A 11and A 12 It is a cyclic group formed together with the carbon atom to which it is bonded. 10 A specific example of a cyclic group represented by A 11 and A 12 Examples of divalent cyclic groups represented by include those similar to the divalent alicyclic groups and divalent aromatic ring groups exemplified above. Among these, A 10 Preferred specific examples of the cyclic group represented by the formulas (10a-1) to (10a-6) below include the group represented by the formulas (10a-1) to (10a-6) below, and the group in which a substituent is introduced to the ring portion of these groups. [ka] (In the formula, "*" represents a combination.)

[0140] A 10 Among the cyclic groups represented by the above formulas (10a-1) to (10a-3), the groups represented by each of the above formulas and groups in which substituents are introduced to the ring portion are preferred, and groups having a fluorene structure (i.e., the group represented by formula (10a-1) and groups in which substituents are introduced to the ring portion) are particularly preferred.

[0141] The cardi structure represented by formula (10) above is particularly favorable in that it is highly effective in improving the development adhesion and curing adhesion of films obtained using this composition, and among them, the structure represented by formula (10-1) below is preferred. [ka] (In formula (10-1), Ar 11 and Ar 12 These are, independently, divalent aromatic ring groups. 68 and R 69 Each of these is independently an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. a1 and a2 are each independently integers from 0 to 3. If a1 is 2 or 3, multiple R 68 They are the same or different. If a2 is 2 or 3, there are multiple R 69 They are either the same or different. (* represents a combination.)

[0142] The functional group (X) of the cardo compound is at least one selected from the group consisting of an alkoxysilyl group, an oxyranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group.

[0143] An alkoxysilyl group is defined as having a structure in which an alkoxy group is bonded to a silicon atom, for example, the formula "-Si(R 61 )(R 62 )(R 63 A group represented by ) is given. Here, R 61 , R 62 and R 63 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, and R 61 , R 62 and R 63 At least one of these is an alkoxy group having 1 to 6 carbon atoms. Specific examples of alkoxysilyl groups include those similar to the group represented by formula (1) above. Of these, R 61 , R 62 and R 63 Preferably, one of the groups is an alkoxy group having 1 to 6 carbon atoms, and the rest are alkoxy groups having 1 to 6 carbon atoms or alkyl groups having 1 to 10 carbon atoms. In particular, R 61 , R 62 and R 63 It is preferable that one of the groups is an alkoxy group having 1 to 3 carbon atoms, and the remaining groups are alkoxy groups having 1 to 3 carbon atoms or alkyl groups having 1 to 3 carbon atoms, as this can further improve the development adhesion and curing adhesion properties.

[0144] In order to improve the development adhesion and curing adhesion of the film obtained using this composition, the functional group (X) is preferably at least one selected from the group consisting of an alkoxysilyl group, an oxyranyl group, an oxetanyl group, and a (meth)acryloyl group, with an alkoxysilyl group being particularly preferred.

[0145] The cardo compound contained in this composition only needs to have one or more cardo structures and one or more functional groups (X) in one molecule, and the structure of the other parts is not particularly limited. Examples of cardo compounds include oligomers containing structural units having a cardo structure, and silane coupling agents having a cardo structure. Specifically, examples of cardo compounds include compounds represented by the following formula (11) and compounds represented by the following formula (12). In addition, as a cardo compound, a photosensitive resin obtained by adding a carboxylic acid-reactive (meth)acrylate compound to a polymer compound obtained by reacting a compound having a fluorene skeleton described in International Publication No. 2009 / 119622 with a tetrabasic acid dianhydride can be used, for example, the photosensitive resin (A2) described in Example 2 of the same publication can be used.

[0146] [ka] (In formula (11), Y 61 and Y 62 Each of these is independently a divalent organic group having one or more carbon atoms. 61 and X 62 Each of these is independently an alkoxysilyl group, an oxyranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, or an amino group. Each of b1 and b2 is independently an integer from 1 to 5. Ar 11 Ar 12 , R 68 , R 69 a1 and a2 are equivalent to those in equation (10-1) above.

[0147] [ka] (In formula (12), Y 63 and Y 64 Each of these is independently a divalent organic group having one or more carbon atoms. 61 and X 63 Each of these is independently an alkoxysilyl group, an oxyranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, or an amino group. n1 is an integer from 2 to 100. Ar11 Ar 12 , R 68 , R 69 a1 and a2 are equivalent to those in equation (10-1) above.

[0148] In equations (11) and (12) above, Y 61 ~Y 64 Examples of divalent organic groups represented by include divalent hydrocarbon groups having 1 to 40 carbon atoms, and divalent groups in which at least one methylene group of the hydrocarbon group is replaced by a heteroatom-containing group. Examples of heteroatom-containing groups include -O-, -S-, -CO-, -COO-, -OCO-, and -NR 67 CO-, -CONR 67 -, -NR 67 -COO-, -OCO-NR 67 - etc. (however, R 67 Examples include hydrogen atoms or alkyl groups.

[0149] Of the above, the compound represented by formula (11) is preferred in that it can improve the developability and curing adhesion of the film formed by this composition, and in formula (11), X 61 and X 62 Compounds in which the group is an alkoxysilyl group are particularly preferred.

[0150] Commercially available products may be used as the cardo compound. Examples of commercially available cardo compounds include, by trade name, Ogusol SC-001, EA-0200, EA-0300, and CR1030 (all manufactured by Osaka Gas Chemical Co., Ltd.); WR-301 (manufactured by ADEKA Corporation); V-259ME (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); and Oncoat EX series (manufactured by Nagase ChemteX Corporation).

[0151] In the first composition, the content ratio of the caldo compound is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and still more preferably 1 part by mass or more with respect to 100 parts by mass of the polymer component contained in the first composition. Also, the content ratio of the caldo compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less with respect to 100 parts by mass of the polymer component contained in the first composition. By setting the content ratio of the caldo compound to 0.1 part by mass or more, the effects of improving the development adhesion, curing adhesion, and chemical resistance of the film formed by this composition can be sufficiently obtained. On the other hand, by setting the content ratio of the caldo compound to 20 parts by mass or less, it is suitable in that the decrease in the sensitivity of this composition can be suppressed while obtaining the effects due to the addition of the caldo compound.

[0152] Incidentally, the reason why the composition containing the (E) compound having the functional group (X) and the caldo structure could achieve excellent development adhesion, curing adhesion, and even chemical resistance is not clear, but as one hypothesis, in the coating film formed on the substrate by this composition, the (E) compound is likely to localize at the interface between the substrate and the coating film, and it is considered that the penetration of the developer between the substrate and the coating film could be suppressed due to the caldo structure of the (E) compound causing the substrate interface to be in a hydrophobic environment. Also, it is considered that the shrinkage of the film due to heating could be suppressed because the mechanical strength of the film increased.

[0153] <Other components> In addition to the above-described (A-1) polymer component, (B-1) photoacid generator, (C-1) solvent, and (E) compound, the first composition may further contain components other than these (hereinafter also referred to as "other components"). As the other components, at least one of an adhesion aid and an acid diffusion controller can be preferably used.

[0154] (Adhesion aid) The adhesion promoter is a component that improves the adhesion between the cured film formed using the first composition and the substrate. As the adhesion promoter, a functional silane coupling agent having a reactive functional group can be preferably used. Examples of the reactive functional group of the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, an isocyanate group, etc.

[0155] Specific examples of the functional silane coupling agent include, for example, trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.

[0156] When the first composition contains an adhesion promoter, its content ratio is preferably 0.01 parts by mass or more and 30 parts by mass or less, and more preferably 0.1 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the polymer component contained in the first composition.

[0157] (Acid diffusion control agent) The acid diffusion control agent is a component that controls the diffusion length of the acid generated from the photoacid generator by exposure. By blending the acid diffusion control agent in the first composition, the diffusion length of the acid can be appropriately controlled, and the pattern developability can be improved. Also, it is preferable in that the chemical resistance can be enhanced while improving the development adhesion by blending the acid diffusion control agent.

[0158] As an acid diffusion control agent, any basic compound used in chemical amplification resists can be arbitrarily selected and used. Examples of basic compounds include fatty acid amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium carboxylic acid salts. Specific examples of basic compounds include those described in paragraphs 0128 to 0147 of Japanese Patent Application Publication No. 2011-232632. Preferably, at least one selected from the group consisting of aromatic amines and heterocyclic amines can be used as the acid diffusion control agent.

[0159] Aromatic amines and heterocyclic amines include, for example, aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine; imidazole derivatives such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, and triphenylimidazole; pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2 Examples include pyrrole derivatives such as 5-dimethylpyrrole and N-methylpyrrole; pyridine derivatives such as pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl-4-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, and nicotine, as well as compounds described in Japanese Patent Application Publication No. 2011-232632.

[0160] If the first composition contains an acid diffusion control agent, its content is preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more, per 100 parts by mass of the polymer component, from the viewpoint of sufficiently obtaining the effect of improving chemical resistance due to the inclusion of the acid diffusion control agent. Furthermore, the content of the acid diffusion control agent is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the polymer component.

[0161] In addition to the above, at least one of the following ingredients can preferably be used: sensitizers, crosslinking agents, surfactants (fluorinated surfactants, silicone surfactants, nonionic surfactants, etc.), and antioxidants. The first composition may also contain known additives such as thermal radical generators, thermal acid generators, ultraviolet absorbers, thickeners, development accelerators, acid boosters, plasticizers, precipitation inhibitors, polyfunctional polymerizable compounds (polyfunctional (meth)acrylates, etc.), polymerization inhibitors, and chain transfer agents. The proportions of these ingredients are appropriately selected according to each ingredient, within a range that does not impair the effects of this disclosure.

[0162] The solid content concentration of the first composition (the ratio of the total mass of components other than the solvent in the first composition to the total mass of the first composition) is appropriately selected considering viscosity, volatility, etc. The solid content concentration of the first composition is preferably in the range of 5 to 60% by mass. If the solid content concentration is 5% by mass or more, a sufficient film thickness can be ensured when the first composition is applied to a substrate. If the solid content concentration is 60% by mass or less, the film thickness will not become excessively large, and the viscosity of the first composition can be made appropriately high, ensuring good applicability. The solid content concentration of the first composition is more preferably 10 to 55% by mass, and even more preferably 12 to 50% by mass.

[0163] [Second composition] Next, the second composition will be described. The second composition contains the following components (A-2), (B-2), (C-2), and (E). (A-2) A polymer which is at least one selected from the group consisting of polymers containing structural units having acid groups and siloxane polymers; (B-2) Quinone diazide compounds; (C-2) solvent; (E) Compounds having a cardo structure and at least one functional group (X) selected from the group consisting of alkoxysilyl groups, oxyranyl groups, oxetanyl groups, mercapto groups, (meth)acryloyl groups, vinyl groups, and amino groups.

[0164] <Polymer components> The second composition includes, as a polymer component, at least one polymer selected from the group consisting of polymers containing structural units having acid groups (hereinafter also referred to as "polymer (a2)") and siloxane polymers (also referred to as "(A-2) polymer").

[0165] [Regarding polymer (a2)] Polymer (a2) is a polymer containing a structural unit having an acid group (hereinafter also referred to as "structural unit (III-3)"). Specific examples and preferred examples of structural unit (III-3) are the same as those shown in the description of structural unit (III-1) that polymer (a1-1) may contain.

[0166] In polymer (a2), the content of structural unit (III-3) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, relative to the total structural units constituting polymer (a2), from the viewpoint of providing good solubility in alkaline developer. Furthermore, the content of structural unit (III-3) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer (a2).

[0167] When the second composition contains polymer (a2), the polymer component may further contain structural units other than structural unit (III-3) (hereinafter also referred to as "other structural units (3)"). A preferred specific example of other structural units (3) is structural unit (II-3) having a crosslinkable group. Other structural units (3) may be introduced into the same polymer (a2) as polymer (a2) having structural unit (III-3), or they may be introduced as structural units of a polymer different from polymer (a2), or they may be introduced into both polymer (a2) and a polymer different from polymer (a2).

[0168] • Structural units (II-3) The crosslinkable group of structural unit (II-3) is not particularly limited, as long as it is a group that undergoes a hardening reaction by heat treatment. Among those with high thermosetting properties, oxyranyl group, oxetanyl group, and "-NH-CH2-OR 10 The base represented by " (where R 10 Preferably, at least one selected from the group consisting of a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an ethylenically unsaturated group. Specific examples and preferred examples of structural unit (II-3) are the same as those shown in the description of structural unit (II-1).

[0169] When polymer (a2) contains structural unit (II-3), the content of structural unit (II-3) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to the total structural units constituting polymer (a2). Furthermore, the content of structural unit (II-3) is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to the total structural units constituting polymer (a2). Setting the content of structural unit (II-3) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured film to have sufficiently high heat resistance and chemical resistance.

[0170] When the polymer (a2) substantially does not contain the structural unit (II-3), this composition preferably contains, as a polymer different from the polymer (a2), a polymer that contains the structural unit (II-3) and substantially does not contain the structural unit (III-3) (hereinafter, also referred to as "polymer (b2-1)") together with the polymer (a2).

[0171] The content ratio of the structural unit (II-3) in the polymer (b2-1) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more with respect to all the structural units constituting the polymer (b2-1). Further, the content ratio of the structural unit (II-3) is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less with respect to all the structural units constituting the polymer (b2-1).

[0172] When the second composition contains the polymer (a2) and the polymer (b2-1), the ratio of the polymer (a2) and the polymer (b2-1) is preferably 95:5 to 5:95, more preferably 80:20 to 20:80, and still more preferably 70:30 to 30:70 in terms of mass ratio.

[0173] Further, when the second composition contains the polymer (a2) as a polymer component, examples of the other structural unit (3) that the polymer component may contain include the structural units exemplified as the other structural unit (1) in the description of the first composition.

[0174] The polymer (a2) can be produced, for example, by using an unsaturated monomer into which each of the above-described structural units can be introduced, in a suitable solvent, in the presence of a polymerization initiator or the like, according to a known method such as radical polymerization. The details of the polymerization method are the same as those of the polymer (a1-1).

[0175] For polymer (a2), the weight-average molecular weight (Mw) in polystyrene terms, calculated by GPC, is preferably 1,000 or more. More preferably, Mw is 2,000 or more, and even more preferably 5,000 or more. Furthermore, from the viewpoint of improving film-forming properties, Mw is preferably 200,000 or less, and more preferably 50,000 or less.

[0176] Furthermore, for polymer (a2), the molecular weight distribution (Mw / Mn), which is expressed as the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is preferably 5.0 or less, and more preferably 3.0 or less.

[0177] Preferred embodiments of the polymer component included in the second composition, when the second composition includes polymer (a2) as a polymer component, are shown below. However, the second composition containing polymer (a2) is not limited to the embodiments shown below. <1C> An embodiment in which the polymer (a2) further contains structural unit (II-3), and also contains one or more other structural units other than structural unit (II-3) (hereinafter also referred to as "other structural units (IV-3)"). <2C> An embodiment comprising polymer (a2) and polymer (b2-1), wherein polymer (a2) further comprises one or more other structural units (IV-3) and substantially does not contain structural unit (II-3), and polymer (b2-1) further comprises one or more other structural units (IV-3). <3C> An embodiment further comprising a polymer (a2) and a polymer that substantially does not contain structural units (III-3) and (II-3). <4C> An embodiment consisting of two or more combinations of the embodiments described in <1C> to <3C> above.

[0178] The embodiment <1C> described above is particularly preferred because it allows for improved development adhesion and curing adhesion while minimizing the number of components constituting the second composition.

[0179] [About siloxane polymers] The siloxane polymer included in the second composition is the same as the specific and preferred examples of the siloxane polymer that may be included in the first composition.

[0180] <(B-2) Quinone diazide compounds> The second composition contains a quinone diazide compound as a radiation-sensitive compound. The quinone diazide compound is a radiation-sensitive acid generator that produces a carboxylic acid upon irradiation with radiation. Preferably, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as the "nucleus") and 1,2-naphthoquinone diazidosulfonic acid halide can be used as the quinone diazide compound.

[0181] Examples of parent molecules include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkanes, and other parent molecules.Specific examples of these include trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; and tetrahydroxybenzophenones such as 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, and 2,3,4,4'-tetrahydroxybenzophenone. -3'-methoxybenzophenone, etc.; as pentahydroxybenzophenone, for example 2,3,4,2',6'-pentahydroxybenzophenone, etc.; as hexahydroxybenzophenone, for example 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; as (polyhydroxyphenyl)alkane, for example bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, 1,1, 1-tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl) Examples of parent compounds include -2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirovidene-5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc. Other parent compounds include, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 2-[bis{(5-isopropyl-4-hydroxy-2-methyl)phenyl}methyl], etc.

[0182] Of these, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol are preferred as the core.

[0183] As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferred. Specifically, examples include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Of these, 1,2-naphthoquinone diazide-5-sulfonic acid chloride can be preferably used as the 1,2-naphthoquinone diazide sulfonic acid halide.

[0184] In the condensation reaction to obtain the above condensate, the ratio of the parent nucleus to 1,2-naphthoquinone diazidosulfonic acid halide is such that the amount of 1,2-naphthoquinone diazidosulfonic acid halide used corresponds to 30 to 85 mol%, more preferably 50 to 70 mol%, of the number of OH groups in the parent nucleus. The above condensation reaction can be carried out according to known methods. A 1,2-quinone diazide compound is obtained by the condensation reaction of the parent nucleus and 1,2-naphthoquinone diazidosulfonic acid halide.

[0185] In the second composition, the content of the quinone diazide compound is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, based on 100 parts by mass of the polymer component contained in the second composition. Furthermore, the content of the quinone diazide compound is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less, based on 100 parts by mass of the polymer component contained in the second composition.

[0186] When the quinone diazide compound content is 2 parts by mass or more, sufficient acid is generated by irradiation with active light, and the difference in solubility in the alkaline solution between the irradiated and unirradiated areas can be sufficiently large. This allows for good patterning. In addition, the amount of acid involved in the reaction with the polymer component can be increased, ensuring sufficient heat resistance and chemical resistance. On the other hand, when the quinone diazide compound content is 60 parts by mass or less, the amount of unreacted quinone diazide compound can be sufficiently reduced, which is preferable in that it suppresses the decrease in developability and transparency caused by the residual quinone diazide compound.

[0187] <(C-2) Solvent> The second composition contains a solvent. Preferably, the second composition is a liquid composition in which the polymer component, the (B-2) quinone diazide compound, the (E) compound, and optionally added components are dissolved or dispersed in the solvent. The solvent used is preferably an organic solvent that dissolves each component in the second composition and does not react with each component. Specific examples of the solvent included in the second composition are the same as those included in the first composition.

[0188] In the second composition, the solvent content (total amount if two or more solvents are included) is preferably 50 to 95 parts by mass, and more preferably 60 to 90 parts by mass, per 100 parts by mass of all components of the second composition.

[0189] <(E) Compound> The second composition contains the cardo compound ((E) compound) described above. Specific and preferred examples of the cardo compound included in the second composition are the same as those for the first composition.

[0190] In the second composition, the content of the cardo compound is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, based on 100 parts by mass of the polymer component contained in the second composition. Furthermore, the content ratio of the cardo compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the polymer component contained in the second composition.

[0191] <Other ingredients> The second composition may further contain other components (other components) in addition to the polymer components, (B-2) quinone diazide compound, (C-2) solvent, and (E) compound described above. Specific and preferred examples of other components that may be included in the second composition are the same as those for the first composition.

[0192] The solid content concentration of the second composition is appropriately selected considering viscosity, volatility, etc., but is preferably in the range of 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 12 to 50% by mass.

[0193] [Third composition] Next, the third composition will be described. The third composition contains the following components (A-3-1), (A-3-2), (B-3), (C-3), and (E). (A-3-1) Polymers containing structural units having acid groups; (A-3-2) Polymerizable monomer; (B-3) Photopolymerization initiator; (C-3) solvent; (E) Compounds having a cardo structure and at least one functional group (X) selected from the group consisting of alkoxysilyl groups, oxyranyl groups, oxetanyl groups, mercapto groups, (meth)acryloyl groups, vinyl groups, and amino groups.

[0194] <Polymer components> The third composition includes a polymer containing a structural unit having an acid group (hereinafter also referred to as "polymer (a3)") as a polymer component. Polymer (a3) ​​corresponds to "(A-3-1) polymer".

[0195] [Regarding polymers (a3)] Polymer (a3) ​​is a polymer containing structural units having acid groups (hereinafter also referred to as "structural units (III-4)"). Specific examples and preferred examples of structural units (III-4) are the same as those shown in the description of structural units (III-1) that polymer (a1-1) may contain. In polymer (a3), the content of structural units (III-4) is preferably 1% by mass or more, and more preferably 2% by mass or more, relative to the total structural units constituting polymer (a3), from the viewpoint of providing good solubility in alkaline developer to the unexposed areas. Furthermore, the content of structural units (III-4) is preferably 35% by mass or less, and more preferably 30% by mass or less, relative to the total structural units constituting polymer (a3).

[0196] The polymer component in the third composition may further contain structural units other than structural unit (III-4) (hereinafter also referred to as "other structural units (4)"). A preferred specific example of other structural units (4) is structural unit (II-4) having a crosslinkable group. Other structural units (4) may be introduced into the same polymer (a3) ​​as polymer (a3) ​​having structural unit (III-4), or they may be introduced as structural units of a polymer different from polymer (a3), or they may be introduced into both polymer (a3) ​​and a polymer different from polymer (a3).

[0197] • Structural units (II-4) The crosslinkable group of structural unit (II-4) is not particularly limited, as long as it is a group that undergoes a hardening reaction by heat treatment. Among those with high thermosetting properties, oxyranyl group, oxetanyl group, and "-NH-CH2-OR 10 The base represented by " (where R 10Preferably, at least one selected from the group consisting of a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an ethylenically unsaturated group. Specific examples and preferred examples of structural unit (II-4) are the same as those shown in the description of structural unit (II-1). In polymer (a3), the content of structural unit (II-4) is the same as the preferred range for structural unit (II-3) in polymer (a2).

[0198] If polymer (a3) ​​substantially does not contain structural unit (II-4), it is preferable that the composition contains a polymer different from polymer (a3) ​​that contains structural unit (II-4) but substantially does not contain structural unit (III-4) (hereinafter also referred to as "polymer (b3-1)") together with polymer (a3). The content ratio of structural unit (II-4) in polymer (b3-1) is the same as the preferred range for structural unit (II-3) in polymer (a2). Furthermore, the preferred range for the ratio of polymer (a3) ​​to polymer (b3-1) when the third composition contains polymer (a3) ​​and polymer (b3-1) is the same as that for the second composition.

[0199] Other structural units (4) that may be included in the polymer component of the third composition include the structural units exemplified as other structural units (1).

[0200] Polymer (a3) ​​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, etc., according to a known method such as radical polymerization. The details of the polymerization method are the same as for polymer (a1-1). Furthermore, the preferred range of weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in polymer (a3) ​​is the same as for polymer (a2).

[0201] Preferred embodiments of the polymer component contained in the third composition are shown below. However, the third composition is not limited to the embodiments shown below. <1D> An embodiment in which the polymer (a3) ​​further contains structural unit (II-4), and also contains one or more other structural units other than structural unit (II-4) (hereinafter also referred to as "other structural units (IV-4)"). <2D> An embodiment comprising polymer (a3) ​​and polymer (b3-1), wherein polymer (a3) ​​further comprises one or more other structural units (IV-4) and substantially does not contain structural unit (II-4), and polymer (b3-1) further comprises one or more other structural units (IV-4). <3D> An embodiment further comprising a polymer (a3) ​​and a polymer that substantially does not contain structural units (III-4) and (II-4). <4D> An embodiment consisting of two or more combinations of the embodiments <1D> to <3D> described above.

[0202] The embodiment <1D> of the above is particularly preferred because it can obtain the effect of improving developability and curing adhesion while minimizing the number of components constituting the third composition.

[0203] <(A-3-2) Polymerizable monomer> The third composition contains a polymerizable monomer. The polymerizable monomer contained in the third composition is a compound having one or more polymerizable groups, preferably two or more. Examples of polymerizable groups include ethylenically unsaturated groups, oxyranyl groups, oxetanyl groups, and N-alkoxymethylamino groups. Of these, ethylenically unsaturated groups and N-alkoxymethylamino groups are preferred due to their high polymerizability, and vinyl group-containing groups such as (meth)acryloyl groups, vinyl groups, and vinylphenyl groups are preferred.

[0204] Specifically, the polymerizable monomer is preferably a compound having two or more (meth)acryloyl groups, or a compound having two or more N-alkoxymethylamino groups, with compounds having two or more (meth)acryloyl groups being particularly preferred. The number of polymerizable groups in one molecule of the polymerizable monomer is preferably 2 to 10, and more preferably 2 to 8.

[0205] Specific examples of polymerizable monomers include compounds having two or more (meth)acryloyl groups, such as polyfunctional (meth)acrylates obtained by reacting aliphatic polyhydroxy compounds of trivalent or higher with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting (meth)acrylate having hydroxyl groups with polyfunctional isocyanates, and polyfunctional (meth)acrylates having carboxyl groups obtained by reacting (meth)acrylate having hydroxyl groups with acid anhydrides.

[0206] Examples of compounds having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, or a urea structure. The melamine structure and benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as the basic skeleton, and the concept includes melamine, benzoguanamine, or their condensates. Specific examples of compounds having two or more N-alkoxymethylamino groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, and N,N,N',N'-tetra(alkoxymethyl)glycoluryl.

[0207] Among the polymerizable monomers, polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates having carboxyl groups, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, and N,N,N',N'-tetra(alkoxymethyl)benzoguanamine are preferred, polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, polyfunctional urethane (meth)acrylates, and polyfunctional (meth)acrylates having carboxyl groups are more preferred, and polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid are even more preferred.

[0208] Specific examples of polyfunctional (meth)acrylates obtained by reacting aliphatic polyhydroxy compounds with trivalent or higher nucleotides with (meth)acrylic acid include, for example, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, trimethylolpropanedi(meth)acrylate, and dipentaerythritol polyacrylate. Of these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferred because they increase the intermolecular or intramolecular crosslinking density and further improve the curability of the film even by low-temperature firing.

[0209] The content of polymerizable monomers in the third composition is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, per 100 parts by mass of polymer components contained in the third composition. Furthermore, the content of polymerizable monomers is preferably 1,000 parts by mass or less, and more preferably 500 parts by mass or less, per 100 parts by mass of polymer components contained in the third composition. When the content of polymerizable monomers is within the above range, it is preferable in that sufficient curability and alkali developability can be ensured as a cured film, and the occurrence of background staining, film residue, etc. on the unexposed parts of the substrate or light-shielding layer can be sufficiently suppressed.

[0210] <(B-3) Photopolymerization Initiator> The third composition contains a photopolymerization initiator as a radiation-sensitive compound. The photopolymerization initiator included in the third composition (hereinafter also simply referred to as "photopolymerization initiator") is preferably a compound that is sensitive to active light with a wavelength of 300 nm or higher (preferably 300-450 nm) and initiates and promotes the polymerization of polymerizable monomers. When using a photopolymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or higher, it may be used in combination with a sensitizer to enable it to be sensitive to active light with a wavelength of 300 nm or higher and initiate and promote the polymerization of polymerizable monomers.

[0211] Known compounds can be used as photopolymerization initiators. Specific examples include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboric acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, at least one selected from the group consisting of oxime ester compounds, α-aminoketone compounds, and hexaarylbiimidazole compounds is preferred, with oxime ester compounds or α-aminoketone compounds being more preferred, in order to increase the sensitivity of the third composition. Commercially available photopolymerization initiators may also be used, such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF).

[0212] In the third composition, the content of the photopolymerization initiator is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the polymer component contained in the third composition. Furthermore, the content of the photopolymerization initiator is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of the polymer component contained in the third composition.

[0213] <(C-3) Solvent> The third composition contains a solvent. Preferably, the third composition is a liquid composition in which polymer components, polymerizable monomers, (B-3) photopolymerization initiators, (E) cardo compounds, and optionally added components are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each component in the third composition and does not react with each component. Specific examples of the solvent included in the third composition are the same as those included in the first composition.

[0214] In the third composition, the solvent content (total amount if two or more solvents are included) is preferably 50 to 95 parts by mass, and more preferably 60 to 90 parts by mass, per 100 parts by mass of all components of the third composition.

[0215] <(E) Compound> The third composition contains the cardo compound ((E) compound) described above. Specific and preferred examples of the cardo compound included in the third composition are the same as those for the first composition.

[0216] In the third composition, the content of the cardo compound is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, based on 100 parts by mass of the polymer component contained in the third composition. Furthermore, the content ratio of the cardo compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the polymer component contained in the third composition.

[0217] <Other ingredients> The third composition may further contain, in addition to the polymer components, polymerizable monomers, (B-3) photopolymerization initiators, (C-3) solvents, and (E) compounds described above, other components. Specific and preferred examples of other components that may be included in the third composition are the same as those for the first composition.

[0218] The solid content concentration of the third composition is appropriately selected considering viscosity, volatility, etc., but is preferably in the range of 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 12 to 50% by mass.

[0219] <Cured film and method for producing the same> The cured film of this disclosure is formed from the radiation-sensitive compositions of this disclosure (the first composition, the second composition, and the third composition) prepared as described above. These compositions have high radiation sensitivity, good melt flow properties, and excellent storage stability. Furthermore, by using these compositions, it is possible to form pattern films that exhibit high adhesion to the substrate after development (development adhesion), high adhesion to the substrate after firing (curing adhesion), and excellent chemical resistance. Therefore, these compositions can be preferably used as compositions for forming interlayer insulating films, planarization films, spacers, protective films, colored pattern films for color filters, partitions, banks, etc., and are particularly suitable as compositions for forming interlayer insulating films.

[0220] When manufacturing a cured film, this composition can be used to form either a positive or negative cured film depending on the type of radiation-sensitive compound. Specifically, when forming a positive cured film, the first or second composition can be preferably used. On the other hand, when forming a negative cured film, the third composition can be preferably used. The cured film can be manufactured using this composition by a method including, for example, the following steps 1 to 5. (Step 1) A step of applying the composition onto a substrate. (Step 2) A step to remove the solvent from the composition applied to the substrate. (Step 3) The step of irradiating the composition from which the solvent has been removed with radiation. (Step 4) A step of developing the composition that has been irradiated with radiation. (Step 5) A step of heat-curing the developed composition. The following provides a detailed explanation of each step.

[0221] [Process 1: Coating process] In this process, the composition is applied to the surface on which the film will be formed (hereinafter also referred to as the "film-forming surface"). The material of the film-forming surface is not particularly limited. For example, when forming an interlayer insulating film, the composition is applied to a substrate on which switching elements such as TFTs are provided to form a coating film. Examples of substrates include glass substrates, silicon substrates, and resin substrates. The surface of the substrate on which the coating film is formed may have a thin metal film formed thereon depending on the application, and may also be subjected to various surface treatments such as HMDS (hexamethyldisilazane) treatment.

[0222] Examples of methods for applying this composition include spray coating, roll coating, spin coating, slit die coating, bar coating, and inkjet coating. Among these, spin coating, slit die coating, or bar coating is preferred.

[0223] [Step 2: Solvent Removal Process] In this step, the solvent is removed from the composition applied to the surface to be coated, preferably by heat treatment (pre-baking), thereby forming a coating film on the surface. The pre-baking conditions vary depending on the type and content ratio of each component in the composition, but for example, it is 60 to 130°C for 0.5 to 10 minutes. The thickness of the formed coating film (i.e., the thickness after pre-baking) is preferably 0.1 to 12 μm. Vacuum drying (VCD) may be performed on the composition applied to the surface to be coated before pre-baking.

[0224] [Process 3: Irradiation process] In this step, at least a portion of the coating film made of the composition formed in step 2 above is irradiated with radiation. At this time, a cured film having a pattern can be formed by irradiating the coating film with radiation through a mask having a predetermined pattern. Examples of radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible light, X-rays, and electron beams. Among these, ultraviolet rays are 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.

[0225] [Process 4: Development process] In this step, the coating film irradiated with radiation in step 3 is developed. Specifically, the coating film irradiated with radiation in step 3 is developed with a developer solution to perform positive-type development, which removes the irradiated areas, or negative-type development, which removes the unirradiated areas. Examples of the developer solution 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% by mass.

[0226] 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 material, but is typically 30 to 120 seconds. After the development process, it is preferable to rinse the patterned coating with running water.

[0227] [Process 5: Heat curing process] In this step, the coating developed in step 4 above is subjected to a heating process (post-bake). 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 performing the heating treatment on a hot plate, and 10 to 80 minutes when performing the heating treatment in an oven. This heating treatment promotes the curing reaction, and a cured film having the desired pattern can be formed on the substrate. The shape of the pattern on the cured film is not particularly limited and examples include line-and-space patterns, dot patterns, hole patterns, and grid patterns.

[0228] The cured film obtained from this composition can also be used as a dry etching resist. When the cured film is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be employed as the etching treatment.

[0229] <Display device> The display device of this disclosure comprises a cured film formed using this composition. Examples of display devices include liquid crystal displays and organic electroluminescent (EL) displays. The cured film of a liquid crystal display device formed with this composition can be applied to, for example, interlayer insulating films, planarization films, protective films for color filters, spacers, etc. The cured film of an organic EL display device formed with this composition can be applied to, for example, interlayer insulating films, banks, planarization films, partitions, pixel separation insulating films, etc.

[0230] Based on the details of this disclosure described above, the following means are provided. [Method 1] A radiation-sensitive composition comprising: (A-1) a polymer selected from the group consisting of polymers and siloxane polymers that include a structural unit having a group represented by the above formula (1) or an acid-dissociable group; (B-1) a photoacid generator; (C-1) a solvent; and (E) a compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxyranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group (excluding compounds that correspond to polymers containing a structural unit having a group represented by the following formula (1)). [Method 2] The radiation-sensitive composition according to [Method 1], wherein the polymer (A-1) further comprises structural units having crosslinkable groups, or further comprises a polymer different from the polymer (A-1) and containing structural units having crosslinkable groups. [Method 3] The crosslinkable group is an oxyranyl group, an oxetanyl group, "-NH-CH2-OR 10 The base represented by " (where R 10The radiation-sensitive composition according to [Method 2], wherein is at least one selected from the group consisting of a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an ethylenically unsaturated group. [Method 4] The radiation-sensitive composition according to any one of [Method 1] to [Method 3], wherein the group represented by formula (1) above is bonded to an aromatic ring group or a chain hydrocarbon group. [Method 5] The radiation-sensitive composition according to any one of [Method 1] to [Method 4], wherein the structural unit having the group represented by formula (1) has at least one selected from the group consisting of the group represented by formula (3-1), the group represented by formula (3-2), and the group represented by formula (3-3). [Method 6] The photoacid generator comprises at least one selected from the group consisting of oximesulfonate compounds and sulfonimide compounds, according to any one of [Method 1] to [Method 5]. [Method 7] A radiation-sensitive composition according to any one of [Method 1] to [Method 6], further comprising an acid diffusion control agent. [Method 8] A radiation-sensitive composition comprising: (A-2) a polymer selected from the group consisting of polymers containing a structural unit having an acid group and siloxane polymers; (B-2) a quinone diazide compound; (C-2) a solvent; and (E) a compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxyranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. [Method 9] The radiation-sensitive composition according to [Method 8], wherein the polymer (A-2) further comprises structural units having crosslinkable groups, or further comprises a polymer different from the polymer (A-2) and containing structural units having crosslinkable groups. [Method 10] The crosslinkable group is an oxyranyl group, an oxetanyl group, "-NH-CH2-OR 10 The base represented by " (where R 10 The radiation-sensitive composition according to [Method 9], wherein is at least one selected from the group consisting of a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an ethylenically unsaturated group. [Method 11] The radiation-sensitive composition according to any one of [Method 8] to [Method 10], wherein the quinone diazide compound is a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinone diazidosulfonic acid halide. [Method 12] A radiation-sensitive composition comprising (A-3-1) a polymer containing a structural unit having an acid group, (A-3-2) a polymerizable monomer, (B-3) a photopolymerization initiator, (C-3) a solvent, and (E) a compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxyranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. [Method 13] The radiation-sensitive composition according to [Method 12], wherein the polymer (A-3-1) further comprises structural units having crosslinkable groups, or further comprises a polymer different from the polymer (A-3-1) and comprising structural units having crosslinkable groups. [Method 14] The crosslinkable group is an oxyranyl group, an oxetanyl group, "-NH-CH2-OR 10 The base represented by " (where R 10 The radiation-sensitive composition according to [Method 13], wherein (a) is at least one selected from the group consisting of a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an ethylenically unsaturated group. [Method 15] The radiation-sensitive composition according to any one of [Method 1] to [Method 14], wherein the functional group (X) is at least one selected from the group consisting of an alkoxysilyl group, an oxyranyl group, an oxetanyl group, and a (meth)acryloyl group. [Method 16] The radiation-sensitive composition according to any one of [Method 1] to [Method 15], wherein the functional group (X) is an alkoxysilyl group. [Method 17] The (E) compound is a radiation-sensitive composition according to any one of [Method 1] to [Method 16], having a substructure represented by the above formula (10-1). [Method 18] The radiation-sensitive composition according to any one of [Method 1] to [Method 17], wherein the content of compound (E) is 0.1 to 20 parts by mass per 100 parts by mass of polymer components contained in the radiation-sensitive composition. [Method 19] A method for producing a cured film, comprising the steps of: applying a radiation-sensitive composition described in any of [Method 1] to [Method 18] onto a substrate; removing a solvent from the applied radiation-sensitive composition; irradiating the radiation-sensitive composition from which the solvent has been removed with radiation; developing the radiation-irradiated radiation-sensitive composition; and thermally curing the developed radiation-sensitive composition. [Method 20] A cured film formed using the radiation-sensitive composition described in any of [Method 1] to [Method 18]. [Method 21] The cured film described in [Method 20], which is an interlayer insulating film. [Means 22] A liquid crystal display device comprising the cured film described in [Means 20] or [Means 21]. [Mean 23] An organic EL display device comprising the cured film described in [Mean 20] or [Mean 21]. [Examples]

[0231] 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 "%" refer to mass unless otherwise specified.

[0232] [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: Showa Denko's GPC-101 • GPC columns: Shimadzu GLC's GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 were joined. • Mobile phase: tetrahydrofuran 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

[0233] [monomer] The abbreviations for the monomers used in the synthesis of the polymer are as follows: Monomer having the group represented by the above formula (1) MPTMS: 3-Methacryloxypropyltrimethoxysilane MPTES:3-Methacryloxypropyltriethoxysilane STMS: p-Styryltrimethoxysilane SDMS: p-Styryldimethoxyhydroxysilane STES:p-Styryltriethoxysilane

[0234] Other monomers AA: Acrylic acid MA: Methacrylic acid MI: Maleimide OXMA:OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (3-ethyloxetan-3-yl)methyl methacrylate GMA: Glycidyl methacrylate ECHMA:3,4-Epoxycyclohexylmethyl methacrylate EDCPMA: Methacrylic acid [3,4-Epoxytricyclo(5.2.1.0 2,6 ) Decan-9-il] MATHF: 2-tetrahydrofuranyl methacrylate MMA: Methyl methacrylate ST: Styrene

[0235] <Synthesis of polymer (A)> [Synthesis Example 1] Synthesis of Polymer (A-1) In a flask equipped with a condenser and stirrer, 24 parts of propylene glycol monomethyl ether were charged, followed by 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane. The solution was heated until it reached 60°C. After reaching 60°C, 0.1 parts of formic acid and 19 parts of water were added, and the solution temperature was raised to 75°C while gently stirring, and this temperature was maintained for 2 hours. After cooling to 45°C, 28 parts by mass of trimethyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. The solution temperature was then reduced to 40°C, and the mixture was evaporated while maintaining the temperature to remove water and methanol generated by hydrolysis condensation, thereby obtaining a polymer solution containing polymer (A-1). The solid content concentration of this polymer solution was 35% by mass, the weight-average molecular weight (Mw) of polymer (A-1) was 1,800, and the molecular weight distribution (Mw / Mn) was 2.2.

[0236] [Synthesis Example 2] Synthesis of Polymer (A-2) Except for changing the monomers used to 39 parts phenyltrimethoxysilane and 18 parts 3-methacryloxypropyltrimethoxysilane, polymer (A-2) having the same solid content concentration, weight-average molecular weight, and molecular weight distribution as polymer (A-1) was obtained using the same method as in Synthesis Example 1.

[0237] [Synthesis Example 3] Synthesis of Polymer (A-3) Ten parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methyl ethyl ether were charged into a flask equipped with a condenser and a stirrer. Subsequently, 12 parts of methacrylic acid, 45 parts of glycidyl methacrylate, and 43 parts of 2-tetrahydrofuranyl methacrylate were charged, and after purging with nitrogen, the temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-3). The solid content concentration of this polymer solution was 34.0% by mass, the Mw of polymer (A-3) was 15,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[0238] [Synthesis Examples 4-18] Synthesis of polymers (A-4)-(A-18) Polymer solutions containing polymers (A-4) to (A-18), each having the same solid content concentration, weight-average molecular weight, and molecular weight distribution as polymer (A-3), were obtained using the same method as in Synthesis Example 3, except that the components used were of the types and amounts (parts by mass) shown in Table 1.

[0239] [Table 1]

[0240] <Preparation of radiation-sensitive composition> The polymer (A), cardo compound (E), radioactive compound (B), polymerizable monomer (M), additive (X), and solvent (C) used in the preparation of the radiation-sensitive composition are shown below.

[0241] 《Polymerization (A)》 A-1~A-18: Polymers synthesized in synthesis examples 1~18 (A-1)~(A-18)

[0242] Cardo compounds (E) E-1: WR-301 (Manufactured by ADEKA Corporation) E-2: Photosensitive resin (A2) as described in Example 2 of International Publication No. 2009 / 119622 E-3: V-259ME (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) E-4: Ogusol SC001 (manufactured by Osaka Gas Chemical Co., Ltd.)

[0243] 《Radiation-sensitive compound (B)》 B-1: Irgacure PAG121 (made by BASF) B-2: OS-17 as described in International Publication No. 2016 / 124493 B-3: OS-25 as described in International Publication No. 2016 / 124493 B-4: 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-5: 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 (1.0 mol) B-6: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) B-7: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (1.0 mol) B-8: Irgacure OXE02 (BASF) Polymerizable monomer (M) D-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[0244] Additive (X) X-1:3-Glycidyloxypropyltrimethoxysilane X-2:2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane X-3:2-phenylbenzimidazole X-4:N-(tert-butoxycarbonyl)-2-phenylbenzimidazole X-5: 4-methyl-2-phenylbenzimidazole

[0245] Solvent (C) C-1: Diethylene glycol ethyl methyl ether C-2: Propylene glycol monomethyl ether C-3: Propylene glycol monomethyl ether acetate

[0246] [Reference example 1] To the polymer solution containing polymer (A-1) obtained in Synthesis Example 1 above, 5 parts of cardo compound (E-1), 1 part of radiation-sensitive compound (B-2), and 5 parts of additive (X-1) were mixed in an amount equivalent to 100 parts (solid content) of polymer (A-1). Diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether were added in a 1:1 mass ratio so that the final solid content concentration was 20% by mass. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0247] [Reference Examples 2-21, Examples 22-30, Comparative Examples 1-5] Except for using the types and amounts (parts by mass) of components shown in Table 2, the radiation-sensitive compositions of Reference Examples 2-21, Examples 22-30, and Comparative Examples 1-5 were prepared using the same method as in Reference Example 1.

[0248] [Table 2]

[0249] In Table 2, for solvent (C), in the examples using two compounds (Reference Examples 1, 2, 4-15, 19-21 and Examples 23, 27, 29 and Comparative Examples 2, 4), solvent 1 and solvent 2 were mixed and used in a mass ratio of solvent 1:solvent 2 = 1:1. In the examples using three organic solvents (Reference Examples 3, 16-18 and Examples 22, 24-26, 28, 30 and Comparative Examples 1, 3, 5), solvent 1, solvent 2, and solvent 3 were mixed and used in a mass ratio of solvent 1:solvent 2:solvent 3 = 4:5:1.

[0250] <Rating> The following items were evaluated using the radiation-sensitive compositions of Reference Examples 1-21, Examples 22-30, and Comparative Examples 1-5, according to the method described below. The evaluation results are shown in Table 3.

[0251] [Radiation sensitivity] A radiation-sensitive composition was applied to a silicon substrate that had been HMDS-treated at 60°C for 60 seconds using a spinner. The substrate was then pre-baked on a hot plate at 90°C for 2 minutes to form a coating with an average thickness of 3.0 μm. This coating was then irradiated with a predetermined amount of ultraviolet light from a mercury lamp through a pattern mask having a 10 μm wide line-and-space pattern. Next, development was performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer at 25°C for 60 seconds, followed by rinsing with ultrapure water for 1 minute. At this time, the minimum exposure required to form a 10 μm wide line-and-space pattern was measured. The measured minimum exposure was 300 J / m². 2 When the value is less than 300 J / m³, the radiation sensitivity is good. 2 In the above cases, the radiation sensitivity can be evaluated as poor.

[0252] [Evaluation of chemical resistance of cured films] The chemical resistance of the cured film was evaluated by the degree of swelling caused by the stripping solution. A radiation-sensitive composition was applied to a silicon substrate using a spinner, and then pre-baked on a hot plate at 90°C for 2 minutes to form a coating with an average thickness of 3.0 μm. Subsequently, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to expose the film at 3000 J / m². 2 After irradiating the entire substrate with light, the substrate was baked (post-bake) for 30 minutes in an oven heated to 230°C to form a cured film. The resulting cured film was immersed in an N-methyl-2-pyrrolidone solvent heated to 40°C for 6 minutes, and the percentage change in film thickness before and after immersion was determined. This percentage change in film thickness was used as an indicator of chemical resistance and evaluated according to the following criteria. AA: Film thickness change rate is less than 2% A: Film thickness change rate is 2% or more but less than 5% B: Film thickness change rate is 5% or more but less than 10% C: Film thickness change rate is 10% or more but less than 15% D: Film thickness change rate of 15% or more Chemical resistance can be evaluated as good if the result is AA, A, or B, and as poor if the result is C or D. Film thickness was measured at 25°C using an optical interference film thickness analyzer (Lambda Ace VM-1010).

[0253] [Evaluation of storage stability] The prepared radiation-sensitive composition was sealed in a light-shielding, airtight container. After 7 days at 25°C, the container was opened, and measurements were taken according to the above evaluation of [radiation sensitivity]. The percentage increase in radiation sensitivity (minimum exposure) before and after 7 days of storage was calculated. A value of less than 5% was judged as "AA", 5% or more but less than 10% as "A", 10% or more but less than 20% as "B", 20% or more but less than 30% as "C", and 30% or more as "D". Storage stability can be evaluated as good in the case of AA, A, or B, and as poor in the case of C or D.

