Polyimide-based photosensitive composition

Abstract

The present invention provides a negative-type photosensitive composition and a pattern-forming method utilizing a polyimide precursor and an oxime ester compound. [Solution] Compositions that leave no residue after development accurately achieve a pattern with an error of 0.5 μm or less, while compositions that produce residue show errors of up to 5 μm and significant residue. [Effect] This makes oxime ester-based initiators effective in reducing residue and improving pattern accuracy.

Description

[Technical Field]

[0001] The present invention relates to a negative-type photosensitive composition produced using a polyimide precursor and an oxime ester compound, and to a pattern forming method using the same. The invention also relates to a semiconductor device or display device produced using the produced negative-type photosensitive composition. [Background technology]

[0002] The photolithography process is broadly divided into three stages: a coating stage in which a photoresist composition is applied to a substrate; an exposure stage in which a pattern is formed on the photoresist film using a light source that has passed through a mask, an E-beam, etc.; and a development stage in which a specific area of ​​the photoresist film with the pattern is removed. A baking stage is added between each stage to remove the solvent from the photoresist composition or to cure the film.

[0003] The photolithography process described above is broadly divided into negative and positive processes. In the positive process, the exposed area chemically reacts with the developer during the development stage, and the reaction products are dissolved and removed. Conversely, in the negative process, the unexposed area chemically reacts with the developer, and the reaction products are dissolved and removed. Of these, the negative process uses a photoinitiator that absorbs light and generates radicals during the exposure stage, allowing exposure with a relatively smaller amount of energy compared to the positive process, and has the advantage of superior adhesion to the oxide film.

[0004] Conventional negative photosensitive compositions used in semiconductor devices and display devices can utilize a variety of initiators, including oxime-based, thioxanthone-based, diazo compound-based, azo compound-based, and quinone-based initiators. However, depending on their structure and properties, there are limitations to the resolution and realization of the patterns that can be achieved. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In order to solve the problems of the prior art, the present invention attempts to improve the pattern realization characteristics by introducing an oxime ester initiator with a specific structure.

[0006] In addition, it attempts to provide a negative photosensitive composition using the oxime ester initiator.

[0007] It is also for providing a film formed of the negative photosensitive composition and a semiconductor device or a display device manufactured using the same.

Means for Solving the Problems

[0008] The negative photosensitive composition according to the present invention preferably contains a polyimide-based precursor; and an initiator represented by the following Chemical Formula I.

[0009]

Chemical Formula

[0010] In the Chemical Formula I

[0011] R l or R n is each independently hydrogen; deuterium; a C1-C 30 alkyl group; a C1-C 30 alkylene group; a C2-C 20 alkenyl group; a C2-C 20 alkynyl group; a C3-C 30 cycloalkyl group; a C2-C 30 alkylcyclene group; a C6-C 30 aryl group; a C6-C 30 fused ring group of an aliphatic ring and an aromatic ring; a C2-C 30 alkenyl group; a C2-C 30 alkynyl group; a C1-C 30 alkoxy group; a C6-C 30 aryloxy group; a carbonyl group; an ether group; and is selected from the group consisting of combinations thereof,

[0012] Rl R n These are hydrogen; deuterium; and C1-C, respectively, independently. 30 alkyl groups; C1~C 30 alkylene group; C2~C 20 alkenyl group; C2~C 20 Alkynyl group; C3~C 30 Cycloalkyl groups; C2~C 30 alkylcyclene group; C6~C 30 aryl group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 It is further substituted with one or more substituents selected from the group consisting of aryloxy groups, carbonyl groups, ether groups, and combinations thereof, or adjacent substituents form a ring.

[0013] It is more preferable that the compound of chemical formula I contains the following chemical formula J.

[0014] [ka]

[0015] In the aforementioned chemical formula J,

[0016] R o is hydrogen or C1~C 10 It is an alkyl group,

[0017] R p R q These are hydrogen; deuterium; and C1-C, respectively, independently. 30 alkyl groups; C1~C 30 alkylene group; C2~C 20 alkenyl group; C2~C 20 Alkynyl group; C3~C 30 Cycloalkyl groups; C2~C 30 alkylcyclene group; C6~C 30 aryl group; C6~C30 A fusion ring group of an aliphatic ring and an aromatic ring; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 Selected from the group consisting of aryloxy groups; carbonyl groups; ether groups; and combinations thereof,

[0018] R p R q These are hydrogen; deuterium; and C1-C, respectively, independently. 30 alkyl groups; C1~C 30 alkylene group; C2~C 20 alkenyl group; C2~C 20 Alkynyl group; C3~C 30 Cycloalkyl groups; C2~C 30 alkylcyclene group; C6~C 30 aryl group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 It is further substituted with one or more substituents selected from the group consisting of aryloxy groups, carbonyl groups, ether groups, and combinations thereof, or adjacent substituents form a ring.

[0019] It is preferable that the compound represented by the aforementioned chemical formula I is selected from I-1 to I-60.

[0020] [ka]

[0021] The repeating units of the polyimide precursor according to the present invention preferably include repeating units selected from the group consisting of the following chemical formulas 1-1, 1-2, and combinations thereof.

[0022] [ka]

[0023] [ka]

[0024] In the above chemical formulas 1-1 and 1-2,

[0025] 1) * is a portion to which a bond is connected with a repeating unit or a reactive terminal group represented by the chemical formula Q.

[0026] 2) R1 to R4 are represented by the following chemical formula 2,

[0027] 3) X is given by the following chemical formula 3,

[0028] 4) m and n are integers from 1 to 1000.

[0029] [ka]

[0030] In the aforementioned chemical formula 2,

[0031] 5)* is the part where the connection is made.

[0032] 6) a is an integer between 1 and 30,

[0033] 7) R5 is either a hydrogen or a methyl group.

[0034] 8) Y is C6~C 30 Arylene group; C2-C containing at least one heteroatom of O, N, S, Si and P 30 heterocyclic group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 20 alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C20 Cycloalkenylene group; C2~C 20 Alkynylene group; C3~C 20 A cycloalkylene group; chemical formula 3; and selected from the group consisting of combinations thereof,

[0035] 9) Z is C6~C 30 Arylene group; C2-C containing at least one heteroatom of O, N, S, Si and P 30 heterocyclic group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 20 alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkynylene group; C3~C 20 A cycloalkylene group; chemical formula 3; and selected from the group consisting of combinations thereof,

[0036] [ka]

[0037] 10) L1 is selected from the group consisting of a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, -Si(CH3)2-, -C6H4-, -OC6H4O-, -CO-, -NHCO-, and -COO-,

[0038] 11) R6 or R 15 Two of these are linking sites with amide groups of chemical formula 1-1 or chemical formula 1-2.

[0039] 12) The remaining R6 to R excluding the aforementioned connecting portion 15 These are hydrogen; deuterium; hydroxyl group; C6~C, independently of each other. 30 An aryl group; containing at least one heteroatom of O, N, S, Si, and P (C2-C2). 30a heterocyclic group; C6-C 30 a fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 an alkyl group; C2-C 20 an alkenyl group; C2-C 20 an alkynyl group; C1-C 20 an alkoxy group; C6-C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 an alkoxycarbonyl group; or adjacent R6 and R 15 ; and R 10 and R 11 form a ring,

[0040] 13) The ring formed by bonding the Y, Z, R6 to R 15 , and adjacent groups to each other is each deuterium; halogen; C1-C 30 an alkyl group or a C6-C 30 an aryl group substituted or unsubstituted with a silane group; a siloxane group; a boron group; a germanium group; a cyano group; an amino group; a nitro group; C1-C 30 an alkylthio group; C1-C 30 an alkoxy group; C6-C 30 an arylalkoxy group; C1-C 30 an alkyl group; C2-C 30 an alkenyl group; C2-C 30 an alkynyl group; C6-C 30 an aryl group; a C6-C substituted with deuterium 30 an aryl group; a fluorenyl group; a C2-C containing at least one heteroatom selected from the group consisting of O, N, S, Si and P 30 a heterocyclic group; C3-C 30 an aliphatic ring group; C7-C 30 an arylalkyl group; C8-C 30 an arylalkenyl group; and is further substituted with one or more substituents selected from the group consisting of these combinations, or adjacent substituents form a ring with each other.

