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

Abstract

A photosensitive composition containing: a polymer that contains a structural unit (a1) that is derived from a monomer having a C1-3 halogenated alkyl group containing at least one hydrogen atom and that has a hydroxyl group; and a photosensitive compound.

Description

TECHNICAL FIELD

[0001] [REFERENCE TO RELATED APPLICATIONS]

[0002] This application claims priority based on Japanese Patent Application No. 2023-138370 filed on August 28, 2023, and incorporates the entire disclosure thereof by reference into the present specification.

[0003] The present disclosure relates to a photosensitive composition, a hardened product and a manufacturing method thereof, a liquid crystal device, a semiconductor device, a polymer, and a compound. BACKGROUND

[0004] In electronic devices such as display devices or semiconductor devices, an insulating hardened film such as a planarization film or an interlayer insulating film is provided. In addition, it has been proposed to use a polyimide or a precursor thereof, or a polyamide as a material for forming such a hardened film (for example, refer to Patent Document 1). In Patent Document 1, it is disclosed that a polyamide acid or a polyamide is synthesized using a diamine or a tetracarboxylic dianhydride having a perfluoromethyl group and a hydroxyl group, and a patterned hardened film is formed by a photosensitive composition containing the obtained polyamide acid or polyamide.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT DOCUMENTS

[0007] Patent Document 1: Japanese Patent Application Publication No. 2020-33277 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] For a hardened film provided in a display device or a semiconductor device, it is required that the hardened film has excellent reliability such as less impurities generated and less permeation of moisture. In addition, as a low refractive material for a display device or a semiconductor device, it is desired to develop a new material that can obtain a hardened film having excellent patterning property, sufficiently low refractive index, and excellent reliability.

[0010] The present disclosure was made in view of the above-described problems, and a main object thereof is to provide a photosensitive composition that can obtain a hardened product having excellent patterning property, low dielectric constant, and excellent reliability.

[0011] MEANS OF SOLVING THE PROBLEMS

[0012] According to the present disclosure, the following photosensitive composition, hardened product and manufacturing method thereof, liquid crystal device, semiconductor device, polymer, and compound can be provided.

[0013] [1] A photosensitive composition comprising: a polymer containing a structural unit (al) derived from a monomer having a halogenated alkyl group having 1 to 3 carbon atoms containing at least 1 hydrogen atom and having a hydroxyl group; and a photosensitive compound.

[0014] [2] A hardened product comprising the photosensitive composition according to the [1].

[0015] [3] A display device comprising the hardened product according to the [2].

[0016] [4] A semiconductor device comprising the hardened product according to the [3].

[0017] [5] A method for manufacturing a hardened product, comprising: a step of applying the photosensitive composition according to the [1] to a substrate; a step of exposing the photosensitive composition after the application; a step of developing the photosensitive composition after the exposure; and a step of hardening the photosensitive composition after the development.

[0018] [6] A polymer having a partial structure represented by the following formula (1).

[0019] [Chemical Formula 1]

[0020]

[0021] (In formula (1), R 1 is a (m+n+p+2)-valent organic group; R 2 is a (q+r+2)-valent organic group; R 3 is a hydrogen atom, an alkali metal ion, an ammonium ion, or a monovalent organic group having 1 to 20 carbon atoms; X 1 and X 2 are each independently a halogenated alkyl group having 1 to 3 carbon atoms containing at least 1 hydrogen atom; in the case where p is 2 or more, a plurality of R 3 are the same or different; m, n, q, and r are integers of 0 or more; wherein m≧1 and n≧1 are satisfied, or q≧1 and r≧1 are satisfied; and p is an integer of 0 to 2)

[0022] [7] A compound represented by the following formula (2).

[0023] [Chemical Formula 2]

[0024]

[0025] (In formula (2), R 2 is a (q+r+2)-valent organic group; and q and r are integers of 1 or more)

[0026] [8] A compound represented by the following formula (3).

[0027] [Chemical Formula 3]

[0028]

[0029] (In formula (3), R 1 is an (m+n+4)-valent organic group; m and n are integers of 1 or more)

[0030] Effects of the Invention

[0031] According to the composition of the present disclosure, a hardened product having a low dielectric constant, excellent reliability, and good patterning properties can be obtained. DETAILED DESCRIPTION

[0032] Hereinafter, matters related to the embodiments will be described in detail. In addition, in the present specification, a numerical range written using “~” includes the numerical values written before and after “~” as lower limit values and upper limit values. The so-called “structural unit” refers to a unit that mainly constitutes a main chain structure, and is at least a unit including two or more units in the main chain structure.

[0033] In the present specification, “hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The so-called “chain hydrocarbon group” refers to a straight-chain hydrocarbon group and a branched-chain hydrocarbon group that do not include a cyclic structure and are composed only of a chain structure. Among them, the chain hydrocarbon group can be saturated or unsaturated. The so-called “alicyclic hydrocarbon group” refers to a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. Among them, the alicyclic hydrocarbon group does not necessarily consist only of an alicyclic hydrocarbon structure, and also includes a group having a chain structure in a part thereof. The so-called “aromatic hydrocarbon group” refers to a hydrocarbon group that includes an aromatic ring structure as a ring structure. Among them, the aromatic hydrocarbon group does not necessarily consist only of an aromatic ring structure, and can include a chain structure or an alicyclic hydrocarbon structure in a part thereof. The ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group can also have a substituent group including a hydrocarbon structure.

[0034] In the present specification, “(meth)acrylic acid” includes “acrylic acid” and “methacrylic acid”. “(Meth)acryloyl group” includes “acryloyl group” and “methacryloyl group”. In the present specification, “epoxy group” also includes an oxiranyl group and an oxetanyl group. “Radiation” includes an electron beam (visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet (EUV), etc.) and an electromagnetic wave (X-ray, γ-ray, etc.).

[0035] Photosensitive composition

[0036] The composition disclosed herein (hereinafter also referred to as "the composition") is preferably used as a film-forming composition for forming an insulating film. The film formed by the composition is preferably used as an insulating film disposed in various display devices such as organic electroluminescence (EL) display devices or liquid crystal display devices, or in semiconductor devices. The composition contains the polymer (A) shown below and a photosensitive compound. Furthermore, unless otherwise specifically mentioned, each component may be used alone or in combination of two or more.

[0037] <Polymer (A)>

[0038] Polymer (A) is a polymer containing a structural unit (a1) derived from a monomer having a halogenated alkyl group having 1 to 3 carbon atoms and containing at least 1 hydrogen atom and having a hydroxyl group.

[0039] The alkyl halide in structural unit (a1) can be any group formed by replacing some of the hydrogen atoms of an alkyl group having 1 to 3 carbon atoms with halogen atoms. As a preferred example of the alkyl halide, the group represented by the following formula (5) can be listed:

[0040] -(CR 5 R 6 ) n -CR 7 R 8 R 9 …(5)

[0041] (In equation (5), R) 5 R 6 R 7 R 8 and R 9 Each of the two R atoms is independently a hydrogen atom or a halogen atom; n is an integer from 0 to 2; when n is 2, the two R atoms in the formula are... 5 Same or different, 2 R 6 Same or different; where, in the formula, n R 5 n R 6 R 7 R 8 and R 9 They will not all simultaneously become halogen atoms, nor will they all simultaneously become hydrogen atoms; "Indicates a bond".

[0042] Examples of halogen atoms in the alkyl halide of structural unit (a1) include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, fluorine atoms or bromine atoms are preferred, and fluorine atoms are more preferred.

[0043] The number of halogen atoms in the halogenated alkyl group is preferably from 1 to (2 x n + 1), more preferably from 1 to (n + 1).

[0044] n in the formula (5) is preferably 0 or 1, more preferably 0.

[0045] As specific examples of the halogenated alkyl group in the structural unit (al), there can be mentioned fluoromethyl group, difluoromethyl group, dibromomethyl group, 1-fluoroethyl group, 1-bromoethyl group, 1,1-difluoroethyl group, 1,1-dibromoethyl group, 1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 1,1-difluoropropyl group, 1,2-difluoropropyl group, 1,1,2-trifluoropropyl group, 1,1,2,3-tetrafluoropropyl group, 3-fluoropropyl group, 2,3-difluoropropyl group, and the like. Among these, the halogenated alkyl group in the structural unit (al) is preferably difluoromethyl group, 1-fluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, 1,1-difluoropropyl group, 1,2-difluoropropyl group, 1,1,2-trifluoropropyl group, or 1,1,2,3-tetrafluoropropyl group, particularly preferably difluoromethyl group.

[0046] The number of halogenated alkyl groups in the structural unit (al) is, for example, from 1 to 6. From the viewpoint of good patterning properties of the present composition, the number of halogenated alkyl groups in the structural unit (al) is preferably from 2 to 6, more preferably from 2 to 4. The "halogenated alkyl group having a carbon number of 1 to 3 containing at least 1 hydrogen atom" in the structural unit (al) can be bonded to a carbon atom or a heteroatom (preferably an oxygen atom). For example, the halogenated alkyl group in the halogenated alkoxy group containing at least 1 hydrogen atom also corresponds to the "halogenated alkyl group having a carbon number of 1 to 3 containing at least 1 hydrogen atom" in the present specification. In the case where the "halogenated alkyl group having a carbon number of 1 to 3 containing at least 1 hydrogen atom" in the structural unit (al) is bonded to a carbon atom, the halogenated alkyl group can be bonded to an aliphatic structure (specifically, a chain structure or an alicyclic structure) or an aromatic ring structure. The halogenated alkyl group in the structural unit (al) is preferably bonded to an aliphatic structure (chain structure or alicyclic structure).

[0047] The structural unit (al) has one or more hydroxyl groups. The hydroxyl group in the structural unit (al) can be bonded to an aliphatic structure (specifically, a chain structure or an alicyclic structure) or an aromatic ring structure. From the viewpoint of moderately improving the solubility of the polymer (A) in a developer (specifically, an alkali developer), the hydroxyl group in the structural unit (al) is preferably bonded to a carbon atom to which a fluorine atom or a fluoroalkyl group is bonded, or is bonded to an aromatic ring. Furthermore, in the case where the 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 a carbon number of 1 to 3 containing at least 1 hydrogen atom, more preferably a difluoromethyl group.

[0048] From the viewpoint of making the dielectric constant of the obtained hardened product lower, the hydroxyl group in the structural unit (a1) is preferably bonded to an aliphatic structure, and further from the viewpoint of improving the solubility of the polymer (A) in a developer, more preferably bonded to a carbon atom bonded to a fluorine atom or a fluoroalkyl group.

[0049] From the viewpoint of moderately improving the solubility of the polymer (A) in a developer, the number of hydroxyl groups in the structural unit (a1) is preferably 1 to 6, and more preferably 2 to 4.

[0050] The main chain of the polymer (A) is not particularly limited. From the viewpoint of high strength or excellent solvent resistance, heat resistance, and low dielectricity, the polymer (A) is preferably at least one selected from the group consisting of a polyimide, a polyamide acid ester, a polyamide acid, a polyamide, and a polybenzoxazole, and more preferably at least one selected from the group consisting of a polyimide, a polyamide acid ester, a polyamide acid, and a polyamide. Among these, from the viewpoint of exhibiting good patternability, at least one of a polyimide and a polyamide acid ester is preferred, and from the viewpoint of high effect of low dielectric constant, a polyimide is more preferred.

[0051] Further, in the present specification, a "polyamide acid" is a polymer having an amic acid structure and not having an amic acid ester structure and an imide ring structure. A "polyimide" is a polymer having an imide ring structure. Among these, the polyimide can have only an imide structure, or can have an imide ring structure and an amic acid structure. A "polyamide acid ester" is a polymer having an amic acid ester structure. Among these, the polyamide acid ester can have only an amic acid ester structure, or can be a partial ester in which an amic acid structure and an amic acid ester structure coexist, and further can have an imide ring structure. That is, in the present specification, a polymer having an imide ring structure and an amic acid ester structure can be classified as a polyamide acid ester.

[0052] As a monomer providing the structural unit (a1), a diamine is preferred from the viewpoint of easiness of design of the monomer. That is, the polymer (A) preferably contains a structural unit derived from a diamine having a halogenated alkyl group containing one or more hydrogen atoms and a hydroxyl group as the structural unit (a1). In addition, as a monomer providing the structural unit (a1), a diamine is not limited, and for example, an acid or an anhydride thereof having a halogenated alkyl group containing one or more hydrogen atoms and a hydroxyl group can be used.

[0053] As the polymer (A), a polymer obtained by polycondensation of an acid or an acid anhydride and a diamine can be preferably used. As a specific example of such a polymer (A), a polymer having a partial structure represented by the following formula (1) can be exemplified.

[0054] [Chem. 4]

[0055]

[0056] (R1)m(R2)n(R3)p 1 is a (m+n+p+2)-valent organic group; R 2 is a (q+r+2)-valent organic group; R 3 is a hydrogen atom, an alkali metal ion, an ammonium ion, or a monovalent organic group having a carbon number of 1 to 20; X 1 and X 2 are each independently a halogenated alkyl group having a carbon number of 1 to 3 containing at least one hydrogen atom; in the case where p is 2 or more, a plurality of R 3 are the same or different; m, n, q, and r are integers of 0 or more; wherein m≧1 and n≧1 are satisfied, or q≧1 and r≧1 are satisfied; p is an integer of 0 to 2

[0057] In the formula (1), R 1 (R1)m(R2)n(R3)p represents a (m+n+p+2)-valent organic group derived from an acid, an acid anhydride, or a partial ester, R 2 (R1)m(R2)n(R3)p represents a (q+r+2)-valent organic group derived from a diamine. Here, as the acid, a dicarboxylic acid, a tricarboxylic acid can be exemplified. As the acid anhydride, a tricarboxylic acid anhydride, a tetracarboxylic acid dianhydride can be exemplified. As the partial ester, a tetracarboxylic acid diester, a tetracarboxylic acid diester dihalide can be exemplified. Further, hereinafter, the acid, the acid anhydride, and the partial ester are also referred to as "acid derivatives" for convenience.

[0058] Here, in the present specification, the "tetracarboxylic acid diester" means a compound in which 2 of the 4 carboxyl groups of a tetracarboxylic acid are esterified and the remaining 2 are carboxyl groups. The "tetracarboxylic acid diester dihalide" means a compound in which 2 of the 4 carboxyl groups of a tetracarboxylic acid are esterified and the remaining 2 are halogenated.

[0059] As R 3 (R1)m(R2)n(R3)p represents an alkali metal ion, a potassium ion, a sodium ion, and the like can be exemplified. As the monovalent organic group having a carbon number of 1 to 20, an alkyl group having a carbon number of 1 to 20, an alkynyl group having a carbon number of 2 to 20, a cycloalkyl group having a carbon number of 3 to 20, an aryl group having a carbon number of 6 to 20, an aralkyl group having a carbon number of 7 to 20, an alkoxysilane group, and the like can be exemplified.

[0060] As the specific examples and the preferred examples of X 1 and X 2 , the same groups as the specific examples and the preferred examples of the halogenated alkyl group possessed by the structural unit (a1) can be exemplified.

[0061] m, n, q, and r are integers of 0 or more, for example, integers of 0 to 6. As X 1 or X 2From the viewpoint of ease of introduction to the polymer (A), the partial structure represented by the formula (1) is preferably one in which q is 1 or more and r is 1 or more. Further, in the synthesis of the polymer (A), by using an acid derivative having a halogenated alkyl group having a carbon number of 1 to 3 and a hydroxyl group in which at least one hydrogen atom is contained (hereinafter, also referred to as "specific acid derivative"), a polymer satisfying m > 1 and n > 1 can be obtained. In addition, in the synthesis of the polymer (A), by using a diamine having a halogenated alkyl group having a carbon number of 1 to 3 and a hydroxyl group in which at least one hydrogen atom is contained (hereinafter, also referred to as "specific diamine"), a polymer satisfying q > 1 and r > 1 can be obtained.

[0062] As a preferable example of the specific acid derivative used in the synthesis of the polymer (A), a compound represented by the following formula (3) or a compound represented by the following formula (4) can be given.

[0063] [Chemical Formula 5]

[0064]

[0065] (In the formula (3), R 1 is a (m+n+4)-valent organic group; m and n are integers of 1 or more)

[0066] [Chemical Formula 6]

[0067]

[0068] (In the formula (4), R 1 is a (m+n+2)-valent organic group; m and n are integers of 1 or more)

[0069] In the formula (3) and the formula (4), as the (m+n+4)-valent organic group or the (m+n+2)-valent organic group represented by R 1 , a hydrocarbon group having a carbon number of 1 to 20, a group having a carbon number of 2 to 20 containing -0-, -S-, -NH-, -N(CH3)-, -N(C2H5)-, -CO-, -COO-, -CONH-, -SO-, -SO2-, -OCONH-, or -NHCONH- between carbon-carbon bonds of the hydrocarbon group can be given.

[0070] m is preferably 1 to 4, and more preferably 1 or 2.

[0071] n is preferably 1 to 4, and more preferably 1 or 2.

[0072] The specific acid derivative preferably has a carboxyl group or an anhydride group bonded to an aromatic ring or an aliphatic ring. As further specific examples of the specific acid derivative, a dicarboxylic acid represented by the following formula (t1-1) or formula (t1-2), a tetracarboxylic dianhydride represented by the following formula (t2-1) to formula (t2-5), and the like can be given.

[0073] [Chemical Formula 7]

[0074]

[0075] [Chemical Formula 8]

[0076]

[0077] As a specific diamine used at the time of synthesizing the polymer (A), a compound represented by the following formula (2) can be exemplified.

[0078] [Chemical Formula 9]

[0079]

[0080] (In formula (2), R 2 is a (q+r+2)-valent organic group; q and r are integers of 1 or more)

[0081] In the formula (2), as the (q+r+2)-valent organic group represented by R 2 the same as the group exemplified as R 1 in the formula (4).

[0082] r is preferably 1 to 4, and more preferably 1 or 2.

[0083] q is preferably 1 to 4, and more preferably 1 or 2.

[0084] From the viewpoint of achieving low dielectric constant of the obtained hardened product, the specific diamine is preferably an aromatic diamine. As further specific examples of the specific diamine, diamines represented by the following formula (d1-1) to formula (d1-20), respectively, and the like can be exemplified.

[0085] [Chemical Formula 10]

[0086]

[0087] [Chemical Formula 11]

[0088]

[0089] From the viewpoint of low dielectric constant, the specific diamine is preferably one having no amide bond in the molecule. Specifically, among the formula (d1-1) to formula (d1-20), the compounds represented by formula (d1-5) to formula (d1-7), formula (d1-9) to formula (d1-13), and formula (d1-17) to formula (d1-20), respectively, are preferred. Further, from the viewpoint of low dielectric constant, the specific diamine is preferably one having a structure capable of introducing an ether bond into the polymer main chain.

[0090] The compound represented by the formula (3) and the compound represented by the formula (2) can be synthesized by appropriately combining conventional methods of organic chemistry. For example, the compound represented by the formula (3) can be obtained by reacting a difunctional compound including a partial structure having a halogenated alkyl group having 1 to 3 carbon atoms including at least one hydrogen atom and a hydroxyl group, with a compound having an acid anhydride group and reacting with the difunctional compound. In addition, the compound represented by the formula (2) can be obtained by, for example, synthesizing a compound represented by the formula (2) in which the primary amino group is a nitro group, and then reducing the nitro group to an amino group. Among others, the compound represented by the formula (3) and the synthesis method of the compound represented by the formula (2) are not limited to the above-described methods.

[0091] The content ratio of the structural unit (al) in the polymer (A) with respect to the total amount of the structural units constituting the polymer (A) is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and still further preferably 40 mol% or more. By setting the content ratio of the structural unit (al) in the above range, the patterning property and the reliability of the hardened product can be ensured while sufficiently achieving the low dielectric constant of the obtained hardened product, which is preferable in terms of this aspect.

[0092] In addition, in the synthesis of the polymer (A), a specific diamine can be preferably used as a monomer. In this case, the content ratio of the structural unit derived from the specific diamine in the polymer (A) with respect to the total amount of the structural units derived from the diamines constituting the polymer (A) is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, and still further preferably 80 mol% or more.

[0093] In the synthesis of the polymer (A), a monomer that provides the structural unit (al) and a monomer (hereinafter, also referred to as "another monomer") different from the monomer that provides the structural unit (al) can be used together. As the other monomer, there is no particular limitation, and known acid derivatives and diamines can be appropriately used.

[0094] For example, in the case where a polymer having a partial structure of the formula (1) in which p is 0 or 1 is obtained as the polymer (A), as specific examples of the acid derivative, there can be mentioned: alicyclic dicarboxylic acids such as cyclobutane dicarboxylic acid, 1-cyclobutene dicarboxylic acid, cyclopentane dicarboxylic acid, cyclohexane dicarboxylic acid, and the like; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 2,5-dimethylterephthalic acid, naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-carbonylbiphenyl dicarboxylic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3'-[4,4'-(methylenebis-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxybis-p-phenylene)]dibutyric acid, 3,4-diphenyl-1,2-cyclobutane dicarboxylic acid, azobenzene-4,4'-dicarboxylic acid, and the like; aromatic tricarboxylic acids such as trimellitic acid, trimesic acid, and the like. Furthermore, in order to activate the reactivity of the carboxyl group, the dicarboxylic acid and the tricarboxylic acid are preferably subjected to reaction with the diimidazole compound or the chlorinating agent, and then subjected to reaction with the diamine.

[0095] In addition, in the case where a polymer having a partial structure of the formula (1) in which p is 2 is obtained as the polymer (A), as specific examples of the acid derivative used, there can be mentioned: 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic 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[3.3.0]octane-2:4,6:8-dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, and the like aliphatic tetracarboxylic dianhydride; pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bis-trimellitic anhydride, 4,4'-carbonylbiphthalic anhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and the like aromatic tetracarboxylic dianhydride; diester bodies and diester dihalides of these tetracarboxylic dianhydrides, and the like.