[0254] [Evaluation of adhesion during alkaline development (development adhesion)] Using a spinner, a radiation-sensitive composition was applied to a silicon substrate that had not undergone HMDS treatment. The mixture was then pre-baked on a hot plate at 90°C for 2 minutes to form a coating with an average thickness of 3.0 μm. This coating was then exposed to a mercury lamp at 365 nm with an exposure dose of 400 J / m² through a pattern mask having a line-and-space pattern with a width of 1 to 50 μm. 2 The substrate was irradiated with ultraviolet light. Next, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used as the developer, and development was performed at 25°C for 60 seconds, followed by rinsing with ultrapure water for 1 minute. At this time, the minimum width of the line-and-space pattern that remained on the substrate without peeling off was measured. If the measured minimum width was 2 μm or less, it was judged as "AA"; if it was greater than 2 μm and 5 μm or less, it was judged as "A"; if it was greater than 5 μm and 10 μm or less, it was judged as "B"; if it was greater than 10 μm and 30 μm or less, it was judged as "C"; and if it was greater than 30 μm, it was judged as "D". In the case of AA, A, or B, the development adhesion was evaluated as good, and in the case of C or D, the development adhesion was evaluated as poor.

[0255] [Evaluation of adhesion (hardened adhesion) after firing] Using a spinner, a radiation-sensitive composition was applied to a glass substrate that had not undergone HMDS treatment. The substrate was then pre-baked on a hot plate at 90°C for 2 minutes to form a coating with an average thickness of 3.0 μm. Subsequently, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to expose the substrate at 3000 J / m². 2 After irradiating the entire substrate with light, a cured film was formed by baking (post-bake) in an oven heated to 230°C for 30 minutes. A cross-cut test was performed on this cured film in accordance with JIS K5600-5-6 (ISO2409). Of the 25 2mm square grids formed with a cutter, the cured film remaining after tape removal was observed with an optical microscope, and the cured adhesion was evaluated according to the following criteria. AA: 100% film retention rate A: Film retention rate is 95% or more but less than 100% B: Film retention rate is 90% or more but less than 95% C: Film retention rate is 85% or more but less than 90% D: Film retention rate is less than 85% In cases AA, A, or B, the adhesion during firing is good, while in cases C or D, the adhesion during firing is poor.

[0256] [Evaluation of melt flow properties] Measurements were taken according to the above evaluation of [radiation sensitivity] to form a line-and-space pattern with a width of 10 μm. The cross-sections of this pattern before and after firing were observed with a scanning electron microscope, and the difference in the taper angle of the film after development and firing was determined. A value of less than 20° was judged as "AA", 20° or more and less than 25° as "A", 25% or more and less than 30% as "B", 30% or more and less than 35% as "C", and 35% or more as "D". Melt flow properties can be evaluated as good in the case of AA, A, or B, and as poor in the case of C or D.

[0257] [Table 3]

[0258] As shown in Table 3, each of the radiation-sensitive compositions in Reference Examples 1-21 and Examples 22-30 exhibited good practical properties in terms of radiation sensitivity, chemical resistance, storage stability, development adhesion, curing adhesion, and melt flow, demonstrating a good balance of various properties. In contrast, Comparative Examples 1-5 received a "D" rating for development adhesion, indicating inferior practical properties. Furthermore, Comparative Examples 1-5 also received a "D" rating in one or more of the following areas: radiation sensitivity, chemical resistance, storage stability, curing adhesion, and melt flow, which were inferior to Reference Examples 1-21 and Examples 22-30.

Claims

1. (A-2) A polymer containing a structural unit having an acid group, (B-2) Quinone diazide compounds, (C-2) Solvent and (E) A compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. A radiation-sensitive composition containing the following:

2. The radiation-sensitive composition according to claim 1, wherein the polymer (A-2) further comprises a structural unit having a crosslinkable group, or further comprises a polymer different from the polymer (A-2) and having a structural unit having a crosslinkable group.

3. The radiation-sensitive composition according to claim 1, wherein the quinone diazide compound is a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinone diazidosulfonic acid halide.

4. (A-3-1) A polymer containing a structural unit having an acid group, (A-3-2) Polymerizable monomers, (B-3) Photopolymerization initiator, (C-3) Solvent and (E) A compound having a cardi structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. A radiation-sensitive composition containing the following:

5. The radiation-sensitive composition according to claim 4, wherein the polymer (A-3-1) further comprises a structural unit having a crosslinkable group, or further comprises a polymer different from the polymer (A-3-1) and having a structural unit having a crosslinkable group.

6. The aforementioned crosslinkable groups are oxyranyl group, oxetanyl group, and "-NH-CH ２ -O-R １０ The group represented by " (where R １０ The radiation-sensitive composition according to claim 2 or 5, wherein is at least one selected from the group consisting of a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an ethylenically unsaturated group.

7. The radiation-sensitive composition according to claim 1 or 4, wherein the functional group (X) is at least one selected from the group consisting of an alkoxysilyl group, an oxetanyl group, and a (meth)acryloyl group.

8. The radiation-sensitive composition according to claim 1 or 4, wherein the functional group (X) is an alkoxysilyl group.

9. The (E) compound has a substructure represented by the following formula (10-1), the radiation-sensitive composition according to claim 1 or 4. 【Chemistry 1】 (In formula (10-1), Ar １１ and Ar １２ These are, independently, divalent aromatic ring groups. ６８ and R ６９ Each of these is independently an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. a1 and a2 are each independently integers from 0 to 3. If a1 is 2 or 3, multiple R ６８ They are the same or different. When a2 is 2 or 3, the plurality of Rs ６９ are the same or different. 「*」 represents a bond.)

10. The radiation-sensitive composition according to claim 1 or 4, wherein the cardi structure is represented by the following formula (10). 【Chemistry 2】 (In formula (10), A １０ is, A １１ and A １２ A is a cyclic group formed together with the carbon atom to which it is bonded, and the cyclic group is a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aliphatic hydrocarbon ring, or a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aromatic hydrocarbon ring. １１ and A １２ Each of these groups is independently either a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aliphatic hydrocarbon ring, or a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aromatic hydrocarbon ring. (* indicates a bond.)

11. The radiation-sensitive composition according to claim 1 or 4, wherein the content of compound (E) is 0.1 to 20 parts by mass per 100 parts by mass of polymer components contained in the radiation-sensitive composition.

12. A step of applying the radiation-sensitive composition according to claim 1 or 4 onto a substrate, A step of removing the solvent from the coated radiation-sensitive composition, A step of irradiating the radiation-sensitive composition from which the solvent has been removed with radiation, A step of developing the radiation-sensitive composition that has been irradiated with the aforementioned radiation, The process of thermally curing the developed radiation-sensitive composition, A method for manufacturing a cured film, including [the specified element].

13. A cured film formed using the radiation-sensitive composition described in claim 1 or 4.

14. The cured film according to claim 13, which is an interlayer insulating film.

15. A liquid crystal display device comprising the cured film described in claim 13.

16. An organic EL display device comprising the cured film described in claim 13.

Images