Photosensitive composition, cured product, method for producing same, liquid crystal device, semiconductor device, polymer, and compound

Abstract

This photosensitive composition contains: a polymer derived from a monomer having a C1-C3 halogenated alkyl group containing at least one hydrogen atom, and including a structural unit (a1) having a hydroxyl group; and a photosensitive compound.

Description

Photosensitive composition, cured product and its manufacturing method, liquid crystal device, semiconductor device, polymer and compound

[0001] [Cross-reference to related applications] This application claims priority to Japanese Patent Application No. 2023-138370, filed on August 28, 2023, the entire contents of which are incorporated herein by reference. The present disclosure relates to a photosensitive composition, a cured product and a method for producing the same, a liquid crystal device, a semiconductor device, a polymer, and a compound.

[0002] Electronic devices such as display devices and semiconductor devices are provided with insulating cured films such as planarizing films and interlayer insulating films. It has also been proposed to use polyimide, its precursor, or polyamide as a material for forming these cured films (see, for example, Patent Document 1). Patent Document 1 discloses synthesizing a polyamic acid or polyamide using a diamine or tetracarboxylic dianhydride having a perfluoromethyl group and a hydroxyl group, and forming a patterned cured film using a photosensitive composition containing the obtained polyamic acid or polyamide.

[0003] Japanese Patent Application Laid-Open No. 2020-33277

[0004] Cured films provided in display devices and semiconductor devices are required to have excellent reliability, such as low generation of impurities from the cured film and low moisture permeability, etc. Furthermore, as a low refractive index material for display devices and semiconductor devices, it is desired to develop a new material that has excellent patterning ability, a sufficiently low refractive index, and allows for the formation of a cured film with excellent reliability.

[0005] The present disclosure has been made in consideration of the above-mentioned problems, and has as its main object to provide a photosensitive composition that has good patterning properties, a low dielectric constant, and is capable of giving a cured product with excellent reliability.

[0006] According to the present disclosure, the following photosensitive composition, cured product and method for producing the same, liquid crystal device, semiconductor device, polymer, and compound are provided.

[0007] [1] A photosensitive composition comprising a polymer derived from a monomer having a halogenated alkyl group of 1 to 3 carbon atoms containing at least one hydrogen atom and comprising a structural unit (a1) having a hydroxyl group, and a photosensitive compound. [2] A cured product comprising the photosensitive composition according to [1] above. [3] A display device comprising the cured product according to [2] above. [4] A semiconductor device comprising the cured product according to [3] above. [5] A method for producing a cured product, comprising the steps of applying the photosensitive composition according to [1] above onto a substrate, exposing the applied photosensitive composition to light, developing the exposed photosensitive composition, and curing the developed photosensitive composition. [6] A polymer having a partial structure represented by the following formula (1): (In formula (1), R １ is an organic group with a valence of (m+n+p+2). ２ is a (q+r+2) valent organic group. ３ is a hydrogen atom, an alkali metal ion, an ammonium ion, or a monovalent organic group having 1 to 20 carbon atoms. １ and X ２ are each independently a halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom. When p is 2 or more, multiple R ３ are the same or different. m, n, q, and r are integers of 0 or more, provided that m≧1 and n≧1, or q≧1 and r≧1, and p is an integer of 0 to 2.) [7] A compound represented by the following formula (2): (In formula (2), R ２ is a (q+r+2)-valent organic group, and q and r are integers of 1 or more. [8] A compound represented by the following formula (3): (In formula (3), R １ is an (m+n+4)-valent organic group, where m and n are integers of 1 or more.

[0008] The composition of the present disclosure can provide a cured product that has good patterning properties, a low dielectric constant, and excellent reliability.

[0009] Matters related to the embodiments will be explained in detail below. In this specification, a numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure.

[0010] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure and is composed solely of a chain structure. However, the chain hydrocarbon group may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, the alicyclic hydrocarbon group does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and also includes groups that have a chain structure as part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, the aromatic hydrocarbon group does not necessarily have to be composed solely of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure as part of it. The ring structure of the alicyclic hydrocarbon group or aromatic hydrocarbon group may have a substituent consisting of a hydrocarbon structure.

[0011] In this specification, "(meth)acrylic" is intended to encompass "acrylic" and "methacrylic". "(meth)acryloyl" is intended to encompass "acryloyl" and "methacryloyl". In this specification, the term "epoxy group" is also intended to encompass oxiranyl groups and oxetanyl groups. "Radiation" is intended to encompass electron beams (visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), etc.) and electromagnetic waves (X-rays, gamma rays, etc.).

[0012] <Photosensitive 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. A film formed from the composition is suitable as an insulating film provided in various display devices such as organic EL display devices and liquid crystal display devices, and in semiconductor devices. The composition contains the polymer (A) shown below and a photosensitive compound. Unless otherwise specified, each component may be used alone or in combination of two or more.

[0013] <Polymer (A)> The polymer (A) is a polymer derived from a monomer having a halogenated alkyl group having 1 to 3 carbon atoms and at least one hydrogen atom, and containing a structural unit (a1) having a hydroxyl group.

[0014] The halogenated alkyl group in the structural unit (a1) may be a group in which some of the hydrogen atoms in an alkyl group having 1 to 3 carbon atoms have been replaced with halogen atoms. Preferred examples of the halogenated alkyl group include those represented by the following formula (5): *-(CR ５ R ６ ) ｎ -CR ７ R ８ R ９ ...(5) (In formula (5), R ５ , R ６ , R ７ , R ８ and R ９ are each independently a hydrogen atom or a halogen atom. n is an integer of 0 to 2. When n is 2, two R ５ are the same or different, and two R ６ are the same or different, provided that n R ５ , n R ６ , R ７ , R ８ and R ９ are not all halogen atoms at the same time, and are not all hydrogen atoms at the same time. "*" represents a bond.

[0015] Examples of the halogen atom contained in the halogenated alkyl group in the structural unit (a1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom or a bromine atom is preferred, and a fluorine atom is more preferred. The number of halogen atoms contained in the halogenated alkyl group is preferably 1 to (2×n+1), and more preferably 1 to (n+1). In the above formula (5), n is preferably 0 or 1, and more preferably 0.

[0016] Specific examples of the halogenated alkyl group in the structural unit (a1) include a fluoromethyl group, a difluoromethyl group, a dibromomethyl group, a 1-fluoroethyl group, a 1-bromoethyl group, a 1,1-difluoroethyl group, a 1,1-dibromoethyl group, a 1,2-difluoroethyl group, a 1,1,2-trifluoroethyl group, a 2-fluoroethyl group, a 2,2-difluoroethyl group, a 1,1-difluoropropyl group, a 1,2-difluoropropyl group, a 1,1,2-trifluoropropyl group, a 1,1,2,3-tetrafluoropropyl group, a 3-fluoropropyl group, and a 2,3-difluoropropyl group. Of these, the halogenated alkyl group in the structural unit (a1) is preferably a difluoromethyl group, a 1-fluoroethyl group, a 1,1-difluoroethyl group, a 1,2-difluoroethyl group, a 1,1,2-trifluoroethyl group, a 1,1-difluoropropyl group, a 1,2-difluoropropyl group, a 1,1,2-trifluoropropyl group, or a 1,1,2,3-tetrafluoropropyl group, and particularly preferably a difluoromethyl group.

[0017] The number of halogenated alkyl groups in the structural unit (a1) is, for example, 1 to 6. From the viewpoint of improving the patterning properties of the present composition, the number of halogenated alkyl groups in the structural unit (a1) is preferably 2 to 6, and more preferably 2 to 4. The "halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom" in the structural unit (a1) may be bonded to a carbon atom or a heteroatom (preferably an oxygen atom). For example, the halogenated alkyl group in a halogenated alkoxy group containing at least one hydrogen atom also falls under the category of "halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom" in this specification. When the "halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom" in the structural unit (a1) is bonded to a carbon atom, the halogenated alkyl group may be bonded to an aliphatic structure (specifically, a linear structure or an alicyclic structure) or an aromatic ring structure. The halogenated alkyl group in the structural unit (a1) is preferably bonded to an aliphatic structure (a linear structure or an alicyclic structure).

[0018] The structural unit (a1) has one or more hydroxyl groups. The hydroxyl group in the structural unit (a1) may be bonded to an aliphatic structure (specifically, a chain structure or an alicyclic structure) or may be bonded to an aromatic ring structure. From the viewpoint of appropriately increasing the solubility of the polymer (A) in a developer (specifically, an alkaline developer), the hydroxyl group in the structural unit (a1) is preferably bonded to a carbon atom to which a fluorine atom or a fluoroalkyl group is bonded, or to an aromatic ring. In addition, when a hydroxyl group is bonded to a carbon atom to which a fluoroalkyl group is bonded, the fluoroalkyl group to which the hydroxyl group is bonded is preferably a halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom, and more preferably a difluoromethyl group.

[0019] From the viewpoint of further reducing the dielectric constant of the obtained cured product, the hydroxyl group in the structural unit (a1) is preferably bonded to an aliphatic structure, and from the viewpoint of further increasing the solubility of the polymer (A) in a developer, it is more preferable that the hydroxyl group be bonded to a carbon atom to which a fluorine atom or a fluoroalkyl group is bonded.

[0020] The number of hydroxyl groups in the structural unit (a1) is preferably 1 to 6, and more preferably 2 to 4, from the viewpoint of appropriately increasing the solubility of the polymer (A) in a developer.

[0021] The main chain of the polymer (A) is not particularly limited. In terms of high strength, excellent solvent resistance, heat resistance, and low dielectric constant, the polymer (A) is preferably at least one selected from the group consisting of polyimide, polyamic acid ester, polyamic acid, polyamide, and polybenzoxazole, and more preferably at least one selected from the group consisting of polyimide, polyamic acid ester, polyamic acid, and polyamide. Among these, at least one of polyimide and polyamic acid ester is preferred in terms of exhibiting good patterning properties, and polyimide is more preferred in terms of its high effect of reducing the dielectric constant.

[0022] In this specification, a "polyamic acid" is a polymer that has an amic acid structure but does not have an amic acid ester structure or an imide ring structure. A "polyimide" is a polymer that has an imide ring structure. However, a polyimide may have only an imide structure, or may have an amic acid structure together with an imide ring structure. A "polyamic acid ester" is a polymer that has an amic acid ester structure. However, a polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist, or may further have an imide ring structure. In other words, in this specification, a polymer that has an imide ring structure and an amic acid ester structure is classified as a polyamic acid ester.

[0023] As a monomer that provides the structural unit (a1), a diamine is preferred in terms of ease of monomer design. That is, the polymer (A) preferably contains, as the structural unit (a1), a structural unit derived from a diamine having a halogenated alkyl group having one or more hydrogen atoms and a hydroxyl group. Furthermore, the monomer that provides the structural unit (a1) is not limited to a diamine, and may also be, for example, an acid or an anhydride thereof having a halogenated alkyl group having one or more hydrogen atoms and a hydroxyl group.

[0024] As the polymer (A), a polymer obtained by condensation polymerization of an acid or an acid anhydride with a diamine can be preferably used. Specific examples of such polymer (A) include a polymer having a partial structure represented by the following formula (1): (In formula (1), R １ is an organic group with a valence of (m+n+p+2). ２ is a (q+r+2) valent organic group. ３ is a hydrogen atom, an alkali metal ion, an ammonium ion, or a monovalent organic group having 1 to 20 carbon atoms. １ and X ２ are each independently a halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom. When p is 2 or more, multiple R ３ are the same or different. m, n, q, and r are integers of 0 or greater, provided that m ≥ 1 and n ≥ 1, or q ≥ 1 and r ≥ 1, and p is an integer from 0 to 2.

[0025] In the above formula (1), R １ The (m+n+p+2)-valent organic group represented by the formula (I) is a group derived from an acid, an acid anhydride, or a partial ester, and R ２ The (q+r+2)-valent organic group represented by the formula (2) is a group derived from a diamine. Examples of the acid include dicarboxylic acids and tricarboxylic acids. Examples of the acid anhydride include tricarboxylic acid anhydrides and tetracarboxylic acid dianhydrides. Examples of the partial ester include tetracarboxylic acid diesters and tetracarboxylic acid diester dihalides. For convenience, hereinafter, acids, acid anhydrides, and partial esters are collectively referred to as "acid derivatives."

[0026] Here, in this specification, "tetracarboxylic acid diester" means a compound in which two of the four carboxy groups in a tetracarboxylic acid are esterified and the remaining two are carboxy groups. "Tetracarboxylic acid diester dihalide" means a compound in which two of the four carboxy groups in a tetracarboxylic acid are esterified and the remaining two are halogenated.

[0027] R ３Examples of the alkali metal ion represented by the formula (I) include a potassium ion, a sodium ion, etc. Examples of the monovalent organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an alkoxysilyl group.

[0028] X １ and X ２ Specific and preferred examples of X include the same groups as the specific and preferred examples of the halogenated alkyl group contained in the structural unit (a1). m, n, q, and r are integers of 0 or more, for example, integers of 0 to 6. １ or X ２ From the viewpoint of ease of introduction into polymer (A), the partial structure represented by formula (1) preferably has q of 1 or greater and r of 1 or greater. In the synthesis of polymer (A), a polymer satisfying m≧1 and n≧1 can be obtained by using an acid derivative having a hydroxyl group and a halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom (hereinafter also referred to as a "specific acid derivative"). In the synthesis of polymer (A), a polymer satisfying q≧1 and r≧1 can be obtained by using a diamine having a hydroxyl group and a halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom (hereinafter also referred to as a "specific diamine").

[0029] Preferred examples of the specific acid derivative used in the synthesis of the polymer (A) include a compound represented by the following formula (3) and a compound represented by the following formula (4). (In formula (3), R １ is an (m+n+4)-valent organic group, where m and n are integers of 1 or more. (In formula (4), R １ is an (m+n+2)-valent organic group, where m and n are integers of 1 or greater.

[0030] In the above formulas (3) and (4), R １The (m+n+4)-valent organic group or the (m+n+2)-valent organic group represented by the formula (I) is a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -NH-, -N(CH ３ ) -, -N(C ２ H ５ )-, -CO-, -COO-, -CONH-, -SO-, -SO ２ Examples include groups having 2 to 20 carbon atoms containing -, -OCONH-, or -NHCONH-. m is preferably 1 to 4, and more preferably 1 or 2. n is preferably 1 to 4, and more preferably 1 or 2.

[0031] The specific acid derivative preferably has a carboxy group or an acid anhydride group bonded to an aromatic ring or an aliphatic ring. Further specific examples of the specific acid derivative include dicarboxylic acids represented by the following formula (t1-1) or (t1-2); tetracarboxylic dianhydrides represented by each of the following formulas (t2-1) to (t2-5); and the like.

[0032] A preferred example of the specific diamine used in synthesizing the polymer (A) is a compound represented by the following formula (2). (In formula (2), R ２ is a (q+r+2)-valent organic group, where q and r are integers of 1 or greater.

[0033] In the above formula (2), R ２ The (q+r+2)-valent organic group represented by the formula (4) is R １ Examples thereof include the same groups as those exemplified as the groups below. r is preferably 1 to 4, and more preferably 1 or 2. q is preferably 1 to 4, and more preferably 1 or 2.

[0034] The specific diamine is preferably an aromatic diamine from the viewpoint of reducing the dielectric constant of the resulting cured product. Further specific examples of the specific diamine include diamines represented by the following formulas (d1-1) to (d1-20).

[0035]

[0036] From the viewpoint of achieving a low dielectric constant, it is preferable that the specific diamine does not have an amide bond in the molecule. Specifically, among the above formulas (d1-1) to (d1-20), compounds represented by formulas (d1-5) to (d1-7), formulas (d1-9) to (d1-13), and formulas (d1-17) to (d1-20) are preferred. Furthermore, from the viewpoint of achieving a low dielectric constant, it is preferable that the specific diamine has a structure that allows an ether bond to be introduced into the polymer main chain.

[0037] The compound represented by formula (3) and the compound represented by formula (2) can be synthesized by appropriately combining standard methods in organic chemistry. For example, the compound represented by formula (3) can be obtained by reacting a bifunctional compound having a partial structure containing a halogenated alkyl group having 1 to 3 carbon atoms and at least one hydrogen atom and a hydroxyl group with a compound having an acid anhydride group and reactive with the bifunctional compound. The compound represented by formula (2) can be obtained by, for example, synthesizing a compound in which the primary amino group of the compound represented by formula (2) is a nitro group, followed by reducing the nitro group to an amino group. However, the synthesis methods for the compound represented by formula (3) and the compound represented by formula (2) are not limited to those described above.

[0038] The content of the structural unit (a1) in the polymer (A) is preferably 10 mol % or more, more preferably 20 mol % or more, even more preferably 30 mol % or more, and even more preferably 40 mol % or more, based on the total amount of structural units constituting the polymer (A). By setting the content of the structural unit (a1) within the above range, it is possible to sufficiently reduce the dielectric constant of the obtained cured product while ensuring patterning properties and the reliability of the cured product.

[0039] In addition, in synthesizing the polymer (A), a specific diamine can be preferably used as a monomer. In this case, the content of the structural units derived from the specific diamine in the polymer (A) is preferably 50 mol % or more, more preferably 60 mol % or more, even more preferably 70 mol % or more, and even more preferably 80 mol % or more, based on the total amount of the structural units derived from the diamine constituting the polymer (A).

[0040] In synthesizing the polymer (A), a monomer that provides the structural unit (a1) may be used together with a monomer that provides the structural unit (a1) (hereinafter, also referred to as "other monomer"). The other monomer is not particularly limited, and known acid derivatives and diamines may be used as appropriate.

[0041] For example, when obtaining a polymer having a partial structure in which p in the above formula (1) is 0 or 1 as the polymer (A), specific examples of the acid derivative include alicyclic dicarboxylic acids such as cyclobutanedicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclopentanedicarboxylic acid, and cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 2,5-dimethylterephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and 4,4'-diphenylmethanedicarboxylic acid; Examples of the aromatic dicarboxylic acids include 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3'-[4,4'-(methylenedi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dibutyric acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, and azobenzene-4,4'-dicarboxylic acid; and aromatic tricarboxylic acids such as trimellitic acid and trimesic acid. In order to activate the reactivity of the carboxy group, the dicarboxylic acid and tricarboxylic acid are preferably reacted with a diimidazolide compound or a chlorinating agent before being reacted with the diamine.

[0042] Furthermore, when a polymer having a partial structure in which p is 2 in the above formula (1) is obtained as the polymer (A), specific examples of the acid derivative to be used include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3. Aliphatic tetracarboxylic dianhydrides such as octane-2:4,6:8-dianhydride, cyclopentane tetracarboxylic dianhydride, and cyclohexane tetracarboxylic dianhydride; aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bisanhydrotrimate, 4,4'-carbonyldiphthalic anhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; diesterified products and diester dihalides of these tetracarboxylic dianhydrides.

[0043] From the viewpoint of obtaining a polymer having high heat resistance and solvent resistance, the polymer (A) preferably contains a structural unit derived from at least one selected from the group consisting of aromatic tetracarboxylic acid dianhydrides and alicyclic tetracarboxylic acid dianhydrides. Of these, aromatic tetracarboxylic acid dianhydrides are preferred from the viewpoint of low expansion, and alicyclic tetracarboxylic acid dianhydrides are preferred from the viewpoint of transparency and flatness of the cured product. Specifically, it is preferable to contain at least one selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentane tetracarboxylic acid dianhydride, cyclohexane tetracarboxylic acid dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyl tetracarboxylic acid dianhydride, and 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride.

[0044] Specific examples of diamines as other monomers (hereinafter also referred to as "other diamines") include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)fluorene, 4,4'-(p-phenylenediamine), N-(m-phenylenediisopropylidene)bisaniline, 4,4'-(m-phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N' -bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl)piperazine-4-carboxylic acid, 4-(morpholin-4-yl) Benzene-1,3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, 4-(2-aminoethyl)aniline, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, ethylenediamine, 1,3-diaminopropane, 1,5-diaminopentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-bis(2-aminoethoxy)ethane, 1,Examples include 3-bis(3-aminopropyl)-tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0045] Diaminoorganosiloxanes (e.g., 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane) are preferably used as the diamine for obtaining polymer (A) because they can improve adhesion to substrates (particularly silicon substrates). In polymer (A), the content of structural units derived from diaminoorganosiloxane is preferably 1 to 10 mol % based on the total amount of structural units derived from diamines constituting polymer (A).

[0046] Synthetic Method of Polymer (A) Polymer (A) can be obtained by condensation polymerization of the above-mentioned acid derivative and diamine. For example, polyamic acid as polymer (A) (hereinafter also referred to as "polyamic acid (A)") can be obtained by reacting the above-mentioned tetracarboxylic dianhydride with diamine, optionally together with a molecular weight modifier.

[0047] In the synthesis reaction of the polyamic acid (A), the ratio of the tetracarboxylic dianhydride to the diamine is preferably such that 0.2 to 2 equivalents, and more preferably 0.8 to 1.2 equivalents, of the acid anhydride group of the tetracarboxylic dianhydride per equivalent of the amino group of the diamine.

[0048] Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, n-butylamine, and 3-aminophenol; and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The proportion of the molecular weight modifier used is preferably 20 parts by mole or less, and more preferably 15 parts by mole or less, per 100 parts by mole of the total of the tetracarboxylic dianhydride and diamine used.

[0049] The synthesis reaction of the polyamic acid (A) is preferably carried out in an organic solvent. The reaction temperature is preferably −20° C. to 150° C., and the reaction time is preferably 0.1 to 24 hours. Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents include one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, and halogenated phenols, or a mixture of one or more of these solvents with another organic solvent (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount (a) of the organic solvent used is preferably an amount such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50% by mass relative to the total amount (a+b) of the reaction solution.

[0050] In this manner, a reaction solution containing the polyamic acid (A) dissolved therein is obtained. This reaction solution may be used directly in the preparation of a photosensitive composition, or the polyamic acid (A) contained in the reaction solution may be isolated and then used in the preparation of a photosensitive composition, or the isolated polyamic acid (A) may be purified and then used in the preparation of a photosensitive composition. When the polyamic acid (A) is converted into a polyimide by dehydration ring closure or into a polyamic acid ester by esterification, the reaction solution may be used directly in the reaction, or the polyamic acid (A) contained in the reaction solution may be isolated and then used in the reaction, or the isolated polyamic acid (A) may be purified and then used in the reaction. The isolation and purification of the polyamic acid (A) can be carried out according to known methods.

[0051] When a polyamic acid ester is obtained as the polymer (A), the polyamic acid ester (hereinafter also referred to as "polyamic acid ester (A)") can be obtained, for example, by [I] a method of reacting the polyamic acid (A) obtained above with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine. The above methods [II] and [III] are preferably methods using a specific diamine.

[0052] Examples of the esterifying agent used in the method [I] include hydroxyl group-containing compounds, acetal compounds, halides, and epoxy group-containing compounds. Specific examples of these include hydroxyl group-containing compounds such as alcohols such as methanol, ethanol, and propanol; and phenols such as phenol and cresol. Examples of acetal compounds include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, and N,N-diethylformamide diethyl acetal. Examples of halides include methyl bromide, ethyl bromide, methyl chloride, and ethyl chloride. Examples of epoxy group-containing compounds include propylene oxide.

[0053] The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic acid dianhydride exemplified in the synthesis of the polyamic acid (A) using an alcohol such as methanol or ethanol. In the reaction with the diamine, the tetracarboxylic acid diester may be used in combination with the tetracarboxylic acid dianhydride. Examples of the diamine to be used include the specific diamines exemplified above and other diamines.

[0054] The reaction in method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst. Examples of the organic solvent include those exemplified as those used in the synthesis of polyamic acid (A). Examples of the dehydration catalyst include 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium halide, carbonylimidazole, and phosphorus-based condensing agents. The reaction temperature is preferably −20 to 150°C, more preferably 0 to 100°C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

[0055] The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with a suitable halogenating agent. In the reaction with the diamine, a tetracarboxylic acid dianhydride may be used in combination with the tetracarboxylic acid diester dihalide. Examples of the diamine to be used include the specific diamines exemplified above and other diamines.

[0056] The reaction in method [III] is preferably carried out in an organic solvent in the presence of a suitable base. Examples of the organic solvent include those exemplified for use in the synthesis of polyamic acid (A). Examples of the base that can be preferably used include tertiary amines such as pyridine and triethylamine; and alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, and potassium. The reaction temperature is preferably −20 to 150°C, more preferably 0 to 100°C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

[0057] The reaction solution containing the polyamic acid ester (A) dissolved therein may be used as is for preparing a photosensitive composition, or the polyamic acid ester (A) contained in the reaction solution may be isolated and then used for preparing a photosensitive composition, or the isolated polyamic acid ester (A) may be purified and then used for preparing a photosensitive composition. The isolation and purification of the polyamic acid ester (A) may be carried out according to known methods.

[0058] The esterification rate of the polyamic acid ester (A) is preferably 30% or more, more preferably 40% or more, and even more preferably 50 mol% or more. By setting the esterification rate of the polyamic acid ester (A) within the above range, a cured film having high heat resistance and solvent resistance and a low dielectric constant can be obtained. The esterification rate is expressed as a percentage of the number of amic acid ester structures relative to the total number of amic acid structures, amic acid ester structures, and imide ring structures in the polyamic acid ester. In this specification, the esterification rate of the polyamic acid ester is １ It is a value calculated from the peak areas derived from the protons of the esterified alkyl group, the NH group, and the aromatic ring, as measured by H-NMR.

[0059] When the polymer (A) is a polyimide, the polymer (hereinafter also referred to as "polyimide (A)") can be obtained, for example, by imidizing the polyamic acid (A) through dehydration and cyclization. The dehydration and cyclization of the polyamic acid is preferably carried out by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration and cyclization catalyst to the solution, and optionally heating the solution.

[0060] In the method of heating the polyamic acid, the reaction temperature is preferably 50 to 200°C, more preferably 60 to 170°C. By setting the reaction temperature to 50°C or higher, the dehydration ring-closing reaction can be sufficiently promoted. Furthermore, by setting the reaction temperature to 200°C or lower, a decrease in the molecular weight of the resulting imidized polymer can be suppressed. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

[0061] In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyamic acid solution, the dehydrating agent can be, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. The amount of dehydrating agent used is preferably 0.01 to 20 moles per mole of the amic acid structure of the polyamic acid. The dehydration ring-closing catalyst can be, for example, a tertiary amine such as pyridine, collidine, lutidine, or triethylamine. The amount of dehydration ring-closing catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. Examples of organic solvents used in the dehydration ring-closing reaction include the organic solvents exemplified for use in the synthesis of polyamic acid (A). The reaction temperature for the dehydration ring-closing reaction is preferably 0 to 180°C, more preferably 10 to 150°C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

[0062] In this way, a reaction solution containing polyimide (A) is obtained. This reaction solution may be used directly for preparing a photosensitive composition, or may be used for preparing a photosensitive composition after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or polyimide (A) may be isolated and used for preparing a photosensitive composition, or the isolated polyimide (A) may be purified and used for preparing a photosensitive composition. These purification operations can be carried out according to known methods. Alternatively, polyimide (A) may be obtained by imidizing polyamic acid ester (A).

[0063] The imidization ratio of the polyimide (A) is preferably 30% or more, more preferably 50% or more, and even more preferably 60% or more. From the viewpoint of ensuring the solubility of the polymer and improving the coatability, the imidization ratio of the polyimide (A) is preferably 95% or less, more preferably 90% or less. The imidization ratio is the ratio of the number of imide ring structures to the total number of amic acid structures and imide ring structures of the polyimide, expressed as a percentage. In this specification, the imidization ratio of the polyimide is １ This is a value measured by H-NMR.

[0064] When a polyamide is obtained as the polymer (A), the polyamide (hereinafter also referred to as "polyamide (A)") can be obtained, for example, by a polycondensation reaction between a dicarboxylic acid and a diamine. In synthesizing the polyamide (A), it is preferable to use a specific diamine.

[0065] The reaction of dicarboxylic acid with diamine is preferably carried out in an organic solvent in the presence of a base. The ratio of dicarboxylic acid to diamine used in the reaction is preferably such that 0.2 to 2 equivalents of carboxyl groups of the dicarboxylic acid are used per equivalent of amino groups of the diamine, more preferably 0.8 to 1.2 equivalents. The reaction temperature is preferably -100°C to 200°C, more preferably 10 to 100°C. The reaction time is preferably 0.5 to 48 hours, more preferably 1 to 36 hours.

[0066] As the organic solvent used in the reaction, an organic solvent such as diethyl ether, tetrahydrofuran, dioxane, toluene, methylene chloride, chloroform, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, or N-methyl-2-pyrrolidone can be preferably used. The amount of the organic solvent used is preferably 400 to 900 parts by mass, and more preferably 500 to 700 parts by mass, per 100 parts by mass of the total amount of the dicarboxylic acid dihalide and the diamine.

[0067] Preferred examples of the base used in the above reaction include tertiary amines such as pyridine, triethylamine, tripropylamine, triisopropylamine, N-ethyl-N,N-diisopropylamine, and diazabicycloundecene; and alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydride, sodium hydride, potassium hydride, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, and t-butyllithium. The amount of the base used is preferably 2 to 4 moles, and more preferably 2 to 3 moles, per mole of diamine.

[0068] When polybenzoxazole is obtained as the polymer (A), the polybenzoxazole (hereinafter also referred to as "polybenzoxazole (A)") can be obtained, for example, by a method of heating the polyamide (A) obtained as described above at 150 to 250°C; a method of adding an acidic catalyst to cause ring closure; or the like. The heating and ring closure reaction to obtain polybenzoxazole (A) are preferably carried out in an organic solvent. Examples of the organic solvent include the same organic solvents as those exemplified as organic solvents that can be used in synthesizing polyamide (A).

[0069] The solution viscosity of the polymer (A) is preferably 5 to 800 mPa·s, and more preferably 10 to 500 mPa·s, when the polymer (A) is prepared into a 10% by mass solution. The solution viscosity (mPa·s) of the polymer (A) is a value measured at 25°C using an E-type rotational viscometer for a 10% by mass polymer solution prepared using a good solvent for the polymer (A) (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0070] The number average molecular weight (Mn) of the polymer (A) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 2,000 or more. An Mn of 2,000 or more is preferable in that a cured product having sufficiently high heat resistance and solvent resistance and good developability can be obtained. The Mn of the polymer (A) is more preferably 3,000 or more, and even more preferably 4,000 or more. Furthermore, from the viewpoint of improving film-forming properties, the Mn of the polymer (A) is preferably 150,000 or less, and more preferably 120,000 or less.

[0071] 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.

[0072] In the present composition, the content of polymer (A) is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, based on the total amount of solids contained in the present composition (i.e., components other than the solvent in the present composition), from the viewpoint of obtaining a cured film that exhibits good heat resistance and solvent resistance.

[0073] <Photosensitive Compound> The photosensitive compound may be any component that changes the solubility of the composition upon irradiation with radiation. Examples of photosensitive compounds include quinone diazide compounds, photoacid generators, and photopolymerization initiators. Among these, quinone diazide compounds are substances that change to indene carboxylic acid upon irradiation with radiation. Photoacid generators are substances that generate acid upon irradiation with radiation and are capable of eliminating acid-dissociable groups contained in components in the composition. When a positive-type photosensitive composition is to be obtained, a quinone diazide compound or a photoacid generator is preferably used as the photosensitive compound. When a negative-type photosensitive composition is to be obtained, a photopolymerization initiator is preferably used as the photosensitive compound.

[0074] The present composition is preferably used as a positive photosensitive composition. Specifically, the photosensitive compound blended in the present composition is preferably a quinone diazide compound or a photoacid generator, more preferably a quinone diazide compound.

[0075] 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 the mother nucleus with an orthonaphthoquinone diazide compound. Specific examples of the mother nucleus include the compounds described in paragraphs 0065 to 0070 of JP 2014-186300 A. The orthonaphthoquinone diazide compound is preferably 1,2-naphthoquinone diazide sulfonic acid halide.

[0076] As the quinone diazide compound, a condensation product of a phenolic compound or alcoholic compound as the mother nucleus with 1,2-naphthoquinone diazide sulfonic acid halide can be preferably used, and a condensation product of a phenolic compound with 1,2-naphthoquinone diazide sulfonic acid halide can be more preferably used.

[0077] Specific examples of the quinone diazide compound 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.

[0078] In the condensation reaction to obtain the above condensation product, the ratio of the mother nucleus to the 1,2-naphthoquinone diazide sulfonyl halide is preferably such that the amount of 1,2-naphthoquinone diazide sulfonyl halide used corresponds to 30 to 85 mol %, and more preferably 50 to 70 mol %, of the number of OH groups in the mother nucleus. The above condensation reaction can be carried out according to a known method.

[0079] Examples of the photoacid generator 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 carboxylic acid ester compounds.

[0080] Specific examples of the oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, and carboxylic acid ester compounds include the compounds described in paragraphs

[0034] to

[0038] of JP 2012-252343 A, the compounds described in paragraphs

[0078] to

[0106] of JP 2014-157252 A, and the compounds described in WO 2016 / 124493. Of these, at least one selected from the group consisting of oxime sulfonate compounds, sulfonimide compounds, onium salts, halogen-containing compounds, sulfone compounds, and sulfonate ester compounds can be preferably used as the photoacid generator.

[0081] The content of the photosensitive compound in the composition can be selected depending on the type of photosensitive compound used.For example, 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.In addition, 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.

[0082] When the content of the quinone diazide compound is 2 parts by mass or more, sufficient acid is generated by irradiation with actinic rays, and the difference in solubility in the developer between the exposed and unexposed areas can be sufficiently increased. This allows for good patterning. Furthermore, the amount of acid involved in the reaction with the polymer component can be increased, ensuring sufficient heat resistance of the cured film obtained using this composition. On the other hand, when the content of the quinone diazide compound is 60 parts by mass or less, the amount of unreacted quinone diazide compound can be sufficiently reduced, which is advantageous in that it can suppress a decrease in developability and film transmittance due to the remaining quinone diazide compound.

[0083] When a photoacid generator is used as the photosensitive compound, the content of the photoacid generator in the composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, per 100 parts by mass of the polymer (A) contained in the composition, and is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, per 100 parts by mass of the polymer (A) contained in the composition.

[0084] <Other Components> The present composition may further contain components other than the polymer (A) and the photosensitive compound (hereinafter also referred to as "other components"). Examples of the other components include a crosslinkable compound, an adhesion aid, a developing aid, a surfactant, a solvent, etc.

[0085] Crosslinkable Compound The crosslinkable compound is a component that has a crosslinkable functional group and thereby forms a crosslinked structure between or within the molecules of the polymer (A) by light or heat, or forms bonds between crosslinkable compounds. By making the present composition a composition that contains the crosslinkable compound together with the polymer (A), the reliability of the cured film obtained using the present composition can be further improved.

[0086] Examples of the crosslinkable functional group possessed by the crosslinkable compound include a cyclic ether group, a cyclic thioether group, a carboxy group, a cyclocarbonate group, an alcoholic hydroxyl group, a protected alcoholic hydroxyl group, an amino group, a protected amino group, a protected isocyanate group, a polymerizable unsaturated bond group (for example, a (meth)acryloyl group), a hydroxyalkylamide group, a protected hydroxyalkylamide group, and an oxazoline group.

[0087] 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 crosslinkable compound is preferably at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a thiirane group, a hydroxyalkylamide group, a protected hydroxyalkylamide group, a methylol group, a protected methylol group, an alkoxymethyl 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 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 hydroxymethylphenyl group, and an alkoxymethylphenyl group.

[0088] From the viewpoints of sufficiently improving the reliability of the cured film and suppressing film shrinkage, the number of crosslinkable functional groups that the crosslinkable compound has in one molecule is preferably 2 to 10, and more preferably 3 to 8. The molecular weight of the crosslinkable compound is, for example, 1,000 or less, preferably 800 or less, and more preferably 600 or less.

[0089] Specific examples of the crosslinkable compound 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, trimethylol diglycidyl propane triglycidyl 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 reaction products of 2,2'-diallyl bisphenol A diallyl ether with hydrogen peroxide, and the like; Examples of compounds having a cyclocarbonate group include compounds in which the epoxy group of the above-exemplified compounds having an epoxy group has been protected (for example, N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)ethyl]-4,4'-diaminodiphenylmethane); Examples of compounds having a thiirane group include compounds in which the epoxy group of the above-exemplified compounds has been replaced with a thiirane group; Examples of compounds having a hydroxyalkylamide group or a protected hydroxyalkylamide group include compounds represented by the following formulas (c-1) to (c-7):; Examples of compounds having at least one of a methylol group, a protected methylol group, and an alkoxymethyl group include 2,2-bis(4-hydroxymethylphenyl)propane, 2,2-bis(2,3,4-trihydroxymethylphenyl)propane, and compounds represented by the following formulas (c-8) to (c-17):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.

[0090] 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 dimethanols or polycycloalkane dimethanols, such as cyclohexanedimethanol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; trimethylolpropane poly(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, pentaerythritol poly(meth)acrylate, and dipentaerythritol poly(meth)acrylate. polyfunctional (meth)acrylic acid esters of trihydric or higher polyhydric alcohols such as trimethylol 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, and 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.

[0091] When the composition contains a crosslinkable compound, the content of the crosslinkable compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the polymer (A) contained in the composition. The content of the crosslinkable compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, per 100 parts by mass of the polymer (A) contained in the composition.

[0092] Adhesion Aid The adhesion aid is a component that improves the adhesion between the cured film formed 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 possessed by the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0093] 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.

[0094] When the present 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 present composition.

[0095] Developing Aid The developing aid is a component that improves the developability of the present composition (shortening development time, reducing development residue, and improving resolution and sensitivity). As the developing aid, a low molecular weight compound having a phenolic hydroxyl group (hereinafter also referred to as a "phenolic low molecular weight compound") can be preferably used. The number of phenolic hydroxyl groups in one molecule of the phenolic low molecular weight compound is preferably 1 to 10, and more preferably 2 to 6, from the viewpoints of sufficiently obtaining the effect of improving the developability of the present composition and suppressing film shrinkage.

[0096] Specific examples of the phenolic low molecular weight compound include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, and 1,1,2,2-tetra(4-hydroxyphenyl)ethane.

[0097] When the present composition contains a developing aid, the content thereof is preferably 1 to 100 parts by mass, more preferably 1 to 60 parts by mass, and even more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the polymer (A) contained in the present composition. By setting the content of the phenolic low molecular weight compound to 1 part by mass or more, the effect of improving developability by incorporating the phenolic low molecular weight compound can be fully obtained. Furthermore, by setting the content of the phenolic low molecular weight compound to 100 parts by mass or less, the effect of improving developability can be obtained while suppressing a decrease in the mechanical strength of the film.

[0098] Surfactants Surfactants can be used to improve the coating properties of the composition (wetting and spreading properties and reduction of coating unevenness). Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. The surfactant can be selected from known surfactants, such as commercially available products.

[0099] 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.

[0100] The present composition is preferably a liquid composition in which the polymer (A), the photosensitive compound, and other components blended as necessary are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each of the components blended in the present composition but does not react with each of the components.

[0101] 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.

[0102] 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 acetate, diethylene glycols, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate.

[0103] The content of the solvent in the present composition (the total amount of solvents 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 present composition.

[0104] In addition to the above, other components may also be contained, such as known additives as acid diffusion controllers, sensitizers, antioxidants, thermal radical generators, thermal acid generators, ultraviolet absorbers, thickeners, acid multipliers, plasticizers, suspending agents, polymerization inhibitors, chain transfer agents, etc. The amounts of these components to be added are appropriately selected depending on the respective components within a range that does not impair the effects of the present disclosure.

[0105] The solids concentration of the 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 taking into consideration viscosity, volatility, and the like. The solids concentration of the composition is preferably in the range of 5 to 60 mass%. A solids concentration of 5 mass% or more ensures a sufficient coating thickness when the composition is applied to a substrate. Furthermore, a solids concentration of 60 mass% or less prevents the coating thickness from becoming excessively thick, and further allows the viscosity of the composition to be appropriately increased, ensuring good coatability. The solids concentration of the composition is more preferably 10 to 55 mass%, and even more preferably 10 to 50 mass%.

[0106] Cured Product and Manufacturing Method Thereof The cured product of the present disclosure is formed from the photosensitive composition prepared as described above. By using this composition, it is possible to form a film that exhibits good patterning properties and a cured product that has a low dielectric constant and excellent reliability. Therefore, this composition can be preferably used as a material for forming, for example, an interlayer insulating film, a planarizing film, a spacer, a protective film (passivation film), a colored pattern film for a color filter, a partition wall, a bank, etc., which are provided in a display device, a semiconductor device, etc.

[0107] When a cured product is produced using the present composition, a positive- or negative-tone cured product can be formed depending on the type of photosensitive compound. A patterned cured product can be produced using the present composition, for example, by a method including the following steps 1 to 4: Step 1: Applying the present composition to a substrate (applying step); Step 2: Exposing the applied photosensitive composition to light (exposing step); Step 3: Developing the exposed photosensitive composition (developing step); Step 4: Curing the developed photosensitive composition (curing step). Each step will be described in detail below.

[0108] [Coating Step] In the coating step, the composition is applied to a surface on which a film is to be formed (hereinafter also referred to as "film-forming surface"), and the solvent in the composition is removed, preferably by heat treatment (pre-baking), to form a coating film on the substrate. The material of the substrate surface is not particularly limited. For example, when forming an interlayer insulating film, the composition is applied to a substrate provided with switching elements such as TFTs to form a coating film. Examples of substrates that can be used include glass substrates, silicon substrates, and resin substrates. The surface of the substrate on which the coating film is to be formed may have a metal thin film formed thereon depending on the application, or may have been subjected to various surface treatments such as HMDS (hexamethyldisilazane) treatment.

[0109] Examples of methods for applying the composition include spraying, roll coating, spin coating, slit die coating, bar coating, and inkjet coating. Of these, spin coating, slit die coating, and bar coating are preferred. Prebaking conditions vary depending on the type and content of each component in the composition, but may include heating at 60 to 130°C for 0.5 to 10 minutes. The thickness of the coating film formed (i.e., the film thickness after prebaking) is preferably 0.1 to 12 μm. The composition applied to the substrate may be subjected to reduced pressure drying (VCD) before prebaking.

[0110] [Exposure Step] In the exposure step, at least a portion of the coating film formed in the coating step is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured product having a pattern can be formed. Examples of radiation include charged particle rays such as ultraviolet rays, far ultraviolet rays, visible light, X-rays, and electron beams. Among these, ultraviolet rays are preferred, and examples thereof include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m ２ is preferred.

[0111] [Development Step] In the development step, the coating film irradiated in the exposure step is developed. Specifically, the coating film irradiated in the exposure step is developed using a developer, thereby performing positive development, which removes the irradiated portions, or negative development, which removes the unirradiated portions. Examples of the developer include an aqueous solution of an alkali (basic compound). Examples of alkali include sodium hydroxide, tetramethylammonium hydroxide, and the alkalis exemplified in paragraph

[0127] of JP 2016-145913 A. The alkali concentration in the aqueous alkali solution is preferably 0.1 to 5% by mass from the viewpoint of achieving appropriate developability. Examples of development methods include a puddle method, a dipping method, a swing 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, the patterned coating film is preferably rinsed with running water.

[0112] [Curing Step] In the curing step, the coating film developed in the developing step is preferably heated (post-baked) to cure the composition. This heating treatment further promotes the curing reaction, resulting in a cured product with excellent heat resistance. Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120 to 300°C. The heating time is, for example, 5 to 80 minutes when the heating treatment is performed on a hot plate, and 10 to 120 minutes when the heating treatment is performed in an oven. This heating treatment allows a cured product having a desired pattern to be formed on the substrate. The shape of the pattern of the cured product is not particularly limited, and examples include a line-and-space pattern, a dot pattern, a hole pattern, and a lattice pattern.

[0113] The cured film obtained from the composition can also be used as a dry etching resist. When the cured film is used as a dry etching resist, dry etching treatments such as ashing, plasma etching, and ozone etching can be used as the etching treatment.

[0114] Display Devices and Semiconductor Devices The present disclosure provides a display device or semiconductor device comprising a cured product formed using the present composition. Specific examples of display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, mini-LED display devices, and micro-LED display devices. In the display device or semiconductor device of the present disclosure, the type of cured product formed using the present composition is not particularly limited. The present composition can provide a cured film that exhibits excellent developability (particularly alkaline developability), a low refractive index, and excellent reliability. Therefore, the present composition is particularly suitable as a film-forming composition for display devices or semiconductor devices, i.e., a film-forming composition for forming a planarizing film, which is an insulating layer that covers steps in TFT circuits or wiring formed on a substrate, an interlayer insulating film, which is an insulating layer that insulates wiring between wirings in multilayer wiring or between wiring and a substrate, or a semiconductor passivation film.

[0115] A cured film formed using this composition is resistant to performance degradation even under high temperature and high humidity conditions and is highly reliable, making it suitable for use in organic EL devices that require higher resolution. Furthermore, the cured film is poorly water-permeable and has excellent bending resistance, making it suitable for use in display devices for flexible displays. Flexible displays include foldable displays, bendable displays, and rollable displays.

[0116] According to the present disclosure detailed above, the following means are provided. [Means 1] A photosensitive composition containing a polymer derived from a monomer having a halogenated alkyl group of 1 to 3 carbon atoms containing at least one hydrogen atom and containing a hydroxyl group, and a photosensitive compound. [Means 2] The photosensitive composition of [Means 1], wherein the polymer contains, as the structural unit (a1), a structural unit derived from a diamine having a halogenated alkyl group of 1 to 3 carbon atoms containing at least one hydrogen atom and a hydroxyl group. [Means 3] The photosensitive composition of [Means 1] or [Means 2], wherein the polymer is at least one selected from the group consisting of polyimide, polyamic acid ester, polyamic acid, polyamide, and polybenzoxazole. [Means 4] The photosensitive composition of any of [Means 1] to [Means 3], wherein the polymer has a partial structure represented by formula (1) above. [Means 5] The photosensitive composition of [Means 4], wherein q is 1 or more and r is 1 or more in the above formula (1). [Means 6] The photosensitive composition of any of [Means 1] to [Means 5], wherein the photosensitive compound comprises a quinone diazide compound or a photoacid generator. [Means 7] The photosensitive composition of any of [Means 1] to [Means 6], wherein the photosensitive compound comprises a crosslinkable compound. [Means 8] The photosensitive composition of [Means 7], wherein the crosslinkable compound is at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a thiirane group, a hydroxyalkylamide group, a protected hydroxyalkylamide group, a methylol group, a protected methylol group, an alkoxymethyl group, a cyclocarbonate group, and a protected isocyanate group. [Means 9] A cured product comprising the photosensitive composition of any of [Means 1] to [Means 8]. [Means 10] A display device comprising the cured product of [Means 9]. [Means 11] A semiconductor device comprising the cured product of [Means 9]. [Means 12] A method for producing a cured product, comprising the steps of applying the photosensitive composition of any of [Means 1] to [Means 8] onto a substrate, exposing the applied photosensitive composition to light, developing the exposed photosensitive composition, and curing the developed photosensitive composition. [Means 13] A polymer having a partial structure represented by formula (1) above. [Means 14] A compound represented by formula (2) above. [Means 15] A compound represented by formula (3) above.

[0117] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified.

[0118] The methods for measuring the physical properties of the polymer are as follows. <Weight average molecular weight (Mw) and number average molecular weight (Mn)> The weight average molecular weight (Mn) and number average molecular weight (Mn) of the polymer are polystyrene-equivalent values ​​measured by GPC under the following conditions: Column: TSKgel GRCXLII, manufactured by Tosoh Corporation Solvent: N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40°C Pressure: 68 kgf / cm ２ <Imidization rate of polyimide> Polyimide was dissolved in deuterated dimethyl sulfoxide and measured at room temperature using tetramethylsilane as a reference substance. １ H-NMR was measured. １ The imidization rate [%] was calculated from the H-NMR spectrum using the following formula (1): Imidization rate [%] = (1 - (β1 / (β2 × α))) × 100 ... (1) (In formula (1), β1 is the peak area derived from the NH group proton appearing at a chemical shift of approximately 10 ppm, β2 is the peak area derived from other protons, and α is the ratio of the number of other protons to one NH group proton in the polymer precursor (polyamic acid).) <Esterification rate of polyamic acid ester> Polyimide was dissolved in deuterated dimethyl sulfoxide, and the imidization rate was measured at room temperature using tetramethylsilane as a reference substance. １ H-NMR was measured. １ The esterification rate [%] was calculated from the H-NMR spectrum using the following formula (2): Esterification rate (%) = ((A / B) / (C / D)) × 100 (2) (In formula (2), A is the peak area derived from the ester, B is the peak area derived from the aromatic compound, C is the number of protons in the ester when 100% esterification is achieved, and D is the number of protons derived from the aromatic compound.)

[0119] The details of the compounds used in the synthesis of the polymer and the preparation of the photosensitive composition are as follows: Tetracarboxylic acid dianhydride

[0120] Diamines and monoamines

[0121] Crosslinking agent

[0122] 1. Synthesis of Compounds [Example 1-1] Synthesis of Compound (DA-1)

[0123] Synthesis of DA-1-1: 6.20 g of 3-nitrobenzoyl chloride and 5.00 g of 5,5'-methylenebis(2-aminobenzoic acid) were added to 50 mL of THF and cooled in an ice bath. Then, 4.83 g of triethylamine dissolved in 50 mL of THF was added dropwise. After the addition was complete, the mixture was returned to room temperature and stirred for 12 hours. The reaction solution was poured into 500 mL of 1 M aqueous hydrochloric acid, and the precipitated solid was filtered and washed with distilled water. The solid was redissolved in THF and recrystallized by adding ethanol. After filtration, the mixture was vacuum dried at 60°C for 12 hours to obtain 9.03 g of compound (DA-1-1). Synthesis of DA-1-2: 6.00 g of compound (DA-1-1), 10 mL of thionyl chloride, and two drops of N,N-dimethylformamide were added and reacted at 80°C for 2 hours. After the reaction, the thionyl chloride was removed under reduced pressure. Subsequently, 20 mL of acetonitrile and 20 mL of NMP were added, followed by the addition of 10.4 g of (bromodifluoromethyl)trimethylsilane, 12.1 g of triphenylphosphine, and 7.89 g of N,N'-dimethylpropyleneurea, and the mixture was allowed to react at room temperature for 5 hours. A solution of 3.25 g of pyridine and 10.3 mL of distilled water was then added, and the mixture was allowed to react at 80°C for 1.5 hours. The reaction solution was poured into 500 mL of distilled water, and the precipitated solid was filtered and washed with distilled water. 4.64 g of compound (DA-1-2) was obtained by vacuum drying at 60°C for 12 hours. Synthesis of DA-1: 4.50 g of compound (DA-1-2), 7.75 g of zinc, and 3.17 g of ammonium chloride were weighed out, and nitrogen substitution was performed. 14 mL of THF, 4 mL of NMP, and 4 mL of ethanol were added, and the mixture was cooled in an ice bath, followed by the dropwise addition of 3.05 g of distilled water. After the dropwise addition was completed, the mixture was returned to room temperature and stirred for 4 hours. After the reaction, insoluble components were removed by filtration through Celite, and 150 mL of methanol and 150 mL of distilled water were added to the filtrate. The precipitated solid was filtered and washed with distilled water. The mixture was dried in vacuo at 60°C for 12 hours to obtain 3.61 g of compound (DA-1).

[0124] Example 1-2 Synthesis of Compound (DA-2) 4.8 g of compound (DA-2) was obtained in the same manner as in Example 1-1, except that 3-nitrophenoxyacetyl chloride was used instead of 3-nitrobenzoyl chloride in Synthesis Example 1.

[0125] Example 1-3 Synthesis of Compound (DA-3) 3.3 g of compound (DA-3) was obtained in the same manner as in Example 1-1, except that 3,5-diaminobenzoic acid was used instead of 5,5′-methylenebis(2-aminobenzoic acid).

[0126] [Example 1-4] Synthesis of compound (DA-4)

[0127] 4.3 g of compound (DA-4-1) was obtained by the same method as in Example 1-1, except that compound (DA-7) was used instead of 5,5'-methylenebis(2-aminobenzoic acid) in Example 1-1. Subsequently, 3.5 g of compound (DA-4) was obtained by the same method as in Example 1-1, except that compound (DA-4-1) was used instead of compound (DA-1-2) in Example 1-1.

[0128] [Example 1-5] Synthesis of compound (DA-6)

[0129] The same method as in Example 1-1 was repeated except that 3,5-dinitrobenzoic acid was used instead of compound (DA-1-1), to obtain 4.2 g of compound (DA-6).

[0130] [Example 1-6] Synthesis of compound (DA-8)

[0131] 4.4 g of compound (DA-8-1) was obtained by the same method as in Example 1-1, except that 1,1-bis(4-aminophenyl)-2,2-difluoroethan-1-ol was used instead of 5,5'-methylenebis(2-aminobenzoic acid) in compound (DA-1-1) of Example 1-1. Subsequently, 3.1 g of compound (DA-8) was obtained by the same method as in Example 1-1, except that compound (DA-8-1) was used instead of compound (DA-1-2) in Example 1-1.

[0132] [Example 1-7] Synthesis of compound (DA-9)

[0133] 3.32 g of 6M hydrochloric acid was added to 6.84 g of o-toluidine and heated to 100°C. Subsequently, a solution prepared by mixing 3.00 g of 4-(difluoromethoxy)-3-hydroxybenzaldehyde and 10 mL of DMF was added dropwise, and the mixture was allowed to react at 100°C for 12 hours. After the reaction, the mixture was returned to room temperature and neutralized with an aqueous triethylamine solution. The solution extracted with ethyl acetate was washed with distilled water, and then magnesium sulfate was added and dried. After filtration and concentration, the mixture was purified using a silica gel column (ethyl acetate / hexane = 2 / 1). The fraction containing the target compound was collected, and hexane was added to the concentrated solution to carry out recrystallization. Filtration and vacuum drying at 60°C yielded 3.26 g of compound (DA-9).

[0134] [Example 1-8] Synthesis of compound (DA-10)

[0135] In the compound (DA-1-2) of Example 1-1, except that 4-fluoro-2-nitrobenzoic acid was used instead of compound (DA-1-1), 4.81 g of compound (DA-10-1) was obtained by the same method as in Example 1-1. Subsequently, a mixture of 4.00 g of compound (DA-10-1), 1.68 g of bisphenol A, 4.08 g of potassium carbonate, and 40 mL of DMF was reacted for 12 hours with vigorously stirring at 120 ° C. The reaction solution was returned to room temperature and added to 500 mL of distilled water, and the precipitated solid was filtered and washed with distilled water. 4.03 g of compound (DA-10-2) was obtained by vacuum drying at 60 ° C. for 12 hours. Thereafter, 3.2 g of compound (DA-10) was obtained by the same method as in Example 1-1, except that in the compound (DA-1) of Example 1-1, compound (DA-10-2) was used instead of compound (DA-1-2).

[0136] [Example 1-9] Synthesis of compound (DA-11)

[0137] 3.11 g of compound (DA-11) was obtained in the same manner as in Example 1-8, except that 3-fluorobenzoic acid was used instead of 4-fluoro-2-nitrobenzoic acid and bis(3-nitro-4-hydroxyphenyl)sulfone was used instead of bisphenol A.