[0096] 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 dianhydride and alicyclic tetracarboxylic dianhydride. Among these, from the viewpoint of low expansibility, the aromatic tetracarboxylic dianhydride is preferred, and from the viewpoint of transparency or planarity of the cured product, the alicyclic tetracarboxylic dianhydride is preferred. Specifically, at least one selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxylic cyclopentylacetic dianhydride, 2,4,6,8-tetracarboxylic bicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is preferred.

[0097] As specific examples of the diamine other than the above-mentioned diamine (hereinafter, also referred to as "other diamine"), the following can be given: 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-phenylenediisopropylidene)dianiline, 4,4'-(m-phenylenediisopropylidene)dianiline, 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(piperidin-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, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0098] As the diamine used for obtaining the polymer (A), a diaminoorganosiloxane (for example, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane, or the like) can be preferably used in terms of improving the adhesiveness to a substrate, particularly a silicon substrate. In the polymer (A), the proportion of the structural unit derived from the diaminoorganosiloxane, relative to the total amount of the structural units derived from the diamine constituting the polymer (A), is preferably 1 to 10 mol%.

[0099] Synthesis method of the polymer (A)

[0100] The polymer (A) can be obtained by polycondensation of an acid derivative as described with a diamine. For example, a polyamic acid (hereinafter, also referred to as "polyamic acid (A)") as the polymer (A) can be obtained by reacting a tetracarboxylic dianhydride as described with a diamine and, if necessary, a molecular weight adjustor.

[0101] In the synthesis reaction of the polyamic acid (A), the ratio of the tetracarboxylic dianhydride to the diamine used is preferably 0.2 equivalents to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine, more preferably 0.8 equivalents to 1.2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine.

[0102] As the molecular weight adjustor, for example, acid monomers such as maleic anhydride, phthalic anhydride, itaconic anhydride, and the like; monoamine compounds such as aniline, cyclohexylamine, n-butylamine, 3-aminophenol, and the like; monoisocyanate compounds such as phenyl isocyanate, naphthyl isocyanate, and the like can be exemplified. The ratio of the molecular weight adjustor used is preferably set to 20 mol or less, more preferably 15 mol or less, with respect to 100 mol of the total of the tetracarboxylic dianhydride and the diamine used.

[0103] The synthesis reaction of the polyamic acid (A) is preferably performed in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. As the organic solvent used in the reaction, for example, aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like can be exemplified. A particularly preferred organic solvent is preferably one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea, hexamethylphosphoric triamide, m-cresol, dimethylphenol, and halogenated phenol, or a mixture of one or more of these and another organic solvent (for example, butyl cellosolve, diethylene glycol diethyl ether, and the like) is used as the solvent. The amount of the organic solvent used (a) is preferably set to an amount such that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1 mass% to 50 mass% with respect to the total amount (a+b) of the reaction solution.

[0104] The reaction solution in which the polyamic acid (A) is dissolved can be obtained as above. The reaction solution can be used directly for the production of the photosensitive composition, or can be used for the production of the photosensitive composition after the polyamic acid (A) contained in the reaction solution is separated, or can be used for the production of the photosensitive composition after the separated polyamic acid (A) is refined. In the case where the polyamic acid (A) is dehydrated and ring-closed to produce a polyimide, or in the case where the polyamic acid (A) is produced into a polyamic acid ester by an esterification reaction, the reaction solution can be used directly for the reaction, or can be used for the reaction after the polyamic acid (A) contained in the reaction solution is separated, or can be used for the reaction after the separated polyamic acid (A) is refined. The separation and refinement of the polyamic acid (A) can be performed according to known methods.

[0105] In the case where 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 the following methods: [I] a method in which the obtained polyamic acid (A) is reacted with an esterification agent; [II] a method in which a dicarboxylic acid diester is reacted with a diamine; [III] a method in which a dicarboxylic acid diester dihalide is reacted with a diamine; and the like. The method [II] and the method [III] are preferably methods in which a specific diamine is used.

[0106] As the esterification agent used in the method [I], for example, a hydroxyl group-containing compound, an acetal-based compound, a halide, an epoxy group-containing compound, and the like can be exemplified. As the hydroxyl group-containing compound, for example, alcohols such as methanol, ethanol, propanol, and the like; phenols such as phenol, cresol, and the like; and the like can be exemplified. As the acetal-based compound, for example, N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-diethylformamide diethyl acetal, and the like can be exemplified. As the halide, for example, bromomethane, bromoethane, chloromethane, chloroethane, and the like can be exemplified. As the epoxy group-containing compound, for example, propylene oxide, and the like can be exemplified.

[0107] The dicarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the dicarboxylic acid dianhydride exemplified in the synthesis of the polyamic acid (A) using an alcohol such as methanol or ethanol. At the time of reaction with the diamine, the dicarboxylic acid diester can be used together with the dicarboxylic acid dianhydride. As the diamine used, the specific diamines exemplified above and other diamines can be exemplified.

[0108] The reaction of the method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydrating catalyst. As the organic solvent, the organic solvents exemplified as used in the synthesis of the polyamic acid (A) can be exemplified. As the dehydrating catalyst, for example, 4-(4, 6-dimethoxy-l, 3, 5-triazin-2-yl)-4-methylmorpholinium halide, carbonylimidazole, phosphorus-based condensing agents, and the like can be exemplified. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0°C to 100°C. The reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours.

[0109] The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described with a suitable halogenating agent. At the time of reaction with the diamine, the tetracarboxylic acid diester dihalide can also be used together with the tetracarboxylic dianhydride. As the diamine used, the specific diamines exemplified as described and other diamines can be exemplified.

[0110] The reaction of the method [III] is preferably carried out in an organic solvent in the presence of a suitable base. As the organic solvent, the organic solvents exemplified as used in the synthesis of the polyamic acid (A) can be exemplified. As the base, for example, tertiary amines such as pyridine, triethylamine, and the like; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, potassium, and the like; and the like can be preferably used. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0°C to 100°C. The reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours.

[0111] The reaction solution in which the polyamic acid ester (A) is dissolved can be directly used for the preparation of the photosensitive composition, can be used for the preparation of the photosensitive composition after the polyamic acid ester (A) contained in the reaction solution is separated, or can be used for the preparation of the photosensitive composition after the separated polyamic acid ester (A) is refined. The separation and refinement of the polyamic acid ester (A) can be carried out according to known methods.

[0112] The esterification rate of the polyamic acid ester (A) is preferably 30% or more, more preferably 40% or more, and further preferably 50 mol% or more. By setting the esterification rate of the polyamic acid ester (A) to the range described, a hardened film having high heat resistance and solvent resistance and a low dielectric constant can be obtained. Furthermore, the esterification rate is the proportion of the number of the amic acid ester structures with respect to the total of the number of the amic acid structures, the number of the amic acid ester structures, and the number of the imide ring structures of the polyamic acid ester, expressed in percentage. In the present specification, the esterification rate of the polyamic acid ester is determined according to the method described in the Examples. 1A value calculated from the peak area of each proton source of the esterified alkyl group, NH group, and aromatic ring determined by H-nuclear magnetic resonance (NMR).

[0113] In the case where the polymer (A) is a polyimide, the polymer (hereinafter, also referred to as "polyimide (A)") can be obtained, for example, by dehydrating and ring-closing and imidizing a polyamic acid (A). The dehydrating and ring-closing of the polyamic acid is preferably performed by a method of heating the polyamic acid, or a method of dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating and ring-closing catalyst to the solution, and heating as necessary.

[0114] The reaction temperature in the method of heating the polyamic acid is preferably 50°C to 200°C, and more preferably 60°C to 170°C. By setting the reaction temperature to 50°C or higher, the dehydrating and ring-closing reaction can be made to proceed sufficiently. In addition, by setting the reaction temperature to 200°C or lower, the molecular weight of the obtained imidized polymer can be inhibited from decreasing. The reaction time is preferably 1.0 hour to 24 hours, and more preferably 1.0 hour to 12 hours.

[0115] In the method of adding a dehydrating agent and a dehydrating and ring-closing catalyst to a solution of the polyamic acid, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, or the like can be used. The amount of the dehydrating agent used is preferably set to 0.01 mol to 20 mol per 1 mol of the amic acid structure of the polyamic acid. As the dehydrating and ring-closing catalyst, for example, a tertiary amine such as pyridine, collidine, dimethylpyridine, triethylamine, or the like can be used. The amount of the dehydrating and ring-closing catalyst used is preferably set to 0.01 mol to 10 mol per 1 mol of the dehydrating agent used. As the organic solvent used in the dehydrating and ring-closing reaction, the organic solvents exemplified as the organic solvents used in the synthesis of the polyamic acid (A) can be cited. The reaction temperature of the dehydrating and ring-closing reaction is preferably 0°C to 180°C, and more preferably 10°C to 150°C. The reaction time is preferably 1.0 hour to 120 hours, and more preferably 2.0 hours to 30 hours.

[0116] The reaction solution containing the polyimide (A) can be obtained as described above. The reaction solution can be used directly for the production of the photosensitive composition, can be used for the production of the photosensitive composition after the dehydrating agent and the dehydrating and ring-closing catalyst are removed from the reaction solution, can be used for the production of the photosensitive composition after the polyimide (A) is separated, or can be used for the production of the photosensitive composition after the separated polyimide (A) is refined. These refining operations can be performed according to known methods. In addition thereto, the polyimide (A) can be obtained by imidization of the polyamic acid ester (A).

[0117] The imidization ratio of the polyimide (A) is preferably 30% or more, more preferably 50% or more, and further preferably 60% or more. In addition, 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, and more preferably 90% or less. Furthermore, the imidization ratio is a proportion of the number of imide ring structures with respect to the total number of amic acid structures and the number of imide ring structures, expressed in percentage. In the present specification, the imidization ratio of the polyimide is a value determined by H-NMR. 1 H-NMR.

[0118] In the case where 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 of a dicarboxylic acid and a diamine, or the like. In the synthesis of the polyamide (A), it is preferable to use a specific diamine.

[0119] The reaction of the dicarboxylic acid and the diamine is preferably performed in the presence of a base in an organic solvent. The ratio of the dicarboxylic acid to the diamine used in the reaction is preferably 0.2 equivalents to 2 equivalents of the carboxyl group of the dicarboxylic acid with respect to 1 equivalent of the amino group of the diamine, and more preferably 0.8 equivalents to 1.2 equivalents of the carboxyl group of the dicarboxylic acid with respect to 1 equivalent of the amino group of the diamine. The reaction temperature at this time is preferably set to -100°C to 200°C, and more preferably set to 10°C to 100°C. The reaction time is preferably set to 0.5 hours to 48 hours, and more preferably set to 1 hour to 36 hours.

[0120] As the organic solvent used in the reaction, an organic solvent can be preferably used. For example, diethyl ether, tetrahydrofuran, dioxane, toluene, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, or the like can be preferably used. The amount of the organic solvent used is preferably set to 400 parts by mass to 900 parts by mass, and more preferably set to 500 parts by mass to 700 parts by mass, with respect to 100 parts by mass of the total amount of the dicarboxylic acid dihalide and the diamine.

[0121] As the base used in the reaction, for example, tertiary amines such as pyridine, triethylamine, tripropylamine, triisopropylamine, N-ethyl-N,N-diisopropylamine, diazabicycloundecene; 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 tert-butyllithium can be preferably used. The amount of the base used is preferably set to 2 moles to 4 moles, and more preferably set to 2 moles to 3 moles, with respect to 1 mole of the diamine.

[0122] In the case where 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 by the above operation at 150°C to 250°C, a method of adding an acidic catalyst and ring-closing, or the like. The heating and ring-closing reaction for obtaining the polybenzoxazole (A) is preferably performed in an organic solvent. As the organic solvent, the same organic solvents as exemplified as the organic solvents which can be used at the time of synthesizing the polyamide (A) can be listed.

[0123] The solution viscosity of the polymer (A) is preferably 5 mPa-s to 800 mPa-s, more preferably 10 mPa-s to 500 mPa-s, when a solution having a concentration of 10 mass% is prepared. Further, the solution viscosity (mPa-s) of the polymer (A) is a value determined by using an E-type rotational viscometer at 25°C for a polymer solution having a concentration of 10 mass% prepared using a good solvent (for example, gamma-butyrolactone, N-methyl-2-pyrrolidone, or the like) for the polymer (A).

[0124] With respect to the polymer (A), the number average molecular weight (Mn) in terms of polystyrene obtained by gel permeation chromatography (GPC) is preferably 2,000 or more. If the Mn is 2,000 or more, a hardened product which is sufficiently high in heat resistance or solvent resistance and exhibits good developability can be obtained, which is preferable in this respect. The Mn of the polymer (A) is more preferably 3,000 or more, and further preferably 4,000 or more. In addition, from the viewpoint of good film formability, the Mn of the polymer (A) is preferably 150,000 or less, and more preferably 120,000 or less.

[0125] With respect to the polymer (A), the molecular weight distribution (Mw / Mn) represented by 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 further preferably 6.0 or less.

[0126] In the present composition, from the viewpoint of obtaining a hardened film which exhibits good heat resistance and solvent resistance, the content of the polymer (A) is preferably 50 mass% or more, more preferably 55 mass% or more, and further preferably 60 mass% or more, relative to the total amount of the solid components contained in the present composition (i.e., the components other than the solvent in the present composition).

[0127]

[0128] ​The photosensitive compound is only a component that changes the solubility of the present composition by irradiation of radiation. As the photosensitive compound, for example, a quinonediazide compound, a photo-acid generator, a photopolymerization initiator, and the like can be listed. Among these, the quinonediazide compound is a substance that is changed to an indenecarboxylic acid by irradiation of radiation. The photo-acid generator is a substance that can generate an acid by irradiation of radiation and causes an acid dissociable group possessed by a component in the composition to be detached. Further, in the case of obtaining a positive type photosensitive composition, as the photosensitive compound, a quinonediazide compound or a photo-acid generator can be preferably used. In the case of obtaining a negative type photosensitive composition, as the photosensitive compound, a photopolymerization initiator can be preferably used.

[0129] The present composition can be preferably used as a positive type photosensitive composition. Specifically, the photosensitive compound disposed in the present composition is preferably a quinonediazide compound or a photo-acid generator, more preferably a quinonediazide compound.

[0130] As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter, also referred to as "a mother nucleus") and a naphthoquinonediazide compound can be listed. Among these, the quinonediazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the mother nucleus and a naphthoquinonediazide compound. As specific examples of the mother nucleus, for example, the compounds described in paragraphs 0065 to 0070 of Japanese Patent Laid-Open No. 2014-186300 can be listed. The naphthoquinonediazide compound is preferably a 1,2-naphthoquinonediazidosulfonyl halide.

[0131] As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound as the mother nucleus and a 1,2-naphthoquinonediazidosulfonyl halide can be preferably used, and a condensate of a phenolic compound and a 1,2-naphthoquinonediazidosulfonyl halide can be more preferably used.

[0132] As specific examples of the quinonediazide compound, a compound having a phenolic hydroxyl group selected from 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 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, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and an ester compound with 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride can be listed.

[0133] In the condensation reaction for obtaining the condensate, as to the ratio of the parent nucleus to the 1,2-naphthoquinonediazide sulfonyl halide, it is preferable to set the amount of use of the 1,2-naphthoquinonediazide sulfonyl halide to an amount corresponding to 30 mol% to 85 mol% with respect to the number of OH groups in the parent nucleus, and more preferably to an amount corresponding to 50 mol% to 70 mol%. Furthermore, the condensation reaction can be performed in accordance with a known method.

[0134] As the photoacid generator, onium salts (sulfonium salts, iodonium salts, quaternary ammonium salts, etc.), sulfonylimine compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, etc. can be exemplified.

[0135] As specific examples of the sulfonylimine compound, the onium salt, the sulfonylimine compound, the halogen-containing compound, the diazomethane compound, the sulfone compound, the sulfonic acid ester compound, and the carboxylic acid ester compound, the compounds described in Paragraphs 0034 to 0038 of Japanese Patent Laid-Open No. 2012-252343, the compounds described in Paragraphs 0078 to 0106 of Japanese Patent Laid-Open No. 2014-157252, the compounds described in International Publication No. 2016 / 124493, etc. can be exemplified. As the photoacid generator, of these, at least one selected from the group consisting of a sulfonylimine compound, a sulfonylimine compound, an onium salt, a halogen-containing compound, a sulfone compound, and a sulfonic acid ester compound can be preferably used.

[0136] The content of the photosensitive compound in the present composition can be selected depending on the kind of the photosensitive compound used. For example, in the case where a quinonediazide compound is used as the photosensitive compound, the content of the quinonediazide compound in the present composition is preferably set to 2 parts by mass or more, more preferably to 5 parts by mass or more, and further preferably to 10 parts by mass or more, with respect to 100 parts by mass of the polymer (A) contained in the present composition. In addition, the content of the quinonediazide compound is preferably set to 60 parts by mass or less, more preferably to 50 parts by mass or less, and further preferably to 40 parts by mass or less, with respect to 100 parts by mass of the polymer (A) contained in the present composition.

[0137] If the content of the quinonediazide compound is 2 parts by mass or more, sufficient acid is generated by irradiation with actinic rays, and the difference in solubility in a developer between the exposed portion and the unexposed portion can be sufficiently increased. Thus, good patterning can be performed. In addition, the amount of acid involved in the reaction with the polymer component can be increased, and the heat resistance of the hardened film obtained using the present composition can be sufficiently ensured. On the other hand, if the content of the quinonediazide compound is 60 parts by mass or less, the amount of unreacted quinonediazide compound can be sufficiently reduced, and the decrease in the developing property and the transmittance of the film due to the presence of the quinonediazide compound can be suppressed, which is preferable in this respect.

[0138] In the case of using a photoacid generator as the photosensitive compound, the content of the photoacid generator in the present composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the polymer (A) contained in the present composition. In addition, the content of the photoacid generator is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the polymer (A) contained in the present composition.

[0139] <Other Components>

[0140] The present composition can also contain a component other than the polymer (A) and the photosensitive compound (hereinafter, also referred to as "other component"). As the other component, for example, a crosslinkable compound, an adhesion aid, a developing aid, a surfactant, a solvent, and the like can be exemplified.

[0141] Crosslinkable Compound

[0142] The crosslinkable compound is a component that forms a crosslinked structure between or within the molecules of the polymer (A) by light or heat due to the presence of a crosslinkable functional group, or that forms a bond between the crosslinkable compounds. By making the present composition a composition that contains both the polymer (A) and the crosslinkable compound, the reliability of the hardened film obtained using the present composition can be further improved.

[0143] As the crosslinkable functional group possessed by the crosslinkable compound, for example, a cyclic ether group, a cyclic sulfide group, a carboxyl group, a cyclic carbonate 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, etc.), a hydroxyalkylamide group, a protected hydroxyalkylamide group, an oxazoline group, and the like can be exemplified.

[0144] From the viewpoint that the crosslinking compound reacts with polymer (A) to form a crosslinked structure between or within the molecules of polymer (A), thereby improving the heat resistance of the hardened film, the crosslinking functional group is preferably selected from at least one of the group consisting of oxetyl, oxetyl, cyclothioethane, hydroxyalkylamide, protected hydroxyalkylamide, hydroxymethyl, protected hydroxymethyl, alkoxymethyl, cyclic carbonate, and protected isocyanate, more preferably at least one of the group consisting of oxetyl, oxetyl, hydroxyalkylamide, hydroxymethylphenyl, and alkoxymethylphenyl, and even more preferably at least one of the group consisting of oxetyl, oxetyl, hydroxymethylphenyl, and alkoxymethylphenyl.

[0145] From the viewpoint of fully achieving the effect of improving the reliability of the hardened film and suppressing film shrinkage, the number of crosslinking functional groups in one molecule of the crosslinking compound is preferably 2 to 10, more preferably 3 to 8.

[0146] The molecular weight of the crosslinking compound is, for example, 1,000 or less, preferably 800 or less, and more preferably 600 or less.

[0147] Specific examples of crosslinkable compounds, such as those containing epoxy groups, include: 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-cyclohexanediethanol diglycidyl ether, N,N',N',N'-tetraglycidylglycerol, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2- The products of hydrogen peroxide-based epoxidation reactions of dibromonepentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylamine, 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, and 2,2'-diallyl bisphenol A diallyl ether, etc.

[0148] As compounds having a cyclic carbonate group, examples of epoxy compounds with protected epoxy groups can be listed (e.g., N,N,N',N'-tetratetra[(2-oxo-1,3-dioxacyclopentan-4-yl)ethyl]-4,4'-diaminodiphenylmethane).

[0149] As the compound having a cycloalkyl group, for example, a compound represented by the following formula (a-1) to formula (a-7) can be exemplified.

[0150] As the compound having a hydroxylalkylamide group or a protected hydroxylalkylamide group, for example, a compound represented by the following formula (c-1) to formula (c-7), respectively, can be exemplified.

[0151] As the compound having at least any one of a hydroxymethyl group, a protected hydroxymethyl group, and an alkoxymethyl group, for example, 2,2-bis(4-hydroxymethylphenyl)propane, 2,2-bis(2,3,4-trihydroxymethylphenyl)propane, a compound represented by the following formula (c-8) to formula (c-17), respectively, can be exemplified.

[0152] As the compound having a protected isocyanate group, for example, a compound in which an isocyanate group in toluene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, or diphenylmethane diisocyanate is protected can be exemplified.

[0153] [Chemical Formula 12]

[0154]

[0155] In addition, as the compound having a polymerizable unsaturated bond group, for example, the following can be exemplified: a polyfunctional (meth)acrylate of an alkylene glycol or a polyalkylene glycol such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate; a polyfunctional (meth)acrylate of a monocycloalkane dimethanol or a polycycloalkane dimethanol such as cyclohexane dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; a polyfunctional (meth)acrylate of a polyhydric alcohol of three or more valences such as trimethylolpropane poly(meth)acrylate, di-trimethylolpropane poly(meth)acrylate, pentaerythritol poly(meth)acrylate, di-pentaerythritol poly(meth)acrylate; an AO-modified or succinic acid-modified polyfunctional (meth)acrylate such as pentaerythritol alkylene oxide (AO)-modified polyfunctional (meth)acrylate, trimethylolpropane AO-modified polyfunctional (meth)acrylate, di-pentaerythritol AO-modified polyfunctional (meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified di-pentaerythritol penta(meth)acrylate; a polyfunctional urethane (meth)acrylate such as ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris-(2-(meth)acryloyloxyethyl) isocyanurate; and tris(2-(meth)acryloyloxyethyl) phosphate. Furthermore, "AO-modified" means ethylene oxide (EO)-modified, propylene oxide (PO)-modified, or the like.

[0156] In the case where the present 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 further preferably 5 parts by mass or more, relative to 100 parts by mass of the polymer (A) contained in the present composition. In addition, the content of the crosslinkable compound is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less, relative to 100 parts by mass of the polymer (A) contained in the present composition.

[0157] adhesion aid

[0158] The adhesion aid is a component that improves the adhesion of the hardened film formed using the present composition to a substrate. As the adhesion aid, a functional silane coupling agent having a reactive functional group can be preferably used. As the reactive functional group possessed by the functional silane coupling agent, a carboxyl group, a (meth)acryloyl group, an epoxy group, a vinyl group, an isocyanate group, and the like can be exemplified.

[0159] As specific examples of the functional coupling agent, for example, the following can be exemplified: trimethoxysilyl benzoic acid, glycidyloxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyl trimethoxysilane, 3- (meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like.

[0160] In the case where the present composition contains a close contact aid, the content of the close contact aid is preferably 0.01 parts by mass or more and 30 parts by mass or less, 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.

[0161] Developing aid

[0162] The developing aid is a component that improves the developability (shortens the developing time, reduces the developing residue, improves the resolution or the sensitivity) of the present composition. As the developing aid, a low molecular compound having a phenolic hydroxyl group (hereinafter, also referred to as "phenolic low molecular compound") can be preferably used. From the viewpoint of sufficiently obtaining the effect of improving the developability of the present composition and suppressing the film shrinkage of the film, the number of the phenolic hydroxyl groups within one molecule of the phenolic low molecular compound is preferably 1 to 10, more preferably 2 to 6.

[0163] As specific examples of the phenolic low molecular compound, for example, 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, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, and the like can be exemplified.

[0164] In the case where the present composition contains a developing aid, the content of the developing aid is preferably set to 1 part by mass to 100 parts by mass, more preferably set to 1 part by mass to 60 parts by mass, and further preferably set to 5 parts by mass 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 compound to 1 part by mass or more, the effect of improving the developability brought by the addition of the phenolic low molecular compound can be sufficiently obtained. In addition, by setting the content of the phenolic low molecular compound to 100 parts by mass or less, the effect of improving the developability can be obtained while suppressing the decrease in the mechanical strength of the film.

[0165] surfactant

[0166] The surfactant can be used to improve the coatability (wetting spreadability or reduction of coating unevenness) of the present composition. As the surfactant, for example, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant can be exemplified. As the surfactant, any one can be used from among the known surfactants, such as commercially available products.

[0167] In the case where the surfactant is formulated in the present composition, the content of the surfactant is preferably 0.01 parts by mass to 1.5 parts by mass, more preferably 0.02 parts by mass to 1.2 parts by mass, and further preferably 0.05 parts by mass to 1.0 parts by mass, with respect to 100 parts by mass of the polymer (A) contained in the present composition.

[0168] solvent

[0169] The present composition is preferably a liquid composition in which the polymer (A), the photosensitive compound, and the optional component(s) are dissolved or dispersed in a solvent. As the solvent used, an organic solvent that dissolves each component formulated in the present composition and does not react with each component is preferable.

[0170] As specific examples of the solvent, for example, alcohols such as methanol, ethanol, isopropanol, butanol, octanol, and the like; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl methyl acetate, 3-ethoxypropyl ethyl acetate, and the like; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethyleneglycol dimethyl ether, diethyleneglycol dimethyl ether, diethyleneglycol ethyl methyl ether, and the like; amides such as dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and the like can be exemplified.

[0171] Among 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 glycol, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate.

[0172] The content of the solvent in the present composition (the total amount in the case where two or more kinds of solvents are contained) is preferably 50 parts by mass to 95 parts by mass, and more preferably 60 parts by mass to 90 parts by mass, with respect to 100 parts by mass of the total components of the present composition.

[0173] As other components, in addition to the above, known additives such as an acid diffusion control agent, a sensitizer, an antioxidant, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickening agent, an acid proliferating agent, a plasticizer, a deposit preventing agent, a polymerization inhibitor, a chain transfer agent, and the like can be contained. The blending amounts of these components can be appropriately selected depending on each component within a range not impairing the effects of the present disclosure.

[0174] The solid content concentration of the present composition (the proportion of the total mass of the components other than the solvent in the composition, relative to the total mass of the composition) can be appropriately selected in consideration of viscosity or volatility, etc. The solid content concentration of the present composition is preferably in the range of 5 to 60 mass%. If the solid content concentration is 5 mass% or more, the film thickness of the coating film can be sufficiently ensured when the present composition is applied to a substrate. In addition, if the solid content concentration is 60 mass% or less, the film thickness of the coating film will not become excessively large, and furthermore, the viscosity of the present composition can be moderately increased, and good coatability can be ensured. The solid content concentration of the present composition is more preferably 10 to 55 mass%, and furthermore preferably 10 to 50 mass%.

[0175] "Hardened product and method for producing the same"

[0176] The hardened product of the present disclosure can be formed from the photosensitive composition produced as described above. By using the present composition, a film exhibiting good patterning properties can be formed, and a hardened product having a low dielectric constant and excellent reliability can be formed. Therefore, the present composition can be preferably used, for example, as a forming material for an interlayer insulating film, a planarization film, a spacer, a protective film (a passivation film), a colored pattern film for a color filter, a barrier wall, a bank, or the like included in a display device or a semiconductor device, etc.

[0177] In the case of using the present composition to produce a hardened product, a positive or negative type hardened product can be formed depending on the type of the photosensitive compound. Using the present composition, and by a method including, for example, the following Process 1 to Process 4, a hardened product having a pattern can be produced.

[0178] Process 1: a process of applying the present composition to a substrate (coating process)

[0179] Process 2: a process of exposing the photosensitive composition after the application (exposure process)

[0180] Process 3: a process of developing the photosensitive composition after the exposure (development process)

[0181] Process 4: a process of hardening the photosensitive composition after the development (hardening process)

[0182] Hereinafter, each process will be described in detail.

[0183] [Coating process]

[0184] In the coating step, the present composition is coated on a film-forming surface (hereinafter, also referred to as "film-forming surface"), and preferably, the solvent in the present composition is removed by performing a heating treatment (pre-baking), thereby forming a coating film on a substrate. The material of the surface of the substrate is not particularly limited. For example, in the case of forming an interlayer insulating film, the present composition is coated on a substrate provided with a switching element such as a thin film transistor (TFT), thereby forming a coating film. As the substrate, for example, a glass substrate, a silicon substrate, a resin substrate can be used. On the surface of the substrate on which the coating film is formed, a metal thin film corresponding to the use can be formed, and various surface treatments such as hexamethyl disilazane (HMDS) treatment can be performed.

[0185] As the coating method of the present composition, for example, a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, an inkjet method, and the like can be exemplified. Among these, the coating is preferably performed by the spin coating method, the slit die coating method, or the bar coating method. As the pre-baking conditions, they are also different depending on the kind and content of each component in the present composition, and for example, heating is performed at 60°C to 130°C for 0.5 minutes to 10 minutes. The film thickness of the coating film formed (i.e., the film thickness after pre-baking) is preferably 0.1 μm to 12 μm. The present composition coated on the substrate can also be subjected to reduced pressure drying (vacuum drying (VCD) ) before pre-baking.

[0186] [Exposure Step]

[0187] In the exposure step, a radiation is irradiated to at least a part of the coating film formed by the coating step. At this time, the coating film is irradiated with the radiation through a mask having a predetermined pattern, whereby a hardened product having a pattern can be formed. As the radiation, for example, ultraviolet rays, far ultraviolet rays, visible rays, X-rays, an electron beam, and the like can be exemplified. Among these, ultraviolet rays are preferred, and for example, g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm) can be exemplified. As the exposure amount of the radiation, 0.1 J / m 2 ~ 20,000 J / m 2 .

[0188] [Developing Step]

[0189] In the developing step, the coating film on which the radiation has been irradiated in the exposing step is developed. Specifically, the coating film on which the radiation has been irradiated in the exposing step is developed with a developing solution, whereby positive development in which the irradiated portion of the radiation is removed or negative development in which the non-irradiated portion of the radiation is removed is performed. As the developing solution, for example, an aqueous solution of an alkali (basic compound) can be cited. As the alkali, for example, sodium hydroxide, tetramethylammonium hydroxide, and the alkali exemplified in paragraph 0127 of Japanese Patent Laid-Open No. 2016-145913 can be cited. As the concentration of the alkali in the aqueous solution, from the viewpoint of obtaining moderate developability, it is preferably 0.1 to 5 mass%. As the developing method, for example, a suitable method such as a liquid covering method, an immersion method, a shake immersion method, a spraying method, and the like can be cited. The developing time also varies depending on the composition of the composition, and for example, it is 30 seconds to 120 seconds. Further, it is preferable that, after the developing step, the patterned coating film is subjected to a rinsing treatment with running water.

[0190] [Hardening Step]

[0191] In the hardening step, it is preferable that the hardening of the composition is performed by performing a process of heating the coating film developed in the developing step (post-baking). By the heating process, the hardening reaction is further performed, and a hardening product having excellent heat resistance can be obtained. The post-baking can be performed using a heating device such as an oven or a hot plate. As the post-baking conditions, the heating temperature is, for example, 120°C to 300°C. For example, in the case where the heating process is performed on a hot plate, the heating time is 5 minutes to 80 minutes, and in the case where the heating process is performed in an oven, the heating time is 10 minutes to 120 minutes. By the heating process, a hardening product having a target pattern can be formed on the substrate. The shape of the pattern possessed by the hardening product is not particularly limited, and for example, a line-and-space pattern, a dot pattern, a hole pattern, a lattice pattern can be cited.

[0192] The hardening film obtained from the present composition can also be used as a dry etching resist. In the case where the hardening film is used as a dry etching resist, as the etching process, a dry etching process such as ashing, plasma etching, ozone etching, and the like can be adopted.

[0193] Display device and semiconductor device

[0194] According to the present disclosure, it is possible to provide a display device or a semiconductor device including a hardened product formed using the present composition. Specifically, as the display device, various display devices such as a liquid crystal display device, an organic EL display device, a mini (Mini) light emitting diode (LED) display device, a micro (Micro) LED display device, and the like can be exemplified. In the display device or the semiconductor device of the present disclosure, the type of the hardened product formed using the present composition is not particularly limited. According to the present composition, it is possible to obtain a hardened film which is excellent in reliability and has a low refractive index while being excellent in developability (particularly, alkali developability). Therefore, the present composition is particularly preferable as a film-forming composition for a display device or a semiconductor device, that is, a film-forming composition for forming an insulating layer, that is, a planarization film, which covers a step difference of a TFT circuit or a wiring formed on a substrate, or an insulating layer, that is, an interlayer insulating film, which insulates a wiring from each other or a wiring from a substrate in a multilayer wiring, or a passivation film of a semiconductor.

