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

Abstract

To provide a radiation-sensitive composition that can form a film excelling in development adhesion and curing adhesion.SOLUTION: A radiation-sensitive composition comprises (A-1) a polymer which is at least one selected from the group consisting of a polymer including a structural unit having a group represented by the formula (1) or an acid-dissociable group and a siloxane polymer, (B-1) a photoacid generator, (C-1) a solvent, and (E) a compound having at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group and an amino group, and a cardo structure. In the formula (1), R1, R2 and R3 each denote a hydrogen atom, a halogen atom, a hydroxy group, a C1-6 alkoxy group, a C1-10 alkyl group or a phenyl group. where at least one of R1, R2 and R3 is a C1-6 alkoxy group.SELECTED DRAWING: None

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 device, and a display device. [Background technology]

[0002] Cured films (e.g., interlayer insulating films, spacers, protective films, etc.) included in display devices such as liquid crystal display devices and organic EL display devices are generally formed using radiation-sensitive compositions containing a polymer component and a radiation-sensitive compound (e.g., a photoacid generator, a photopolymerization initiator, etc.) (see, for example, Patent Documents 1 to 3). For example, a patterned cured film can be formed by irradiating a coating film formed from the radiation-sensitive composition with radiation and subjecting it to a development treatment to form a pattern, and then subjecting it to a heat treatment for thermal curing. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-107024 [Patent Document 2] International Publication No. 2011 / 065215 [Patent Document 3] Japanese Patent Application Laid-Open No. 2003-5357 Summary of the Invention [Problem to be solved by the invention]

[0004] If the adhesion between the coating film and the substrate after irradiation is insufficient, the developer may penetrate from the interface between the film and the substrate during development, resulting in peeling of the film pattern. In particular, in recent years, there has been a demand for even higher quality display devices, and as patterns become thinner in response to the demand for even higher quality display devices, there is a tendency for film pattern peeling to occur easily during development.

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

[0006] The present invention has been made in view of the above-mentioned problems, and a main object of the present invention is to provide a radiation-sensitive composition capable of forming a film having excellent development adhesion and curing adhesion. [Means for solving the problem]

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

[0008] [1] (A-1) at least one polymer selected from the group consisting of a polymer containing a structural unit having a group represented by the following formula (1) or an acid-dissociable group and a siloxane polymer; (B-1) a photoacid generator; (C-1) a solvent; (E) a compound having at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group, and a cardo structure (excluding compounds corresponding to a polymer containing a structural unit having a group represented by the following formula (1)), A radiation-sensitive composition comprising: [ka] (In formula (1), R 1 , R 2 and R 3are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, provided that R 1 , R 2 and R 3 At least one of the groups is an alkoxy group having 1 to 6 carbon atoms. "*" represents a bond.)

[0009] [2] (A-2) at least one polymer selected from the group consisting of a polymer containing a structural unit having an acid group and a siloxane polymer; (B-2) a quinone diazide compound, (C-2) a solvent; (E) a compound having at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group, and a cardo structure; A radiation-sensitive composition comprising:

[0010] [3] (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; (E) a compound having at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group, and a cardo structure; A radiation-sensitive composition comprising:

[0011] [4] a step of applying any one of the radiation-sensitive compositions [1] to [3] above onto a substrate; removing the solvent from the applied radiation-sensitive composition; irradiating the radiation-sensitive composition from which the solvent has been removed with radiation; developing the radiation-exposed radiation-sensitive composition; thermally curing the developed radiation-sensitive composition; A method for producing a cured film, comprising:

[0012] [5] A cured film formed using the radiation-sensitive composition according to any one of [1] to [3] above. [6] A liquid crystal display device comprising the cured film according to [5] above. [7] An organic EL display device comprising the cured film according to [5] above. [Effects of the Invention]

[0013] The radiation-sensitive composition of the present invention contains a compound having a specific functional group and a cardo structure in addition to a polymer component, a radiation-sensitive compound, and a solvent, and thus can form a film having excellent development adhesion and curing adhesion. DETAILED DESCRIPTION OF THE INVENTION

[0014] Matters related to the embodiments will be explained in detail below. In this specification, a numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure.

[0015] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed solely of a chain structure. However, it may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and it also includes groups that have a chain structure as part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, it does not necessarily have to be composed solely of an aromatic ring structure, and it may also contain a chain structure or an alicyclic hydrocarbon structure as part of it. The ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent composed of a hydrocarbon structure. The term "cyclic hydrocarbon group" refers to both alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0016] In this specification, "(meth)acrylic" is intended to encompass "acrylic" and "methacrylic". "(meth)acryloyl group" is intended to encompass "acryloyl group" and "methacryloyl group". In this specification, the term "epoxy group" is also used to encompass oxiranyl group and oxetanyl group.

[0017] 《Radiation sensitive composition》 The radiation-sensitive composition of the present disclosure (hereinafter also referred to as "the composition") is a resin composition containing 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 electroluminescence display device). Specifically, the composition is applied to a substrate, the solvent is removed, the solvent-removed composition is irradiated with radiation, developed with a developer, and further thermally cured to obtain a cured film.

[0018] The components contained in the first, second, and third compositions, which are specific embodiments of the present composition, and other components that may be blended as needed, are described in detail below. 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-tone resin compositions, and the third composition is preferably used as a negative-tone resin composition.

[0019] [First composition] The first composition of the present disclosure comprises the following components (A-1), (B-1), (C-1) and (E). (A-1) at least one polymer selected from the group consisting of a polymer containing a structural unit having a group represented by the following formula (1) or an acid-dissociable group, and a siloxane polymer; (B-1) a photoacid generator; (C-1) solvent; (E) A compound having at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group, and a cardo structure (excluding compounds corresponding to 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 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, provided that R 1 , R 2 and R 3 At least one of the groups is an alkoxy group having 1 to 6 carbon atoms. "*" represents a bond.)

[0020] <Polymer component> 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 "polymer (A-1)"). 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.

[0021] [Regarding polymer (a1-1)] The polymer (a1-1) is a polymer containing a structural unit (I-1) having a group represented by the above formula (1). 1 ~R 3 Examples of the alkoxy group having 1 to 6 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group. 1 ~R 3 The alkoxy group represented by the formula (1) 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 formula (1) is bonded to an aromatic ring group, R 1 ~R 3 The alkoxy group represented by the formula (1) is preferably a methoxy group. When the group represented by the formula (1) is bonded to a chain hydrocarbon group, R 1 ~R 3 The alkoxy group represented by the formula (I) is preferably an ethoxy group.

[0022] R 1 ~R 3 The alkyl group having 1 to 10 carbon atoms represented by the formula (R) may be either linear or branched. 1 ~R 3 Examples of the alkyl group represented by R 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. 1 ~R 3The alkyl group represented by the formula (I) is preferably a methyl group, an ethyl group or a propyl group.

[0023] R 1 ~R 3 One of the groups represented by the formula (I) is an alkoxy group having 1 to 6 carbon atoms. The remaining group is preferably a hydroxy 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 hydroxy 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.

[0024] From the viewpoint of obtaining a cured film with excellent heat resistance by forming a crosslinked structure, R 1 ~R 3 Among these, it is preferred that two or more are alkoxy groups having 1 to 6 carbon atoms, and it is particularly preferred that all are alkoxy groups having 1 to 6 carbon atoms.

[0025] In the structural unit (I-1), the group represented by the above formula (1) is preferably bonded to an aromatic ring group or a chain hydrocarbon group. In this specification, the term "aromatic ring group" refers to a group obtained by removing n hydrogen atoms (n is an integer) from the ring portion of an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. These rings may have a substituent such as an alkyl group. Examples of the chain hydrocarbon group to which the group represented by the above formula (1) is bonded include an alkanediyl group and an alkenediyl group.

[0026] The group represented by the formula (1) is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. Specifically, the structural unit (I-1) preferably has at least one selected from the group consisting of a group represented by the following formula (3-1), a group represented by the following formula (3-2), and a group represented by the following formula (3-3). [ka] (In formula (3-1), formula (3-2) and formula (3-3), A 1and A 2 are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. n1 is an integer of 0 to 4. n2 is an integer of 0 to 6. However, when n1 is 2 or more, multiple A 1 are the same or different groups. When n2 is 2 or more, multiple A 2 are the same or different groups. 6 is an alkanediyl group. 1 , R 2 and R 3 is the same as the above formula (1). "*" represents a bond.

[0027] In the above formula (3-1) and formula (3-2), A 1 and A 2 Examples of the alkoxy group having 1 to 6 carbon atoms and the alkyl group having 1 to 6 carbon atoms are R 1 ~R 3 The group bonded to the aromatic ring, "-SiR 1 R 2 R 3 " is located at A 1 and A 2 For example, in the case of the above formula (3-1), "-SiR 1 R 2 R 3 The position of " may be any of the ortho, meta, and para positions, 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.

[0028] In the above formula (3-3), R 6 From the viewpoint of increasing the heat resistance of the resulting cured film, R 6 The carbon number is preferably 1 to 6, and more preferably 1 to 4.

[0029] In terms of increasing 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 the formula (3-1) and the group represented by the formula (3-2) among the formulas (3-1) to (3-3). 1 R 2 R 3 When " is directly bonded, it is possible to stabilize the silanol groups generated in the presence of water. This is preferable in that the solubility of the exposed area in an alkaline developer can be increased, and a good pattern can be formed. Among these, the structural unit (I-1) is particularly preferably a structural unit having a group represented by the above formula (3-1).

[0030] 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 "unsaturated monomer"), and more specifically, is preferably at least one selected from the group consisting of structural units represented by the following formula (4-1) and structural units represented by the following formula (4-2). [ka] (In formula (4-1) and formula (4-2), R A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. 7 and R 8 R are each independently a divalent aromatic ring group or a chain hydrocarbon group. 1 , R 2 and R 3 is the same as the above formula (1).

[0031] In the above formula (4-1) and formula (4-2), R 7 , R 8 The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalene 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.

[0032] R is advantageous in that it can produce a cured film with higher heat resistance, chemical resistance, and hardness, and can increase the solubility of exposed areas in alkaline developing solutions. 7 , R 8 Among the above, is preferably a divalent aromatic ring group, and particularly preferably a substituted or unsubstituted phenylene group.

[0033] Specific examples of the structural unit represented by the formula (4-1) include structural units represented by the following formulas (4-1-1) and (4-1-2): Specific examples of the structural unit represented by the formula (4-2) include structural units represented by the following formulas (4-2-1) and (4-2-2): [ka] (In formula (4-1-1), formula (4-1-2), formula (4-2-1) and formula (4-2-2), R 11 and R 12 are each independently an alkyl group having 1 to 4 carbon atoms, and R 13 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. n3 is an integer of 1 to 4. A 1 , A 2 , n1 and n2 have the same meanings as in the formulas (3-1) and (3-2). A has the same meaning as the above formula (4-1) and formula (4-2).

[0034] Specific examples of the monomer constituting the structural unit (I-1) include compounds having a group represented by the above formula (3-1), such as styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, and (meth)acryloxyphenylethyldiethoxysilane; Examples of compounds having a 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, and (meth)acryloxynaphthyltrimethoxysilane; Examples of compounds having a 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.

[0035] The content of the structural unit (I-1) in the 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, based on all structural units constituting the polymer (a1-1). The content of the 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, based on all structural units constituting the polymer (a1-1). By setting the content of the structural unit (I-1) within the above range, the heat resistance and chemical resistance of the resulting cured film can be sufficiently improved, sensitivity can be increased, and the coating film exhibits better resolution.

[0036] When the polymer component contained in the first composition contains a polymer (a1-1), the polymer component may further contain a structural unit other than the structural unit (I-1) (hereinafter also referred to as "other structural unit (1)"). Examples of the other structural unit (1) include a structural unit (II-1) having a crosslinkable group and a structural unit (III-1) having an acid group. The other structural unit (1) may be introduced into the same polymer as the polymer (a1-1) having the structural unit (I-1), or may be introduced as a structural unit into a polymer different from the polymer (a1-1), or may be introduced into both the polymer (a1-1) and a polymer different from the polymer (a1-1).

[0037] Structural Unit (II-1) The polymer component containing the structural unit (II-1) is preferred in that it can further improve the film resolution, development adhesion, and curing adhesion, and can form a cured film that has high chemical resistance and can suppress deterioration 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 upon heat treatment, but in terms of high thermosetting properties, an oxiranyl group, an oxetanyl group, or a "-NH-CH2-OR 10 " (wherein R 10 is a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms), and at least one selected from the group consisting of an ethylenically unsaturated group. Among these, an oxiranyl group, an oxetanyl group, and "-NH-CH2-OR 10 " is preferred, and an epoxy group is particularly preferred.

[0038] (Structural unit having an epoxy group) When the crosslinkable 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 at least one selected from the group consisting of structural units represented by the following formula (5-1) and structural units represented by the following formula (5-2): [ka] (In formula (5-1) and formula (5-2), R 20 is a monovalent group having an oxiranyl group or an oxetanyl group. A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. 1 is a single bond or a divalent linking group.

[0039] In the above formula (5-1) and formula (5-2), R 20 Examples include oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl group, 3-ethyloxetanyl group, and the like.

[0040] X 1 Examples of the divalent linking group include alkanediyl groups such as a methylene group, an ethylene group, and a 1,3-propanediyl group; and divalent groups in which any methylene group of an alkanediyl group has been replaced with an oxygen atom.

[0041] Specific examples of the monomer 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, 3,4-epoxytricyclo[5.2.1.0 2,6 ]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-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

[0042] ("-NH-CH2-OR 10 ") a structural unit having a group represented by The crosslinking group is “-NH-CH2-OR 10 " is preferred in that thermal curing can be carried out under mild conditions. 10 The monovalent saturated aliphatic hydrocarbon group represented by R 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.

[0043] The crosslinking group is “-NH-CH2-OR 10 ", the structural unit (II-1) is a group represented by "-NH-CH2-OR 10It is preferable that the structural unit is derived from an unsaturated monomer having a group represented by the formula (6-1). Specific examples thereof include structural units represented by the following formula (6-1). [ka] (In formula (6-1), R 10 is a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group. A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group.

[0044] (Structural unit having an ethylenically unsaturated group) When the crosslinkable group is an ethylenically unsaturated group, the structural unit (II-2) preferably has an ethylenically unsaturated group in a side chain, and more preferably has a side chain structure having 3 to 20 carbon atoms and an ethylenically unsaturated group at the terminal. Specific examples include structural units represented by the following formula (7-1). [ka] (In formula (7-1), X 3 is a divalent linking group having 1 to 12 carbon atoms. 11 is a hydrogen atom or a methyl group. A is the same as the above formula (6-1).

[0045] In the above formula (7-1), X 3 Examples of the divalent linking group represented by the formula (7-1) include a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent group in which any methylene group in the divalent hydrocarbon group is replaced with -O-, -COO-, -OCO-, -NHCO-, -CONH-, -OCONH-, or -NHCOO- (hereinafter also referred to as a "divalent heteroatom-containing group"), and a divalent group in which any hydrogen atom in the divalent hydrocarbon group or divalent heteroatom-containing group is replaced with a hydroxyl group, a carboxyl group, or the like. 3 -C(=CH2)-R 11 The side chain represented by the formula "" preferably has a (meth)acryloyl group at the end.

[0046] When the polymer (a1-1) has the structural unit (II-1), the content of the structural unit (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, based on all structural units constituting the polymer (a1-1). The content of the 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, based on all structural units constituting the polymer (a1-1). By setting the content of the structural unit (II-1) within the above range, a coating film exhibiting good development adhesion and resolution can be formed, and the resulting cured film can be advantageously provided with sufficiently high cured adhesion, heat resistance, and chemical resistance.

[0047] When polymer (a1-1) is substantially free of structural unit (II-1), the first composition preferably contains, as a polymer different from polymer (a1-1), a polymer containing structural unit (II-1) but substantially free of structural unit (I-1) (hereinafter also referred to as "polymer (b1-1)") together with polymer (a1-1). In this specification, "substantially free of" a certain structural unit means that the content of the structural unit is less than 1% by mass, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less, of all structural units constituting the polymer.

[0048] The content of the structural unit (II-1) in the 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, based on all structural units constituting the polymer (b1-1). The content of the 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, based on all structural units constituting the polymer (b1-1).

[0049] When the first composition contains polymer (a1-1) and polymer (b1-1), the mass ratio of polymer (a1-1) to polymer (b1-1) is preferably 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.

[0050] 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 increase the solubility (alkali solubility) of the polymer (a1-1) in an alkaline developer and increase the curing reactivity. In this specification, "alkali soluble" means soluble in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0051] The structural unit (III-1) is not particularly limited as long as it has an acid group. Preferred examples of the structural unit (III-1) include a structural unit having a carboxy group, a structural unit having a phenolic hydroxyl group, a structural unit having a sulfonic acid group, a structural unit having a sulfonamide group, a structural unit having a phosphonic acid group, a maleimide unit, etc. Among these, at least one selected from the group consisting of a structural unit having a carboxy group, a structural unit having a phenolic hydroxyl group, a structural unit having a sulfonic acid group, and a maleimide unit is preferred, and at least one selected from the group consisting of a structural unit having a carboxy group, a structural unit having a phenolic hydroxyl group, and a maleimide unit is more preferred. In this specification, the term "phenolic hydroxyl group" refers to a hydroxy group directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0052] The structural unit (III-1) is preferably a structural unit derived from an unsaturated monomer having an acid group, such as a styrene compound, a vinyl compound, a (meth)acrylic compound, or a maleimide compound.

[0053] Specific examples of unsaturated monomers having an acid group include unsaturated monomers constituting structural units having a carboxy group, such as unsaturated monocarboxylic acids (e.g., (meth)acrylic acid, crotonic acid, 4-vinylbenzoic acid), unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid), unsaturated monomers constituting structural units having a sulfonic acid group, such as vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acryloyloxyethylsulfonic acid, and the like; and unsaturated monomers constituting structural units having a phenolic hydroxyl group, such as 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl(meth)acrylate, and the like. Furthermore, maleimide can also be used as a monomer constituting structural unit (III-1).

[0054] When the polymer (a1-1) contains the structural unit (III-1), the content of the 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, based on the total structural units constituting the polymer (a1-1), from the viewpoint of imparting good solubility in an alkaline developer. On the other hand, if the content of the structural unit (III-1) is too high, the difference in solubility in an alkaline developer between the exposed and unexposed areas becomes small, which may make it difficult to obtain a good pattern shape. From this viewpoint, the content of the 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, based on the total structural units constituting the polymer (a1-1).

[0055] When the polymer (a1-1) is substantially free of the structural unit (III-1), the composition preferably contains, as a polymer different from the polymer (a1-1), a polymer containing the structural unit (III-1) but substantially free of the structural unit (I-1) (hereinafter also referred to as "polymer (b1-2)"). As the polymer (b1-2), a polymer having a carboxyl group in the side chain can be preferably used.

[0056] Specific examples of polymers having a carboxy group in the side chain include (meth)acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, carboxy group-containing acidic cellulose derivatives, and acid anhydride adducts of hydroxy group-containing polymers.

[0057] From the viewpoint of imparting good solubility in an alkaline developer, the content of the structural unit (III-1) in the 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, based on all structural units constituting the polymer (b1-2). The content of the 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, based on all structural units constituting the polymer (b1-2).

[0058] When the first composition contains polymer (a1-1) and polymer (b1-2), the mass ratio of polymer (a1-1) to polymer (b1-2) is preferably 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.

[0059] Further examples of the monomer constituting the other structural unit (1) include at least one selected from the group consisting of (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, aromatic vinyl compounds, N-substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, and unsaturated dicarboxylic acid dialkyl ester compounds. By introducing structural units derived from these monomers into the polymer, it is possible to adjust the glass transition temperature of the polymer component and further improve the pattern shape and chemical resistance of the resulting cured film.

[0060] Specific examples of the above-mentioned monomers include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate; Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, and the like. 2,6 ] decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 2,5 ] decan-8-yloxyethyl, isoboronyl (meth)acrylate, etc.; Examples of (meth)acrylic acid esters having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate; Aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, 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, and N-naphthylmaleimide. 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, (meth)acrylic acid glycerin carbonate, (γ-lactam-2-yl) (meth)acrylate, and N-(meth)acryloxyethylhexahydrophthalimide; Conjugated diene compounds include 1,3-butadiene and isoprene; Nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; Examples of unsaturated dicarboxylic acid dialkyl ester compounds include diethyl itaconate, etc. In addition to the above, examples of monomers constituting the other structural unit (1) include monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate.

[0061] From the viewpoint of electrical properties, the monomer constituting the other structural unit (1) is preferably at least one selected from the group consisting of aromatic vinyl compounds and (meth)acrylic acid esters having an alicyclic structure. Preferred 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.

[0062] Furthermore, as a monomer constituting the other structural unit (1), from the viewpoint of improving adhesion to the substrate, (meth)acrylic acid alkyl esters can be preferably used. Specific preferred examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate, with methyl (meth)acrylate being preferred. The polymer component may further have a structural unit having an oxazoline group as another structural unit.

[0063] When the polymer (a1-1) has structural units other than the structural units (II-1) and (III-1) (hereinafter also referred to as "other structural units (IV-1)"), the content of the other structural units (IV-1) is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total structural units constituting the polymer (a1-1). The content of the other structural units (IV-1) is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total structural units constituting the polymer (a1-1).

[0064] Polymer (a1-1) can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in an appropriate solvent in the presence of a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyrate) dimethyl. The proportion of the 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 the polymerization solvent include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of the polymerization solvent used is preferably such that the total amount of the monomers used in the reaction is 0.1 to 60% by mass relative to the total amount of the reaction solution.

[0065] In the polymerization, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the types 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 for preparing the radiation-sensitive composition while still dissolved in the reaction solution, or may be used for preparing the radiation-sensitive composition after being isolated from the reaction solution. The polymer can be isolated by known isolation methods, such as a method of pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or a method of distilling the reaction solution under reduced pressure using an evaporator.

[0066] The weight average molecular weight (Mw) of the polymer (a1-1) in terms of polystyrene as determined by gel permeation chromatography (GPC) is preferably 3,000 or more. An Mw of 3,000 or more is preferred in that a cured film having sufficiently high heat resistance and chemical resistance and exhibiting good developability can be obtained. Mw is more preferably 5,000 or more, even more preferably 6,000 or more, and particularly preferably 7,000 or more. Furthermore, from the viewpoint of improving film-forming properties, 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.

[0067] Furthermore, the molecular weight distribution (Mw / Mn) of the polymer (a1-1), which is 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.

[0068] When the first composition contains polymer (a1-1) as a polymer component, preferred embodiments of the polymer component contained in the first composition are shown below, although the first composition containing polymer (a1-1) is not limited to the following embodiments. <1A> An embodiment in which the polymer (a1-1) further contains the structural unit (II-1) and the structural unit (III-1), and also contains one or more other structural units (IV-1). <2A> An embodiment comprising a polymer (a1-1) and a polymer (b1-1) or a polymer (b1-2), wherein the polymer (a1-1) further comprises a structural unit (III-1) and one or more other structural units (IV-1) and is substantially free of a structural unit (II-1), and the polymer (b1-1) or (b1-2) comprises the structural unit (II-1), the structural unit (III-1), and one or more other structural units (IV-1) and is substantially free of a structural unit (I-1). <3A> An embodiment further comprising, together with the polymer (a1-1), a polymer that is substantially free of the structural unit (I-1) and the structural unit (II-1). <4A> An embodiment consisting of a combination of two or more of the above embodiments <1A> to <3A>.

[0069] Of the above, the embodiment <1A> is particularly preferred in that it is possible to obtain the effect of improving the development adhesion and the curing adhesion while minimizing the number of components constituting the first composition.

[0070] [Regarding polymer (a1-2)] The polymer (a1-2) is a polymer containing a structural unit (I-2) having an acid-dissociable group. The acid-dissociable group is a group that substitutes a hydrogen atom of an acid group such as a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, or a sulfo group, and is a group that dissociates under the action of an acid. When the composition containing the polymer (a1-2) is irradiated with radiation, the acid-dissociable group is eliminated by the acid generated, resulting in the formation of an acid group. This allows the solubility of the polymer component in a developer to be changed, and a cured film having a pattern formed thereon can be obtained.

[0071] The structural unit (I-2) is preferably a structural unit in which an acid-dissociable group is eliminated by the action of an acid to generate a carboxyl group (hereinafter also referred to as "structural unit (I-2-1)"), or a structural unit in which an acid-dissociable group is eliminated by the action of an acid to generate a phenolic hydroxyl group (hereinafter also referred to as "structural unit (I-2-2)").

[0072] About structural units (I-2-1) The structural unit (I-2-1) may be a structural unit derived from a protected unsaturated carboxylic acid. The unsaturated carboxylic acid to be used is not particularly limited, and examples thereof include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, and unsaturated polycarboxylic acids.

[0073] 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 acid anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of unsaturated polycarboxylic acids include ω-carboxypolycaprolactone mono(meth)acrylate.

[0074] Examples of the acid-dissociable group contained in the structural unit (I-2-1) include an acetal functional group, a tertiary alkyl group, a tertiary alkyl carbonate group, etc. Among these, an acetal functional group is preferred because it is easily dissociated by an acid.

[0075] When the acid-dissociable group is an acetal functional group, the structural unit (I-2-1) preferably has an acetal ester structure of a carboxylic acid as the protected carboxy group, and specifically, preferably has a group represented by the following formula (X-1): [ka] (In formula (X-1), R 31 , R 32 and R 33 is either (1) or (2) below. (1)R 31 R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. 32 and R 33 are each 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. (2) R 31 R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. 32 and R 33 are aligned with each other. 32 and OR 33 represents a cyclic ether structure formed together with the carbon atom to which it is bonded. "*" represents a bond.)

[0076] R 31 , R 32 and R 33 The alkyl group having 1 to 12 carbon atoms represented by the formula (I) may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 4. Specific examples 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.

[0077] R 31, R 32 and R 33 Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by the formula (R) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an isobornyl group, and an adamantyl group. 32 and R 33 Examples of the aralkyl group having 7 to 20 carbon atoms represented by the formula include a phenylmethyl group, a phenylethyl group, and a methylphenylmethyl group.

[0078] R 32 and R 33 The cyclic ether structure formed by combining these rings preferably has 5 or more ring members. Specific examples include a tetrahydrofuran ring structure and a tetrahydropyran ring structure.

[0079] In particular, R 31 is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.

[0080] Specific examples of the acetal ester structure of a carboxylic acid represented by the above formula (X-1) include a 1-methoxyethoxycarbonyl group, a 1-ethoxyethoxycarbonyl group, a 1-propoxyethoxycarbonyl group, a 1-butoxyethoxycarbonyl group, a 1-cyclohexyloxyethoxycarbonyl group, a 2-tetrahydrofuranyloxycarbonyl group, a 2-tetrahydropyranyloxycarbonyl group, and a 1-phenylmethoxyethoxycarbonyl group.

[0081] Among the above, the structural unit (I-2-1) is preferably a structural unit represented by the following formula (Y-1) or a structural unit represented by the following formula (Y-2). [ka] (In formula (Y-1), R 30 is a hydrogen atom or a methyl group. 30 is a single bond or an arylene group. 40 is a hydrogen atom or an alkyl group.41 and R 42 are each 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 is a hydrogen atom or a methyl group. 31 is a single bond or an arylene group. 43 ~R 49 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and k is 1 or 2.

[0082] A preferred example of the structural unit (I-2-1) is a structural unit represented by the following formula: 30 is a hydrogen atom or a methyl group. [ka]

[0083] About 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. Among them, from the viewpoint of the sensitivity of the present composition, a structural unit derived from hydroxystyrene or a derivative thereof and a structural unit derived from a (meth)acrylic compound having a hydroxybenzene structure are preferred.

[0084] The acid-dissociable group contained in the structural unit (I-2-2) is not particularly limited, but from the viewpoints of the sensitivity, pattern shape, storage stability, etc. of the present composition, an acetal-based functional group is preferred. Examples of the acetal-based functional group that can be used in the structural unit (I-2-2) include the same acid-dissociable groups that can be used in the structural unit (I-2-1). Among these, "-OC(R 31 )(R 32 )(OR 33 )" (However, R 31 , R 32 and R 33is synonymous with formula (X-1). In this case, the protected phenolic hydroxyl group contained in the structural unit (I-2-2) can be represented by the following formula (Z-1): [ka] (In formula (Z-1), Ar 1 is an arylene group. 31 , R 32 and R 33 is synonymous with formula (X-1). "*" represents a bond.

[0085] -C(R 31 )(R 32 )(OR 33 )" can include a 1-alkoxyalkyl group and a 1-arylalkoxyalkyl group, and specific examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, a 1-(2-ethylhexyloxy)ethyl group, a 1-propoxyethyl group, a 1-cyclohexyloxyethyl group, a 1-(2-cyclohexylethoxy)ethyl group, and a 1-benzyloxyethyl group.

[0086] A preferred example of the structural unit (I-2-2) is a structural unit represented by the following formula: 30 is a hydrogen atom or a methyl group. [ka]

[0087] The content of the structural unit (I-2) in the 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, based on all structural units constituting the polymer (a1-2). The content of the 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, based on all structural units constituting the polymer (a1-2). By setting the content of the structural unit (I-2) within the above range, the sensitivity of the first composition can be increased, and the coating film exhibits better resolution, which is preferable.

[0088] When the first composition contains a polymer (a1-2) as a polymer component, the polymer component may further contain a structural unit other than the structural unit (I-2) (hereinafter also referred to as "other structural unit (2)"). Examples of the other structural unit (2) include a structural unit (II-2) having a crosslinkable group and a structural unit (III-2) having an acid group. The other structural unit (2) may be introduced into the same polymer as the polymer (a1-2) having the structural unit (I-2), or may be introduced as a structural unit into a polymer different from the polymer (a1-2), or may be introduced into both the polymer (a1-2) and a polymer different from the polymer (a1-2).

[0089] Structural Unit (II-2) The crosslinkable group contained in the structural unit (II-2) is not particularly limited as long as it is a group that undergoes a curing reaction upon heat treatment. In particular, an oxiranyl group, an oxetanyl group, a "-NH-CH2-OR" group, etc. are preferred because of their high thermosetting properties. 10 " (wherein R 10 is 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 and preferred examples of the structural unit (II-2) are the same as those given in the description of the structural unit (II-1).

[0090] When the polymer (a1-2) contains the structural unit (II-2), the content of the 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, based on all structural units constituting the polymer (a1-2). The content of the 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, based on all structural units constituting the polymer (a1-2).

[0091] When the polymer (a1-2) is substantially free of the structural unit (II-2), the first composition preferably contains, as a polymer different from the polymer (a1-2), a polymer that contains the structural unit (II-2) and is substantially free of the structural unit (I-2) (hereinafter also referred to as "polymer (b1-3)"), together with the polymer (a1-2).

[0092] The content of the structural unit (II-2) in the 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, based on all structural units constituting the polymer (b1-3). The content of the 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, based on all structural units constituting the polymer (b1-3).

[0093] When the composition contains polymer (a1-2) and polymer (b1-3), the mass ratio of polymer (a1-2) to polymer (b1-3) is preferably 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.

[0094] Structural Unit (III-2) The polymer (a1-2) preferably further contains a structural unit (III-2) having an acid group, which can improve the solubility in an alkaline developer and the curing reactivity. Specific and preferred examples of the structural unit (III-2) are the same as those described in the description of the structural unit (III-1).

[0095] When the polymer (a1-2) contains the structural unit (III-2), the content of the 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, based on all structural units constituting the polymer (a1-2), from the viewpoint of imparting good solubility in an alkaline developer. The content of the 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, based on all structural units constituting the polymer (a1-2).

[0096] When the polymer (a1-2) is substantially free of the structural unit (III-2), the composition preferably contains, as a polymer different from the polymer (a1-2), a polymer that contains the structural unit (III-2) and is substantially free of the structural unit (I-2) (hereinafter also referred to as "polymer (b1-4)"). As the polymer (b1-4), a polymer having a carboxyl group in the side chain can be preferably used, and the description of the polymer (b1-2) applies as a specific example.

[0097] From the viewpoint of imparting good solubility in an alkaline developer, the content of the structural unit (III-2) in the 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, based on all structural units constituting the polymer (b1-4). The content of the 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, based on all structural units constituting the polymer (b1-4).

[0098] When the composition contains polymer (a1-2) and polymer (b1-4), the mass ratio of polymer (a1-2) to polymer (b1-4) is preferably 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.

[0099] Furthermore, when the first composition contains a polymer (a1-2) as a polymer component, examples of the other structural unit (2) that may be contained in the polymer component include the structural units exemplified as the other structural unit (1).

[0100] When the polymer (a1-2) contains structural units other than the structural units (II-2) and (III-2) (hereinafter also referred to as "other structural units (IV-2)"), the content of the other structural units (IV-2) is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total structural units constituting the polymer (a1-2). The content of the other structural units (VI-2) is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total structural units constituting the polymer (a1-2).

[0101] The polymer (a1-2) can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in a suitable solvent in the presence of a polymerization initiator, etc. The details of the polymerization method are the same as those for the polymer (a1-1).

[0102] The weight average molecular weight (Mw) of the polymer (a1-2) measured by GPC in terms of polystyrene is preferably 1,000 or more. Mw is more preferably 2,000 or more, and even more preferably 5,000 or more. From the viewpoint of improving film-forming properties, Mw is preferably 200,000 or less, and more preferably 50,000 or less.

[0103] Furthermore, the molecular weight distribution (Mw / Mn) of the polymer (a1-2), which is 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.

[0104] When the first composition contains polymer (a1-2) as a polymer component, preferred embodiments of the polymer component contained in the first composition are shown below, although the first composition containing polymer (a1-2) is not limited to the following embodiments. <1B> An embodiment in which the polymer (a1-2) further contains the structural unit (II-2) and the structural unit (III-2), and also contains one or more other structural units (IV-2). <2B> An embodiment comprising a polymer (a1-2) and a polymer (b1-3) or a polymer (b1-4), wherein the polymer (a1-2) further comprises the structural unit (III-2) and one or more other structural units (IV-2) and is substantially free of the structural unit (II-2), and the polymer (b1-3) or (b1-4) comprises the structural unit (II-2), the structural unit (III-2), and one or more other structural units (IV-2) and is substantially free of the structural unit (I-2). <3B> An embodiment further comprising, together with the polymer (a1-2), a polymer that is substantially free of the structural unit (I-2) and the structural unit (II-2). <4B> An embodiment consisting of a combination of two or more of the above embodiments <1B> to <3B>.

[0105] Of the above, the embodiment <1B> is particularly preferred in that it is possible to obtain the effect of improving the development adhesion and the curing adhesion while minimizing the number of components constituting the first composition.

[0106] [Regarding siloxane polymers] When the first composition contains a siloxane polymer as a polymer component, by irradiating the first composition with radiation, the acid generated from the photoacid generator by the radiation exposure acts as a catalyst to promote self-crosslinking of the siloxane polymer, thereby forming a cured film.

[0107] The siloxane polymer is not particularly limited as long as it can form a cured film by hydrolysis and condensation. The siloxane polymer is preferably 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 21is a non-hydrolyzable monovalent group. 22 is an alkyl group having 1 to 4 carbon atoms. r is an integer of 0 to 3. However, when r is 2 or 3, multiple R 21 are the same or different groups. When r is 0 to 2, multiple R 22 are the same or different groups.

[0108] R 21 Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a group having a (meth)acryloyl group, and a group having an epoxy group. R 22 Examples of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. 22 is preferably a methyl group or an ethyl group. r is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0109] Specific examples of the monomer constituting the siloxane polymer include silane compounds having four hydrolyzable groups, such as tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, 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, and 3-(meth)acryloxypropyltriethoxysilane; Examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane; Examples of silane compounds having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane.

[0110] The siloxane polymer 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 an organic solvent. The proportion of water used in the hydrolysis and condensation reaction depends on the hydrolyzable group (-OR) possessed by the hydrolyzable silane compound. 22 The amount of water is preferably 0.1 to 3 mol, more preferably 0.2 to 2 mol, and even more preferably 0.5 to 1.5 mol, relative to 1 mol of the total amount of (a) and (b). By using such an amount of water, the reaction rate of the hydrolysis and condensation can be optimized.

[0111] Examples of catalysts used in the hydrolysis and condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, etc. 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 mol, more preferably 0.0005 to 0.1 mol, per 1 mol of the hydrolyzable silane compound.

[0112] Examples of organic solvents used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, water-insoluble or slightly water-soluble organic solvents are preferred, such as ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid ester compounds. The organic solvent is preferably used in an amount of 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.

[0113] During the hydrolysis and condensation reaction, the reaction temperature is preferably 130°C or lower, more preferably 40 to 100°C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. During the reaction, the mixture may be stirred or may be placed under reflux. After the hydrolysis and condensation reaction, a dehydrating agent may be added to the reaction solution, followed by evaporation to remove water and the produced alcohol from the reaction system.

[0114] The siloxane polymer contained in the first composition preferably has a weight average molecular weight (Mw) of 500 or more, as calculated on a polystyrene basis by GPC. An Mw of 500 or more is preferred in that a cured film having sufficiently high heat resistance and solvent resistance and good developability can be obtained. Mw is more preferably 1,000 or more. Furthermore, from the viewpoints of improving film-forming properties and suppressing a decrease in radiation sensitivity, Mw is preferably 10,000 or less, more preferably 5,000 or less.

[0115] Furthermore, the molecular weight distribution (Mw / Mn) of the polysiloxane polymer is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0116] 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, more preferably 90% by mass or less, based on the total amount of solids contained in the first composition. By keeping the content of the (A-1) polymer within the above ranges, a cured film having sufficiently high heat resistance and chemical resistance, as well as good developability and transparency, can be obtained.

[0117] <(B-1) Photoacid generator> The first composition contains a photoacid generator as a radiation-sensitive compound. The photoacid generator (hereinafter also simply referred to as "photoacid generator") contained in the first composition is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more (preferably 300 to 450 nm) and generates an acid. When a photoacid generator that is not directly sensitive to actinic rays with a wavelength of 300 nm or more is used, it may be used in combination with a sensitizer so that it responds to actinic rays with a wavelength of 300 nm or more and generates an acid.

[0118] As the photoacid generator, a compound that generates an acid having 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.

[0119] Specific examples of photoacid generators include oxime sulfonate 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, sulfonate ester compounds, and carboxylate ester compounds.

[0120] Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, and carboxylate ester compounds include the compounds described in paragraphs 0078 to 0106 of JP 2014-157252 A and the compounds described in WO 2016 / 124493 A. 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.

[0121] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (7). [ka] (In formula (7), R 23 is a monovalent hydrocarbon group or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group have been substituted with substituents. "*" represents a bond.

[0122] In the above formula (7), R 23 Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an oxo group, and a halogen atom.

[0123] Preferred specific examples of the compound having a sulfonate group represented by the above formula (7) include compounds represented by the following formulas (7-1) to (7-3). [ka] (In formula (7-1), R 51 is a substituted or unsubstituted monovalent hydrocarbon group. 51 is an alkyl group, an alkoxy group, or a halogen atom. m1 is an integer of 0 to 3. When m1 is 2 or 3, a plurality of X 51 are the same or different. In formula (7-2), R 52 is a substituted or unsubstituted monovalent hydrocarbon group. 52 is an alkyl group, an alkoxy group, or a halogen atom. m2 is an integer of 0 to 3. When m2 is 2 or 3, a plurality of X 52 are the same or different. In formula (7-3), R 53 R is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a heteroaryl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, or a cyano group. 54 is a substituted or unsubstituted monovalent hydrocarbon group. 53 -O-, -S-, -NR 59 -or-C(R 59 )(R 60 )-. R59 and R 60 are each independently a hydrogen atom or a monovalent hydrocarbon group. 55 ~R 58 are each 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 amido group, a sulfo group, or a cyano group, provided that R 55 ~R 58 Two adjacent groups may be bonded to form a ring.

[0124] Specific examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, [(2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in WO 2016 / 124493. Commercially available oxime sulfonate compounds include Irgacure PAG121 manufactured by BASF.

[0125] Specific examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide.

[0126] In the first composition, the content of the photoacid generator is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, per 100 parts by mass of the (A-1) polymer contained in the first composition, and is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the polymer component contained in the first composition.

[0127] When 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 an alkaline solution can be sufficiently increased. This allows for good patterning. Furthermore, the amount of acid involved in the reaction with the polymer component can be increased, ensuring sufficient heat resistance and solvent resistance. On the other hand, when 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 advantageous in that it can prevent a decrease in developability due to residual photoacid generator.

[0128] <(C-1) Solvent> The first composition contains a solvent. The first composition is preferably a liquid composition in which the polymer component, the photoacid generator (B-1), the compound (E), and other components added as needed are dissolved or dispersed in the solvent. The solvent used is preferably an organic solvent that dissolves each of the components added to the first composition but does not react with each of the components.

[0129] Specific examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene 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.

[0130] Of these, the solvent preferably contains 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.

[0131] In the first composition, the content of the solvent (the total amount when two or more solvents are contained) 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.

[0132] <(E) compound> The first composition contains a compound having a cardo structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group (hereinafter, also simply referred to as a "cardo compound").

[0133] A cardo structure has a first ring structure, a second ring structure, and a third ring structure, and the second ring structure and the third ring structure are directly bonded to the same carbon atom contained in the ring skeleton of the first ring structure. Specifically, the cardo structure can be represented by the following formula (10). [ka] (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 attached. 11 and A 12 are each independently a divalent cyclic group. "*" represents a bond.

[0134] In the above formula (10), A 11 and A 12 The divalent cyclic group represented by the formula (I) may be either an alicyclic group or an aromatic ring 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 fused alicyclic hydrocarbon group, and may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. A fused alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group formed in such a way that multiple alicyclic rings share a side (a bond between two adjacent carbon atoms).

[0135] 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]heptane-2,2-diyl. 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group), and the like; and as a condensed alicyclic hydrocarbon group, a decahydronaphthalenediyl group, and the like can be mentioned.

[0136] 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 either monocyclic or polycyclic. When the divalent aromatic ring group is a polycyclic hydrocarbon group, the polycyclic hydrocarbon group may be either a bridged aromatic hydrocarbon group or a fused aromatic hydrocarbon group.

[0137] Specific examples of monocyclic aromatic hydrocarbon groups include a phenylene group, etc. Polycyclic aromatic hydrocarbon groups are preferably condensed aromatic ring hydrocarbon groups, such as a naphthalene group, an anthracenediyl group, a fluorenediyl group, and a phenalenediyl group.

[0138] When the divalent alicyclic group and aromatic ring group have a substituent on the ring portion, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, and a cyano group.

[0139] A 11 and A 12 The divalent cyclic group represented by the formula (I) is preferably a divalent aromatic ring group, and particularly preferably a substituted or unsubstituted phenylene group.

[0140] A 10 is A 11and A 12 A is a cyclic group formed together with the carbon atom to which it is attached. 10 Specific examples of the cyclic group represented by the formula: 11 and A 12 Examples of the divalent cyclic group represented by the formula (I) include the same divalent alicyclic groups and divalent aromatic ring groups as those exemplified above. 10 Preferred specific examples of the cyclic group represented by the formula (10a-1) include groups represented by the following formulas (10a-1) to (10a-6) and groups in which a substituent has been introduced into the ring moiety of these groups. [ka] (In the formula, "*" represents a bond.)

[0141] A 10 Among the above, the cyclic group represented by formula (10a-1) is preferably a group represented by each of formulas (10a-1) to (10a-3) above, or a group in which a substituent has been introduced into the ring moiety thereof, and a group having a fluorene structure (i.e., a group represented by formula (10a-1) above, or a group in which a substituent has been introduced into the ring moiety) is particularly preferred.

[0142] The cardo structure represented by the above formula (10) is highly effective in improving the development adhesion and curing adhesion of the film obtained using the present composition, and among these, the structure represented by the following formula (10-1) is preferred. [ka] (In formula (10-1), Ar 11 and Ar 12 are each independently a divalent aromatic ring group. 68 and R 69 are each independently an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. a1 and a2 are each independently an integer of 0 to 3. When a1 is 2 or 3, multiple R 68 are the same or different. When a2 is 2 or 3, multiple R 69 are the same or different. "*" represents a bond.)

[0143] The functional group (X) possessed by the cardo compound is at least one selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group.

[0144] The alkoxysilyl group may have a structure in which an alkoxy group is bonded to a silicon atom, and may be, for example, a group represented by the formula "-Si(R 61 )(R 62 )(R 63 )" where R 61 , R 62 and R 63 are each independently a hydrogen atom, a halogen atom, a hydroxy 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 the groups R is an alkoxy group having 1 to 6 carbon atoms. Specific examples of the alkoxysilyl group include the same as the group represented by the above formula (1). 61 , R 62 and R 63 It is preferable that one of R is an alkoxy group having 1 to 6 carbon atoms, and the rest are an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 10 carbon atoms. 61 , R 62 and R 63 It is preferred that one of the groups be an alkoxy group having 1 to 3 carbon atoms and the rest be an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, since this can further enhance the effect of improving development adhesion and curing adhesion.

[0145] In order to improve the development adhesion and curing adhesion of a film obtained using the present composition, the functional group (X) is preferably at least one selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, and a (meth)acryloyl group, and an alkoxysilyl group is particularly preferred.

[0146] The cardo compound contained in the composition may have at least one cardo structure and at least one functional group (X) per molecule, and the structure of the other components is not particularly limited. Examples of cardo compounds include oligomers containing structural units with a cardo structure and silane coupling agents with a cardo structure. Specific examples of cardo compounds include compounds represented by the following formula (11) and compounds represented by the following formula (12). Furthermore, the cardo compound may be 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 with a tetrabasic acid dianhydride, as described in International Publication No. 2009 / 119622. For example, the photosensitive resin (A2) described in Example 2 of the same publication may be used.

[0147] [ka] (In formula (11), Y 61 and Y 62 are each independently a divalent organic group having one or more carbon atoms. 61 and X 62 are each independently an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, or an amino group. b1 and b2 are each independently an integer of 1 to 5. Ar 11 , Ar 12 , R 68 , R 69 , a1 and a2 have the same meanings as in the above formula (10-1).

[0148] [ka] (In formula (12), Y 63 and Y 64 are each independently a divalent organic group having one or more carbon atoms. 61 and X 63 are each independently an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, or an amino group. n1 is an integer of 2 to 100. Ar11 , Ar 12 , R 68 , R 69 , a1 and a2 have the same meanings as in the above formula (10-1).

[0149] In the above formulas (11) and (12), Y 61 ~Y 64 Examples of the divalent organic group represented by the formula (I) include a divalent hydrocarbon group having 1 to 40 carbon atoms, and a divalent group in which at least one methylene group of the hydrocarbon group is replaced with a heteroatom-containing group. Examples of the heteroatom-containing group include -O-, -S-, -CO-, -COO-, -OCO-, and -NR 67 CO-, -CONR 67 -, -NR 67 -COO-, -OCO-NR 67 - etc. (However, R 67 is a hydrogen atom or an alkyl group).

[0150] Of the above cardo compounds, the compound represented by the formula (11) is preferred because it can improve the development adhesion and curing adhesion of the film formed from the present composition. 61 and X 62 Particularly preferred are compounds in which is an alkoxysilyl group.

[0151] Commercially available cardo compounds may be used, such as OGSOL SC-001, EA-0200, EA-0300, and CR1030 (all manufactured by Osaka Gas Chemicals Co., Ltd.), WR-301 (manufactured by ADEKA Corporation), V-259ME (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and Oncoat EX series (manufactured by Nagase ChemteX Corporation).

[0152] In the first composition, the content of the cardo compound is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1 part by weight or more, per 100 parts by weight of the polymer component contained in the first composition. Furthermore, the content of the cardo compound is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, per 100 parts by weight of the polymer component contained in the first composition. By setting the content of the cardo compound to 0.1 parts by weight or more, the film formed from the composition can be sufficiently improved in terms of development adhesion, curing adhesion, and chemical resistance. On the other hand, setting the content of the cardo compound to 20 parts by weight or less is advantageous in that it can obtain the effects of adding the cardo compound while suppressing a decrease in the sensitivity of the composition.

[0153] Although it is unclear why the present composition containing the (E) compound having a functional group (X) and a cardo structure is able to provide excellent development adhesion, curing adhesion, and even chemical resistance, one hypothesis is that in a coating film formed on a substrate using the present composition, the (E) compound tends to localize at the interface between the substrate and the coating film, and the cardo structure of the (E) compound creates a hydrophobic environment at the substrate interface, preventing the developer from penetrating between the substrate and the coating film. Furthermore, it is thought that the increased mechanical strength of the film prevents film shrinkage due to heating.

[0154] <Other ingredients> The first composition may further contain components other than the above-mentioned (A-1) polymer component, (B-1) photoacid generator, (C-1) solvent, and (E) compound (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.

[0155] (adhesion aid) The adhesion aid is a component that improves the adhesion between the cured film formed using the first composition and the substrate. A functional silane coupling agent having a reactive functional group can be preferably used as the adhesion aid. Examples of the reactive functional group possessed by the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0156] Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0157] When the first composition contains an adhesion aid, the content ratio thereof 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, per 100 parts by mass of the polymer component contained in the first composition.

[0158] (acid diffusion control agent) The acid diffusion controller is a component that controls the diffusion length of the acid generated from the photoacid generator upon exposure. By incorporating an acid diffusion controller into the first composition, the diffusion length of the acid can be appropriately controlled, thereby improving pattern developability. In addition, by incorporating an acid diffusion controller, chemical resistance can be enhanced while improving development adhesion, which is preferable.

[0159] The acid diffusion controller can be arbitrarily selected from basic compounds used in chemically amplified resists. Examples of basic compounds include fatty acid amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium carboxylates. Specific examples of basic compounds include compounds described in paragraphs

[0128] to

[0147] of JP-A No. 2011-232632. The acid diffusion controller can preferably be at least one selected from the group consisting of aromatic amines and heterocyclic amines.

[0160] Examples of aromatic amines and heterocyclic amines include 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, and 2H-pyrrole derivatives. pyrrole derivatives such as 5-dimethylpyrrole and N-methylpyrrole; 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, nicotine, and other pyridine derivatives, as well as compounds described in JP 2011-232632 A.

[0161] When the first composition contains an acid diffusion controller, the content thereof is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, per 100 parts by mass of the polymer component, from the viewpoint of fully obtaining the effect of improving chemical resistance due to the incorporation of the acid diffusion controller, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the polymer component.

[0162] In addition to the above, at least one of a sensitizer, a crosslinking agent, a surfactant (e.g., a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant), and an antioxidant may be preferably used as other components. The first composition may also contain other known additives such as a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, a development accelerator, an acid multiplier, a plasticizer, a suspending agent, a polyfunctional polymerizable compound (e.g., a polyfunctional (meth)acrylate), a polymerization inhibitor, and a chain transfer agent. The blending ratio of these components is appropriately selected depending on each component within a range that does not impair the effects of the present disclosure.

[0163] The solids 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 taking into consideration viscosity, volatility, and the like. The solids concentration of the first composition is preferably in the range of 5 to 60 mass%. When the solids concentration is 5 mass% or more, a sufficient coating thickness can be ensured when the first composition is applied to a substrate. On the other hand, when the solids concentration is 60 mass% or less, the coating thickness does not become too large, and furthermore, the viscosity of the first composition can be appropriately increased, ensuring good coatability. The solids concentration of the first composition is more preferably 10 to 55 mass%, and even more preferably 12 to 50 mass%.

[0164] [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) at least one polymer selected from the group consisting of a polymer containing a structural unit having an acid group and a siloxane polymer; (B-2) quinone diazide compounds; (C-2) solvent; (E) A compound having at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group, and a cardo structure.

[0165] <Polymer component> The second composition contains, as a polymer component, at least one polymer selected from the group consisting of a polymer containing a structural unit having an acid group (hereinafter also referred to as "polymer (a2)") and a siloxane polymer (hereinafter also referred to as "polymer (A-2)").

[0166] [Regarding polymer (a2)] The polymer (a2) is a polymer containing a structural unit having an acid group (hereinafter also referred to as "structural unit (III-3)"). Specific and preferred examples of the structural unit (III-3) are the same as those described in the description of the structural unit (III-1) that may be contained in the polymer (a1-1).

[0167] In order to provide good solubility in an alkaline developer, the content of the structural unit (III-3) in the polymer (a2) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, based on the total structural units constituting the polymer (a2). The content of the 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, based on the total structural units constituting the polymer (a2).

[0168] When the second composition contains a polymer (a2), the polymer component may further contain a structural unit other than the structural unit (III-3) (hereinafter also referred to as "other structural unit (3)"). A preferred example of the other structural unit (3) is a structural unit (II-3) having a crosslinkable group. The other structural unit (3) may be introduced into the same polymer as the polymer (a2) having the structural unit (III-3), or may be introduced as a structural unit into a polymer different from the polymer (a2), or may be introduced into both the polymer (a2) and a polymer different from the polymer (a2).

[0169] Structural Unit (II-3) The crosslinkable group contained in the structural unit (II-3) is not particularly limited as long as it is a group that undergoes a curing reaction upon heat treatment. In particular, an oxiranyl group, an oxetanyl group, a "-NH-CH2-OR" group, etc. are preferred because of their high thermosetting properties. 10 " (wherein R 10 is 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 and preferred examples of the structural unit (II-3) are the same as those given in the description of the structural unit (II-1).

[0170] 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, based on all 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, based on all structural units constituting polymer (a2). By setting the content of structural unit (II-3) within the above range, the coating film exhibits better resolution, and the resulting cured film can be made to have sufficiently high heat resistance and chemical resistance. This is preferable.

[0171] When the polymer (a2) is substantially free of the structural unit (II-3), the composition preferably contains, together with the polymer (a2), a polymer that contains the structural unit (II-3) but is substantially free of the structural unit (III-3) (hereinafter also referred to as "polymer (b2-1)") as a polymer different from the polymer (a2).

[0172] The content 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 even more preferably 20% by mass or more, based on all structural units constituting the polymer (b2-1). The content of the 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, based on all structural units constituting the polymer (b2-1).

[0173] When the second composition contains the polymer (a2) and the polymer (b2-1), the mass ratio of the polymer (a2) to the polymer (b2-1) is preferably polymer (a2):polymer (b2-1)=95:5 to 5:95, more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.

[0174] Furthermore, when the second composition contains a 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.

[0175] The polymer (a2) can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in a suitable solvent in the presence of a polymerization initiator, etc. The details of the polymerization method are the same as those for the polymer (a1-1).

[0176] The weight average molecular weight (Mw) of the polymer (a2) measured by GPC in terms of polystyrene is preferably 1,000 or more. Mw is more preferably 2,000 or more, and even more preferably 5,000 or more. From the viewpoint of improving film-forming properties, Mw is preferably 200,000 or less, and more preferably 50,000 or less.

[0177] Furthermore, the molecular weight distribution (Mw / Mn) of the polymer (a2), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably 5.0 or less, more preferably 3.0 or less.

[0178] When the second composition contains polymer (a2) as a polymer component, preferred embodiments of the polymer component contained in the second composition are shown below, although the second composition containing polymer (a2) is not limited to the following embodiments. <1C> An embodiment in which the polymer (a2) further contains the structural unit (II-3) and one or more structural units other than the structural unit (II-3) (hereinafter also referred to as "other structural units (IV-3)"). <2C> An embodiment comprising a polymer (a2) and a polymer (b2-1), wherein the polymer (a2) further comprises one or more other structural units (IV-3) and is substantially free of the structural unit (II-3), and the polymer (b2-1) further comprises one or more other structural units (IV-3). <3C> An embodiment further comprising, together with the polymer (a2), a polymer that is substantially free of the structural unit (III-3) and the structural unit (II-3). <4C> An embodiment consisting of a combination of two or more of the above embodiments <1C> to <3C>.

[0179] Of the above, the embodiment <1C> is particularly preferred in that it is possible to obtain the effect of improving the development adhesion and the curing adhesion while minimizing the number of components constituting the second composition.

[0180] [Regarding siloxane polymers] The siloxane polymer contained in the second composition is the same as the specific and preferred examples of the siloxane polymer that may be contained in the first composition.

[0181] <(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 generates a carboxylic acid upon irradiation with radiation. As the quinone diazide compound, a condensation product of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother nucleus") with 1,2-naphthoquinone diazide sulfonic acid halide can be preferably used.

[0182] Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other mother nuclei.Specific examples of these include trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; 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, 2,3,4,4'-tetrahydroxybenzophenone, 3'-methoxybenzophenone, etc.; pentahydroxybenzophenones such as 2,3,4,2',6'-pentahydroxybenzophenone, etc.; hexahydroxybenzophenones such as 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; (polyhydroxyphenyl)alkanes such as 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) -2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiindene-5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc.; other mother nuclei 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.

[0183] 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 mother nucleus.

[0184] The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride. Specific 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 is preferably used as the 1,2-naphthoquinone diazide sulfonic acid halide.

[0185] In the condensation reaction to obtain the above condensation product, the ratio of the mother nucleus to the 1,2-naphthoquinone diazide sulfonic acid halide is preferably 30 to 85 mol %, more preferably 50 to 70 mol %, based on the number of OH groups in the mother nucleus. The above condensation reaction can be carried out according to a known method. A 1,2-quinone diazide compound is obtained by the condensation reaction of the mother nucleus with the 1,2-naphthoquinone diazide sulfonic acid halide.

[0186] 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, per 100 parts by mass of the polymer component contained in the second composition. 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, per 100 parts by mass of the polymer component contained in the second composition.

[0187] When the content of the quinone diazide compound is 2 parts by mass or more, sufficient acid is generated by irradiation with actinic rays, and the difference in solubility in alkaline solution between the irradiated and unirradiated areas can be sufficiently increased. This allows for good patterning. Furthermore, 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 content of the quinone diazide compound is 60 parts by mass or less, the amount of unreacted quinone diazide compound can be sufficiently reduced, which is advantageous in that it can suppress deterioration in developability and transparency due to residual quinone diazide compound.

[0188] <(C-2) Solvent> The second composition contains a solvent. The second composition is preferably a liquid composition in which the polymer component, the (B-2) quinone diazide compound, the (E) compound, and components blended as needed are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each component blended in the second composition but does not react with each component. Specific examples of the solvent contained in the second composition are the same as those of the solvent contained in the first composition.

[0189] In the second composition, the content of the solvent (the total amount when two or more solvents are contained) 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.

[0190] <(E) compound> The second composition contains the cardo compound (compound (E)) described above. Specific and preferred examples of the cardo compound contained in the second composition are the same as those of the first composition.

[0191] In the second composition, the content of the cardo compound is preferably at least 0.1 parts by weight, more preferably at least 0.5 parts by weight, and even more preferably at least 1 part by weight, per 100 parts by weight of the polymer component contained in the second composition, and is preferably at most 20 parts by weight, more preferably at most 15 parts by weight, and even more preferably at most 10 parts by weight, per 100 parts by weight of the polymer component contained in the second composition.

[0192] <Other ingredients> The second composition may further contain components other than the above-mentioned polymer component, (B-2) quinone diazide compound, (C-2) solvent, and (E) compound (other components). Specific and preferred examples of the other components that may be contained in the second composition are the same as those for the first composition.

[0193] The solid content of the second composition is appropriately selected taking into consideration the viscosity, volatility, etc., but is preferably in the range of 5 to 60 mass %, more preferably 10 to 55 mass %, and even more preferably 12 to 50 mass %.

[0194] [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) A polymer containing a structural unit having an acid group; (A-3-2) Polymerizable monomer; (B-3) photopolymerization initiator; (C-3) solvent; (E) A compound having at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group, and a cardo structure.

[0195] <Polymer component> The third composition contains, as a polymer component, a polymer containing a structural unit having an acid group (hereinafter also referred to as "polymer (a3)"). The polymer (a3) ​​corresponds to "polymer (A-3-1)".

[0196] [Regarding polymer (a3)] The polymer (a3) ​​is a polymer containing a structural unit having an acid group (hereinafter also referred to as "structural unit (III-4)"). Specific and preferred examples of the structural unit (III-4) are the same as those described in the description of the structural unit (III-1) that may be contained in the polymer (a1-1). In the polymer (a3), the content of the structural unit (III-4) is preferably 1% by mass or more, more preferably 2% by mass or more, based on all structural units constituting the polymer (a3), from the viewpoint of imparting good solubility in an alkaline developer to the unexposed area. Furthermore, the content of the structural unit (III-4) is preferably 35% by mass or less, more preferably 30% by mass or less, based on all structural units constituting the polymer (a3).

[0197] The polymer component in the third composition may further contain a structural unit other than the structural unit (III-4) (hereinafter also referred to as "other structural unit (4)"). A preferred example of the other structural unit (4) is the structural unit (II-4) having a crosslinkable group. The other structural unit (4) may be introduced into the same polymer as the polymer (a3) ​​having the structural unit (III-4), or may be introduced as a structural unit into a polymer different from the polymer (a3), or may be introduced into both the polymer (a3) ​​and a polymer different from the polymer (a3).

[0198] Structural Unit (II-4) The crosslinkable group contained in the structural unit (II-4) is not particularly limited as long as it is a group that undergoes a curing reaction upon heat treatment. In particular, an oxiranyl group, an oxetanyl group, a "-NH-CH2-OR" group, etc. are preferred because of their high thermosetting properties. 10 " (wherein R 10is 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 the structural unit (II-4) are the same as those described in the description of the structural unit (II-1). The content of the structural unit (II-4) in the polymer (a3) ​​is the same as the preferred range of the structural unit (II-3) in the polymer (a2).

[0199] When polymer (a3) ​​is substantially free of structural unit (II-4), the composition preferably contains, together with polymer (a3), a polymer (hereinafter also referred to as "polymer (b3-1)") that contains structural unit (II-4) but is substantially free of structural unit (III-4) as a polymer different from polymer (a3). The content 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, when the third composition contains polymer (a3) ​​and polymer (b3-1), the preferred range for the ratio of polymer (a3) ​​to polymer (b3-1) is the same as that for the second composition.

[0200] Examples of the other structural unit (4) that may be contained in the polymer component in the third composition include the structural units exemplified as the other structural unit (1).

[0201] The polymer (a3) ​​can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in an appropriate solvent in the presence of a polymerization initiator. Details of the polymerization method are the same as those for the polymer (a1-1). The preferred ranges of the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer (a3) ​​are the same as those for the polymer (a2).

[0202] Preferred embodiments of the polymer component contained in the third composition are shown below, although the third composition is not limited to the following embodiments. <1D> An embodiment in which the polymer (a3) ​​further contains the structural unit (II-4) and one or more structural units other than the structural unit (II-4) (hereinafter also referred to as "other structural units (IV-4)"). <2D> An embodiment comprising a polymer (a3) ​​and a polymer (b3-1), wherein the polymer (a3) ​​further comprises one or more other structural units (IV-4) and is substantially free of the structural unit (II-4), and the polymer (b3-1) further comprises one or more other structural units (IV-4). <3D> An embodiment further comprising, together with the polymer (a3), a polymer that is substantially free of the structural unit (III-4) and the structural unit (II-4). <4D> An embodiment consisting of a combination of two or more of the above embodiments <1D> to <3D>.

[0203] Of the above, the embodiment <1D> is particularly preferred in that it is possible to obtain the effect of improving the development adhesion and the curing adhesion while minimizing the number of components constituting the third composition.

[0204] <(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, preferably two or more, polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Among these, ethylenically unsaturated groups and N-alkoxymethylamino groups are preferred because of their high polymerizability, and vinyl-containing groups such as a (meth)acryloyl group, a vinyl group, and a vinylphenyl group are preferred.

[0205] 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, and particularly preferably a compound having two or more (meth)acryloyl groups. The number of polymerizable groups per molecule of the polymerizable monomer is preferably 2 to 10, more preferably 2 to 8.

[0206] Specific examples of the polymerizable monomer include compounds having two or more (meth)acryloyl groups, such as polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional (meth)acrylates having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride.

[0207] Examples of compounds having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The terms "melamine structure" and "benzoguanamine structure" refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and include melamine, benzoguanamine, and condensates thereof. 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)glycoluril.

[0208] Among the polymerizable monomers, preferred are 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 a carboxy group, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, and N,N,N',N'-tetra(alkoxymethyl)benzoguanamine; more preferred are 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 a carboxy group; and even more preferred are polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid.

[0209] Specific examples of polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipentaerythritol polyacrylate, etc. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferred, since they increase the inter- or intramolecular crosslinking density and can further improve the curability of the film even by low-temperature baking.

[0210] The content of the polymerizable monomer 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 the polymer component contained in the third composition. Furthermore, the content of the polymerizable monomer is preferably 1,000 parts by mass or less, and more preferably 500 parts by mass or less, per 100 parts by mass of the polymer component contained in the third composition. A content of the polymerizable monomer within the above range is preferable in that it ensures sufficient curability and alkaline developability as a cured film, and also sufficiently suppresses the occurrence of background smears, film residues, and the like on the substrate or light-shielding layer in unexposed areas.

[0211] <(B-3) Photopolymerization initiator> The third composition contains a photopolymerization initiator as a radiation-sensitive compound. The photopolymerization initiator (hereinafter also simply referred to as "photopolymerization initiator") contained in the third composition is preferably a compound that is sensitive to actinic rays with a wavelength of 300 nm or more (preferably 300 to 450 nm) and initiates and promotes polymerization of polymerizable monomers. When using a photopolymerization initiator that is not directly sensitive to actinic rays with a wavelength of 300 nm or more, it may be used in combination with a sensitizer so that it is sensitive to actinic rays with a wavelength of 300 nm or more and initiates and promotes polymerization of polymerizable monomers.

[0212] Known compounds can be used as the photopolymerization initiator. Specific examples include oxime ester compounds, organic halogenated compounds, oxidiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric 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, as they can further 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).

[0213] 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. 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.

[0214] <(C-3) Solvent> The third composition contains a solvent. The third composition is preferably a liquid composition in which the polymer component, polymerizable monomer, (B-3) photopolymerization initiator, (E) cardo compound, and other components added as needed are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each component added to the third composition but 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.

[0215] In the third composition, the content of the solvent (the total amount when two or more solvents are contained) 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.

[0216] <(E) compound> The third composition contains the cardo compound (compound (E)) described above. Specific and preferred examples of the cardo compound contained in the third composition are the same as those of the first composition.

[0217] In the third composition, the content of the cardo compound is preferably at least 0.1 parts by weight, more preferably at least 0.5 parts by weight, and even more preferably at least 1 part by weight, per 100 parts by weight of the polymer component contained in the third composition, and is preferably at most 20 parts by weight, more preferably at most 15 parts by weight, and even more preferably at most 10 parts by weight, per 100 parts by weight of the polymer component contained in the third composition.

[0218] <Other ingredients> The third composition may further contain components other than the above-mentioned polymer component, polymerizable monomer, (B-3) photopolymerization initiator, (C-3) solvent, and (E) compound (other components). Specific and preferred examples of the other components that may be contained in the third composition are the same as those for the first composition.

[0219] The solid content of the third composition is appropriately selected taking into consideration the viscosity, volatility, etc., but is preferably in the range of 5 to 60 mass %, more preferably 10 to 55 mass %, and even more preferably 12 to 50 mass %.

[0220] <Cured film and method for producing same> The cured film of the present disclosure is formed from the radiation-sensitive composition of the present disclosure (first composition, second composition, and third composition) prepared as described above. The present composition has high radiation sensitivity, good melt flow properties, and excellent storage stability. Furthermore, by using the present composition, it is possible to form a pattern film that exhibits high adhesion to the substrate even after development (development adhesion), high adhesion to the substrate after baking (curing adhesion), and excellent chemical resistance. Therefore, the present composition can be preferably used as a composition for forming, for example, an interlayer insulating film, a planarizing film, a spacer, a protective film, a colored pattern film for a color filter, a partition wall, a bank, etc., and is particularly suitable as a composition for forming an interlayer insulating film.

[0221] When producing a cured film, the present composition can be used to form a positive- or negative-tone cured film depending on the type of radiation-sensitive compound. Specifically, when forming a positive-tone cured film, the first composition or the second composition can be preferably used. On the other hand, when forming a negative-tone cured film, the third composition can be preferably used. The cured film can be produced using the present 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 of removing the solvent from the composition applied onto the substrate. (Step 3) A 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 thermally curing the developed composition. Each step will be described in detail below.

[0222] [Process 1: Coating process] In this process, the composition is applied to a surface on which a film is to 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 that can be used include glass substrates, silicon substrates, and resin substrates. The surface of the substrate on which the coating film is to be formed may have a metal thin film formed thereon depending on the application, or may have been subjected to various surface treatments such as HMDS (hexamethyldisilazane) treatment.

[0223] Examples of methods for applying the present composition include spraying, roll coating, spin coating, slit die coating, bar coating, inkjet coating, etc. Among these, spin coating, slit die coating, or bar coating is preferred.

[0224] [Step 2: Solvent removal step] In this step, the composition applied to the surface to be coated is preferably subjected to a heat treatment (pre-baking) to remove the solvent and form a coating film on the surface to be coated. The pre-baking conditions vary depending on the type and content of each component in the composition, but are, for example, 60 to 130°C for 0.5 to 10 minutes. The thickness of the coating film formed (i.e., the film thickness after pre-baking) is preferably 0.1 to 12 μm. The composition applied to the surface to be coated may be subjected to vacuum drying (VCD) before pre-baking.

[0225] [Process 3: Irradiation process] In this step, at least a portion of the coating film made of the present composition formed in step 2 above is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured film having a pattern can be formed. Examples of radiation include charged particle beams such as ultraviolet light, far ultraviolet light, visible light, X-rays, and electron beams. Among these, ultraviolet light is preferred, and examples thereof include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m 2 is preferred.

[0226] [Process 4: Development process] In this step, the coating film irradiated in step 3 above is developed. Specifically, the coating film irradiated in step 3 is developed using a developer to perform positive development, which removes the irradiated areas, or negative development, which removes the unirradiated areas. Examples of the developer include aqueous solutions of alkalis (basic compounds). Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and alkalis exemplified in paragraph

[0127] of JP 2016-145913 A. The alkali concentration in the aqueous alkali solution is preferably 0.1 to 5% by mass, from the viewpoint of obtaining appropriate developability.

[0227] Examples of the developing method include a puddle method, a dipping method, a swing immersion method, a shower method, etc. The developing time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. After the developing step, it is preferable to rinse the patterned coating film with running water.

[0228] [Process 5: Heat curing process] In this step, the coating film developed in step 4 above is subjected to a heating treatment (post-baking). Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when the heating treatment is performed on a hot plate, and 10 to 80 minutes when the heating treatment is performed in an oven. This heating treatment causes a curing reaction to proceed, and a cured film having a desired pattern can be formed on the substrate. The shape of the pattern of the cured film is not particularly limited, and examples include a line-and-space pattern, a dot pattern, a hole pattern, and a lattice pattern.

[0229] The cured film obtained from the composition can also be used as a dry etching resist. When the cured film is used as a dry etching resist, dry etching treatments such as ashing, plasma etching, and ozone etching can be used as the etching treatment.

[0230] <Display device> The display device of the present disclosure includes a cured film formed using the present composition. Examples of display devices include liquid crystal display devices and organic electroluminescence (EL) display devices. The cured film of a liquid crystal display device formed using the present composition can be used, for example, as an interlayer insulating film, a planarizing film, a protective film for a color filter, a spacer, etc. Furthermore, the cured film of an organic EL display device formed using the present composition can be used, for example, as an interlayer insulating film, a bank, a planarizing film, a partition wall, a pixel separation insulating film, etc.

[0231] According to the present disclosure described above in detail, the following means are provided. [Means 1] A radiation-sensitive composition comprising: (A-1) 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; (B-1) a photoacid generator; (C-1) a solvent; and (E) a compound having at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group, and a cardo structure (excluding compounds corresponding to a polymer containing a structural unit having a group represented by the following formula (1)). [Means 2] The radiation-sensitive composition according to [Means 1], wherein the polymer (A-1) further contains a structural unit having a crosslinkable group, or the radiation-sensitive composition further contains a polymer different from the polymer (A-1) and containing a structural unit having a crosslinkable group. [Means 3] The crosslinkable group is an oxiranyl group, an oxetanyl group, or a —NH—CH—OR 10 " (wherein R 10The radiation-sensitive composition according to [means 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. [Measure 4] The radiation-sensitive composition according to any one of [Measure 1] to [Measure 3], wherein the group represented by the formula (1) is bonded to an aromatic ring group or a chain hydrocarbon group. [Means 5] The radiation-sensitive composition according to any one of [Means 1] to [Means 4], wherein the structural unit having a group represented by the formula (1) has at least one selected from the group consisting of a group represented by the formula (3-1), a group represented by the formula (3-2), and a group represented by the formula (3-3). [Means 6] The radiation-sensitive composition according to any one of [Means 1] to [Means 5], wherein the photoacid generator comprises at least one compound selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds. [Means 7] The radiation-sensitive composition according to any one of [Means 1] to [Means 6], further comprising an acid diffusion controller. [Means 8] A radiation-sensitive composition comprising: (A-2) at least one polymer selected from the group consisting of a polymer containing a structural unit having an acid group and a siloxane polymer; (B-2) a quinonediazide compound; (C-2) a solvent; and (E) a compound having a cardo structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. [Means 9] The radiation-sensitive composition according to [Means 8], wherein the polymer (A-2) further contains a structural unit having a crosslinkable group, or the radiation-sensitive composition further contains a polymer different from the polymer (A-2) and containing a structural unit having a crosslinkable group. [Means 10] The crosslinkable group is an oxiranyl group, an oxetanyl group, or a group such as "-NH-CH2-OR 10 " (wherein R 10 The radiation-sensitive composition according to [means 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. [Means 11] The radiation-sensitive composition according to any one of [Means 8] to [Means 10], wherein the quinone diazide compound is a condensate of a phenolic compound or an alcoholic compound with 1,2-naphthoquinone diazide sulfonic acid halide. [Means 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 cardo structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. [Means 13] The radiation-sensitive composition according to [Means 12], wherein the polymer (A-3-1) further contains a structural unit having a crosslinkable group, or the radiation-sensitive composition further contains a polymer different from the polymer (A-3-1) and containing a structural unit having a crosslinkable group. [Means 14] The crosslinkable group is an oxiranyl group, an oxetanyl group, or a group such as "-NH-CH2-OR 10 " (wherein R 10 The radiation-sensitive composition according to [means 13], 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. [Means 15] The radiation-sensitive composition according to any one of [Means 1] to [Means 14], wherein the functional group (X) is at least one selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, and a (meth)acryloyl group. [Means 16] The radiation-sensitive composition according to any one of [Means 1] to [Means 15], wherein the functional group (X) is an alkoxysilyl group. [Means 17] The radiation-sensitive composition according to any one of [Means 1] to [Means 16], wherein the compound (E) has a partial structure represented by the above formula (10-1). [Means 18] The radiation-sensitive composition according to any one of [Means 1] to [Means 17], wherein the content of the compound (E) is 0.1 to 20 parts by mass per 100 parts by mass of the polymer component contained in the radiation-sensitive composition. [Means 19] A method for producing a cured film, comprising the steps of: applying the radiation-sensitive composition according to any one of [Means 1] to [Means 18] onto a substrate; removing the 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. [Means 20] A cured film formed using the radiation-sensitive composition according to any one of [Means 1] to [Means 18]. [Means 21] The cured film according to [Means 20], which is an interlayer insulating film. [Means 22] A liquid crystal display device comprising the cured film according to [Means 20] or [Means 21]. [Means 23] An organic EL display device comprising the cured film according to [Means 20] or [Means 21]. [Example]

[0232] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified.

[0233] [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 GPC-101 GPC column: Shimadzu GLC GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 Mobile phase: Tetrahydrofuran Column temperature: 40℃ ·Flow rate: 1.0mL / min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: Differential refractometer Standard material: Monodisperse polystyrene

[0234] [Monomer] The abbreviations of the monomers used in the synthesis of the polymers are as follows: <<Monomer having a group represented by the above formula (1)>> MPTMS: 3-methacryloxypropyltrimethoxysilane MPTES: 3-methacryloxypropyltriethoxysilane STMS: p-styryltrimethoxysilane SDMS: p-styryldimethoxyhydroxysilane STES: p-Styryltriethoxysilane

[0235] Other Monomers AA: acrylic acid MA: methacrylic acid MI: Maleimide OXMA: OXE-30 (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-yl] MATHF: 2-Tetrahydrofuranyl methacrylate MMA: methyl methacrylate ST: styrene

[0236] <Synthesis of Polymer (A)> [Synthesis Example 1] Synthesis of polymer (A-1) A flask equipped with a condenser and a stirrer was charged with 24 parts of propylene glycol monomethyl ether, followed by 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane. The solution was heated to 60°C. After the solution temperature reached 60°C, 0.1 parts of formic acid and 19 parts of water were added. With gentle stirring, the solution temperature was raised to 75°C and maintained at this temperature for 2 hours. After cooling to 45°C, 28 parts by mass of trimethyl orthoformate was added as a dehydrating agent and stirred for 1 hour. The solution temperature was then raised to 40°C and evaporated while maintaining the temperature to remove water and methanol generated by hydrolysis and condensation, yielding a polymer solution containing polymer (A-1). The solids concentration of this polymer solution was 35% by mass, and the weight-average molecular weight (Mw) of polymer (A-1) was 1,800, with a molecular weight distribution (Mw / Mn) of 2.2.

[0237] [Synthesis Example 2] Synthesis of polymer (A-2) Polymer (A-2) having the same solid content concentration, weight average molecular weight and molecular weight distribution as polymer (A-1) was obtained in the same manner as in Synthesis Example 1, except that the monomers used were changed to 39 parts of phenyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane.

[0238] [Synthesis Example 3] Synthesis of polymer (A-3) A flask equipped with a condenser and a stirrer was charged with 10 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methyl ethyl ether. Subsequently, 12 parts of methacrylic acid, 45 parts of glycidyl methacrylate, and 43 parts of 2-tetrahydrofuranyl methacrylate were charged, and the atmosphere was replaced with nitrogen. The temperature of the solution was raised to 70°C with gentle stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-3). The solids concentration of this polymer solution was 34.0% by mass, and the Mw of polymer (A-3) was 15,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[0239] [Synthesis Examples 4 to 18] Synthesis of polymers (A-4) to (A-18) Polymer solutions containing polymers (A-4) to (A-18) each having a solid content concentration, weight average molecular weight, and molecular weight distribution equivalent to those of polymer (A-3) were obtained in the same manner as in Synthesis Example 3, except that the types and amounts (parts by mass) of each component shown in Table 1 were used.

[0240] [Table 1]

[0241] <Preparation of Radiation-Sensitive Composition> The polymer (A), cardo compound (E), radiation-sensitive compound (B), polymerizable monomer (M), additive (X) and solvent (C) used in the preparation of the radiation-sensitive composition are shown below.

[0242] Polymer (A) A-1 to A-18: Polymers (A-1) to (A-18) synthesized in Synthesis Examples 1 to 18

[0243] Cardo Compound (E) E-1: WR-301 (ADEKA Corporation) E-2: Photosensitive resin (A2) described in Example 2 of WO 2009 / 119622 E-3: V-259ME (Nippon Steel Sumikin Chemical Co., Ltd.) E-4: Ogusol SC001 (Osaka Gas Chemicals Co., Ltd.)

[0244] 《Radiation-sensitive compound (B)》 B-1: Irgacure PAG121 (BASF) B-2: OS-17 described in International Publication No. 2016 / 124493 B-3: OS-25 described in International Publication No. 2016 / 124493 B-4: Condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) B-5: Condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol) B-6: Condensation product of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) B-7: Condensation product of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol) B-8: Irgacure OXE02 (BASF) <Polymerizable monomer (M)> D-1: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

[0245] 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

[0246] Solvent (C) C-1: Diethylene glycol ethyl methyl ether C-2: Propylene glycol monomethyl ether C-3: Propylene glycol monomethyl ether acetate

[0247] [Example 1] To the polymer solution containing the polymer (A-1) obtained in Synthesis Example 1, 5 parts of a cardo compound (E-1), 1 part of a radiation-sensitive compound (B-2), and 5 parts of an additive (X-1) were mixed in an amount corresponding to 100 parts (solid content) of the polymer (A-1), and diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether were added in a mass ratio of 1:1 so that the final solid content concentration was 20 mass%. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0248] [Examples 2 to 30, Comparative Examples 1 to 5] Radiation-sensitive compositions of Examples 2 to 30 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of each component shown in Table 2 were used.

[0249] [Table 2]

[0250] In Table 2, in examples where two types of compounds were used as solvent (C) (Examples 1, 2, 4 to 15, 19 to 21, 23, 27, 29 and Comparative Examples 2 and 4), solvent 1 and solvent 2 were mixed at a mass ratio of solvent 1:solvent 2 = 1:1. In examples where three types of organic solvents were used (Examples 3, 16 to 18, 22, 24 to 26, 28, 30 and Comparative Examples 1, 3, 5), solvent 1, solvent 2, and solvent 3 were mixed at a mass ratio of solvent 1:solvent 2:solvent 3 = 4:5:1.

[0251] <Evaluation> The radiation-sensitive compositions of Examples 1 to 30 and Comparative Examples 1 to 5 were evaluated for the following items by the methods described below. The evaluation results are shown in Table 3.

[0252] [Radiation sensitivity] Using a spinner, the radiation-sensitive composition was applied to a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was irradiated with a predetermined amount of ultraviolet light from a mercury lamp through a pattern mask with a 10 μm-wide line-and-space pattern. Next, a development process was carried out at 25°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer, followed by rinsing with running ultrapure water for 1 minute. The minimum exposure dose required to form a 10 μm-wide line-and-space pattern was measured. The measured minimum exposure dose was 300 J / m. 2 The radiation sensitivity is good when the radiation level is less than 300 J / m 2 In the above cases, the radiation sensitivity can be evaluated as poor.

[0253] [Evaluation of chemical resistance of cured film] The chemical resistance of the cured film was evaluated based on the degree of swelling caused by the stripping solution. The radiation-sensitive composition was applied to a silicon substrate using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film 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 to 3000 J / m 2 After irradiating the entire substrate with light, the substrate was post-baked for 30 minutes in an oven heated to 230°C to form a cured film. The resulting cured film was immersed in N-methyl-2-pyrrolidone solvent heated to 40°C for 6 minutes, and the change in film thickness (%) before and after immersion was determined. This change in film thickness was used as an index of chemical resistance and was evaluated according to the following criteria. AA: Film thickness change rate is less than 2% A: Film thickness change rate is 2% or more and less than 5% B: Film thickness change rate is 5% or more and less than 10% C: Film thickness change rate is 10% or more and less than 15% D: Film thickness change rate is 15% or more The chemical resistance can be evaluated as good in the cases of AA, A, or B, and poor in the case of C or D. The film thickness was measured at 25°C using an optical interference film thickness measuring device (Lambda Ace VM-1010).

[0254] [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 made according to the above-mentioned [Radiation Sensitivity] evaluation, and the rate of increase in radiation sensitivity (minimum exposure dose) before and after 7 days of storage was calculated. A value of less than 5% was rated as "AA," a value of 5% or more but less than 10% was rated as "A," a value of 10% or more but less than 20% was rated as "B," a value of 20% or more but less than 30% was rated as "C," and a value of 30% or more was rated as "D." A value of AA, A, or B indicates good storage stability, while a value of C or D indicates poor storage stability.

[0255] [Evaluation of adhesion during alkaline development (development adhesion)] The radiation-sensitive composition was applied to a silicon substrate that had not been subjected to HMDS treatment using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was exposed to light from 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 sample was then exposed to ultraviolet light. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used as the developer, and the sample was then developed for 60 seconds at 25°C, followed by rinsing with running ultrapure water for 1 minute. The minimum width of the line-and-space pattern remaining on the substrate was measured. A minimum width measurement of 2 μm or less was rated as "AA," greater than 2 μm and less than 5 μm as "A," greater than 5 μm and less than 10 μm as "B," greater than 10 μm and less than 30 μm as "C," and greater than 30 μm as "D." AA, A, or B indicates good developer adhesion, while C or D indicates poor developer adhesion.

[0256] [Evaluation of adhesion after baking (hardening adhesion)] The radiation-sensitive composition was applied to a glass substrate that had not been subjected to HMDS treatment using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. Subsequently, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to apply a radiation-sensitive composition to the glass substrate at 3000 J / m 2 After irradiating the entire substrate with light, it was baked (post-baked) for 30 minutes in an oven heated to 230°C to form a cured film. A cross-cut test was carried out on this cured film in accordance with JIS K5600-5-6 (ISO2409). 25 2mm squares were cut with a cutter, and the cured film remaining after tape peeling was observed under an optical microscope, and the cured adhesion was evaluated according to the following criteria. AA: 100% film remaining A: Film remaining rate is 95% or more but less than 100% B: Film remaining rate is 90% or more but less than 95% C: Film remaining rate is 85% or more but less than 90% D: Film remaining rate is less than 85% Adhesion after firing can be evaluated as good in the cases of AA, A, or B, and as poor in the cases of C or D.

[0257] [Melt flow evaluation] Measurements were performed according to the above-mentioned [Radiation Sensitivity] evaluation, and a 10 μm-wide line-and-space pattern was formed. The cross sections of this pattern before and after firing were observed with a scanning electron microscope, and the difference in taper angle between the film after development and firing was determined. A value of less than 20° was rated "AA," a value of 20° or more but less than 25° was rated "A," a value of 25% or more but less than 30% was rated "B," a value of 30% or more but less than 35% was rated "C," and a value of 35% or more was rated "D." AA, A, or B indicates good melt flow, while C or D indicates poor melt flow.

[0258] [Table 3]

[0259] As shown in Table 3, the radiation-sensitive compositions of Examples 1 to 30 were all good in terms of practical properties, including radiation sensitivity, chemical resistance, storage stability, development adhesion, curing adhesion, and melt flow, and the various properties were well-balanced. In contrast, the development adhesion of Comparative Examples 1 to 5 was rated "D," indicating poor practical properties. Furthermore, in Comparative Examples 1 to 5, one or more of the radiation sensitivity, chemical resistance, storage stability, curing adhesion, and melt flow were rated "D," indicating that the compositions were inferior to Examples 1 to 30.

Claims

1. (A-1) a siloxane polymer obtained by hydrolysis and condensation of a hydrolyzable silane compound; (B-1) a photoacid generator; (C-1) a solvent; (E) a compound having 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, and a cardo structure (excluding compounds corresponding to a polymer containing a structural unit having a group represented by the following formula (1)); Contains The radiation-sensitive composition, wherein the cardo structure is represented by the following formula (10): 【Chemistry 1】 (In formula (1), R １ , R ２ and R ３ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. １ , R ２ and R ３ At least one of the groups is an alkoxy group having 1 to 6 carbon atoms. "*" indicates a bond.) 【Chemistry 2】 (In formula (10), A １０ A １１ and A １２ is a cyclic group formed together with the carbon atom to which A 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, and when the cyclic group has a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. １１ and A １２ are each independently 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, and when substituted, the substituent is an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. "*" represents a bond.)

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

3. The crosslinkable group includes an oxiranyl group, an oxetanyl group, and a —NH—CH ２ -O-R １０ " (wherein R １０ 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.

4. The radiation-sensitive composition according to claim 1 , wherein the photoacid generator comprises at least one selected from the group consisting of an oxime sulfonate compound and a sulfonimide compound.

5. The radiation-sensitive composition according to claim 1 , further comprising an acid diffusion controller.

6. (A-2) a siloxane polymer obtained by hydrolysis and condensation of a hydrolyzable silane compound; (B-2) a quinone diazide compound, (C-2) a solvent; (E) a compound having 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, and a cardo structure; Contains The radiation-sensitive composition, wherein the cardo structure is represented by the following formula (10): 【Transformation 3】 (In formula (10), A １０ A １１ and A １２ is a cyclic group formed together with the carbon atom to which A 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, and when the cyclic group has a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. １１ and A １２ are each independently 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, and when substituted, the substituent is an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. "*" represents a bond.)

7. 7. The radiation-sensitive composition according to claim 6, wherein the siloxane polymer (A-2) further contains a structural unit having a crosslinkable group, or the radiation-sensitive composition further contains a polymer different from the siloxane polymer (A-2) and containing a structural unit having a crosslinkable group.

8. The crosslinkable group includes an oxiranyl group, an oxetanyl group, and a —NH—CH ２ -O-R １０ " (wherein R １０ 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.

9. 7. The radiation-sensitive composition according to claim 6, wherein the quinone diazide compound is a condensation product of a phenolic compound or an alcoholic compound with 1,2-naphthoquinone diazide sulfonic acid halide.

10. 7. The radiation-sensitive composition according to claim 1, 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.

11. The radiation-sensitive composition according to claim 1 or 6, wherein the functional group (X) is an alkoxysilyl group.

12. 7. The radiation-sensitive composition according to claim 1, wherein the compound (E) has a partial structure represented by the following formula (10-1): 【Chemistry 4】 (In formula (10-1), Ar １１ and Ar １２ are each independently a group in which two hydrogen atoms have been removed from the ring portion of a substituted or unsubstituted aromatic hydrocarbon, and when substituted, the substituent is an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. ６８ and R ６９ are each independently an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. a1 and a2 are each independently an integer of 0 to 3. When a1 is 2 or 3, multiple R ６８ are the same or different. When a2 is 2 or 3, a plurality of R ６９ are the same or different. "*" represents a bond.)

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

14. A step of applying the radiation-sensitive composition according to claim 1 or 6 onto a substrate; removing the solvent from the applied radiation-sensitive composition; irradiating the radiation-sensitive composition from which the solvent has been removed with radiation; developing the radiation-exposed radiation-sensitive composition; thermally curing the developed radiation-sensitive composition; A method for producing a cured film, comprising:

15. A cured film formed using the radiation-sensitive composition according to claim 1 or 6.

16. The cured film according to claim 15, which is an interlayer insulating film.

17. A liquid crystal display device comprising the cured film according to claim 15.

18. An organic electroluminescence display device comprising the cured film according to claim 15.

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