[0138] [Example 1-10] Synthesis of compound (DA-12)

[0139] Compound (DA-12-1) and compound (DA-12-2) were synthesized according to the method described in the non-patent document "Org. Lett., 2011, 13, 5342." Subsequently, 2.9 g of compound (DA-12) was obtained by the same method as in Example 1-8, except that compound (DA-12-1) and compound (DA-12-2) were used instead of compound (DA-10-1) and bisphenol A, respectively.

[0140] [Example 1-11] Synthesis of compound (DA-13)

[0141] A mixture of 3.00 g of 4-hydroxybenzoic acid, 5.6 g of 3,5-dinitrobenzyl chloride, 3.60 g of potassium carbonate, and 40 mL of DMF was reacted for 12 hours at 80°C with vigorous stirring. Ethyl acetate was added to the reaction solution, which was returned to room temperature, and the mixture was separated and washed with distilled water, and the organic layer was concentrated. Dichloromethane and hexane were added to carry out recrystallization. Filtration and vacuum drying at 60°C yielded 4.97 g of compound (DA-13-1). Subsequently, 3.2 g of compound (DA-13) was obtained by the same method as in Example 1-1, except that compound (DA-13-1) was used instead of compound (DA-1-1).

[0142] [Example 1-12] Synthesis of compound (DA-14)

[0143] The same method as in Example 1-1 was repeated except that 3,5-dinitro-4-methylbenzoic acid was used instead of compound (DA-1-1), to obtain 5.3 g of compound (DA-14).

[0144] [Example 1-13] Synthesis of compound (DA-15)

[0145] Compound (DA-15-1) was synthesized according to the method described in the non-patent document "Org. Lett., 2011, 13, 5342." Subsequently, compound (DA-15-1) and bisphenol A were prepared in a molar ratio of 2:1, and the mixture was heated in DMF in the presence of potassium carbonate to synthesize compound (DA-15-3). Subsequently, 3.3 g of compound (DA-15-4) was obtained by the same method as in Example 1-1, except that compound (DA-15-3) was used instead of compound (DA-1-1).

[0146] 2. Polymer Synthesis - Synthesis of Polyamic Acid Ester (P1) [Example 2-1] Under a dry nitrogen stream, 90 mole parts of compound (DA-1) and 5 mole parts of compound (DC-1) as diamines were dissolved in 80 g of N-methyl-2-pyrrolidone (NMP), and 100 mole parts of compound (TA-2) as a tetracarboxylic dianhydride was added thereto and reacted at 40°C for 6 hours. Next, a solution prepared by diluting 10 mole parts of 3-aminophenol with 5 g of NMP as an end-capping agent was added, and the reaction was carried out at 50°C for 2 hours. Thereafter, a solution prepared by diluting 200 mole parts of N,N-dimethylformamide dimethyl acetal as an esterifying agent in 20 g of NMP was added dropwise over 10 minutes, and the reaction was carried out at 50°C for 3 hours. After completion of the reaction, the solution was cooled to room temperature and then reprecipitated with 1 L of water. The resulting white precipitate was filtered, washed three times with water, and then vacuum dried at 80°C to obtain the target polyamic acid ester (referred to as "polymer (P-1)"). The number average molecular weight of polymer (P-1) was 8,100.

[0147] [Examples 2-2 to 2-15, 2-18, and 2-19, and Comparative Synthesis Examples 1 to 3] Polymerization was carried out in the same manner as in Example 2-1, except that the types and amounts of the tetracarboxylic dianhydrides and diamines used in the polymerization were changed as shown in Table 1, to obtain polymers (P-2) to (P-15) and (P-18) to (P-22), which are polyamic acid esters.

[0148] Synthesis of Polyimide [Example 2-16] Under a dry nitrogen stream, 100 moles of compound (DA-5) as a diamine were dissolved in 80 g of N-methyl-2-pyrrolidone (NMP), and 100 moles of compound (TA-5) as a tetracarboxylic dianhydride were added thereto, followed by a reaction at 40°C for 6 hours. Next, NMP was added to the resulting polyamic acid solution, and pyridine and acetic anhydride were added in amounts of 1.8 molar equivalents relative to the carboxy groups derived from the tetracarboxylic dianhydride possessed by the polyamic acid, followed by a dehydration ring-closing reaction at 100°C for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with fresh NMP and further concentrated. Next, the resulting polymer solution was poured into a large excess of methanol to precipitate the reaction product. This precipitate was washed with methanol and vacuum-dried at 80°C to obtain the desired polyimide with an imidization rate of 70% (referred to as "Polymer (P-16)"). The number-average molecular weight of Polymer (P-16) was 9,000.

[0149] [Example 2-17] Polymerization was carried out in the same manner as in Example 2-16, except that the types and amounts of tetracarboxylic dianhydride and diamine used in the polymerization were changed as shown in Table 1, to obtain a polyimide polymer (P-17).

[0150]

[0151] In Table 1, the numerical values ​​for tetracarboxylic dianhydride represent the ratio (parts by mole) of each monomer to 100 parts by mole of the total amount of tetracarboxylic dianhydride used in the synthesis of each polymer. The numerical values ​​for diamine represent the ratio (parts by mole) of each monomer to 100 parts by mole of the total amount of diamine used in the synthesis of each polymer. The numerical value for 3AP (3-aminophenol), a terminal modifier, represents the ratio (parts by mole) to 100 parts by mole of the total amount of diamine used in the synthesis of each polymer. Blank spaces indicate that the compound was not used.

[0152] 3. Preparation and Evaluation of Photosensitive Compositions [Example 3-1] (1) Preparation of Composition (R-1) 100 parts by mass of polymer P-1 as a polymer, 20 parts by mass of a quinone diazide compound (condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol)) as a photosensitive compound, 20 parts by mass of compound (Add-1) as a crosslinking agent, 5 parts by mass of an adhesion aid (γ-glycidoxypropyltrimethoxysilane), and 0.5 parts by mass of a surfactant (FTX-218, manufactured by Neos Corporation) were mixed together. Furthermore, 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).

[0153] (2) Evaluation of Patterning Ability Composition (R-1) was applied using a spinner onto a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 100°C for 2 minutes to form a coating film with a thickness of 3.0 μm. This coating film was then exposed to 2,000 J / m irradiated light through a pattern mask having a line-and-space pattern with a width of 10 μm using a Canon "MPA-600FA" exposure machine. ２ The sample was irradiated with ultraviolet light of 1000 kJ / cm. Then, a developing treatment was carried out using a developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) at 25° C. for 60 seconds, followed by rinsing with running ultrapure water for 1 minute. The evaluation was rated as "good (◯)" when a 10 μm wide line and space pattern was completely formed, and as "bad (×)" when a 10 μm wide line and space pattern was not obtained. As a result, this example was rated as "good (◯)."

[0154] (3) Evaluation of Dielectric Constant (Measurement of Relative Dielectric Constant) Composition (R-1) was applied to a SUS304 substrate whose surface had been smoothed by polishing with a sisal buff (linen buff), and then the solvent was removed from the composition (R-1) on the substrate under vacuum by setting the ultimate pressure to 100 Pa. The composition was then prebaked at 100°C for 2 minutes to form a coating film having an average film thickness of 3.0 µm. Next, a proximity exposure machine (Canon's "MA-1200" (ghi line mixed)) was used to expose the coating film to 3,000 J / m ２ The entire substrate was irradiated with light of 1000 kJ / cm 2 and then heated in a nitrogen-purged clean oven at 250°C for 60 minutes to form a cured film (insulating film) on the substrate. A Pt / Pd electrode pattern was formed on this insulating film by vapor deposition to prepare a dielectric constant measurement sample. Using the prepared dielectric constant measurement sample, the dielectric constant was measured by the CV method at a frequency of 1 kHz using an LCR meter (HP16451B electrode and HP4284A precision LCR meter, manufactured by Hewlett-Packard Japan, LLC). The dielectric constant was evaluated as "excellent" (◎) when the dielectric constant was 3.3 or less, "good" (○) when it was greater than 3.3 and less than 3.5, "fair" (△) when it was greater than 3.5 and less than 3.7, and "unacceptable" (×) when it was greater than 3.7. As a result, this example was rated as "good" (○).

[0155] (4) Element Evaluation (Preparation of Organic EL Element Substrate) Using a spinner, the prepared composition (R-1) was applied onto a glass substrate ("OA-10" manufactured by Nippon Electric Glass Co., Ltd.) on which ITO transparent electrodes had been formed in an array, and then the applied composition (R-1) was prebaked on a hot plate at 100°C for 2 minutes to form a coating film with a thickness of 3.0 µm. This coating film was exposed to 2,000 J / m 2 light using a Canon "MPA-600FA" exposure machine through a pattern mask having a 10 µm contact hole pattern. ２ The sample was then irradiated with ultraviolet light of 3,000 J / m using a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)). The sample was then developed at 25°C for 60 seconds, and then washed with running ultrapure water for 1 minute. The minimum exposure dose required to form a 10 μm contact hole pattern was measured.２After irradiating the entire substrate with light, the substrate was heated at 250°C for 1 hour in a nitrogen-substituted clean oven to form a cured film (also referred to as a "patterned cured resin layer") with contact holes on the glass substrate. For the glass substrate with the patterned cured resin layer, a 100 nm thick Al film was formed on the patterned cured resin layer by DC sputtering using an Al target through a metal mask with a predetermined pattern. A 20 nm thick ITO film was formed on the Al film by RF sputtering using an ITO target. In this way, an anode layer consisting of an Al film and an ITO film was formed. A coating film was formed on the anode layer using a resist material ("Optomer NN803" manufactured by JSR), and a series of processes including i-line (wavelength 365 nm) irradiation, development, running water rinsing, air drying, and heat treatment were performed to form a pixel-defining layer with a portion of the anode layer as an opening region. The substrate on which the anode and pixel-defining layer were formed was moved to a vacuum deposition chamber, and the deposition chamber was evacuated to 1E-4 Pa. Then, using a deposition mask with a predetermined pattern, a film of molybdenum oxide (MoOx) having hole injection properties was formed on the substrate by resistance heating deposition at a deposition rate of 0.004 to 0.005 nm / sec, forming a hole injection layer with a thickness of 1 nm. Using a deposition mask with a predetermined pattern, a film of 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD) having hole transport properties was formed on the hole injection layer by resistance heating deposition under the same evacuation conditions as for the hole injection layer, forming a hole transport layer with a thickness of 35 nm. The deposition rate was 0.2 to 0.3 nm / sec. Using a vapor deposition mask with a predetermined pattern, a green light-emitting material, tris(8-quinolinolato)aluminum, an alkylate complex, was deposited on the hole transport layer by resistance heating vapor deposition under the same conditions as for the hole transport layer, to form a 35 nm-thick light-emitting layer. The deposition rate was 0.5 nm / sec or less. Using a vapor deposition mask with a predetermined pattern, a film of lithium fluoride was deposited on the light-emitting layer by resistance heating vapor deposition under the same exhaust conditions as for the hole injection layer, to form a 0.8 nm-thick electron injection layer. The deposition rate was 0.004 nm / sec or less.Next, using a vapor deposition mask with a predetermined pattern, Mg and Ag were simultaneously deposited on the electron injection layer by resistance heating vapor deposition under the same exhaust conditions as the hole injection layer, forming a first cathode layer with a thickness of 5 nm. The deposition rate was 0.5 nm / sec or less. Next, the substrate was transferred to another deposition chamber (sputtering chamber), and using a mask with a predetermined pattern, a second cathode layer with a thickness of 100 nm was formed on the first cathode layer by RF sputtering using an ITO target. In this manner, an organic EL element was formed on the substrate, and an organic EL element substrate was obtained.

[0156] (Thin-film encapsulation of organic EL element) A thin-film encapsulation layer was formed on the organic EL element obtained above using the following procedure. The organic EL element substrate was transferred to a film-forming chamber (sputtering chamber), and a 100-nm-thick inorganic encapsulation layer (SiNx film) was formed on the cathode layer by RF sputtering using a SiNx target and a mask with a predetermined pattern. Next, the organic EL element substrate was transferred to an N2-substituted glove box, and a curable composition containing an epoxy compound, an oxetane compound, and a polymerization initiator was ejected in a predetermined pattern using a piezo-type inkjet printer. Next, a UniJet E110ZHD 395 nm LED lamp manufactured by Ushio Inc. was used, and an exposure dose of 1000 mJ / cm was applied. ２ The curable composition was irradiated with light to cure the film, forming an organic sealing layer with a thickness of 10 μm. The organic EL element substrate was transferred to a film-forming chamber (sputtering chamber), and an inorganic sealing layer (SiNx film) with a thickness of 100 nm was formed on the organic sealing layer by RF sputtering using a mask with a predetermined pattern and a SiNx target. In this manner, an organic EL element substrate with a sealing layer was obtained.

[0157] (Evaluation of Reliability (EL Reliability) of Organic EL Element) The reliability of the obtained organic EL element substrate with a patterned cured resin layer was evaluated by the following procedure. After storing the organic EL element substrate with a patterned cured resin layer in an oven set at 60°C and humidity of 90% for 300 hours, a current of 20 mA / cm was applied between the anode layer and cathode layer of the organic EL element by a constant current source via an organic EL lighting jig. ２A current was passed at a density of 0.05 to 0.05, and the organic EL element was illuminated. Next, the luminance of the organic EL element in the front direction was measured using a luminance meter. The illumination of the organic EL element and the measurement of the front luminance using a luminance meter were performed on both the organic EL element substrate with the patterned cured resin layer and the reference organic EL element substrate without the patterned cured resin layer. The smaller the impurities generated from the patterned cured resin layer and the moisture that permeated through the patterned cured resin layer, and the smaller the impact of impurities and moisture on the organic EL element, the closer the front luminance of the organic EL element substrate with the sealing layer will be to that of the reference organic EL element substrate. The reliability of the organic EL element was evaluated as follows: "Good (○)" when the organic EL element substrate with the sealing layer illuminated at a luminance of 80% or more of the front luminance of the reference organic EL element substrate; "Fair (△)" when the organic EL element substrate illuminated at a luminance of 50% to less than 80%; and "Unacceptable (×)" when the organic EL element did not illuminate normally. As a result, in this example, the evaluation was "Good (○)."

[0158] [Examples 3-2 to 3-19 and Comparative Examples 1 to 3] Compositions (R-2) to (R-22) were prepared as photosensitive compositions in the same manner as in Example 3-1, except that the types and amounts of the polymer, photosensitive compound, and crosslinking agent used were changed as shown in Table 2. Each composition was used to perform evaluations in the same manner as in Example 3-1. The results are shown in Table 2. In Table 2, "NQD" represents a condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol).

[0159]

[0160] As shown in Table 2, the photosensitive compositions of Examples 3-1 to 3-19 were rated excellent, good, or fair for patterning ability, dielectric constant, and EL reliability, demonstrating well-balanced improvements in various properties. A more detailed examination revealed that Examples 3-16 and 3-17, which used polyimide, were able to produce cured films with lower dielectric constants than Examples 3-5 and 3-14, which used polyamic acid esters with the same monomer composition. Furthermore, the cured films obtained from the photosensitive compositions of Examples 3-9 to 3-13 and 3-19, which contained polymers synthesized using compounds (DA-9) to (DA-13) and (DA-15) as the specific diamine, had sufficiently low dielectric constants and were rated excellent.

[0161] In contrast, the photosensitive compositions of Comparative Examples 1 and 2, which contained polymers (P-20, P-21) synthesized using a diamine having a perfluoromethyl group, were evaluated as unacceptable in EL reliability, and the photosensitive composition of Comparative Example 3, which contained a polymer (P-22) synthesized using a diamine having no hydroxyl group, was evaluated as unacceptable in patterning ability.

Claims

1. A photosensitive composition comprising: a polymer derived from a monomer having a halogenated alkyl group having 1 to 3 carbon atoms and including at least one hydrogen atom, and including a structural unit (a1) having a hydroxyl group; and a photosensitive compound.

2. The photosensitive composition according to claim 1, wherein the polymer contains, as the structural unit (a1), a structural unit derived from a diamine having a hydroxyl group and a halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom.

3. The photosensitive composition according to claim 1, wherein the polymer is at least one selected from the group consisting of polyimide, polyamic acid ester, polyamic acid, polyamide, and polybenzoxazole.

4. The photosensitive composition according to claim 1, wherein the polymer has a partial structure represented by the following formula (1): (In formula (1), R １ is an organic group having a valence of (m+n+p+2). ２ is a (q+r+2)-valent organic group. ３ is a hydrogen atom, an alkali metal ion, an ammonium ion, or a monovalent organic group having 1 to 20 carbon atoms. １ and X ２ are each independently a halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom. When p is 2 or more, multiple R ３ are the same or different. m, n, q, and r are integers of 0 or more, provided that m ≧ 1 and n ≧ 1, or q ≧ 1 and r ≧ 1, and p is an integer of 0 to 2.

5. The photosensitive composition according to claim 4, wherein q is 1 or more and r is 1 or more in the above formula (1).

6. The photosensitive composition of claim 1, wherein the photosensitive compound comprises a quinone diazide compound or a photoacid generator.

7. The photosensitive composition according to claim 1, which contains a crosslinking compound.

8. The photosensitive composition according to claim 7, wherein the crosslinkable compound is at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a thiirane group, a hydroxyalkylamide group, a protected hydroxyalkylamide group, a methylol group, a protected methylol group, an alkoxymethyl group, a cyclocarbonate group, and a protected isocyanate group.

9. A cured product comprising the photosensitive composition according to any one of claims 1 to 8.

10. A display device comprising the cured product according to claim 9.

11. A semiconductor device comprising the cured product according to claim 9.

12. A method for producing a cured product, comprising the steps of: applying the photosensitive composition according to any one of claims 1 to 8 onto a substrate; exposing the applied photosensitive composition to light; developing the exposed photosensitive composition; and curing the developed photosensitive composition.

13. A polymer having a partial structure represented by the following formula (1): (In formula (1), R １ is an organic group having a valence of (m+n+p+2). ２ is a (q+r+2)-valent organic group. ３ is a hydrogen atom, an alkali metal ion, an ammonium ion, or a monovalent organic group having 1 to 20 carbon atoms. １ and X ２ are each independently a halogenated alkyl group having 1 to 3 carbon atoms and containing at least one hydrogen atom. When p is 2 or more, multiple R ３ are the same or different. m, n, q, and r are integers of 0 or more, provided that m ≧ 1 and n ≧ 1, or q ≧ 1 and r ≧ 1, and p is an integer of 0 to 2.

14. A compound represented by the following formula (2): (In formula (2), R ２ is a (q+r+2)-valent organic group. q and r are integers of 1 or more.

15. A compound represented by the following formula (3): (In formula (3), R １ is an organic group having a valence of (m+n+4). m and n are integers of 1 or more.

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