[0195] The hardened film formed using the present composition is less likely to undergo a decrease in performance and is high in reliability even under high temperature and high humidity, and thus can be preferably applied to an organic EL device which requires higher fineness. In addition, the hardened film is less permeable to water and is excellent in bending resistance, and thus can be preferably applied to a display device for a flexible display. As the flexible display, a foldable display capable of being folded, a bendable display capable of being folded or bent, a rollable display capable of being rolled, and the like can be exemplified.

[0196] According to the present disclosure described in detail above, the following means can be provided.

[0197] [Means 1] A photosensitive composition containing: a polymer containing a structural unit (a1) derived from a monomer having a halogenated alkyl group having a carbon number of 1 to 3 containing at least one hydrogen atom and having a hydroxyl group; and a photosensitive compound.

[0198] [Means 2] The photosensitive composition according to [Means 1], wherein the polymer contains a structural unit derived from a diamine having a halogenated alkyl group having a carbon number of 1 to 3 containing at least one hydrogen atom and a hydroxyl group as the structural unit (a1).

[0199] [Means 3] The photosensitive composition according to [Means 1] or [Means 2], wherein the polymer is at least one selected from the group consisting of a polyimide, a polyamide acid ester, a polyamide acid, a polyamide, and a polybenzoxazole.

[0200] [Means 4] The photosensitive composition according to any one of [Means 1] to [Means 3], wherein the polymer has a partial structure represented by the formula (1).

[0201] [Means 5] The photosensitive composition according to [Means 4], wherein q in the formula (1) is 1 or more, and r is 1 or more.

[0202] [Means 6] The photosensitive composition according to any one of [Means 1] to [Means 5], wherein the photosensitive compound comprises a quinonediazide compound or a photoacid generator.

[0203] [Means 7] The photosensitive composition according to any one of [Means 1] to [Means 6], which contains a crosslinkable compound.

[0204] [Means 8] The photosensitive composition according to [Means 7], wherein the crosslinkable compound is at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a thiiranyl group, a hydroxyalkylamide group, a protected hydroxyalkylamide group, a hydroxymethyl group, a protected hydroxymethyl group, an alkoxymethyl group, a cyclic carbonate group, and a protected isocyanate group.

[0205] [Means 9] A hardened product comprising the photosensitive composition according to any one of [Means 1] to [Means 8].

[0206] [Means 10] A display device comprising the hardened product according to [Means 9].

[0207] [Means 11] A semiconductor device comprising the hardened product according to [Means 9].

[0208] [Means 12] A method for producing a hardened product, comprising: a step of applying the photosensitive composition according to any one of [Means 1] to [Means 8] to a substrate; a step of exposing the applied photosensitive composition; a step of developing the exposed photosensitive composition; and a step of hardening the developed photosensitive composition.

[0209] [Means 13] A polymer having a partial structure represented by the formula (1).

[0210] [Means 14] A compound represented by the formula (2).

[0211] [Means 15] A compound represented by the formula (3).

[0212] Examples

[0213] Hereinafter, the present disclosure will be specifically described by way of examples, but the present disclosure is not limited to these examples. Furthermore, unless otherwise specified, "parts" and "%" in the examples and comparative examples are on a mass basis.

[0214] The measurement method of each property value of the polymer is as described below.

[0215] <Weight average molecular weight (Mw) and number average molecular weight (Mn)>

[0216] The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer are polystyrene conversion values obtained by GPC under the following conditions.

[0217] Column: manufactured by Tosoh (stock), TSKgel GRCXLII

[0218] Solvent: N, N-dimethylformamide solution containing lithium bromide and phosphoric acid

[0219] Temperature: 40°C

[0220] Pressure: 68 kgf / cm 2

[0221] <Imidization rate of polyimide>

[0222] The polyimide is dissolved in deuterated dimethyl sulfoxide, and H-NMR measurement is performed at room temperature with tetramethylsilane as a reference substance. 1 The imidization rate [%] is calculated from the obtained 1 H-NMR spectrum by the following equation (1).

[0223] Imidization rate [%] = (1 - (β1 / (β2 x α))) x 100... (1)

[0224] (In equation (1), β1 is the peak area of the proton source of the NH group appearing near 10 ppm in chemical shift, β2 is the peak area of other proton sources, and α is the number ratio of other protons to 1 proton of the NH group in the precursor (polyamic acid) of the polymer)

[0225] <Esterification rate of polyamic acid ester>

[0226] The polyimide is dissolved in deuterated dimethyl sulfoxide, and H-NMR measurement is performed at room temperature with tetramethylsilane as a reference substance. 1 The esterification rate [%] is calculated from the obtained 1 H-NMR spectrum by the following equation (2).

[0227] Esterification rate (%) = ((A / B) / (C / D)) x 100... (2)

[0228] (In equation (2), A is the peak area of the ester source, B is the peak area of the aromatic source, C is the number of protons of the ester when 100% esterification, and D is the number of protons of the aromatic source)

[0229] Details of the compounds used in the synthesis of the polymers and the preparation of the photosensitive composition are described below.

[0230] Tetracarboxylic dianhydride

[0231] [Chemical Formula 13]

[0232]

[0233] Diamines and monoamines

[0234] [Chemical Formula 14]

[0235]

[0236] [Chemical Formula 15]

[0237]

[0238] [Chemical Formula 16]

[0239]

[0240] Crosslinking agent

[0241] [Chemical Formula 17]

[0242]

[0243] 1. Synthesis of compounds

[0244] [Example 1-1] Synthesis of compound (DA-1)

[0245] [Chemical Formula 18]

[0246]

[0247] Synthesis of DA-1-1

[0248] To 3-nitrobenzoyl chloride 6.20 g and 5,5'-methylenebis(2-aminobenzoic acid) 5.00 g was added tetrahydrofuran (THF) 50 mL, and after cooling in an ice bath, triethylamine 4.83 g dissolved in THF 50 mL was added dropwise. After the dropwise addition was completed, it was returned to room temperature and stirred for 12 hours. The reaction solution was poured into 1 M aqueous hydrochloric acid 500 mL, and the precipitated solid was filtered and washed with distilled water. It was redissolved in THF and recrystallized by adding ethanol. After filtration, vacuum drying at 60°C for 12 hours was performed, thereby obtaining compound (DA-1-1) 9.03 g.

[0249] Synthesis of DA-1-2

[0250] To compound (DA-1-1) 6.00 g, thionyl chloride 10 mL, N,N-dimethylformamide 2 drops, was added at 80°C for 2 hours. After the reaction, thionyl chloride was removed under reduced pressure. Subsequently, after adding acetonitrile 20 mL and N-methyl-2-pyrrolidone (NMP) 20 mL, (bromodifluoromethyl)trimethylsilane 10.4 g, triphenylphosphine 12.1 g, N,N'-dimethylpropyleneurea 7.89 g, was added at room temperature for 5 hours. Thereafter, a solution in which pyridine 3.25 g and distilled water 10.3 mL were mixed was added, and the mixture was reacted at 80°C for 1.5 hours. The reaction solution was poured into distilled water 500 mL, and the precipitated solid was filtered and washed with distilled water. Vacuum drying was performed at 60°C for 12 hours, thereby obtaining compound (DA-1-2) 4.64 g.

[0251] Synthesis of DA-1

[0252] Compound (DA-1-2) 4.50 g, zinc 7.75 g, and ammonium chloride 3.17 g were weighed, and nitrogen substitution was performed. After THF 14 mL, NMP 4 mL, and ethanol 4 mL were added and the mixture was cooled in an ice bath, distilled water 3.05 g was added dropwise. After the addition was completed, the mixture was allowed to return to room temperature and stirred for 4 hours. After the reaction, insoluble components were removed by filtration through celite, and methanol 150 mL and distilled water 150 mL were added to the filtrate. The precipitated solid was filtered and washed with distilled water. Vacuum drying was performed at 60°C for 12 hours, thereby obtaining compound (DA-1) 3.61 g.

[0253] [Example 1-2] Synthesis of compound (DA-2)

[0254] In Synthesis Example 1, 3-nitrophenoxyacetyl chloride was used instead of 3-nitrobenzoyl chloride, and otherwise, compound (DA-2) 4.8 g was obtained by the same method as in Example 1-1.

[0255] [Example 1-3] Synthesis of compound (DA-3)

[0256] In Example 1-1, 3,5-diaminobenzoic acid was used instead of 5,5'-methylenebis(2- aminobenzoic acid), and otherwise, compound (DA-3) 3.3 g was obtained by the same method as in Example 1-1.

[0257] [Example 1-4] Synthesis of compound (DA-4)

[0258] [Chem. 19]

[0259]

[0260] In Example 1-1, compound (DA-7) was used instead of 5,5'-methylenebis(2- aminobenzoic acid), and otherwise, compound (DA-4-1) 4.3 g was obtained by the same method as in Example 1-1. Then, in Example 1-1, compound (DA-4-1) was used instead of compound (DA-1-2), and otherwise, compound (DA-4) 3.5 g was obtained by the same method as in Example 1-1.

[0261] [Example 1-5] Synthesis of compound (DA-6)

[0262] [Chem. 20]

[0263]

[0264] In Example 1-1, 3,5-dinitrobenzoic acid was used instead of compound (DA-1-1), and otherwise, compound (DA-6) 4.2 g was obtained by the same method as in Example 1-1.

[0265] [Example 1-6] Synthesis of compound (DA-8)

[0266] [Chem. 21]

[0267]

[0268] In Example 1-1, 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), and otherwise, compound (DA-8-1) 4.4 g was obtained by the same method as in Example 1-1. Then, in Example 1-1, compound (DA-8-1) was used instead of compound (DA-1-2), and otherwise, compound (DA-8) 3.1 g was obtained by the same method as in Example 1-1.

[0269] [Example 1-7] Synthesis of compound (DA-9)

[0270] [Chem. 22]

[0271]

[0272] To 6.84 g of o-toluidine, 3.32 g of 6M hydrochloric acid was added and heated to 100°C. Then, after dropwise addition of a solution in which 3.00 g of 4-(difluoromethoxy)-3-hydroxybenzaldehyde and 10 mL of dimethyl formamide (DMF) were mixed, it was reacted at 100°C for 12 hours. After the reaction, it was returned to room temperature and neutralized with an aqueous triethylamine solution. After washing the solution extracted with ethyl acetate with distilled water, it was dried with the addition of magnesium sulfate. After filtration and concentration, it was purified with a silica gel column (ethyl acetate / hexane = 2 / 1). The fraction containing the target compound was recovered, and hexane was added to the concentrated solution to recrystallize. By performing filtration and vacuum drying at 60°C, the compound (DA-9) 3.26 g was obtained.

[0273] [Example 1-8] Synthesis of Compound (DA-10)

[0274] [Formula 23]

[0275]

[0276] In the compound (DA-1-2) of Example 1-1, 4-fluoro-2-nitrobenzoic acid was used instead of the compound (DA-1-1), and, other than that, the compound (DA-10-1) 4.81 g was obtained by the same method as Example 1-1.

[0277] Then, a mixture of the compound (DA-10-1) 4.00 g, bisphenol A 1.68 g, potassium carbonate 4.08 g, and DMF 40 mL was vigorously stirred at 120°C while reacting for 12 hours. The reaction solution returned to room temperature was added to distilled water 500 mL, and the precipitated solid was filtered and washed with distilled water. Vacuum drying at 60°C for 12 hours thereby obtained the compound (DA-10-2) 4.03 g.

[0278] After that, in the compound (DA-1) of Example 1-1, the compound (DA-10-2) was used instead of the compound (DA-1-2), and, other than that, the compound (DA-10) 3.2 g was obtained by the same method as Example 1-1.

[0279] [Example 1-9] Synthesis of Compound (DA-11)

[0280] [Formula 24]

[0281]

[0282] In Example 1-8, 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, and otherwise, the compound (DA-11) 3.11 g was obtained by the same method as in Example 1-8.

[0283] [Example 1-10] Synthesis of compound (DA-12)

[0284] [Formula 25]

[0285]

[0286] The compound (DA-12-1) and the compound (DA-12-2) were synthesized according to the method described in the non-patent literature "Organic Letters, 2011, 13, 5342".

[0287] Then, in Example 1-8, the compound (DA-12-1) and the compound (DA-12-2) were used instead of the compound (DA-10-1) and bisphenol A, respectively, and otherwise, the compound (DA-12) 2.9 g was obtained by the same method as in Example 1-8.

[0288] [Example 1-11] Synthesis of compound (DA-13)

[0289] [Formula 26]

[0290]

[0291] A mixture of 4-hydroxybenzoic acid 3.00 g, 3,5-dinitrobenzyl chloride 5.6 g, potassium carbonate 3.60 g, and DMF 40 mL was vigorously stirred at 80°C while reacting for 12 hours. To the reaction solution which was returned to room temperature, ethyl acetate was added, and after being washed with distilled water, the organic layer was concentrated. Recrystallization was performed using dichloromethane and hexane. The compound (DA-13-1) 4.97 g was obtained by filtration and vacuum drying at 60°C.

[0292] Then, in Example 1-1, the compound (DA-13-1) was used instead of the compound (DA-1-1), and otherwise, the compound (DA-13) 3.2 g was obtained by the same method as in Example 1-1.

[0293] [Example 1-12] Synthesis of compound (DA-14)

[0294] [Formula 27]

[0295]

[0296] In Example 1-1, 3,5-dinitro-4-methylbenzoic acid was used instead of the compound (DA-1-1), and otherwise, the compound (DA-14) 5.3 g was obtained by the same method as in Example 1-1.

[0297] [Example 1-13] Synthesis of compound (DA-15)

[0298] [Formula 28]

[0299]

[0300] The compound (DA-15-1) was synthesized according to the method described in the non-patent literature "Org. Lett., 2011, 13, 5342".

[0301] Next, the compound (DA-15-1) and bisphenol A were prepared in a molar ratio of 2:1, and the compound (DA-15-3) was synthesized by heating in the presence of potassium carbonate in DMF.

[0302] Next, in Example 1-1, the compound (DA-15-3) was used instead of the compound (DA-1-1), and otherwise, the compound (DA-15-4) 3.3 g was obtained by the same method as in Example 1-1.

[0303] 2. Synthesis of polymer

[0304] Synthesis of polyamic acid ester (P1)

[0305] [Example 2-1]

[0306] Under a dry nitrogen stream, 90 mol parts of the compound (DA-1) as a diamine and 5 mol parts of the compound (DC-1) were dissolved in N-methyl-2-pyrrolidone (NMP) 80 g, 100 mol parts of the compound (TA-2) as a tetracarboxylic dianhydride was added thereto, and reacted at 40°C for 6 hours. Next, a solution in which 10 mol parts of 3-aminophenol as an end-capping agent was diluted with NMP 5 g was added, and reacted at 50°C for 2 hours. Thereafter, a solution in which 200 mol parts of N,N-dimethylformamide dimethyl acetal as an esterification agent was diluted with NMP 20 g was added dropwise over 10 minutes, and reacted at 50°C for 3 hours. After the completion of the reaction, the solution was cooled to room temperature, and the solution was reprecipitated with water 1 L. The obtained white precipitate was filtered, washed with water 3 times, and vacuum-dried at 80°C, whereby the target polyamic acid ester (which will be referred to as "polymer (P-1)") was obtained. The number average molecular weight of the polymer (P-1) was 8,100.

[0307] [Examples 2-2 to 2-15, 2-18, 2-19, and Comparative Synthesis Examples 1 to 3]

[0308] The kind and amount of the tetracarboxylic dianhydride and diamine used in the polymerization were changed as described in Table 1, and otherwise, the polymerization was performed similarly to Example 2-1 to obtain polymers (P-2) to (P-15), (P-18) to (P-22) as polyamic acid esters, respectively.

[0309] Synthesis of polyimide

[0310] [Example 2-16]

[0311] Under a dry nitrogen stream, 100 parts by mole of compound (DA-5) as a diamine was dissolved in 80 g of N-methyl-2-pyrrolidone (NMP), and 100 parts by mole of compound (TA-5) as a tetracarboxylic dianhydride was added thereto, and the mixture was reacted at 40°C for 6 hours. Subsequently, NMP was added to the obtained polyamic acid solution, and 1.8 mole equivalents of pyridine and acetic anhydride were added to the carboxyl groups derived from the tetracarboxylic dianhydride of the polyamic acid, respectively, and dehydration ring closure reaction was performed at 100°C for 4 hours. After the dehydration ring closure reaction, solvent replacement was performed using fresh NMP, and concentration was further performed. Subsequently, the obtained polymer solution was injected into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol, and vacuum drying was performed at 80°C to obtain a polyimide having an imidization rate of 70% (which will be referred to as "polymer (P-16)"). The number average molecular weight of polymer (P-16) was 9,000.

[0312] [Example 2-17]

[0313] The kind and amount of the tetracarboxylic dianhydride and diamine used in the polymerization were changed as described in Table 1, and otherwise, the polymerization was performed similarly to Example 2-16 to obtain polymer (P-17) as a polyimide.

[0314] [Table 1]

[0315]

[0316] In Table 1, the numerical value of the tetracarboxylic dianhydride indicates the proportion (mole) of each monomer with respect to the total amount of 100 mole of the tetracarboxylic dianhydride used in the synthesis of each polymer. The numerical value of the diamine indicates the proportion (mole) of each monomer with respect to the total amount of 100 mole of the diamine used in the synthesis of each polymer. The numerical value of 3-aminophenol (3AP) as a terminal modifier indicates the proportion (mole) with respect to the total amount of 100 mole of the diamine used in the synthesis of each polymer. The blank portion indicates that the compound was not used.

[0317] 3. Preparation and evaluation of photosensitive composition

[0318] [Example 3-1]

[0319] (1) Preparation of composition (R-1)

[0320] Polymer P-1 as a polymer 100 parts by mass, a condensate of a quinonediazide compound (4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mole) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mole) as a photosensitive compound 20 parts by mass, compound (Add-1) as a crosslinking agent 20 parts by mass, an adhesion aid (γ-glycidoxypropyltrimethoxysilane) 5 parts by mass, a surfactant ("FTX-218", manufactured by NEOS Corporation) 0.5 parts by mass were mixed. Further, a mixed solution of γ-butyrolactone and diethylene glycol ethyl methyl ether (γ-butyrolactone: diethylene glycol ethyl methyl ether = 50:50 (mass ratio)) as a solvent was added so that the solid content concentration became 20 mass%, and filtration was performed using a membrane filter having a pore diameter of 0.2 μm, whereby a composition (R-1) was prepared.

[0321] (2) Evaluation of patternability

[0322] After the composition (R-1) was applied to a silicon substrate on which HMDS treatment was performed at 60°C for 60 seconds using a spinner, prebaking was performed at 100°C for 2 minutes on a hot plate, and a coating film having a film thickness of 3.0 μm was formed. With respect to the coating film, an "MPA-600FA" exposure machine manufactured by Canon Inc. was used, and 2,000 J / m 2ultraviolet light. Subsequently, after development treatment with a developer (tetramethylammonium hydroxide 2.38 mass% aqueous solution) at 25°C for 60 seconds, water washing was performed with ultrapure water for 1 minute. The case where a line-and-space pattern with a width of 10 μm was completely formed was evaluated as "good (O)", and the case where a line-and-space pattern with a width of 10 μm could not be obtained was evaluated as "not good (X)". As a result, in the example, the evaluation was "good (O)".

[0323] (3) Evaluation of dielectric constant (measurement of relative dielectric constant)

[0324] On a SUS304 substrate on which surface smoothing was performed by polishing with an agave polishing wheel (jute polishing wheel), the composition (R-1) was applied, the pressure to be applied was set to 100 Pa, and the solvent was removed from the composition (R-1) on the substrate under vacuum, and further, prebaking was performed at 100°C for 2 minutes, to form a coating film with an average film thickness of 3.0 μm. Subsequently, after the entire surface of the substrate was irradiated with light of 3,000 J / m 2 of "MA-1200" (ghi-ray mixed) manufactured by Canon Inc. using a proximity exposure machine, the substrate was heated at 250°C for 60 minutes in a clean oven replaced with nitrogen, to form a hardened film (insulating film) on the substrate. On the insulating film, a Pt / Pd electrode pattern was formed by an evaporation method, to produce a sample for measurement of dielectric constant.

[0325] The sample for measurement of dielectric constant was used, and using an inductance-capacitance-resistance meter (LCR meter) (HP 16451B electrode and HP 4284A Precision LCR meter manufactured by Hewlett Packard Contract Co.), measurement of relative dielectric constant was performed by a capacitance-voltage (CV) method at a frequency of 1 kHz. With respect to the evaluation of dielectric constant, the case where the relative dielectric constant was 3.3 or less was evaluated as "excellent (O)", the case where the relative dielectric constant exceeded 3.3 and was 3.5 or less was evaluated as "good (O)", the case where the relative dielectric constant exceeded 3.5 and was 3.7 or less was evaluated as "fair (D)", and the case where the relative dielectric constant exceeded 3.7 was evaluated as "not good (X)". As a result, in the example, the evaluation was "good (O)".