[0041] The polyimide precursor preferably contains a polyimide repeating unit and a reactive end group represented by the following chemical formula Q that is bonded to the end of the polyimide repeating unit.

[0042] [ka]

[0043] In the aforementioned chemical formula Q,

[0044] 1) R a R c These are independently hydrogen; deuterium; hydroxyl group; C6~C 30 An aryl group; containing at least one heteroatom of O, N, S, Si, and P (C2-C2). 30 heterocyclic group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 30 alkyl groups; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 aryloxy group; C1~C 30 Hydroxyacrylic group; C1~C 30 Hydroxymethacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 30 It is an alkoxycarbonyl group of; or R a R c The adjacent groups form a ring,

[0045] 2) C1 and C2 are carbon atoms; the double dotted line connecting C1 and C2 is either a single bond or a double bond.

[0046] 3) If the double dotted line connecting C1 and C2 is a single connection, then o and p are each independently integers of 1 or 2; if the double dotted line connecting C1 and C2 is a double connection, then o and p are each integers of 1.

[0047] 4) C3 is either carbon or a direct C2-B2 bond.

[0048] 5) If C3 is carbon, then q is an integer of 1 or 2.

[0049] 6) The dotted line connecting B1 and B2 indicates that there is no connection or that there is a single connection.

[0050] 7) If there is no dotted line connecting B1 and B2, B1 is hydrogen; deuterium; hydroxyl group; C6~C 30 An aryl group; containing at least one heteroatom of O, N, S, Si, and P (C2-C2). 30 heterocyclic group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 20 alkyl groups; C2~C 20 alkenyl group; C2~C 20 Alkynyl group of C1~C 20 alkoxy group; C6~C 30 aryloxy group; C1~C 20 Hydroxyacrylic group; C1~C 20 Hydroxymethacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 20 It is an alkoxycarbonyl group; B2 is a carbon linked to a polyimide repeating unit.

[0051] 8) When the dotted line connecting B1 and B2 is a single bond, B1 is nitrogen linked to the polyimide repeating unit, and B2 is carbon.

[0052] 9) The above R a R c And the rings formed by the bonding of adjacent groups to each other are, respectively, deuterium; halogen; C1~C 30 alkyl groups or C6~C 30 Silane groups substituted or unsubstituted with aryl groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C1-C 30 alkylthio group; C1~C 30alkoxy group; C6~C 30 arylalkoxy group; C1~C 30 alkyl groups; C2~C 30 alkenyl group; C2~C 30 Alkynyl group; C6~C 30 aryl group; deuterium-substituted C6-C 30 aryl group; fluorenyl group; C2-C containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P. 30 heterocyclic group; C3~C 30 aliphatic ring group; C7~C 30 Aryl alkyl groups; C8~C 30 The aryl alkenyl group; further substituted with one or more substituents selected from the group consisting of combinations thereof, or adjacent substituents forming a ring.

[0053] The reactive terminal group represented by the chemical formula Q preferably includes compounds represented by the following chemical formulas Q-1 to Q-6.

[0054] [ka]

[0055] In the aforementioned chemical formulas Q-1 to Q-6,

[0056] 1) R d1 , R d2 , R e1 R e3 , R f1 R f4 , R g , R h1 , R h2 , and R i1 R i3 These are, independently, hydrogen; deuterium; hydroxyl group; and C6-C6. 30 An aryl group; containing at least one heteroatom of O, N, S, Si, and P (C2-C2). 30 heterocyclic group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 30alkyl groups; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 aryloxy group; C1~C 30 Hydroxyacrylic group; C1~C 30 Hydroxymethacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 30 It is an alkoxycarbonyl group,

[0057] 2) r and t are integers from 1 to 4,

[0058] 3) s1, s2, and u1 through u3 are each integers of 1 or 2.

[0059] The repeating units of the polyimide precursor preferably include diamine monomers; dianhydride monomers; and anhydride monomers.

[0060] The weight-average molecular weight of the precursor is preferably 5,000 to 40,000 g / mol.

[0061] As another specific example of the present invention, the negative-type photosensitive composition according to the present invention preferably further comprises a reactive unsaturated compound; a solvent; and other additives.

[0062] The initiator is preferably present in an amount of 0.01 to 10% by weight relative to the total amount of the composition.

[0063] The polyimide precursor is preferably present in an amount of 5 to 50% by weight relative to the total amount of the composition.

[0064] The solvent is preferably present in an amount of 50 to 95% by weight relative to the total amount of the composition.

[0065] As another specific example of the present invention, it is preferable to provide a film manufactured from the negative-type photosensitive composition.

[0066] As another specific example of the present invention, it is preferable to provide a semiconductor device or display device manufactured using the film.

[0067] As another specific example of the present invention, it is preferable to provide an electronic device comprising the semiconductor device or display device and a control unit that drives the same. [Effects of the Invention]

[0068] The present invention provides a photosensitive composition that leaves no residue after development by introducing monomers containing reactive working groups at the ends of a polyimide precursor or copolymer resin and applying an oxime ester initiator, as well as a display device or semiconductor device utilizing the same. [Modes for carrying out the invention]

[0069] Hereinafter, some embodiments of the present invention will be described in detail with reference to illustrative drawings. When assigning reference numerals to the components in each drawing, the same reference numerals will be used for the same components as much as possible, even if they are shown in other drawings.

[0070] In the description of the present invention, if a specific description of a related known structure or function is deemed likely to obscure the gist of the invention, such detailed description may be omitted. Where "includes," "has," "constitutes," etc., as used herein, other parts may be added, as long as "only" is not used. Unless otherwise explicitly stated, a singular representation of a component includes multiple components.

[0071] Furthermore, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc., may be used. Such terms are used to distinguish a component from other components, and the terms do not limit the nature, order, sequence, or number of the component.

[0072] When describing the spatial relationships of components, if it is stated that two or more components are “linked,” “joined,” or “connected,” it should be understood that while two or more components may be directly “linked,” “joined,” or “connected,” they may also be “linked” or “connected” through further “intermediation” between two or more components and other components. Here, the other components may be included in one or more of the two or more components that are “linked,” “joined,” or “connected” to each other.

[0073] Furthermore, when we say that a component such as a layer, film, region, or plate is "on top of" or "on" another component, this should be understood to include not only the case where it is "directly on top" of the other component, but also the case where there is another component in between. Conversely, when we say that one component is "directly on top" of another, this should be understood to mean that there is no other component in between.

[0074] In descriptions of temporal relationships related to components, methods of operation, or manufacturing methods, when describing temporal sequence or flow of events using phrases such as "after," "following," "next," or "before," it includes cases that are not continuous unless "immediately" or "directly" is used.

[0075] On the other hand, if numerical values ​​or corresponding information for a component are mentioned, even without further explicit mention, these numerical values ​​or corresponding information can be interpreted as including a range of errors that may arise due to various factors (e.g., process factors, internal or external shocks, noise, etc.).

[0076] The terms used in this specification and the appended claims should not be construed to be limited to their ordinary or dictionary meanings, but rather should be interpreted in a way that is consistent with the technical spirit of the present invention, based on the principle that inventors can appropriately define the concepts of terms in order to best describe their invention.

[0077] As used in this application, the terms "halo" or "halogen" include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise specified.

[0078] As used in this application, the terms "alkyl" or "alkyl group" refer to a radical of a saturated aliphatic active group having 1 to 60 carbon atoms linked by a single bond, including linear alkyl groups, branched alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups, unless otherwise specified.

[0079] As used in this application, the terms "haloalkyl group" or "halogen alkyl group" mean an alkyl group substituted with a halogen, unless otherwise specified.

[0080] As used in this application, the terms "alkenyl" or "alkynyl" each have a double or triple bond, include a linear or side-chain group, and have 2 to 60 carbon atoms, unless otherwise specified.

[0081] As used in this application, the term "cycloalkyl" means, but is not limited to, an alkyl group forming a ring having 3 to 60 carbon atoms, unless otherwise specified.

[0082] In this application, the terms "alkoxy group" or "alkyloxy group" refer to an alkyl group to which an oxygen radical is bonded, and unless otherwise stated, have 1 to 60 carbon atoms, but are not limited thereto.

[0083] In this application, the terms "alkeneoxyl group," "alkenoxy group," "alkenyloxyl group," or "alkenyloxy group" refer to an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, have 2 to 60 carbon atoms, but are not limited thereto.

[0084] In this application, the terms "aryl group" and "arylene group" refer to, but are not limited to, groups having 6 to 60 carbon atoms, unless otherwise specified. In this application, aryl groups and arylene groups include single rings, ring aggregates, and compound systems of multiple joined rings. For example, the aryl group includes a phenyl group, a monovalent activator of biphenyl, a monovalent activator of naphthalene, a fluorenyl group, and a substituted fluorenyl group, while the arylene group includes a fluorenylene group and a substituted fluorenylene group.

[0085] As used in this application, the term "ring assemblies" refers to two or more ring systems (single rings or joined ring systems) directly linked to each other by single or double bonds, where the number of such direct links between rings is one less than the total number of ring systems in the compound. Ring assemblies can consist of identical or different ring systems directly linked to each other by single or double bonds.

[0086] In this application, the aryl group includes ring assemblies, and therefore includes biphenyl and terphenyl, in which a single aromatic ring, such as a benzene ring, is linked by a single bond. Furthermore, the aryl group also includes compounds in which an aromatic ring system bonded to a single aromatic ring is linked by a single bond, such as compounds in which a single aromatic ring, such as a benzene ring, is bonded to a fluorene, which is an aromatic ring system, is linked by a single bond.

[0087] As used in this application, the term "fused ring system" refers to a fused ring form that shares at least two atoms, and includes forms in which two or more hydrocarbon ring systems are fused, and forms in which at least one heterocyclic system containing at least one heteroatom is fused. Such fused ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings, or combinations thereof. For example, in the case of aryl groups, these may be naphthalenyl groups, phenantrenyl groups, fluorenyl groups, etc., but are not limited to these.

[0088] The term "spiro compound" as used in this application refers to a "spiro union," which is a linkage formed by two rings sharing only one atom. In this case, the atom shared by the two rings is called a "spiro atom," and these compounds are called "monospiro-," "dispiro-," and "trispiro-" compounds, respectively, depending on the number of spiro atoms contained in a single compound.

[0089] In this application, the terms “fluorenyl group,” “fluorenylene group,” and “fluorentryyl group” refer to monovalent, divalent, or trivalent working groups in the following structures, respectively, where R, R', R'', and R''' are all hydrogen atoms, unless otherwise specified. “Substitutable fluorenyl group,” “substituted fluorenylene group,” or “substituted fluorentryyl group” means that at least one of the substituents R, R', R'', and R''' is a substituent other than hydrogen, and includes cases where R and R' are bonded to each other to form a spiro compound with the carbon atom to which they are bonded. In this specification, regardless of their valency (monovalent, divalent, trivalent, etc.), fluorenyl groups, fluorenylene groups, and fluorentryyl groups may all be named fluorene groups.

[0090] [ka]

[0091] Furthermore, R, R', R'', and R'' are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms. For example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene, or phenanthrene, and the heterocyclic group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, benzofuranquinazoline, or quinoxaline. For example, the substituted fluorenyl group and fluorenylene group may be monovalent or divalent activators of 9,9-dimethylfluorene, 9,9-diphenylfluorene, and 9,9'-spirobi[9H-fluorene], respectively.

[0092] As used in this application, the term "heterocyclic group" includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group," but also non-aromatic rings, and unless otherwise specified, means a ring with 2 to 60 carbon atoms containing one or more heteroatoms, but is not limited to this. As used in this application, the term "heteroatom" refers to N, O, S, P, or Si unless otherwise specified, and heterocyclic group means a single ring, ring aggregate, joined ring system, spiro compound, etc., containing a heteroatom.

[0093] For example, "heterocyclic group" may include compounds containing heteroatom groups such as SO2 and P=O, as shown in the compounds below, instead of carbon atoms forming a ring.

[0094] [ka]

[0095] The term "ring" as used in this application includes single rings and polyrings, and includes not only hydrocarbon rings but also heterorings containing at least one heteroatom, and includes aromatic and non-aromatic rings.

[0096] As used in this application, the term "polycyclic" includes ring assemblies such as biphenyl and terphenyl, fused ring systems, and spiro compounds, and includes not only aromatic but also non-aromatic compounds, and includes not only hydrocarbon rings but also heterocycles containing at least one heteroatom.

[0097] The term "aliphatic ring group" as used in this application refers to cyclic hydrocarbons excluding aromatic hydrocarbons, and includes single rings, ring aggregates, joined ring systems, spiro compounds, etc. Unless otherwise specified, it refers to rings with 3 to 60 carbon atoms, but is not limited to these. For example, a fusion of the aromatic ring benzene and the non-aromatic ring cyclohexane also constitutes an aliphatic ring.

[0098] Furthermore, when prefixes are used consecutively, it means that the substituents are listed in the order they are listed. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group, where an arylcarbonyl group is a carbonyl group substituted with an aryl group.

[0099] Furthermore, unless otherwise explicitly stated, in the terms "substituted or unsubstituted" used in this application, "substituted" refers to deuterium, halogens, amino groups, nitrile groups, nitro groups, C1-C123 30 alkyl groups, C1-C 30 Alkoxy group of C1~C 30 alkylamine group, C1~C 30 alkylthiophene group, C6~C 30 The arylthiophene group, C2~C 30 alkenyl group, C2~C 30 Alkynyl group, C3~C 30 Cycloalkyl groups, C6~C 30 The aryl group, deuterium-substituted C6-C 30 The aryl group, C8~C 30C2-C2 containing an aryl alkenyl group, silane group, boron group, germanium group, and at least one heteroatom selected from the group consisting of O, N, S, Si, and P. 30 This means that the molecule is substituted with one or more substituents selected from the group consisting of heterocyclic groups, and is not limited to these substituents.

[0100] In this application, the "name of the active group" corresponding to each symbol and its substituent, such as aryl groups, arylene groups, and heterocyclic groups, can be described as the "name of the active group reflecting its valency," or as the "name of the parent compound." For example, in the case of "phenanthrene," a type of aryl group, the monovalent "group" can be described as "phenanthryl(group)" and the divalent group as "phenanthrylene(group)," distinguishing the group by its valency, but it can also be described as "phenanthrene," the name of the parent compound, regardless of its valency.

[0101] Similarly, in the case of pyrimidines, they can be described as "pyrimidine" regardless of their valency, or they can be described as the "name of the group" corresponding to the valency, such as pyrimidinyl (group) for monovalent groups and pyrimidinylene (group) for divalent groups. Therefore, when describing the type of ring group in the name of the parent compound in this application, it may refer to an n-valent "group" formed by the removal of a hydrogen atom bonded to a carbon atom and / or heteroatom of the parent compound.

[0102] Furthermore, in this specification, when describing compound names and substituent names, numbers or letters indicating position may be omitted. For example, pyrido[4,3-d]pyrimidine can be written as pyridopyrimidine, benzoflo[2,3-d]pyrimidine as benzoflopyrimidine, and 9,9-dimethyl-9H-fluorene as dimethylfluorene. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be written as benzoquinoxaline.

[0103] Furthermore, unless otherwise explicitly stated, the chemical formulas used in this application shall be applied in the same manner as the substituent definitions by exponential definition of the chemical formulas below.

[0104] [ka]

[0105] Here, if a is an integer of 0, the substituent R 1 This means that there are no atoms; that is, if a is 0, it means that all the carbon atoms forming the benzene ring are bonded to hydrogen atoms, in which case the hydrogen atoms bonded to the carbon atoms can be omitted, and the chemical formula or compound can be written. Also, if a is an integer of 1, one substituent R 1 It bonds to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, for example, it can bond as follows, and when a is an integer of 4 to 6, it bonds to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R 1 They may be identical or different to one another.

[0106] [ka]

[0107] Unless otherwise stated in this application, forming a ring means that adjacent groups bond to each other to form a single ring or multiple joined rings, the single ring and the multiple joined rings formed include a hydrocarbon ring as well as a heteroring containing at least one heteroatom, and include aromatic and non-aromatic rings.

[0108] Furthermore, unless otherwise stated herein, when a fused ring is indicated, the number in "number-fused ring" indicates the number of rings being fused. For example, a form in which three rings are fused together, such as anthracene, phenanthrene, and benzoquinazoline, can be written as a 3-fused ring.

[0109] On the other hand, the term "bridged bicyclic compound" as used in this application, unless otherwise specified, refers to a compound in which two rings share three or more atoms to form a ring. In this case, the shared atoms include carbon or heteroatoms.

[0110] The following describes in detail some examples of the implementation of the present invention. However, these are presented as examples only and do not limit the present invention; rather, the present invention is defined only within the scope of the claims described below.

[0111] A negative-type photosensitive composition comprising a polyimide precursor or copolymer according to one embodiment of the present invention is used in the manufacture of insulating films, surface protective films, and redistribution layers for semiconductor devices; and pixel definition layers (PDLs) for display devices.

[0112] In the manufacture of a negative-type photosensitive composition for application to a semiconductor device or display device according to one embodiment of the present invention, the following additives may be further included to improve the required properties.

[0113] As an example of an implementation of the present invention, an additive that can be added may further include a surface smoothing agent to ensure a uniform coating thickness when coating the substrate. A surfactant may further be included to ensure a uniform coating according to the characteristics of the substrate surface, and a silane coupling agent may further be included to adjust the adhesion to the substrate surface. A crosslinking agent may further be included to strengthen the bonds between polymers during the heat treatment stage.

[0114] The elements constituting the negative-type photosensitive composition are as follows:

[0115] (1) Initiator

[0116] To achieve a negative pattern in photolithography, an oxime ester-based initiator must be used.

[0117] The oxime ester initiator is an initiator commonly used in photosensitive resin compositions and preferably has a structure represented by the following chemical formula I.

[0118] [ka]

[0119] In the aforementioned chemical formula I,

[0120] R l R n These are hydrogen; deuterium; and C1-C, respectively, independently. 30 alkyl groups; C1~C 30 alkylene group; C2~C 20 alkenyl group; C2~C 20 Alkynyl group; C3~C 30 Cycloalkyl groups; C2~C 30 alkylcyclene group; C6~C 30 aryl group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 The group is selected from the group consisting of aryloxy groups, carbonyl groups, ether groups, and combinations thereof.

[0121] R l R n These are hydrogen; deuterium; and C1-C, respectively, independently. 30 alkyl groups; C1~C 30 alkylene group; C2~C 20 alkenyl group; C2~C 20 Alkynyl group; C3~C 30 Cycloalkyl groups; C2~C 30 alkylcyclene group; C6~C 30 aryl group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C2~C 30 alkenyl group; C2~C 30Alkynyl group of C1~C 30 alkoxy group; C6~C 30 It can be further substituted with one or more substituents selected from the group consisting of aryloxy groups, carbonyl groups, ether groups, and combinations thereof, or adjacent substituents can form a ring.

[0122] It is more preferable that the compound of chemical formula I contains the following chemical formula J.

[0123] [ka]

[0124] In the aforementioned chemical formula J,

[0125] R o is hydrogen or C1~C 10 It is an alkyl group,

[0126] R p R q These are hydrogen; deuterium; and C1-C, respectively, independently. 30 alkyl groups; C1~C 30 alkylene group; C2~C 20 alkenyl group; C2~C 20 Alkynyl group; C3~C 30 Cycloalkyl groups; C2~C 30 alkylcyclene group; C6~C 30 aryl group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 The group is selected from the group consisting of aryloxy groups, carbonyl groups, ether groups, and combinations thereof.

[0127] R p R q These are hydrogen; deuterium; and C1-C, respectively, independently. 30 alkyl groups; C1~C 30alkylene group; C2~C 20 alkenyl group; C2~C 20 Alkynyl group; C3~C 30 Cycloalkyl groups; C2~C 30 alkylcyclene group; C6~C 30 aryl group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 It can be further substituted with one or more substituents selected from the group consisting of aryloxy groups, carbonyl groups, ether groups, and combinations thereof, or adjacent substituents can form a ring.

[0128] It is preferable that the compound represented by the chemical formula I is selected from I-1 to I-60.

[0129] [ka]

[0130] The polyimide precursor preferably contains a polyimide repeating unit and a reactive end group represented by the following chemical formula Q that is bonded to the end of the polyimide repeating unit.

[0131] The aforementioned oxime ester initiator can also be used in conjunction with a photosensitizer that absorbs light, becomes suspended, and then transmits that energy to initiate a chemical reaction. Examples of the aforementioned photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol tetrakis-3-mercaptopropionate.

[0132] The photoinitiator may be included in amounts of 0.01 to 10% by weight; 0.1 to 10% by weight; 0.5 to 10% by weight; 0.01 to 5% by weight; 0.1 to 5% by weight; 0.5 to 5% by weight; 0.01 to 2% by weight; 0.1 to 2% by weight; or 0.5 to 2% by weight, relative to the total amount of the photosensitive composition. When the photoinitiator is included within the above range, sufficient curing occurs during exposure in the pattern formation process, resulting in excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, excellent resolution and adhesion, and prevention of a decrease in transmittance due to unreacted initiators.

[0133] (2) Polyimide precursors

[0134] The patterning resin according to one embodiment of the present invention may contain a polyimide precursor.

[0135] The aforementioned polyimide precursor refers to a resin containing an amitic acid copolymer that can be converted to a polyimide copolymer by chemical or thermal treatment, and a polyimide precursor (polymer) that has undergone chemical or thermal treatment.

[0136] The polyimide-based precursor resin may be included in an amount of 5% to 50% by weight, preferably 10% to 40% by weight, relative to the total amount of the negative-type photosensitive composition.

[0137] The aforementioned polyimide precursors include, but are not limited to, copolymers represented by the following chemical formulas 1-1 or 1-2. These can be used individually or in combination of two or more.

[0138] The negative polyimide repeating unit according to the present invention more preferably includes a repeating unit selected from the group consisting of the following chemical formulas 1-1, 1-2, and combinations thereof.

[0139] [ka]

[0140] [ka]

[0141] In the above chemical formulas 1-1 and 1-2,

[0142] 1) * is a portion to which a bond is connected with a repeating unit or a reactive terminal group represented by the chemical formula Q.

[0143] 2) R1 to R4 are represented by the following chemical formula 2,

[0144] 3) X is given by the following chemical formula 3,

[0145] 4) m and n are integers from 1 to 1000.

[0146] [ka]

[0147] In the aforementioned chemical formula 2,

[0148] 5)* is the part where the connection is made.

[0149] 6) a is an integer between 1 and 30,

[0150] 7) R5 is either a hydrogen or a methyl group.

[0151] 8) Y is C6~C 30 Arylene group; C2-C containing at least one heteroatom of O, N, S, Si and P 30 heterocyclic group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 20 alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20an alkynylene group; C3-C 20 a cycloalkynylene group; Chemical Formula 3; and a group consisting of a combination thereof, selected from the group consisting of

[0152] 9) Z is a C6-C 30 an arylene group; a heterocyclic group containing at least one heteroatom of O, N, S, Si and P, C2-C 30 a heterocyclic group; C6-C 30 a fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 an alkylene group; C1-C 20 a cycloalkylene group; C2-C 20 an alkenylene group; C3-C 20 a cycloalkenylene group; C2-C 20 an alkynylene group; C3-C 20 a cycloalkynylene group; Chemical Formula 3; and a group consisting of a combination thereof, selected from the group consisting of

[0153]

Chemical formula

[0154] 10) L1 is selected from the group consisting of a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, -Si(CH3)2-, -C6H4-, -OC6H4O-, -CO-, -NHCO-, and -COO-

[0155] 11) Two of R6 to R 15 are a linking site with an amide group of Chemical Formula 1-1 or Chemical Formula 1-2,

[0156] 12) The remaining R6 to R 15 excluding the linking site are, independently of each other, hydrogen; deuterium; a hydroxy group; a C6-C 30 aryl group; a C2-C heterocyclic group containing at least one heteroatom of O, N, S, Si and P; a C6-C 30 heterocyclic group; C6-C 30A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 20 alkyl groups; C2~C 20 alkenyl group; C2~C 20 Alkynyl group of C1~C 20 alkoxy group; C6~C 30 Aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 It is an alkoxycarbonyl group of; or adjacent R6 and R 15 ; and R 10 and R 11 They form a ring,

[0157] 13) The aforementioned Y, Z, R6 to R 15 The rings formed by the bonding of adjacent groups to each other are, respectively, deuterium; halogen; and C1-C. 30 alkyl groups or C6~C 30 Silane groups substituted or unsubstituted with aryl groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C1-C 30 alkylthio group; C1~C 30 alkoxy group; C6~C 30 arylalkoxy group; C1~C 30 alkyl groups; C2~C 30 alkenyl group; C2~C 30 Alkynyl group; C6~C 30 aryl group; deuterium-substituted C6-C 30 aryl group; fluorenyl group; C2-C containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P. 30 heterocyclic group; C3~C 30 aliphatic ring group; C7~C 30 Aryl alkyl groups; C8~C 30 The aryl alkenyl group; further substituted with one or more substituents selected from the group consisting of combinations thereof, or adjacent substituents forming a ring.

[0158] The repeating units of the polyimide precursor preferably contain a reactive group represented by the following chemical formula Q at their terminal groups.

[0159] [ka]

[0160] In the aforementioned chemical formula Q,

[0161] 1) R a R c These are independently hydrogen; deuterium; hydroxyl group; C6~C 30 An aryl group; containing at least one heteroatom of O, N, S, Si, and P (C2-C2). 30 heterocyclic group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 30 alkyl groups; C2~C 30 alkenyl group; C2~C 30 Alkynyl group of C1~C 30 alkoxy group; C6~C 30 aryloxy group; C1~C 30 Hydroxyacrylic group; C1~C 30 Hydroxymethacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 30 It is an alkoxycarbonyl group of; or R a R c The adjacent groups form a ring,

[0162] 2) C1 and C2 are carbon atoms; the double dotted line connecting C1 and C2 is either a single bond or a double bond.

[0163] 3) If the double dotted line connecting C1 and C2 is a single connection, then o and p are each independently integers of 1 or 2; if the double dotted line connecting C1 and C2 is a double connection, then o and p are each integers of 1.

[0164] 4) C3 is either carbon or a direct C2-B2 bond.

[0165] 5) If C3 is carbon, then q is an integer of 1 or 2.

[0166] 6) The dotted line connecting B1 and B2 indicates that there is no connection or that there is a single connection.

[0167] 7) If there is no dotted line connecting B1 and B2, B1 is hydrogen; deuterium; hydroxyl group; C6~C 30 An aryl group; containing at least one heteroatom of O, N, S, Si, and P (C2-C2). 30 heterocyclic group; C6~C 30 A fusion ring group of an aliphatic ring and an aromatic ring; C1~C 20 alkyl groups; C2~C 20 alkenyl group; C2~C 20 Alkynyl group of C1~C 20 alkoxy group; C6~C 30 aryloxy group; C1~C 20 Hydroxyacrylic group; C1~C 20 Hydroxymethacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 20 It is an alkoxycarbonyl group; B2 is a carbon linked to a polyimide repeating unit.

[0168] 8) When the dotted line connecting B1 and B2 is a single bond, B1 is nitrogen linked to the polyimide repeating unit, and B2 is carbon.

[0169] 9) The above R a R c The rings formed by the bonding of adjacent groups to each other are, respectively, deuterium; halogen; and C1-C. 30 alkyl groups or C6~C 30 Silane groups substituted or unsubstituted with aryl groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C1-C 30 alkylthio group; C1~C 30 alkoxy group; C6~C 30 arylalkoxy group; C1~C 30 alkyl groups; C2~C30 an alkenyl group; C2-C 30 an alkynyl group; C6-C 30 an aryl group; C6-C substituted with deuterium 30 an aryl group; a fluorenyl group; a C2-C containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P 30 a heterocyclic group; C3-C 30 an aliphatic ring group; C7-C 30 an arylalkyl group; C8-C 30 an arylalkenyl group; and is further substituted with one or more substituents selected from the group consisting of these combinations, or forms a ring between adjacent substituents.

[0170] The reactive terminal group represented by the chemical formula Q may include compounds represented by the following chemical formulas Q-1 to Q-6.

[0171]

Chemical formula

[0172] In the chemical formulas Q-1 to Q-6,

[0173] 1) R d1 , R d2 , R e1 to R e3 , R f1 to R f4 , R g , R h1 , R h2 , and R i1 to R i3 are each independently hydrogen; deuterium; a hydroxy group; a C6-C 30 aryl group; a C2-C heterocyclic group containing at least one heteroatom of O, N, S, Si, and P 30 heterocyclic group; a C6-C fused ring group of an aliphatic ring and an aromatic ring; a C1-C 30 alkyl group; a C2-C 30 alkenyl group; a C2-C 30 alkynyl group; a C1-C 30 alkynyl group; C1-C 30alkoxy group; C6~C 30 aryloxy group; C1~C 30 Hydroxyacrylic group; C1~C 30 Hydroxymethacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 30 It is an alkoxycarbonyl group,

[0174] 2) r and t are integers from 1 to 4,

[0175] 3) s1, s2, and u1 through u3 are each integers of 1 or 2.

[0176] The weight-average molecular weight of the polyimide precursor is 5,000 to 40,000 g / mol, preferably 5,000 to 30,000 g / mol, and more preferably 6,000 to 25,000 g / mol. When the weight-average molecular weight of the polyimide precursor is within the above range, no residue remains in the exposed layer during development, minimizing the loss of film thickness in the unexposed layer and allowing for the acquisition of a good pattern. The polyimide precursor may be included in an amount of 5 to 50% by weight, more preferably 15 to 45% by weight, relative to the total amount of the photosensitive composition. When the polyimide precursor is included within the above range, a constant film thickness can be obtained during the coating stage, and excellent sensitivity, developability, and adhesion can be obtained.

[0177] (3) Reactive unsaturated compounds

[0178] The reactive unsaturated compounds that are essential for negative patterns have ethylenically unsaturated double bonds, which allows for sufficient polymerization during exposure in the pattern formation process, resulting in patterns with excellent heat resistance, light resistance, and chemical resistance.

[0179] Specific examples of the aforementioned reactive unsaturated compounds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, trimethylolpropane triacrylate, tripentaerythritol octaacrylate, and the like.

[0180] The commercially available products of the aforementioned reactive unsaturated compound are as follows:

[0181] Examples of the difunctional esters of (meth)acrylic acid include Aronix M-210, M-240, and M-6200 from Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA, HX-220, and R-604 from Nippon Kayaku Co., Ltd.; and V-260, V-312, and V-335HP from Osaka Organic Chemical Industry Co., Ltd.

[0182] Examples of the aforementioned trifunctional esters of (meth)acrylic acid include Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, etc. from Toagosei Chemical Industry Co., Ltd.; KAYARAD TMPTA, DPCA-20, DPCA-60, DPCA-120, etc. from Nippon Kayaku Co., Ltd.; and V-295, V-300, V-360, etc. from Osaka Organic Chemical Industry Co., Ltd.

[0183] The aforementioned products can be used individually or in combination of two or more types.

[0184] The reactive unsaturated compound may also be treated with an acid anhydride to provide better developability. The reactive unsaturated compound may be present in an amount of 1 to 40% by weight, for example, 1 to 20% by weight, relative to the total amount of the photosensitive resin composition. When the reactive unsaturated compound is present within the above range, sufficient curing occurs during exposure in the pattern formation process, resulting in excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, as well as excellent resolution and adhesion.

[0185] (4) Solvent

[0186] The solvent can be a substance that is compatible with the polyimide precursor or copolymer resin, the photosensitive agent, and the pigment, but does not react with them.

[0187] Examples of the aforementioned solvents include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethyl glycol monomethyl ester, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4- Ketones such as methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylate alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; alkyl 3-oxypropionates such as methyl 3-oxypropionate and ethyl 3-oxypropionate; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; alkyl 2-oxypropionates such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate;Examples include alkyl esters of 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionate esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylate alkyl esters of alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; and ketone acid esters such as ethyl pyruvate.

[0188] In addition, high-boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be used.

[0189] From the aforementioned solvents, considering their compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

[0190] The solvent may be included in the remainder of the total amount of the photosensitive composition, specifically in amounts of 50 to 95% by weight, 50 to 90% by weight, 50 to 85% by weight, or 50 to 75% by weight. When the solvent is included within the above range, the negative-type photosensitive composition has an appropriate viscosity, resulting in excellent processability during pattern layer manufacturing.

[0191] (5) Other additives

[0192] The negative photosensitive resin composition may further contain additives such as malonic acid; 3-amino-1,2-propanediol; silane coupling agents containing vinyl groups or (meth)acrylooxy groups; surface smoothing agents; surfactants; and crosslinkers in order to prevent stains and spots during application, improve leveling performance, and prevent the formation of residue due to undeveloped material.

[0193] For example, the photosensitive resin composition may further contain a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacrylate group, an isocyanate group, or an epoxy group in order to improve adhesion to the substrate.

[0194] Examples of the silane coupling agents mentioned above include trimethoxysilylbenzoic acid, γ-methacrylateoxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, and silane coupling agents commercially available under names such as KBM-502, KBM-602, KBM-573, and KBE-9007N from Shinetsu Silicon. These may be used individually or in combination of two or more types.

[0195] The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within the above range, the adhesion, storage properties, etc., are excellent.

[0196] Furthermore, the photosensitive resin composition may further contain a surface smoothing agent if necessary to ensure a consistent film thickness during the coating stage.

[0197] As the aforementioned surface smoothing agent, you may use surface smoothing agents that are commercially available under names such as DIC's F-554(registered trademark), F-556(registered trademark), F-557(registered trademark), F-559(registered trademark), F-560(registered trademark), F-563(registered trademark), RS-72-K(registered trademark), R-40(registered trademark), R-41(registered trademark), R-43(registered trademark), etc., or BASF's Efka(registered trademark) FL3740, FL3741, FL3745, FL3770, etc.

[0198] The surface smoothing agent may be used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the photosensitive resin composition. When the surface smoothing agent is included within the above range, the uniformity of the coating can be ensured, and the film thickness can be made uniform.

[0199] Furthermore, the photosensitive resin composition may further contain a surfactant as needed to improve coating properties and prevent the formation of defects.

[0200] Examples of the aforementioned surfactants include BM-1000 (registered trademark), BM-1100 (registered trademark), etc. from BM Chemie; Megafac F142D (registered trademark), F172 (registered trademark), F173 (registered trademark), F183 (registered trademark), etc. from Dainippon Ink and Chemicals, Inc.; and Florard FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark), etc. from Sumitomo 3M Limited. Surfactants such as Asahi Glass Co., Ltd.'s Surflon S-112 (registered trademark), S-113 (registered trademark), S-131 (registered trademark), S-141 (registered trademark), S-145 (registered trademark), etc., and Draysilicon Co., Ltd.'s SH-28PA (registered trademark), SH-190 (registered trademark), SH-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark), etc., which are commercially available, may be used.

[0201] Furthermore, the photosensitive resin composition may further contain a silicone-based surfactant as needed.

[0202] As the aforementioned silicone-based surfactants, you may use commercially available silicone-based surfactants such as DIC's S-101, S-201, S-301, S-601, S-701, S-801, RS-55, RS-56, etc.; BASF's EFKA(registered trademark) 3030, EFKA(registered trademark) 3034, EFKA(registered trademark) 3886, etc.; AFCONA's 3030, 3085, 3236, etc.; or BYK's BYK-378, BYK-3550, BYK-3751, BYK-3754, etc.

[0203] The surfactant may be used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is ensured, stains do not occur, and the wettability to the glass substrate is excellent.

[0204] As the crosslinker, 1,4-bis(methoxymethyl)benzene, diethyl sulfate, 3-aminopropyltriethoxysilane, N,N'-methylenebisacrylamide, etc. may be used, and these may be used individually or in combination of two or more.

[0205] The crosslinker may be used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the photosensitive composition. When the crosslinker is included within the above range, it is advantageous for appropriately imparting physical properties of the cured coating film, such as mechanical properties such as tensile strength.

[0206] Furthermore, the photosensitive resin composition may also contain a certain amount of other additives, provided that these additives do not impair its physical properties.

[0207] The following describes specific examples of synthesis and embodiments of the present invention, but the examples of synthesis and embodiments of the present invention are not limited thereto.

[0208] (Synthesis Example 1)

[0209] (Solution A) A 500 ml heat transfer circulating jacket reactor was fitted with a stirrer, nitrogen injection device, dropping funnel, temperature controller, and condenser. Nitrogen was then added, followed by 141.87 g of N-methylpyrrolidone (NMP). Then, 22.22 g of 3,3',4,4'-benzophenonetetracarboxylic anhydride was added and stirred, maintaining the temperature at 25°C. 19.86 g of 4-hydroxybutyl acrylate was added, followed by 11.17 g of pyridine, which was slowly added to allow the reaction to proceed. Thereafter, the internal temperature of the reactor was maintained at -10°C while the reaction was in progress. A mixture of 35.54 g of N,N'-dicyclohexylcarbodiimide and 71.07 g of N-methylpyrrolidone (NMP) was slowly added dropwise and stirred for 3 hours.

[0210] (Solution B) A 500 ml heat transfer circulating jacket reactor was set up with a stirrer, nitrogen injection device, dropping funnel, temperature controller, and condenser. Nitrogen was then added, followed by the addition of 62.09 g of N-methylpyrrolidone (NMP). The mixture was then stirred while maintaining a temperature of 25°C. Subsequently, 15 g of 3,3'-dimethylbenzidine was added and stirred until completely dissolved. Then, 0.52 g of phthalic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10°C and maintained thereafter.

[0211] (Polymerization reaction) Solution A was added dropwise to solution B, which was maintained at -10°C, using a metering pump while stirring for 1 hour. The temperature was then raised to 25°C over 1 hour, the reaction was maintained for 2 hours, and then the solution was added dropwise to distilled water to precipitate. The resulting solid was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain copolymer polyimide precursor powder.

[0212] (Synthesis Example 2)

[0213] (Solution A) A 500 ml heat transfer circulating jacket reactor was fitted with a stirrer, nitrogen injection device, dropping funnel, temperature controller, and condenser. Nitrogen was then added, followed by 141.87 g of N-methylpyrrolidone (NMP). Then, 22.22 g of 3,3',4,4'-benzophenonetetracarboxylic anhydride was added and stirred, maintaining the temperature at 25°C. 19.86 g of 4-hydroxybutyl acrylate was added, followed by 11.17 g of pyridine being slowly added while the reaction continued. The internal temperature of the reactor was maintained at -10°C during the reaction, and a mixture of 35.54 g of N,N'-dicyclohexylcarbodiimide and 71.07 g of N-methylpyrrolidone (NMP) was slowly added dropwise while stirring for 3 hours.

[0214] (Solution B) A 500 ml heat transfer circulating jacket reactor was set up with a stirrer, nitrogen injection device, dropping funnel, temperature controller, and condenser. Nitrogen was then added, followed by the addition of 61.58 g of N-methylpyrrolidone (NMP). The mixture was then stirred while maintaining a temperature of 25°C. Subsequently, 15 g of 3,3'-dimethylbenzidine was added and stirred until completely dissolved. Then, 0.40 g of citraconic anhydride was added and the mixture was reacted for 5 hours. After that, the internal temperature was cooled to -10°C and maintained thereafter.

[0215] (Polymerization reaction) Solution A was added dropwise to solution B, which was maintained at -10°C, using a metering pump while stirring for 1 hour. The temperature was then raised to 25°C over 1 hour, the reaction was maintained for 2 hours, and then the solution was added dropwise to distilled water to precipitate. The resulting solid was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain copolymer polyimide precursor powder.

[0216] (Manufacturing Example 1) Manufacturing of a negative-type photosensitive composition

[0217] 14.88 g of polyimide precursor obtained from Synthesis Examples 1 and 2, 0.45 g of PBG-304 (Tronly), 7.3 g of Miramer M600, 0.015 g of F-563 (DIC), 1.5 g of KBM-573 (Shinetsu Silicon), and 1.0 g of 1,4-bis(methoxymethyl)benzene were stirred with 53.4 g of propylene glycol methyl ether acetate (PGMEA) at room temperature for 12 hours. Subsequently, the composition was filtered three times to remove impurities and produce a photosensitive composition.

[0218] A photosensitive solution was prepared with the composition shown in Table 1 below.

[0219] [Table 1] JPEG2026096198000024.jpg198164

[0220] The oxime ester initiator structures used in the compositional solutions in Comparative Examples 3 to 6 are I-61 to I-64.

[0221] [ka]

[0222] The method for manufacturing a test piece for pattern evaluation using the aforementioned negative-type photosensitive composition is as follows.

[0223] (1) Application and coating steps

[0224] Photosensitive compositions are low-viscosity liquid samples, and after application to a substrate, a spin coater or slit coater is used to coat them to a consistent thickness. Spin coaters have the advantage that while the thickness decreases as the rotation speed increases, the flatness deviation over area also decreases. For coating large-area substrates, slit coaters are preferable to spin coaters. A disadvantage is that residual solvent after coating causes the surface to become fluid, resulting in poor flatness. To overcome this, a vacuum chamber dry (VCD) is used to partially remove the solvent and reduce fluidity on the surface.

[0225] (2) Pre-baking stage

[0226] This step involves heating the coated substrate on a hot plate or in an oven at a constant temperature and time to remove some of the solvent contained in the coating film. If the surface or depth of the coating film does not dry, contamination of the photomask will occur during exposure in the next step, the curing of the exposed area will not be successful when irradiated with ultraviolet light, and the uncured material will be removed in the development step without a pattern being formed.

[0227] (3) Exposure stage

[0228] After the pre-baking process is completed, the process involves curing the formed film by irradiating it with active light (ultraviolet light) using the photomask on which the pattern has been formed. The lamps used to generate the active light can be LED lamps or metal (mercury) lamps, and the wavelengths are g-line (436nm), h-line (405nm), i-line (365nm), and Deep UV (<260nm), which can be used individually or in combination.

[0229] (4) Development stage

[0230] In the exposure stage, the image is divided into exposed and unexposed areas by a photomask during active ray irradiation. In the case of a positive type, the exposed areas dissolve in the developer, while the unexposed areas withstand the developer and retain their pattern. In the case of a negative type, the exposed areas harden and become resistant to the developer, while the unexposed areas are developed. The composition of the present invention is a negative type, divided into exposed areas (hardened) and unexposed areas (developed) to form a pattern.

[0231] (5) Post-heat treatment stage

[0232] This process involves heating the developed substrate at a high temperature of 210°C or higher to remove any remaining solvent and fumes. If the solvent and fumes are not completely removed in this process, outgassing will occur in the subsequent heat treatment process, affecting the element and potentially causing dark spots or shrinkage.

[0233] (6) Measurement of Hole pattern accuracy and Taper angle

[0234] The taper angle was confirmed by measuring the cross-sectional pattern of the example and comparative example specimens obtained during the post-heat treatment stage of the aforementioned specimens using a scanning electron microscope, JSM-IT800, from JEOL Corporation.

[0235] [Table 2]

[0236] As shown in Table 2 above, in Examples 1 to 29, which contained oxime ester initiators, it was confirmed that no residue remained after development. On the other hand, in Comparative Example 2, which contained an excessive amount of initiator, a large amount of residue remained. This is because, after the excessive initiator was photoinitiated, radicals propagated beyond the irradiated area, causing hardening in the unexposed areas. Furthermore, in Comparative Examples 3 to 6, it was confirmed that residue remained at the edges of the patterns. This is because the initiators used in Comparative Examples 3 to 5 have a structurally higher light absorption rate than the initiators used in Examples 1 to 29, resulting in increased sensitivity and thus faster propagation of radicals to the unexposed areas.

[0237] In Examples 1 to 29, it was confirmed that the taper angle was formed at 76.5° to 80.5°. In contrast, in Comparative Example 1, where the initiator content was lower than the range presented in this patent, it was confirmed that an inverse taper angle of 97.1° was formed, which means that the cured coating film was not sufficiently cured with a small amount of initiator. In Comparative Example 2, where the initiator content was high, it was confirmed that a very low taper angle of 48.5° was formed, which is thought to be due to the easy curing of the unexposed areas due to diffuse reflection of the irradiated light source.

[0238] Furthermore, when the accuracy of pattern realization was confirmed using a 30 μm hole mask, all of Examples 1 to 29 accurately realized patterns with an accuracy of 98% or more within 0.5 μm, while Comparative Examples 1 to 6 showed an accuracy of less than 95%, with an error of up to 5 μm.

[0239] Therefore, it can be confirmed that the selection of the oxime ester-based initiator according to the present invention is effective in improving pattern residue and achieving accurate patterns.

[0240] The present invention is not limited to the above embodiments and can be manufactured in a variety of different forms.

[0241] The above description is merely illustrative, and any person with ordinary skill in the art to which the present invention pertains can make various modifications without departing from the essential characteristics of the present invention.

[0242] Accordingly, the examples disclosed herein are for illustrative purposes only, not to limit the invention, and such examples do not limit the spirit or scope of the invention. The scope of protection of the invention should be interpreted as defined in the claims, and all technologies within an equivalent scope should be interpreted as being included within the scope of the invention.

Claims

1. A negative-type photosensitive composition comprising a polyimide precursor and an initiator represented by chemical formula I. 【Chemistry 1】 In the aforementioned chemical formula I R ｌ or R ｎ is independently hydrogen; deuterium; C １ -C ３０ alkyl group; C １ -C ３０ alkylene group; C ２ -C ２０ alkenyl group; C ２ -C ２０ alkynyl group; C ３ -C ３０ cycloalkyl group; C ２ -C ３０ alkyl cyclene group; C ６ -C ３０ aryl group; C ６ -C ３０ fused ring group of aliphatic ring and aromatic ring; C ２ -C ３０ alkenyl group; C ２ -C ３０ alkynyl group; C １ -C ３０ alkoxy group; C ６ -C ３０ aryloxy group; carbonyl group; ether group; and combinations thereof, and is selected from the group consisting of, R ｌ R ｎ These are hydrogen; deuterium; and C, respectively, independently. １ ~C ３０ alkyl group; C １ ~C ３０ The alkylene group; C ２ ~C ２０ alkenyl group of C ２ ~C ２０ The alkynyl group of C ３ ~C ３０ cycloalkyl groups; C ２ ~C ３０ alkylcyclene group; C ６ ~C ３０ aryl group of; C ６ ~C ３０ A fusion ring group of an aliphatic ring and an aromatic ring; C ２ ~C ３０ alkenyl group of C ２ ~C ３０ The alkynyl group of C １ ~C ３０ alkoxy group of; C ６ ~C ３０ The substituents are further substituted with one or more substituents selected from the group consisting of aryloxy groups, carbonyl groups, ether groups, and combinations thereof, or adjacent substituents form a ring.

2. The negative-type photosensitive composition according to claim 1, characterized in that the compound of chemical formula I contains the following chemical formula J. 【Chemistry 2】 In the aforementioned chemical formula J, R ｏ is hydrogen or C １ ~C １０ It is an alkyl group, R ｐ R ｑ These are hydrogen; deuterium; and C, respectively, independently. １ ~C ３０ alkyl group; C １ ~C ３０ The alkylene group; C ２ ~C ２０ alkenyl group of C ２ ~C ２０ Alkynyl group of C ３ ~C ３０ cycloalkyl groups; C ２ ~C ３０ alkylcyclene group; C ６ ~C ３０ aryl group of; C ６ ~C ３０ A fusion ring group of an aliphatic ring and an aromatic ring; C ２ ~C ３０ alkenyl group of C ２ ~C ３０ Alkynyl group of C １ ~C ３０ alkoxy group of; C ６ ~C ３０ Selected from the group consisting of aryloxy groups; carbonyl groups; ether groups; and combinations thereof, R ｐ or R ｑ is each independently hydrogen; deuterium; C １ -C ３０ alkyl group; C １ -C ３０ alkylene group; C ２ -C ２０ alkenyl group; C ２ -C ２０ alkynyl group; C ３ -C ３０ cycloalkyl group; C ２ -C ３０ alkylcyclene group; C ６ -C ３０ aryl group; C ６ -C ３０ fused ring group of aliphatic ring and aromatic ring; C ２ -C ３０ alkenyl group; C ２ -C ３０ alkynyl group; C １ -C ３０ alkoxy group; C ６ -C ３０ aryloxy group; carbonyl group; ether group; and is further substituted with one or more substituents selected from the group consisting of these combinations, or forms a ring with adjacent substituents.

3. The negative-type photosensitive composition according to claim 1, characterized in that the compound represented by the chemical formula I is selected from I-1 to I-60. 【Transformation 3】

4. The negative-type photosensitive composition according to claim 1, characterized in that the repeating units of the polyimide precursor include repeating units selected from the group consisting of the following chemical formulas 1-1, 1-2, and combinations thereof: 【Chemistry 4】 In the aforementioned chemical formulas 1-1 and 1-2, 1) * represents a repeating unit or a portion to which a bond is connected with a reactive end group represented by the chemical formula Q. 2) R １ R ４ The chemical formula is shown in chemical formula 2 below. 3) X is given by the following chemical formula 3, 4) m and n are integers from 1 to 1000. 【Transformation 5】 In the aforementioned chemical formula 2, 5) * indicates the part where the connection is made. 6) a is an integer between 1 and 30, 7) R ５ is a hydrogen or methyl group, 8) Y is C ６ ~C ３０ Arylene group; C containing at least one heteroatom of O, N, S, Si, and P. ２ ~C ３０ heterocyclic group; C ６ ~C ３０ A fusion ring group of an aliphatic ring and an aromatic ring; C １ ~C ２０ The alkylene group; C １ ~C ２０ cycloalkylene group; C ２ ~C ２０ The alkenylene group of C ３ ~C ２０ The cycloalkenylene group; C ２ ~C ２０ The alkynylene group; C ３ ~C ２０ A cycloalkylene group; chemical formula 3; and selected from the group consisting of combinations thereof, 9) Z is C ６ ~C ３０ Arylene group; C containing at least one heteroatom of O, N, S, Si, and P. ２ ~C ３０ heterocyclic group; C ６ ~C ３０ A fusion ring group of an aliphatic ring and an aromatic ring; C １ ~C ２０ The alkylene group; C １ ~C ２０ cycloalkylene group; C ２ ~C ２０ The alkenylene group of C ３ ~C ２０ The cycloalkenylene group; C ２ ~C ２０ The alkynylene group; C ３ ~C ２０ A cycloalkylene group; chemical formula 3; and selected from the group consisting of combinations thereof, 【Transformation 6】 10) L １ This is a single bond, -CH ２ -ien-CH ２ CH ２ -ien-CH ２ OCH ２ -, -CH(CH ３ )-,-C(CH ３ ) ２ -, -O-, -CH(CF ３ )-,-C(CF ３ ) ２ -, -S-, -SO ２ -, -Si(CH ３ ) ２ -, -C ６ H ４ -, -OC ６ H ４ Selected from the group consisting of O-, -CO-, -N HCO-, and -COO-, 11) R ６ R １５ Two of these are linking sites with amide groups of chemical formula 1-1 or chemical formula 1-2. 12) The remaining R excluding the connecting portion ６ R １５ These are hydrogen; deuterium; hydroxyl group; and C, independently of each other. ６ ~C ３０ The aryl group of; C containing at least one heteroatom of O, N, S, Si, and P. ２ ~C ３０ heterocyclic group; C ６ ~C ３０ A fusion ring group of an aliphatic ring and an aromatic ring; C １ ~C ２０ alkyl group; C ２ ~C ２０ alkenyl group of C ２ ~C ２０ Alkynyl group of C １ ~C ２０ alkoxy group of; C ６ ~C ３０ aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C １ ~C ２０ It is an alkoxycarbonyl group of the adjacent R ６ and R １５ ; and R １０ and R １１ They form a ring, 13) The aforementioned Y, