Film-forming composition, cured film and method for producing the same, and display device

Abstract

To provide a film-forming composition that is capable of forming a film with balanced enhancements in transmittance, heat resistance, and resistance to water penetration.SOLUTION: A composition contains a polymer containing: structural units derived from a compound (M1) having a methylene group adjacent to an electron-withdrawing group and structural units derived from at least one compound (M2) selected from the group consisting of compounds having two or more ethylenically unsaturated bonds and compounds having two or more alkyl halide groups.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Electronic devices such as display elements are provided with insulating cured films such as planarizing films and interlayer insulating films. In addition, polyimides and (meth)acrylic polymers have conventionally been used as materials for forming these cured films (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2021-157173 A [Patent Document 2] JP 2017-107024 A Summary of the Invention [Problem to be solved by the invention]

[0004] A cured film formed from polyimide tends to have high heat resistance but low transmittance. A cured film formed from a (meth)acrylic polymer tends to have high transmittance but low heat resistance. Conventionally, therefore, when forming a cured film, an optimal material is selected according to the required characteristics. However, with the recent advancement of electronic devices, new materials capable of forming a film having both heat resistance and transmittance are required.

[0005] Display elements are prone to deterioration due to contact with moisture and oxygen, and therefore the cured film provided on the display element is required to be difficult to transmit moisture (hereinafter also referred to as "low water permeability"). In particular, the organic light emitting layer of an organic EL element is prone to deterioration due to contact with moisture and oxygen, and there is concern that, for example, moisture that has penetrated into the element over a long period of operation may cause partial non-emitting areas (dark spots) to form, or that light emitting characteristics may deteriorate due to contact with moisture or oxygen. Therefore, it is required to improve the low water permeability while maintaining high heat resistance and transmittance.

[0006] The present invention has been made in consideration of the above problems, and has as its main object to provide a film-forming composition capable of forming a film having a well-balanced improved transmittance, heat resistance, and water impermeability. [Means for solving the problem]

[0007] According to the present invention, there are provided the following film-forming composition, cured film and method for producing the same, and liquid crystal device.

[0008] [1] A film-forming composition comprising a polymer including a structural unit derived from a compound (M1) having a methylene group adjacent to an electron-withdrawing group, and a structural unit derived from at least one compound (M2) selected from the group consisting of compounds having two or more ethylenically unsaturated bonds and compounds having two or more halogenated alkyl groups. [2] A method for producing a cured film, comprising the steps of: forming a coating film using the film-forming composition described in [1] above; irradiating the coating film with radiation; and heating the coating film after irradiation with radiation. [3] A method for producing a cured film, comprising: forming a coating film using the film-forming composition described in [1] above; irradiating at least a portion of the coating film with radiation; developing the coating film after irradiation with radiation; and heating the developed coating film. [4] A cured film formed using the film-forming composition described in [1] above. [5] A display element comprising the cured film described in [4] above. Effect of the Invention

[0009] According to the composition of the present invention, a film having a well-balanced improvement in transmittance, heat resistance, and water impermeability can be formed. In addition, according to the film-forming composition of the present invention, a display element having excellent transmittance, heat resistance, and water impermeability can be obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Matters related to the embodiments will be described in detail below. In this specification, a numerical range described using "~" means that the numerical range includes the numerical values ​​before and after "~" 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.

[0011] In this specification, the term "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "linear hydrocarbon group" means a linear hydrocarbon group and a branched hydrocarbon group that do not include a cyclic structure in the main chain and are composed only of a linear structure. However, the linear hydrocarbon group may be saturated or unsaturated. The term "alicyclic hydrocarbon group" means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, the alicyclic hydrocarbon group does not need to be composed only of an alicyclic hydrocarbon structure, and also includes those that have a linear structure as a part of it. The term "aromatic hydrocarbon group" means a hydrocarbon group that includes an aromatic ring structure as a ring structure. However, the aromatic hydrocarbon group does not need to be composed only of an aromatic ring structure, and may include a linear structure or an alicyclic hydrocarbon structure as a part of it. The ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent group consisting of a hydrocarbon structure.

[0012] In this specification, "(meth)acrylic" is intended to include "acrylic" and "methacrylic". "(meth)acryloyl" is intended to include "acryloyl" and "methacryloyl". In this specification, it is also referred to as "epoxy group" to include oxiranyl group and oxetanyl group.

[0013] 《Composition》 The composition of the present disclosure (hereinafter also referred to as "the composition") is preferably used as a film-forming composition for forming an insulating film. The film formed by the composition is suitable as an insulating film provided on an electronic device such as a display element. The composition contains the polymer [A] shown below. The composition may further contain a component different from the polymer [A] (hereinafter also referred to as "other components"). The components contained in the composition and other components that are blended as necessary will be described in detail below. Note that, unless otherwise specified, each component may be used alone or in combination of two or more types.

[0014] <[A] Polymer> The polymer [A] contains a structural unit (hereinafter also referred to as the "first structural unit") derived from a compound (M1) having a methylene group adjacent to an electron-withdrawing group, and a structural unit (hereinafter also referred to as the "second structural unit") derived from at least one compound (M2) selected from the group consisting of compounds having two or more ethylenically unsaturated bonds and compounds having two or more halogenated alkyl groups.

[0015] (Compound (M1)) The compound (M1) is not particularly limited as long as it has a methylene group adjacent to the electron-withdrawing group. The electron-withdrawing group of the compound (M1) is, for example, -COH, -COR 10 , -C≡N, -SO3H, * 1 -CO-NHR 10 , * 1 -CO-NR 10 R 11 , * 1 -COOR 10 , -NO2, * 1 -CO-NH-, * 1 -CO-NR 10 -, * 1 -CO-O-, -CO-, -SO2-, etc. (R 10 and R 11 are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. 1" represents a bond to a methylene group. The same applies below.) are examples of the electron-withdrawing groups possessed by compound (M1), which can increase the reactivity with compound (M2). Among these, -C≡N, -SO3H, * 1 -CO-NHR 10 , * 1 -CO-NR 10 R 11 , * 1 -COOR 10 , * 1 -CO-NH-, * 1 -CO-NR 10 -, * 1 -CO-O- or -SO2- is preferred.

[0016] The number of methylene groups (hereinafter also referred to as "methylene groups F1") adjacent to the electron-withdrawing group in the compound (M1) may be 1 or more, and is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. Note that the methylene group F1 may be adjacent to the electron-withdrawing group on only one side of -CH2- or on both sides.

[0017] The molecular weight of the compound (M1) is, for example, 1,000 or less, preferably 800 or less, and more preferably 600 or less. In addition, the molecular weight of the compound (M1) is preferably 50 or more.

[0018] The compound (M1) may be a compound consisting of only a chain structure, or may be a compound having at least a part of a cyclic structure. A preferred example of the compound (M1) is a compound represented by the following formula (1). [ka] (In formula (1), X 1 is an electron-withdrawing group with a valence of (n1+1). X 2 is a divalent electron-withdrawing group. Y 1 and Y 2 are each independently a monovalent organic group, or Y 1 and Y 2 are combined together, Y 1 X to which2 and Y 2 X to which 1 and n1 and n2 each independently represent 0 or 1.

[0019] In the above formula (1), when n1=0, X 1 The monovalent electron-withdrawing group represented by the formula: -COH, -COR 10 , -C≡N, -SO3H, * 1 -CO-NHR 10 , * 1 -CO-NR 10 R 11 , * 1 -COOR 10 , -NO2, etc. Among these, -C≡N, -SO3H, * 1 -CO-NHR 10 , * 1 -CO-NR 10 R 11 OR* 1 -COOR 10 is preferred, and a cyano group (-C≡N) is more preferred. X when n1=1 1 or a divalent electron-withdrawing group represented by X 2 As the divalent electron-withdrawing group represented by the formula: 1 -CO-NH-, * 1 -CO-NR 10 -, * 1 -CO-O-, -CO-, -SO2-, etc. 1 -CO-NH-, * 1 -CO-NR 10 -, * 1 -CO-O- or -SO2- is preferred.

[0020] If n2=0, Y 1 Examples of the monovalent organic group represented by the formula (I) include a monovalent alicyclic group having 2 to 20 carbon atoms and a monovalent aromatic ring group having 4 to 20 carbon atoms. Y if n2=1 1 or Y 2Examples of the monovalent organic group represented by the formula (1) include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a monovalent group having 2 to 20 carbon atoms and containing a heterocyclic structure, as well as monovalent groups in which at least a portion of the hydrogen atoms of these groups have been replaced with a substituent.

[0021] The monovalent alicyclic group having 2 to 20 carbon atoms is a group in which one hydrogen atom has been removed from a ring portion of a substituted or unsubstituted alicyclic ring. The alicyclic ring may be a hydrocarbon ring or a heterocyclic ring. The monovalent aromatic ring group having 4 to 20 carbon atoms is a group in which one hydrogen atom has been removed from a ring portion of a substituted or unsubstituted aromatic ring. The aromatic ring may be a hydrocarbon ring or a heterocyclic ring.

[0022] Specific examples of such monovalent alicyclic groups having 2 to 20 carbon atoms include monocyclic saturated aliphatic hydrocarbon rings, monocyclic unsaturated aliphatic hydrocarbon rings, polycyclic saturated or unsaturated aliphatic hydrocarbon rings, and aliphatic heterocycles having 3 to 20 carbon atoms, with one hydrogen atom removed. Specific examples of the aliphatic hydrocarbon ring include monocyclic saturated aliphatic hydrocarbon rings such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane; monocyclic unsaturated aliphatic hydrocarbon rings such as cyclopentene, cyclohexene, cycloheptene, cyclooctene, and cyclodecene; and polycyclic aliphatic hydrocarbon rings such as bicyclo[2.2.1]heptane (norbornane), bicyclo[2.2.2]octane, tricyclo[3.3.1.1]heptane, and the like. 3,7 ]Decane (adamantane), tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecane, bicyclo[2.2.1]heptene (norbornene), etc. Specific examples of the aliphatic heterocycle include nitrogen-containing aliphatic heterocycles such as piperidine and piperazine, oxygen-containing aliphatic heterocycles such as oxirane, oxetane, tetrahydrofuran, 1,3-dioxolane, and tetrahydropyran, and sulfur-containing aliphatic heterocycles such as thiirane, thiane, and dithiane, from which one hydrogen atom has been removed.

[0023] Examples of the monovalent aromatic ring group having 6 to 20 carbon atoms include groups in which one hydrogen atom has been removed from an aromatic hydrocarbon ring such as benzene, biphenyl, naphthalene, anthracene, indene, or fluorene; a nitrogen-containing aromatic heterocycle such as imidazole, pyridine, pyridazine, pyrimidine, pyrazine, or benzimidazole; an oxygen-containing aromatic heterocycle such as furan; or a sulfur-containing aromatic heterocycle such as thiophene.

[0024] When the monovalent alicyclic group having 2 to 20 carbon atoms or the monovalent alicyclic group having 4 to 20 carbon atoms has a substituent, examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyloxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an alkenyloxyalkyl group having 1 to 5 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, a carboxy group, a sulfo group, a protected acidic group, a nitro group, etc.

[0025] If n2=0, Y 1 From the viewpoint of increasing the reactivity with the compound (M2) and of obtaining a cured film having better heat resistance, the monovalent organic group represented by the following formula is preferably a monovalent aromatic ring group having 6 to 20 carbon atoms, and more preferably a group in which one hydrogen atom has been removed from the ring portion of a substituted or unsubstituted benzene ring, naphthalene ring or pyridine ring.

[0026] Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms and linear or branched unsaturated hydrocarbon groups having 1 to 20 carbon atoms. Among these, linear or branched saturated hydrocarbon groups having 1 to 12 carbon atoms or linear or branched unsaturated hydrocarbon groups having 2 to 12 carbon atoms are preferred, and linear or branched saturated hydrocarbon groups having 1 to 6 carbon atoms or linear or branched unsaturated hydrocarbon groups having 2 to 6 carbon atoms are more preferred.

[0027] Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include groups in which one hydrogen atom has been removed from a monocyclic saturated alicyclic hydrocarbon, a monocyclic unsaturated alicyclic hydrocarbon, or a polycyclic saturated or unsaturated alicyclic hydrocarbon having 3 to 20 carbon atoms. Specific examples of the aliphatic hydrocarbon ring contained in these alicyclic hydrocarbons include the same aliphatic hydrocarbon rings as those exemplified in the monovalent alicyclic group having 3 to 20 carbon atoms.

[0028] Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include groups in which one hydrogen atom has been removed from benzene, naphthalene, anthracene, indene, fluorene, methylbenzene, biphenyl, diphenylmethane, 1,3-diphenylpropane, 2,2-diphenylpropane, etc.

[0029] Examples of the monovalent group having 2 to 20 carbon atoms and containing a heterocyclic structure include groups having an aliphatic heterocycle or aromatic heterocycle having 2 to 20 carbon atoms. Specific examples of the aliphatic heterocycle and aromatic heterocycle include the same heterocycles as those exemplified in the monovalent heterocyclic group.

[0030] Y for n2=1 1 Or Y 2 When has a substituent, examples of the substituent include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, a carboxy group, a sulfo group, a protected acidic group, and a nitro group.

[0031] Y 1 and Y 2 are combined together, Y 1 X to which 2 and Y 2 X to which 1 When Y represents a ring structure formed together with the above, the ring structure may be an alicyclic ring or an aromatic ring. An alicyclic ring is preferable. 1 and Y 2 The ring structure formed by combining together may have a substituent such as an alkyl group.

[0032] The compound (M1) may have an acid dissociable group. The acid dissociable group is a group that substitutes a hydrogen atom of an acidic group such as a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a silanol group, or a sulfo group, and is a group that dissociates under the action of an acid. The composition may be made into a chemically amplified composition by synthesizing the polymer [A] using a compound having an acid dissociable group (hereinafter also referred to as "compound (N1)") as the compound (M1), and blending a photoacid generator as a photosensitive compound together with the polymer [A] obtained in the composition. That is, when a part of the composition is irradiated with radiation, the acid dissociable group is eliminated by the acid generated by the irradiation of radiation in the exposed part, and an acidic group is generated, while the hydrogen atom of the acidic group remains substituted by the acid dissociable group in the unexposed part. This allows the exposed part and the unexposed part to have different solubility in a developer, and the composition after exposure can be subsequently developed to obtain a film having a pattern formed thereon.

[0033] Preferred specific examples of compound (N1) include a compound which generates a carboxy group by the action of an acid through elimination of an acid-dissociable group (hereinafter also referred to as "compound (N1-1)"); and a compound which generates a phenolic hydroxyl group by the action of an acid through elimination of an acid-dissociable group (hereinafter also referred to as "compound (N1-2)").

[0034] Examples of the acid-dissociable group contained in the compound (N1-1) include a tertiary carbon-containing hydrocarbon group, an acetal functional group, a tertiary alkyl carbonate group, and an alkyl group-containing silyl group. Among these, a tertiary carbon-containing hydrocarbon group or an acetal functional group is preferred because it is easily dissociated by an acid.

[0035] When the acid-dissociable group is a tertiary carbon-containing hydrocarbon group, the compound (N1-1) preferably has a group represented by the following formula (X-1) as a protected carboxy group. [ka] (In formula (X-1), R 34 , R 35 and R 36is either (1) or (2) below. (1)R 34 , R 35 and R 36 are each independently an alkyl group having 1 to 12 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. (2) R 34 and R 35 are combined with each other. 34 and R 35 R represents an alicyclic hydrocarbon structure having 4 to 20 carbon atoms, which is formed together with the carbon atom to which it is bonded. 36 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms. "*" represents a bond.)

[0036] When the acid-dissociable group is an acetal functional group, the compound (N1-1) 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-2). [ka] (In formula (X-2), 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 combined 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.)

[0037] R 31 , R 32 , R 33 , R34 , R 35 and R 36 The alkyl group having 1 to 12 carbon atoms represented by the formula (1) 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 thereof 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.

[0038] Specific examples of the group represented by the above formula (X-1) include a tert-butoxycarbonyl group, a 1,1-dimethylpropyloxycarbonyl group, a 1-methyl-1-cyclopentyloxycarbonyl group, a 1-ethyl-1-cyclopentyloxycarbonyl group, a 1-methyl-1-cyclohexyloxycarbonyl group, and a 1-ethyl-1-cyclohexyloxycarbonyl group.

[0039] Specific examples of the group represented by the above formula (X-2) 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.

[0040] From the viewpoints of the sensitivity, pattern shape, storage stability, etc. of the present composition, the acid dissociable group possessed by the compound (N1-2) is preferably an acetal-based functional group, a tertiary alkyl group, or an alkyl group-containing silyl group. Examples of the acetal-based functional group include the same as the acid dissociable group usable in the compound (N1-1). Among them, "-OC(R 31 )(R 32 )(OR 33 )" (However, R 31 , R 32 and R 33 has the same meaning as formula (X-2).

[0041] The compound (N1-2) has "-C(R 31 )(R 32 )(OR 33 )" can include a 1-alkoxyalkyl group and a 1-arylalkoxyalkyl group. Specific examples of the group represented by "(1-aryl)-1-(2-phenyl)oxyethyl group 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. Specific examples of the tertiary alkyl group include a tert-butyl group and a 1,1-dimethylpropyl group. Specific examples of the alkyl group-containing silyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl group.

[0042] In addition, when the compound (M1) has an acid dissociable group, Y 1 and Y 2 and Y 1 and Y 2 Both of the above may be included.

[0043] From the viewpoint of enhancing the reactivity with the compound (M2) and obtaining a cured film having excellent heat resistance, the compound (M1) is preferably a compound represented by the formula (1) in which n1 is 0 and X 1 is a cyano group, n1 in the above formula (1) is 0 and X 1 is a cyano group, and X 2 but* 1 -CO-NH-, * 1 -CO-NR 10 -or* 1 A compound in which n2 in the above formula (1) is 0 and X 1 but* 1 -CO-NH-, * 1 -CO-NR 10 -, * 1At least one selected from the group consisting of compounds represented by -CO-O- or -SO2- can be preferably used.

[0044] In terms of increasing the reactivity with compound (M2), the first acid dissociation constant (pKa1) of compound (M1) is preferably 21.0 or less, more preferably 20.5 or less, even more preferably 20.0 or less, and even more preferably 19.5 or less. In this specification, the first acid dissociation constant of a compound represents an acid dissociation constant in water, and specifically, is a value obtained by Gaussian16 based on the density functional theory (B3LYP / 6-311++G(d,p)).

[0045] Specific examples of the compound (M1) include compounds represented by the following formulas (1-1) to (1-21). [ka]

[0046] (Compound (M2)) Compounds containing two or more ethylenically unsaturated bonds Among the compounds (M2), the structure of the compound having two or more ethylenically unsaturated bonds (hereinafter also referred to as "compound (M2-1)") is not particularly limited. The compound (M2-1) may be a compound consisting of only a chain structure, or may be a compound having at least a part of a cyclic structure. The number of ethylenically unsaturated bonds in the compound (M2-1) is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2. The molecular weight of the compound (M2-1) is, for example, 1,000 or less, preferably 800 or less, and more preferably 600 or less. The molecular weight of the compound (M2-1) is preferably 50 or more.

[0047] From the viewpoint of increasing the reactivity with the compound (M1), the compound (M2-1) preferably has an electron-withdrawing group adjacent to the ethylenically unsaturated bond. The electron-withdrawing group adjacent to the ethylenically unsaturated bond is preferably a group represented by the formula: 2 -CO-O-, * 2-CO-NH-, * 2 -CO-NR 12 - or -SO2- (where R 12 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or is a monovalent hydrocarbon group having 1 to 10 carbon atoms. 12 ) to form R 12 represents a part of a ring structure formed together with the nitrogen atom to which it is bonded. 2 " represents a bond to an ethylenically unsaturated bond. The same applies below.) is preferred.

[0048] A preferred example of the compound (M2-1) is a compound represented by the following formula (2A). [ka] (In formula (2A), X 3 and X 4 are each independently a divalent electron-withdrawing group. 3 is a single bond or a divalent organic group. n3 and n4 are each independently 0 or 1.

[0049] In the above formula (2A), X 3 Or X 4 The divalent electron-withdrawing group represented by the formula: 2 -CO-O-, * 2 -CO-NH-, * 2 -CO-NR 12 - or -SO2- is preferred.

[0050] Y 3 is a divalent organic group, examples of the divalent organic group include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a divalent group having 2 to 20 carbon atoms containing a heterocyclic structure, and a divalent group having 2 to 20 carbon atoms containing -O-, -S- or -SO2- between the carbon-carbon bonds of the hydrocarbon group, as well as divalent groups in which at least some of the hydrogen atoms of these groups have been replaced with substituents. Specific examples of the chain hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group and group containing a heterocyclic structure that constitute these divalent organic groups include Y in the above formula (1).1 Or Y 2 Examples of the monovalent organic group represented by the following formula include groups in which one hydrogen atom has been removed from each of the groups exemplified above.

[0051] At least one of n3 and n4 is preferably 1. 3 When n is a divalent organic group, it is more preferable that n3 and n4 are both 1.

[0052] Specific examples of the compound (M2-1) include compounds represented by the following formulas (2A-1) to (2A-18). [ka]

[0053] Compounds containing two or more halogenated alkyl groups Among the compounds (M2), the compound having two or more halogenated alkyl groups (hereinafter also referred to as "compound (M2-2)") is not particularly limited as long as it has two or more halogenated alkyl groups in one molecule. The compound (M2-2) may be a compound consisting of only a chain structure, or may be a compound having at least a part of a cyclic structure.

[0054] The halogenated alkyl group contained in the compound (M2-2) is represented by "*-R 13 -Z 3 " (However, R 13 is an alkanediyl group, Z 3 is a halogen atom. "*" represents a bond. ) is preferred. 13 R is preferably linear. 13 has a carbon number of, for example, 1 to 5, and preferably 1 to 3. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom or a bromine atom is preferred from the viewpoint of reactivity with the compound (M1).

[0055] The compound (M2-2) preferably has 2 to 6 halogenated alkyl groups, more preferably 2 to 4, and further preferably 2. The molecular weight of the compound (M2-2) is, for example, 1,000 or less, preferably 800 or less, and more preferably 600 or less. In addition, the molecular weight of the compound (M2-2) is preferably 50 or more.

[0056] A preferred example of the compound (M2-2) is a compound represented by the following formula (2B). [ka] (In formula (2B), Z 1 and Z 2 are each independently a halogen atom. 4 is a single bond or a divalent organic group.

[0057] In the above formula (2B), Y 4 When Y is a divalent organic group, examples of the divalent organic group include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a divalent group having 2 to 20 carbon atoms containing a heterocyclic structure, a divalent group having 2 to 20 carbon atoms containing -O-, -S- or -SO2- between the carbon-carbon bonds of the hydrocarbon group, and divalent groups in which at least some of the hydrogen atoms of these groups have been replaced with substituents. 4 Specific examples of the chain hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and group containing a heterocyclic structure that constitute the divalent organic group represented by the formula (1) include Y 1 Or Y 2 Examples of the monovalent organic group represented by the formula (I) include groups in which one hydrogen atom has been removed from each of the groups exemplified above. 4 The divalent organic group represented by the formula (I) may be a divalent group having a siloxane structure.

[0058] Y 4From the viewpoint of enhancing the reactivity with compound (M1), among the above, a substituted or unsubstituted monovalent aromatic ring group having 4 to 20 carbon atoms, or a divalent group having 2 to 10 carbon atoms containing -O- between the carbon-carbon bonds of a chain hydrocarbon group is preferred. Specific examples include groups in which two hydrogen atoms have been removed from the ring portion of a substituted or unsubstituted benzene ring, biphenyl ring, naphthalene ring, or pyridine ring, and a divalent group having 2 to 15 carbon atoms containing -O- between the carbon-carbon bonds of an alkanediyl group.

[0059] The compound (M2-2) may have an acid dissociable group. The composition may be a chemically amplified composition by blending a photoacid generator as a photosensitive compound together with the polymer [A] obtained by polymerization using a compound having an acid dissociable group as the compound (M2-2). Specific examples of the acid dissociable group include the same groups as those exemplified as the acid dissociable group that the compound (M1) may have.

[0060] Specific examples of the compound (M2-2) include compounds represented by the following formulas (2B-1) to (2B-12). [ka]

[0061] (Synthesis of polymer [A]) [A] Polymer can be produced, for example, by polymerizing the above-mentioned compound (M1) and compound (M2) as monomers. The polymerization method can be appropriately selected depending on the monomer used. Specific examples of the polymerization method include the following [Method 1] and [Method 2]. [Method 1] A method for obtaining polymer [A] by polyaddition of compound (M1) and compound (M2-1). [Method 2] A method of obtaining polymer [A] by polycondensation of compound (M1) and compound (M2-2).

[0062] In [Method 1] and [Method 2], the ratio of compound (M1) to compound (M2) used in the polymerization is preferably such that the methylene group F1 of compound (M1) is 0.2 to 2 equivalents per equivalent of the ethylenically unsaturated bond or halogenated alkyl group of compound (M2).

[0063] The polymerization by [Method 1] and [Method 2] can be carried out in a suitable solvent. As the polymerization solvent, an organic solvent capable of dissolving or dispersing the monomer and not reacting with the monomer can be preferably used. Specific 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 70% by mass with respect to the total amount of the reaction solution.

[0064] The polymerization by [Method 1] and [Method 2] is preferably carried out in the presence of a catalyst. Examples of the catalyst include acids, alkali metal compounds, organic bases, and the like. Examples of the acids include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, and the like. Examples of the alkali metal compounds include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, and the like. Examples of the organic bases include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and diazabicycloundecene; and quaternary organic amines such as tetramethylammonium hydroxide.

[0065] As the catalyst used in the polymerization, among these, an alkali metal compound or an organic base is particularly preferred. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, and can be appropriately set. For example, the amount of the alkali metal compound used is preferably 0.1 to 5 times by mole, more preferably 0.5 to 3 times by mole, based on the total amount of the monomers. The amount of the organic base used is preferably 0.01 to 3 times by mole, more preferably 0.05 to 1.5 times by mole, based on the total amount of the monomers.

[0066] The polymerization by [Method 1] and [Method 2] is preferably carried out in the presence of a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, and nonionic surfactants. Of these, cationic surfactants can be preferably used. Specific examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts, and quaternary ammonium salts can be preferably used. The amount of the surfactant used is, for example, 0.001 to 5 millimoles per 100 moles of the total amount of the monomers used in the reaction.

[0067] In the polymerization, the reaction temperature is preferably -20°C to 180°C, more preferably 0°C to 150°C. The reaction time can be appropriately set depending on the type of monomer and the reaction temperature. The reaction time is preferably 0.5 to 24 hours. The polymer obtained by the polymerization reaction may be used for the preparation of the present composition as it is dissolved in the reaction solution, or may be used for the preparation of the present composition after being isolated from the reaction solution. The isolation of the polymer can be performed by a known isolation method such as a method of pouring the reaction solution into a large amount of poor solvent and drying the precipitate obtained under reduced pressure; a method of distilling the reaction solution under reduced pressure with an evaporator; etc.

[0068] Preferred embodiments of the polymer [A] obtained by the above polymerization reaction include the following polymer (A1) and polymer (A2). Polymer (A1): A polymer containing a structural unit represented by the following formula (3A): Polymer (A2): A polymer containing a structural unit represented by the following formula (3B): [ka] (In formula (3A), X 1 is an electron-withdrawing group with a valence of (n1+1). X 2 is a divalent electron-withdrawing group. Y 1 and Y 2 are each independently a monovalent organic group, or Y 1 and Y 2 are combined together, Y 1 X to which 2 and Y 2 X to which 1 It represents a ring structure formed together with X 3 and X 4 are each independently a divalent electron-withdrawing group. 3 is a single bond or a divalent organic group. n1 and n2 are each independently 0 or 1. n3 and n4 are each independently 0 or 1. [ka] (In formula (3B), X 1 is an electron-withdrawing group with a valence of (n1+1). X 2 is a divalent electron-withdrawing group. Y 1 and Y 2 are each independently a monovalent organic group, or Y 1 and Y 2 are combined together, Y 1 X to which 2 and Y 2 X to which 1 It represents a ring structure formed together with Y 4 is a divalent organic group. n1 and n2 are each independently 0 or 1.

[0069] The polymer (A1) can be obtained by polyaddition (more specifically, polymerization utilizing the Michael addition reaction) using the compound represented by the above formula (1) and the compound represented by the above formula (2A). The polymer (A2) can be obtained by polycondensation using the compound represented by the above formula (1) and the compound represented by the above formula (2B). The symbols in the above formulas (3A) and (3B) are explained by the same explanations as those in the above formulas (1), (2A), and (2B).

[0070] The polymerization reaction between compound (M1) and compound (M2) is considered to proceed starting from hydrogen abstraction of the methylene group F1 of compound (M1). That is, the polymerization reaction of the present disclosure is a polymerization using active hydrogen, and a polymer is formed via the methylene group derived from compound (M1). For example, when a compound represented by the following formula (m1-1) is used as compound (M1) and a compound represented by the following formula (m2-1) is used as compound (M2), the polymerization reaction proceeds according to the following scheme 1, and a polyaddition type polymer is obtained. [ka]

[0071] Furthermore, when a compound represented by the following formula (m1-2) is used as compound (M1) and a compound represented by the following formula (m2-2) is used as compound (M2), a polymerization reaction proceeds according to the following scheme 2 to obtain a polycondensation type polymer. [ka]

[0072] From the viewpoint of imparting good heat resistance to a cured film, the molar ratio of the first structural units to the second structural units in the polymer [A] is preferably first structural units:second structural units=40:60 to 60:40, and more preferably 45:55 to 55:45.

[0073] From the viewpoints of improving the heat resistance of the cured film and of obtaining a composition capable of obtaining a cured film with high transmittance and low water permeability, the total amount of the first structural unit and the second structural unit in the polymer [A] is preferably 75 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more, based on all the structural units constituting the polymer [A].

[0074] The weight average molecular weight (Mw) of the polymer [A] in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 3,000 or more. Mw of 3,000 or more is preferable in that a cured film having sufficiently high heat resistance and chemical resistance and good developability can be obtained. The Mw of the polymer [A] is more preferably 5,000 or more, and even more preferably 6,000 or more. In addition, from the viewpoint of improving film formability, the Mw of the polymer [A] is preferably 150,000 or less, and more preferably 120,000 or less.

[0075] The molecular weight distribution (Mw / Mn) of the polymer (A), which is expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably 8.0 or less, more preferably 7.0 or less, and even more preferably 6.0 or less.

[0076] In the present composition, the content of the polymer [A] is preferably 50 mass % or more, more preferably 60 mass % or more, and even more preferably 70 mass % or more, based on the total amount of solids contained in the composition (i.e., components other than the solvent in the composition), from the viewpoint of obtaining a membrane that exhibits good heat resistance, high transmittance and low water permeability.

[0077] <Other ingredients> The composition may further contain a component different from the polymer [A] (hereinafter, also referred to as "other component"). Examples of the other component include a compound [B] having two or more crosslinkable functional groups (excluding the polymer [A]. Hereinafter, also referred to simply as "compound [B]"), a photosensitive compound [C], an adhesion assistant [D], a surfactant [E], and a solvent [F].

[0078] ([B] compound) The compound [B] is a component that forms a crosslinked structure between or within the molecules of the polymer [A] by light or heat, or forms bonds between the compounds [B] themselves. By forming the present composition into a composition containing the polymer [A] and the compound [B], the heat resistance of the cured film obtained by using the present composition can be further improved.

[0079] Examples of the crosslinkable functional group possessed by the compound [B] include a cyclic ether group, a cyclic thioether group, a carboxy group, a cyclic carbonate group, an alcoholic hydroxyl group, an amino group, a protected amino group, a protected isocyanate group, a polymerizable unsaturated bond group (e.g., a (meth)acryloyl group, etc.), a β-hydroxyalkylamide group, an oxazoline group, and an alkoxymethylphenyl group.

[0080] From the viewpoint of reacting with the polymer [A] to form a crosslinked structure between or within the molecules of the polymer [A] and providing a cured film with excellent heat resistance, the crosslinkable functional group of the compound [B] is preferably at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a thiirane group, a β-hydroxyalkylamide group, a hydroxymethylphenyl group, an alkoxymethylphenyl group, a cyclocarbonate group, and a protected isocyanate group, more preferably at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a β-hydroxyalkylamide group, a hydroxymethylphenyl group, and an alkoxymethylphenyl group, and even more preferably at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a β-hydroxyalkylamide group, a hydroxymethylphenyl group, and an alkoxymethylphenyl group.

[0081] The number of crosslinkable functional groups that the compound [B] has in one molecule is preferably 2 to 10, and more preferably 3 to 8, from the viewpoints of sufficiently obtaining the effect of improving the heat resistance of the cured film and suppressing film shrinkage. The molecular weight of the compound [B] is, for example, 1,000 or less, preferably 800 or less, and more preferably 600 or less.

[0082] Specific examples of the compound [B] include compounds having an epoxy group, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, triglycidyl isocyanurate, glycerol polyglycidyl ether, pentaerythritol tetraglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, N,N',N',N''-tetraglycidyl glycoluril, 1,6-hexanediol diglycidyl ether, trimethyl methyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, epoxidation product of 2,2'-diallyl bisphenol A diallyl ether with hydrogen peroxide, etc.; As a compound having a cyclocarbonate group, a compound in which the epoxy group of the above-exemplified compound having an epoxy group is protected (for example, N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)ethyl]-4,4'-diaminodiphenylmethane); As the compound having a thiirane group, the above-exemplified compounds in which the epoxy group is replaced with a thiirane group are included; Examples of the compound having a β-hydroxyalkylamide group include compounds represented by the following formulas (c-1) to (c-7): Examples of compounds having one or both of a hydroxymethylphenyl group and an alkoxymethylphenyl group include 2,2-bis(4-hydroxymethylphenyl)propane, 2,2-bis(2,3,4-trihydroxymethylphenyl)propane, and compounds represented by each of the following formulas (c-8) to (c-16); Examples of compounds having a protected isocyanate group include compounds in which the isocyanate group in tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, or diphenylmethane diisocyanate is protected. [ka]

[0083] Examples of the compound having a polymerizable unsaturated bond group include polyfunctional (meth)acrylic acid esters of alkylene glycols or polyalkylene glycols, such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate; polyfunctional (meth)acrylic acid esters of monocycloalkane dimethanol or polycycloalkane dimethanol, such as cyclohexanedimethanol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; trimethylolpropane poly(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, and the like. Polyfunctional (meth)acrylic acid esters of trihydric or higher polyhydric alcohols such as triol poly(meth)acrylate; AO-modified or succinic acid-modified polyfunctional (meth)acrylic acid esters such as pentaerythritol AO-modified polyfunctional (meth)acrylate, trimethylolpropane AO-modified polyfunctional (meth)acrylate, dipentaerythritol AO-modified polyfunctional (meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate; polyfunctional urethane (meth)acrylates such as ethoxylated isocyanuric acid tri(meth)acrylate and ε-caprolactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate; and tri(2-(meth)acryloyloxyethyl)phosphate. The term "AO-modified" refers to alkylene oxide-modified such as ethylene oxide (EO)-modified and propylene oxide (PO)-modified.

[0084] When the composition contains the compound [B], the content thereof 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, based on 100 parts by mass of the polymer [A] contained in the composition. The content of the compound [B] is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, based on 100 parts by mass of the polymer [A] contained in the composition.

[0085] ([C]photosensitive compound) The photosensitive compound may be any component that changes the solubility of the composition by irradiation with radiation. Examples of the photosensitive compound include quinone diazide compounds, photoacid generators, and photopolymerization initiators. Among these, quinone diazide compounds or photoacid generators can be preferably used. Here, in this specification, the "quinone diazide compound" is a substance that changes to indene carboxylic acid by irradiation with radiation. The "photoacid generator" is a substance that generates acid by irradiation with radiation and can eliminate an acid dissociable group possessed by a component in the composition. In addition, when a positive composition is obtained, a quinone diazide compound or a photoacid generator is preferably used as the photosensitive compound. When a negative composition is obtained, a photopolymerization initiator is preferably used as the photosensitive compound.

[0086] Quinone diazide compounds The quinone diazide compound may be a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother nucleus") with an orthonaphthoquinone diazide compound. Of these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as a mother nucleus with an orthonaphthoquinone diazide compound. Specific examples of the mother nucleus include the compounds described in paragraphs 0065 to 0070 of JP-A-2014-186300. The orthonaphthoquinone diazide compound is preferably 1,2-naphthoquinone diazide sulfonic acid halide.

[0087] As the quinone diazide compound, a condensation product of a phenolic compound or alcoholic compound as the mother nucleus and 1,2-naphthoquinone diazide sulfonic acid halide can be preferably used, and a condensation product of a phenolic compound and 1,2-naphthoquinone diazide sulfonic acid halide can be more preferably used.

[0088] Specific examples of quinone diazide compounds include 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4 and ester compounds of a phenolic hydroxyl group-containing compound selected from 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

[0089] In the condensation reaction for obtaining the above condensation product, the ratio of the mother nucleus to the 1,2-naphthoquinone diazide sulfonic acid halide is preferably such that the amount of the 1,2-naphthoquinone diazide sulfonic acid halide used is an amount equivalent to 30 to 85 mol %, more preferably an amount equivalent to 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.

[0090] When a quinone diazide compound is used as the photosensitive compound, the content of the quinone diazide compound in the composition is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the polymer [A] contained in the 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, relative to 100 parts by mass of the polymer [A] contained in the composition.

[0091] When the content of the quinone diazide compound is 2 parts by mass or more, the acid is sufficiently generated by irradiation with actinic rays, and the difference in solubility in the developer between the exposed and unexposed parts can be sufficiently increased. This allows good patterning to be performed. In addition, the amount of acid involved in the reaction with the polymer component can be increased, and the heat resistance of the cured film obtained using the composition can be sufficiently ensured. 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 preferable in that the decrease in developability and film transmittance caused by the remaining quinone diazide compound can be suppressed.

[0092] Photoacid generator As the photoacid generator, a compound that responds to actinic rays having a wavelength of 300 nm or more (preferably 300 to 450 nm) and generates an acid can be preferably used. When a photoacid generator that does not directly respond to actinic rays having 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 having a wavelength of 300 nm or more and generates an acid.

[0093] 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 further preferably 2 or less.

[0094] Specific examples of photoacid generators include oxime sulfonate compounds, onium salts (sulfonium salts, iodonium salts, quaternary ammonium salts, etc.), sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylate compounds.

[0095] Specific examples of the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonate compound, and carboxylate compound include compounds described in paragraphs 0034 to 0038 of JP-A-2012-252343, compounds described in paragraphs 0078 to 0106 of JP-A-2014-157252, and compounds described in WO 2016 / 124493. As the photoacid generator, at least one selected from the group consisting of oxime sulfonate compounds, sulfonimide compounds, onium salts, halogen-containing compounds, sulfone compounds, and sulfonate compounds can be preferably used.

[0096] 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- Examples of the oxime sulfonate compound include 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, compounds described in International Publication No. 2016 / 124493, and compounds described in Japanese Patent No. 5914663. Examples of commercially available oxime sulfonate compounds include Irgacure PAG121 manufactured by BASF.

[0097] Examples of sulfonimide compounds 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, 4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide (naphthalimide trifluoromethanesulfonate).

[0098] Specific examples of onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, and triphenylsulfonium trifluoromethanesulfonate. Examples of such sulfonylsulfonium trifluoromethanesulfonate include 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 1-(4-benzyloxy)tetrahydrothiophenium trifluoromethanesulfonate, 1-(naphthylacetomethyl)tetrahydrothiophenium trifluoromethanesulfonate, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate.

[0099] Specific examples of halogen-containing compounds include phenyl bis(trichloromethyl)-s-triazine, 4-methoxyphenyl bis(trichloromethyl)-s-triazine, and 1-naphthyl bis(trichloromethyl)-s-triazine. Specific examples of sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis(phenylsulfonyl)methane. Examples of sulfonic acid ester compounds include benzoin tosylate, pyrogallol tris(trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonyl bicyclo[2,2,1]hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

[0100] When a photoacid generator is used as the photosensitive compound, the content of the photoacid generator in the present composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the polymer [A] contained in the present composition. The content of the photoacid generator is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the polymer [A] contained in the present composition. When the content of the photoacid generator is 0.5 parts by mass or more, acid is sufficiently generated in the exposed part by irradiation with radiation, and the difference in solubility between the exposed part and the unexposed part in the alkaline solution can be sufficiently increased. This allows good patterning to be performed. In addition, the amount of acid involved in the reaction with the polymer [A] can be increased, and the heat resistance of the obtained cured film can be sufficiently ensured. On the other hand, by setting the content of the photoacid generator to 25 parts by mass or less, the amount of unreacted photoacid generator after exposure can be sufficiently reduced, and the decrease in developability due to the remaining photoacid generator can be suppressed.

[0101] Photopolymerization initiator As the photopolymerization initiator, a photoradical polymerization initiator that generates radicals by light irradiation, heating, or the like is preferably used. Specific examples of the photoradical polymerization initiator include oxime ester compounds, alkylphenone compounds, acylphosphine oxide compounds, biimidazole compounds, triazine compounds, benzoin compounds, and benzophenone compounds. Of these, oxime ester compounds are preferred because they can form fine patterns by exposure. Commercially available oxime ester compounds include IRGACURE OXE01, IRGACURE OXE02, and IRGACURE OXE01 (all manufactured by BASF).

[0102] When a photopolymerization initiator is used as the photosensitive compound, the content of the photopolymerization initiator in the composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the polymer [A] contained in the composition. The content of the photopolymerization initiator is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the polymer [A] contained in the composition.

[0103] ([D] Adhesion aid) The adhesion aid is a component that improves the adhesion between the cured film formed by using the composition and the substrate. As the adhesion aid, a functional silane coupling agent having a reactive functional group can be preferably used. Examples of the reactive functional group of the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0104] Specific examples of functional coupling agents include trimethoxysilylbenzoic acid, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0105] When the composition contains an adhesion aid, the content 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, relative to 100 parts by mass of the polymer [A] contained in the composition.

[0106] ([E] Surfactant) The surfactant can be used to improve the coating properties of the composition (wetting and spreading properties and reducing coating unevenness). Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. The surfactant can be selected from known ones such as these commercially available products.

[0107] When a surfactant is blended in the present composition, the content of the surfactant is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and even more preferably 0.05 to 1.0 part by mass, relative to 100 parts by mass of the polymer [A] contained in the present composition.

[0108] ([F] Solvent) The present composition is preferably a liquid composition in which the polymer [A] and components to be blended as necessary are dissolved or dispersed in a solvent. The solvent to be used is preferably an organic solvent that dissolves each component to be blended in the present composition and does not react with each component.

[0109] 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, ethylene diglycol monomethyl ether, ethylene diglycol 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.

[0110] Of these, the solvent preferably contains at least one selected from the group consisting of ethers and esters, and more preferably contains at least one selected from the group consisting of ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates.

[0111] The content of the solvent in the composition (the total amount when two or more types of 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 composition.

[0112] As other components, in addition to the above, known additives such as an acid diffusion controller, a sensitizer, an antioxidant, 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 polymerization inhibitor, a chain transfer agent, etc. The blending ratio of these components is appropriately selected according to each component within a range that does not impair the effects of the present disclosure.

[0113] The solid content concentration of the present composition (the ratio of the total mass of the components other than the solvent in the composition to the total mass of the composition) is appropriately selected in consideration of viscosity, volatility, etc. The solid content concentration of the present composition is preferably in the range of 5 to 60 mass %. When the solid content concentration is 5 mass % or more, a sufficient thickness of the coating film can be ensured when the present composition is applied onto a substrate. On the other hand, when the solid content concentration is 60 mass % or less, the thickness of the coating film does not become too large, and furthermore, the viscosity of the present composition can be appropriately increased, and good coatability can be ensured. The solid content concentration of the present composition is more preferably 10 to 55 mass %, and even more preferably 12 to 50 mass %.

[0114] <Cured film and manufacturing method thereof> The cured film of the present invention is formed from the composition prepared as described above (i.e., the curable composition). By using the present composition, a cured film having high heat resistance, high transmittance, and excellent water impermeability can be formed. Therefore, the present composition can be preferably used as a material 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. Among these, the present composition is suitable as a material for forming an interlayer insulating film or a planarizing film provided in a display element.

[0115] Using this composition, a cured film can be produced, for example, by carrying out a method including the following steps 1A to 3A. (Step 1A) A step of forming a coating film using the present composition (coating step) (Step 2A) A step of irradiating the coating film with radiation (exposure step) (Step 3A) A step of heating the coating film after irradiation (heating step)

[0116] In addition, when producing a cured film, a composition containing a photosensitive compound can be used to form a positive or negative cured film depending on the type of photosensitive compound. A patterned cured film can be produced using this composition by carrying out a method including, for example, the following steps 1B to 4B. (Step 1B) A step of forming a coating film using the composition (coating step) (Step 2B) A step of irradiating at least a part of the coating film with radiation (exposure step) (Step 3B) A step of developing the coating film after irradiation (development step) (Step 4B) A step of heating the coating film after development (heating step) Each step will be described in detail below.

[0117] [Coating process] In the coating process, the composition is applied to a surface on which a film is to be formed (hereinafter also referred to as "surface on which a film is to be formed"), and the solvent is preferably removed by a heat treatment (pre-baking) to form a coating film on the surface on which a film is to be formed. The material of the surface on which a film is to be formed is not particularly limited. For example, when forming an interlayer insulating film, the composition is applied to a substrate on which a switching element such as a TFT is provided, to form a coating film. Examples of the substrate include a glass substrate, a silicon substrate, and a resin substrate. The surface of the substrate on which the coating film is to be formed may have a metal thin film formed according to the application, or may have been subjected to various surface treatments such as HMDS (hexamethyldisilazane) treatment.

[0118] Examples of the coating method of the present composition include spraying, roll coating, spin coating, slit die coating, bar coating, and inkjet. Among these, spin coating, slit die coating, and bar coating are preferable. Pre-baking conditions vary depending on the type and content of each component in the present composition, but are, for example, 60 to 130°C and 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 present composition applied to the film-forming surface may be subjected to reduced pressure drying (VCD) before pre-baking.

[0119] [Exposure process] In steps 2A and 2B, at least a part of the coating film is irradiated with radiation. In step 2B, the coating film is irradiated with radiation through a mask having a predetermined pattern, thereby forming a cured film having a pattern. Examples of radiation include ultraviolet rays, far ultraviolet rays, visible light, X-rays, and charged particle beams such as electron beams. Among these, ultraviolet rays are preferred, and examples of such beams include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure is 0.1 to 20,000 J / m 2 is preferred.

[0120] [Development process] In the development step, the coating film irradiated with radiation in the exposure step is developed. Specifically, the coating film irradiated with radiation in the exposure step is developed with a developer, thereby performing positive development in which the irradiated portion is removed, or negative development in which the non-irradiated portion is removed. Examples of the developer include an aqueous solution of an alkali (basic compound). Examples of the alkali include sodium hydroxide, tetramethylammonium hydroxide, and the alkalis exemplified in paragraph 0127 of JP-A-2016-145913. From the viewpoint of obtaining appropriate developability, the alkali concentration in the aqueous alkali solution is preferably 0.1 to 5% by mass. Examples of the development method include a suitable method such as a puddle method, a dipping method, a rocking immersion method, and a shower method. The development time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. After the development step, it is preferable to perform a rinse treatment by washing with running water on the patterned coating film.

[0121] [Heating process] In step 3A, the coating film after irradiation is heated (post-baked). In step 4B, the coating film developed in the development step is heated (post-baked). This heat treatment further advances the curing reaction, and a cured film with excellent heat resistance can be obtained. The post-baking can be performed using a heating device such as an oven or a hot plate. Regarding the 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 heat treatment is performed on a hot plate, and 10 to 80 minutes when the heat treatment is performed in an oven. In the heat treatment in step 4B, a cured film having a desired pattern can be formed on a substrate. The shape of the pattern of the cured film is not particularly limited, and examples thereof include a line-and-space pattern, a dot pattern, a hole pattern, and a lattice pattern.

[0122] The cured film obtained from the present 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.

[0123] <Display element> The display element of the present disclosure includes a cured film formed using the present composition. Examples of the display element include a liquid crystal display element and an organic EL element. The type of the cured film formed using the present composition is not particularly limited. The present composition is particularly suitable as a film-forming composition for a display element, that is, a planarizing film which is an insulating layer that covers the steps of a TFT circuit or wiring formed on a substrate, or an interlayer insulating film which is an insulating layer that insulates wiring between wirings in a multilayer wiring or between a wiring and a substrate, because the present composition can provide a cured film with excellent heat resistance, low water permeability and bending resistance (bending resistance) and high transmittance.

[0124] The cured film formed using this composition is poorly permeable and has excellent bending resistance, and therefore can be preferably applied to display elements for flexible displays. Flexible displays include foldable displays that can be folded, bendable displays that can be folded back or bent, and rollable displays that can be rolled up. The cured film formed using this composition is particularly suitable as a cured film provided in a display element for a foldable display, and is particularly suitable as an interlayer insulating film or a planarizing film for a foldable display.

[0125] According to the present disclosure described above in detail, the following means are provided. [Means 1] A film-forming composition containing a polymer including a structural unit derived from a compound (M1) having a methylene group adjacent to an electron-withdrawing group, and a structural unit derived from at least one compound (M2) selected from the group consisting of compounds having two or more ethylenically unsaturated bonds and compounds having two or more halogenated alkyl groups. [Means 2] The film-forming composition according to [Means 1], wherein the compound (M1) is represented by the above formula (1). [Means 3] The film-forming composition according to [Means 1] or [Means 2], wherein the compound (M2) is at least one selected from the group consisting of a compound represented by the above formula (2A) and a compound represented by the above formula (2B). [Measure 4] The film forming composition according to any one of [Measure 1] to [Measure 3], wherein the polymer contains a structural unit represented by the above formula (3A). [Measure 5] The film forming composition according to any one of [Measure 1] to [Measure 4], wherein the polymer contains a structural unit represented by the above formula (3B). [Means 6] The film-forming composition according to any one of [Means 1] to [Means 5], wherein the compound (M1) has a first acid dissociation constant (pKa1) of 20.0 or less. [Means 7] The film-forming composition according to any one of [Means 1] to [Means 6], further comprising a compound having two or more crosslinkable functional groups. [Means 8] The film-forming composition according to any one of [Means 1] to [Means 7], further comprising a photosensitive compound.

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0028]

[0032]

[0029]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0030] [ [Means 10] A method for producing a cured film, comprising the steps of: forming a coating film using the film-forming composition according to any one of [Means 1] to [Means 9]; irradiating the coating film with radiation; and heating the coating film after irradiation with radiation. [Means 11] A method for producing a cured film, comprising the steps of: forming a coating film using the film-forming composition according to any one of [Means 1] to [Means 9]; irradiating at least a part of the coating film with radiation; developing the coating film after irradiation with radiation; and heating the coating film after development. [Means 12] A cured film formed by using the film-forming composition according to any one of [Means 1] to [Means 9]. [Means 13] The cured film according to [Means 12], which is an interlayer insulating film or a planarizing film. [Means 14] A display device comprising the cured film according to [Means 12] or [Means 13]. EXAMPLES

[0126] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by weight unless otherwise specified.

[0127] [Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)] The Mw and Mn of the polymers synthesized in the following Synthesis Examples were measured by gel permeation chromatography (GPC) using the following apparatus and conditions. The molecular weight distribution (Mw / Mn) was calculated from the measured Mw and Mn. Equipment: Showa Denko GPC-101 GPC column: Shimadzu GLC's GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined Mobile phase: Tetrahydrofuran (for (meth)acrylic polymers), or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid (for [A] polymer and polyimide) Column temperature: 40℃ ·Flow rate: 1.0mL / min Sample concentration: 1.0% by mass Sample injection volume: 100μL Detector: Differential refractometer Standard material: Monodisperse polystyrene

[0128] [Monomer] The abbreviations of the monomers used in the synthesis of the polymer are as follows. Compound (M1): Compounds represented by the following formulae AM-1 to AM-7 [ka]

[0129] Compound (M2-1): Compounds represented by the following formulae DO-1 to DO-5 [ka]

[0130] Compound (M2-2): Compounds represented by the following formulae DH-1 to DH-5 [ka]

[0131] [First acid dissociation constant (pKa1) of compound (M1)] Table 1 shows the first-step acid dissociation constant (first acid dissociation constant (pKa1)) generated from compound (M1) obtained by Gaussian 16 based on density functional theory (B3LYP / 6-311++G(d,p)).

[0132] [Table 1]

[0133] 1. Polymer synthesis [Synthesis Example 1] Synthesis of Polymer P-1 (Polyaddition Resin) In a 100mL two-neck flask, 100 mol parts of 2-pyridineacetonitrile and 100 mol parts of 4,4'-diacryloyloxybiphenyl as polymerization monomers, 0.01 mol parts of tetrabutylammonium bromide as a surfactant, and anisole as a solvent were added under nitrogen so that the solid concentration of the polymerization solution was 30% by mass, and the polymerization solution was stirred at room temperature (25°C) until it became uniform. Then, 200 mol parts of diazabicycloundecene were added as a base, and polymerization was performed at room temperature for 30 minutes and at 60°C for 8 hours. After polymerization, the solid obtained by reprecipitation in an aqueous methanol solution was filtered and vacuum dried at room temperature for 8 hours to obtain polymer P-1. The Mw of the obtained polymer P-1 was 15,300, and the molecular weight distribution (Mw / Mn) was 3.92.

[0134] [Synthesis Examples 2 to 5, 13] Synthesis of Polymers P-2 to P-5, P-16 Polymerization was carried out in the same manner as in Synthesis Example 1, except that the types and amounts of monomers used in polymerization were changed as shown in Table 2, to obtain polymers P-2 to P-5 and P-16, respectively.

[0135] [Synthesis Example 6] Synthesis of Polymer P-6 (Polycondensation Resin) In a 100mL two-neck flask, 100 mol parts of phenylacetonitrile and 100 mol parts of 2,6-bis(bromomethyl)pyridine as polymerization monomers, 0.5 mol parts of tetrabutylammonium bromide as a surfactant, and anisole as a solvent were added under nitrogen so that the solid concentration of the polymerization solution was 30 mass%, and the polymerization solution was stirred at room temperature until it became uniform. Then, 1000 mol parts of 40% aqueous sodium hydroxide solution was added as a base, and polymerization was performed at room temperature for 30 minutes and at 50°C for 8 hours. After polymerization, the mixture was reprecipitated in an aqueous methanol solution, and the obtained solid was filtered and vacuum dried at room temperature for 8 hours to obtain polymer P-6. The Mw of the obtained polymer P-6 was 98,100, and the molecular weight distribution (Mw / Mn) was 5.01.

[0136] [Synthesis Examples 7 to 12 and 14] Synthesis of Polymers P-7 to P-12 and P-17 Polymerization was carried out in the same manner as in Synthesis Example 6, except that the types and amounts of monomers used in polymerization were changed as shown in Table 2, to obtain polymers P-7 to P-12 and P-17, respectively.

[0137] [Table 2]

[0138] [Synthesis Example 15] Synthesis of Polymer P-13 (Polyaddition Resin) In a 100 mL two-neck flask, 2 g of polymer P-5 and tetrahydrofuran were added under nitrogen so that the concentration of the polymerization solution was 20 mass%. While stirring the polymerization solution at room temperature, 20 g of 1N hydrochloric acid solution was added and reacted at room temperature for 6 hours to deprotect the tetrahydropyranyl group. After the reaction, the polymer was reprecipitated in an aqueous methanol solution, and the obtained solid was filtered and vacuum dried at room temperature for 8 hours to obtain polymer P-13.

[0139] [Synthesis Example 16] Synthesis of Polymer P-14 ((meth)acrylic polymer) Under nitrogen, 40 mol parts of methyl methacrylate, 20 mol parts of glycidyl methacrylate, 20 mol parts of methacrylic acid, and 20 mol parts of styrene were added as polymerization monomers, 2.0 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator, and 50 mL of N-methyl-2-pyrrolidone (NMP) as a solvent to a 100 mL two-neck flask, and polymerization was carried out at 70°C for 6 hours. After reprecipitation in methanol, the precipitate was filtered and dried in vacuum at room temperature for 8 hours to obtain polymer P-14. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 37,400, and the molecular weight distribution Mw / Mn was 3.02.

[0140] [Synthesis Example 17] Synthesis of Polymer P-15 (Polyimide) 100 parts by mole of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in N-methyl-2-pyrrolidone (NMP), 100 parts by mole of 4,4'-oxydiphthalic anhydride was added thereto, and the mixture was allowed to react at 40°C for 8 hours to obtain a polyamic acid solution containing 20% ​​by mass of polyamic acid. Next, NMP was added to the obtained polyamic acid solution to make the concentration of polyamic acid 10% by mass, and pyridine and acetic anhydride were added thereto, and a dehydration ring-closing reaction was carried out at 90°C for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with fresh NMP to obtain a polyimide solution containing 15% by mass of polyimide with an imidization rate of about 70%. The obtained polyimide solution was added to methanol, and the precipitated solid was washed with an aqueous methanol solution. The obtained solid was dried to obtain polymer P-15. The Mw of the obtained polymer P-15 was 32,000, and the molecular weight distribution (Mw / Mn) was 2.21.

[0141] 2. Preparation and evaluation of film-forming compositions [Example 1] (1) Preparation of composition R-1 100 parts by mass of polymer P-1, 10 parts by mass of crosslinking agent Add-1, 5 parts by mass of adhesion aid (γ-glycidoxypropyltrimethoxysilane), and 0.5 parts by mass of surfactant (product name "FTX-218", manufactured by Neos Co., Ltd.) were mixed. Further, a mixed solution of gamma-butyrolactone and diethylene glycol ethyl methyl ether (gamma-butyrolactone:diethylene glycol ethyl methyl ether = 50:50 (mass ratio)) was added as a solvent so that the solid content concentration was 20 mass%, and then the mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare composition R-1.

[0142] (2) Heat resistance evaluation Composition R-1 was applied onto 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 a thickness of 3.0 μm. Next, a proximity exposure machine (Canon's “MA-1200” (ghi line mixed)) was used to expose the substrate to 3,000 J / m 2After irradiating the entire substrate surface with light, the silicon substrate was heated at 250°C for 60 minutes in a clean oven substituted with nitrogen to form a cured film. The 1% thermal weight loss temperature of the cured film formed was measured in air using a simultaneous differential thermal and thermogravimetric analyzer (Hitachi High-Tech Science Corporation's "TG / DTA220U"). Heat resistance was evaluated as follows: 1% weight loss temperature of 300°C or higher was rated as "good (○)", 250°C or higher but less than 300°C was rated as "passable (△)", and less than 250°C was rated as "not good (×)". As a result, in this example, the evaluation was "good (○)".

[0143] (3) Evaluation of transmittance (light transmittance) Composition R-1 was applied onto a glass substrate using a spinner, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with a thickness of 3.0 μm. Next, a proximity exposure machine (Canon's “MA-1200” (mixed ghi line)) was used to expose the coating film to 3000 J / m 2 After irradiating the entire substrate surface with light, the glass substrate was heated at 250°C for 60 minutes in a clean oven substituted with nitrogen to form a cured film. The transmittance of the formed cured film was measured using an ultraviolet-visible spectrophotometer (JASCO Corporation's "V-630"). The transmittance of light with a wavelength of 380 nm was evaluated as "good (○)" when it was 70% or more, "passable (△)" when it was 50% or more and less than 70%, and "not good (×)" when it was less than 50%. As a result, in this example, the evaluation was "good (○)".

[0144] (4) Evaluation of water impermeability Composition R-1 was applied to a polyimide sheet having a thickness of 25 μm using a spinner so as to give a film thickness of 10 μm, and the sheet was prebaked at 80° C. for 1.5 minutes. Then, the sheet was exposed to 3,000 J / m 2 of light using a proximity exposure machine (Canon's "MA-1200" (mixed ghi line)). 2After irradiating the entire substrate surface with light, the substrate was heated at 250°C for 60 minutes to form a cured film on the polyimide sheet. This laminated film of the polyimide sheet and the cured film was placed in the opening of an aluminum cup containing 15g of distilled water, with the surface on which the cured film was formed facing inward, and the opening of the aluminum cup was covered with the laminated film to seal it. This was placed in a thermostatic chamber at 50°C, and the weight loss of the cup after 150 hours was measured, and the amount of water permeation per unit area was calculated. When the weight loss value was 500g / cm 2 The following cases are considered to be "Good (○)" and 500g / cm 2 Over 700g / cm 2 The following cases are considered "Acceptable (△)" and are 700g / cm 2 If the value exceeds 500g / cm, the water permeability is evaluated as "unacceptable (×)". 2 If the water permeability of the cured film is below this level, it can be said that the water permeability is sufficiently low and good. As a result, this example was evaluated as "good (◯)".

[0145] [Examples 2 to 20, Comparative Examples 1 to 3] Except for the fact that the blending composition was changed as shown in Table 3, compositions R-2 to R-20 and RC-1 to RC-3 were prepared with the same solvent composition and solid content concentration as in Example 1. In addition, the same types and amounts of adhesion aids and surfactants as in Example 1 were blended in Examples 2 to 20 and Comparative Examples 1 to 3. In Examples 15 to 20 and Comparative Examples 2 and 3, a photosensitive compound was blended in the composition. In addition, various evaluations were performed in the same manner as in Example 1 using each composition. Furthermore, for Examples 15 to 20 and Comparative Examples 2 and 3 in which a photosensitive compound was blended, the sensitivity (radiation sensitivity) shown in the following (5) was evaluated. The evaluation results are shown in Table 3. Among Examples 15 to 20 in which a photosensitive compound was blended, Examples 15, 17 to 20 are positive compositions, and Example 16 is a negative composition.

[0146] (5) Evaluation of sensitivity (radiation sensitivity) Using a spinner, the composition was applied onto 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 a thickness of 3.0 μm. This coating film was irradiated with a predetermined amount of ultraviolet light through a pattern mask having a line-and-space pattern with a width of 10 μm, using a Canon "MPA-600FA" exposure machine. Next, a development process was performed at 25°C for 60 seconds using a developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), and then washed with running ultrapure water for 1 minute. The minimum exposure dose capable of forming a line-and-space pattern with a width of 10 μm was measured, and the measured value was 2,000 J / m 2 A line and space pattern with a width of 10 μm was obtained, but the minimum exposure dose was less than 2,000 J / m. 2 The above cases were rated as "pass (△)", and cases where a 10μm-wide line and space pattern was not obtained were rated as "not pass (×)". Note that compositions that did not contain a photosensitive compound were not evaluated for sensitivity (radiation sensitivity), and are therefore shown as "-" in Table 3.

[0147] [Table 3]

[0148] In Table 3, the abbreviations of the compounds are as follows. NQD: quinone diazide compound (condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol)) PI: Irgacure OXE-01 (manufactured by BASF) CAR: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate Add-1 to Add-6: Compounds represented by the following formulas Add-1 to Add-6, respectively. [ka]

[0149] As shown in Table 3, the compositions of Examples 1 to 20 were evaluated as "○" or "△" for heat resistance, transmittance, and poor water permeability, and various properties were improved in a well-balanced manner. Among these, the compositions containing polymers P-1, P-2, P-4 to P-13, P-16, and P-17 synthesized using AM-1 to AM-4, AM-6, and AM-7 as the compound (M1) used in the synthesis of polymer [A] were evaluated as "○" for heat resistance, and were excellent. In addition, the compositions of Examples 15 to 20, which contained a photosensitive compound, also had excellent sensitivity.

[0150] In contrast, in Comparative Examples 1 and 2, in which a (meth)acrylic polymer was used instead of the polymer [A], the transmittance of the cured film was evaluated as "○", but the heat resistance of the cured film was evaluated as "×" and the water impermeability was evaluated as "△", which were inferior to Examples 1 to 20. In Comparative Example 3, in which a polyimide was used instead of the polymer [A], the heat resistance of the cured film was evaluated as "○", but the transmittance was evaluated as "×" and the water impermeability was also evaluated as "△", which were inferior to Examples 1 to 20.

Claims

1. A film-forming composition comprising a polymer including a structural unit derived from a compound (M1) having a methylene group adjacent to an electron-withdrawing group, and a structural unit derived from at least one compound (M2) selected from the group consisting of compounds having two or more ethylenically unsaturated bonds and compounds having two or more halogenated alkyl groups.

2. The film forming composition according to claim 1 , wherein the compound (M1) is represented by the following formula (1): 【Chemistry 1】 (In formula (1), X １ is an electron-withdrawing group having a valence of (n1+1). X ２ is a divalent electron-withdrawing group. １ and Y ２ are each independently a monovalent organic group, or Y １ and Y ２ are combined together to form Y １ X to which ２ and Y ２ X to which １ and n1 and n2 each independently represent 0 or 1.

3. The film-forming composition according to claim 1, wherein the compound (M2) is at least one selected from the group consisting of a compound represented by the following formula (2A) and a compound represented by the following formula (2B): 【Chemistry 2】 (In formula (2A), X ３ and X ４ are each independently a divalent electron-withdrawing group. ３ is a single bond or a divalent organic group. n3 and n4 are each independently 0 or 1. 【Chemistry 3】 (In formula (2-2), Z １ and Z ２ are each independently a halogen atom. ４ is a divalent organic group.

4. The film forming composition according to claim 1 , wherein the polymer contains a structural unit represented by the following formula (3A): 【Chemistry 4】 (In formula (3A), X １ is an electron-withdrawing group having a valence of (n1+1). X ２ is a divalent electron-withdrawing group. １ and Y ２ are each independently a monovalent organic group, or Y １ and Y ２ are combined together to form Y １ X to which ２ and Y ２ X to which １ represents a ring structure formed together with X ３ and X ４ are each independently a divalent electron-withdrawing group. ３ is a single bond or a divalent organic group. n1 and n2 are each independently 0 or 1. n3 and n4 are each independently 0 or 1.

5. The film forming composition according to claim 1 , wherein the polymer contains a structural unit represented by the following formula (3B): 【Chemistry 5】 (In formula (3B), X １ is an electron-withdrawing group having a valence of (n1+1). X ２ is a divalent electron-withdrawing group. １ and Y ２ are each independently a monovalent organic group, or Y １ and Y ２ are combined together to form Y １ X to which ２ and Y ２ X to which １ represents a ring structure formed together with Y. ４ is a divalent organic group. n1 and n2 are each independently 0 or 1.

6. 2. The film forming composition according to claim 1, wherein the compound (M1) has a first acid dissociation constant (pKa1) of 20.0 or less.

7. The film forming composition according to claim 1 , further comprising a compound having two or more crosslinkable functional groups.

8. The film forming composition according to claim 1 , further comprising a photosensitive compound.

9. The film forming composition according to claim 8 , wherein the photosensitive compound is a photoacid generator or a quinone diazide compound.

10. A step of forming a coating film using the film-forming composition according to any one of claims 1 to 9; exposing the coating to radiation; A step of heating the coating film after irradiation with radiation; The method for producing a cured film comprising the steps of:

11. A step of forming a coating film using the film-forming composition according to any one of claims 1 to 9; exposing at least a portion of the coating to radiation; developing the coating film after irradiation; heating the coating after development; The method for producing a cured film comprising the steps of:

12. A cured film formed by using the film-forming composition according to any one of claims 1 to 9.

13. The cured film according to claim 12, which is an interlayer insulating film or a planarizing film.

14. A display device comprising the cured film according to claim 12.

Images