[0326] (4) Evaluation of element

[0327] (Production of organic EL element substrate)

[0328] Using a spinner, a prepared composition (R-1) was coated on a glass substrate ("OA-10" manufactured by Nippon Electric Glass Co., Ltd.) on which an indium tin oxide (ITO) transparent electrode was formed in an array shape, and pre-baked at 100°C for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. With respect to the coating film, an "MPA-600FA" exposure machine manufactured by Canon Inc. was used to irradiate 2,000 J / m 2 of ultraviolet rays through a pattern mask having a contact hole pattern of 10 μm. Subsequently, after development treatment was performed using a developer (tetramethylammonium hydroxide 2.38 mass% aqueous solution) at 25°C for 60 seconds, a 1-minute water rinse was performed using ultrapure water. At this time, the minimum exposure amount capable of forming a contact hole pattern of 10 μm was measured. Subsequently, after the entire surface of the substrate was irradiated with 3,000 J / m 2 of light using a proximity exposure machine ("MA-1200" (ghi-ray hybrid) manufactured by Canon Inc.), the glass substrate was heated at 250°C for 1 hour in a clean oven replaced with nitrogen gas, whereby a hardened film having a contact hole (which is also referred to as a "patterned hardened resin layer") was formed on the glass substrate.

[0329] With respect to the glass substrate having the patterned hardened resin layer, an Al film having a film thickness of 100 nm was formed on the patterned hardened resin layer by a direct current (DC) sputtering method using an Al target material through a metal mask having a predetermined pattern. An ITO film having a film thickness of 20 nm was formed on the Al film using an ITO target material by a radio frequency (RF) sputtering method. Thus, an anode layer including the Al film and the ITO film was formed.

[0330] A resist material ("Optomer NN803" manufactured by JSR) was used to form a coating film on the anode layer, and a series of processes including i-ray (wavelength 365 nm) irradiation, development, water rinse, air drying, and heating treatment were performed, whereby a pixel defining layer having a part of the anode layer as an opening region was formed.

[0331] The substrate on which the anode and the pixel defining layer were formed was moved to a vacuum deposition chamber, and the deposition chamber was evacuated to 1E-4 Pa, and then, on the substrate, molybdenum oxide (MoO x ) having hole injection properties was deposited at a deposition rate of 0.004 nm / sec to 0.005 nm / sec using an evaporation mask having a predetermined pattern by a resistance-heating evaporation method, whereby a hole injection layer having a film thickness of 1 nm was formed.

[0332] On the hole injection layer, 4,4'-bis[N-(1-naphthyl)-N-phenyl amino]biphenyl (α-NPD) having a hole transporting property was deposited by a resistance heating deposition method under the same evacuation condition as that of the hole injection layer using a deposition mask of a predetermined pattern, to form a hole transporting layer having a film thickness of 35 nm. The deposition rate was 0.2 nm / sec to 0.3 nm / sec.

[0333] On the hole transporting layer, tris(8-hydroxyquinoline)aluminum as a green light emitting material was deposited by a resistance heating deposition method under the same deposition condition as that of the hole transporting layer using a deposition mask of a predetermined pattern, to form a light emitting layer having a film thickness of 35 nm. The deposition rate was 0.5 nm / sec or less.

[0334] On the light emitting layer, lithium fluoride was deposited by a resistance heating deposition method under the same evacuation condition as that of the hole injection layer using a deposition mask of a predetermined pattern, to form an electron injection layer having a film thickness of 0.8 nm. The deposition rate was 0.004 nm / sec or less.

[0335] Subsequently, on the electron injection layer, Mg and Ag were simultaneously deposited by a resistance heating deposition method under the same evacuation condition as that of the hole injection layer using a deposition mask of a predetermined pattern, to form a first cathode layer having a film thickness of 5 nm. The deposition rate was 0.5 nm / sec or less.

[0336] Subsequently, the substrate was transferred to another deposition chamber (sputtering chamber), and a second cathode layer having a film thickness of 100 nm was formed on the first cathode layer using an ITO target by an RF sputtering method using a mask of a predetermined pattern.

[0337] In this manner, an organic EL element was formed on the substrate, and an organic EL element substrate was obtained.

[0338] Thin film sealing of organic EL element

[0339] A thin film sealing layer was formed on the obtained organic EL element according to the following procedure.

[0340] The organic EL element substrate was transferred to a deposition chamber (sputtering chamber), and an inorganic sealing layer (SiNx) having a film thickness of 100 nm was formed on the cathode layer using a SiN x target by an RF sputtering method using a mask of a predetermined pattern. x(Film). Next, the organic EL element substrate is transferred to a glove box purged with N2, and a piezoelectric inkjet printer is used to spray a curable composition containing an epoxy compound, an oxetine compound, and a polymerization initiator according to a predetermined pattern. Then, a UniJet E110ZHD 395 nm LED lamp manufactured by Ushio Electric Co., Ltd. is used at an exposure of 1000 mJ / cm². 2 Irradiation is applied to harden the curable composition used in the film deposition process, forming an organic sealing layer with a thickness of 10 μm. The organic EL element substrate is then transferred to the film deposition chamber (sputtering chamber), and SiN is applied to the organic sealing layer using a mask with a predetermined pattern. x The target material is used to form an inorganic sealing layer (SiN) with a thickness of 100 nm by RF sputtering. x (film). An organic EL element substrate with a sealing layer is obtained in the manner described.

[0341] (Evaluation of the reliability of organic EL components (EL reliability))

[0342] The reliability of the obtained organic EL element substrate with patterned curing resin layer was evaluated according to the following procedure. After storing the organic EL element substrate with patterned curing resin layer in an oven set to 60°C and 90% humidity for 300 hours, a constant current source of 20 mA / cm² was applied between the anode and cathode layers of the organic EL element using an organic EL lighting fixture. 2 A high density of current is used to illuminate the organic EL element. Next, a luminance meter is used to measure the brightness of the organic EL element from the front.

[0343] Regarding the illumination of organic EL devices and the measurement of frontal brightness using a luminance meter, tests were performed on organic EL device substrates with patterned curing resin layers and reference organic EL device substrates without patterned curing resin layers. It can be said that the less impurities generated from the patterned curing resin layer or moisture passing through it, the less impact these impurities or moisture have on the organic EL device, and the closer the frontal brightness of the organic EL device substrate with the sealing layer is to that of the reference organic EL device substrate. The reliability of the organic EL device was evaluated by defining the illumination brightness of the organic EL device substrate with the sealing layer as "Good (○)" when it illuminates at 80% or more of the frontal brightness relative to the reference organic EL device substrate, "Acceptable (△)" when it illuminates at 50% or more but less than 80%, and "Unacceptable (×)" when it does not illuminate normally. The result in the described embodiment was an evaluation of "Good (○)".

[0344] [Examples 3-2 to 3-19 and Comparative Examples 1 to 3]

[0345] The kind and amount of the polymer, the photosensitive compound, and the crosslinking agent used were changed as described in Table 2, and otherwise, the composition (R-2) to the composition (R-22) as the photosensitive composition were each prepared in the same manner as in Example 3-1. In addition, using each of the compositions, each evaluation was performed in the same manner as in Example 3-1. The results are shown in Table 2. In addition, in Table 2, "NQD" means a condensate of 4,4'-[l-[4-[l-[4-hydroxyphenyl]-l-methylethyl]phenyl]ethylidene]bisphenol (1.0 mole) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mole).

[0346] [Table 2]

[0347]

[0348] As shown in Table 2, the patterning property, the dielectric constant, and the EL reliability of the photosensitive compositions of Example 3-1 to Example 3-19 were each evaluated as excellent, good, or fair, and various properties were well balanced and improved. Upon more detailed investigation, it was found that, in comparison with Example 3-5 and Example 3-14 using the monomeric polyamic acid ester having the same composition as that of the polyimide, Example 3-16 and Example 3-17 using the polyimide could obtain a hardened film having a lower dielectric constant. In addition, the dielectric constant of the hardened film obtained from the photosensitive compositions of Example 3-9 to Example 3-13 and Example 3-19 containing the polymer synthesized using the compounds (DA-9) to (DA-13) and (DA-15) as the specific diamines was sufficiently low, and was evaluated as excellent.

[0349] In contrast, in the photosensitive compositions of Comparative Example 1 and Comparative Example 2 containing the polymer (P-20 and P-21) synthesized using the diamine having a perfluoromethyl group, the evaluation of the EL reliability was not possible. In addition, in the photosensitive composition of Comparative Example 3 containing the polymer (P-22) synthesized using the diamine having no hydroxyl group, the evaluation of the patterning property was not possible.

Claims

1. A photosensitizing composition comprising: A polymer comprising a structural unit (a1) derived from a monomer having a 1-3 carbon haloalkyl group containing at least one hydrogen atom and having a hydroxyl group; and Photosensitive compounds.

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

3. The photosensitizing 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 photosensitizing composition according to claim 1, wherein, The polymer has a partial structure represented by the following formula (1); [Chemistry 1] (In equation (1), R) 1 It is an organic group with a valence of (m+n+p+2); R 2 It is an organogroup with a valence of (q+r+2); R 3 It is a hydrogen atom, an alkali metal ion, an ammonium ion, or a monovalent organic group having 1 to 20 carbon atoms; X 1 and X 2 Each is an independent alkyl halide containing at least one hydrogen atom and having 1 to 3 carbon atoms; when p is 2 or higher, multiple R 3 Same or different; m, n, q and r are integers greater than or equal to 0; where m ≥ 1 and n ≥ 1, or q ≥ 1 and r ≥ 1; p is an integer from 0 to 2.

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

6. The photosensitizing composition according to claim 1, wherein, The photosensitive compound contains a quinone diazide compound or a photoacid generator.

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

8. The photosensitizing composition according to claim 7, wherein, The crosslinking compound is at least one selected from the group consisting of oxacyclopropyl, oxacyclobutyl, cyclothioethane, hydroxyalkylamide, protected hydroxyalkylamide, hydroxymethyl, protected hydroxymethyl, alkoxymethyl, cyclic carbonate, and protected isocyanate.

9. A hardened material comprising the photosensitive composition as described in any one of claims 1 to 8.

10. A display device comprising the hardened material as claimed in claim 9.

11. A semiconductor device comprising the hardened material as claimed in claim 9.

12. A method for manufacturing a hardened material, comprising: The process of coating the photosensitive composition as described in any one of claims 1 to 8 onto a substrate; The process of exposing the coated photosensitive composition; The process of developing the exposed photosensitive composition; and A process for hardening the developed photosensitive composition.

13. A polymer having a partial structure represented by the following formula (1); [Chemistry 2] (In equation (1), R) 1 It is an organic group with a valence of (m+n+p+2); R 2 It is an organogroup with a valence of (q+r+2); R 3 It is a hydrogen atom, an alkali metal ion, an ammonium ion, or a monovalent organic group having 1 to 20 carbon atoms; X 1 and X 2 Each is an independent alkyl halide containing at least one hydrogen atom and having 1 to 3 carbon atoms; when p is 2 or higher, multiple R 3 Same or different; m, n, q, and r are integers greater than or equal to 0; among them, The condition is that m ≥ 1 and n ≥ 1, or q ≥ 1 and r ≥ 1; p is an integer from 0 to 2.

14. A compound represented by the following formula (2); [Chemistry 3] (In equation (2), R) 2 (A (q+r+2) valence organic group; q and r are integers greater than or equal to 1).

15. A compound represented by the following formula (3); [Chemistry 4] (In equation (3), R) 1 (a (m+n+4) valence organic group; m and n are integers greater than or equal to 1).

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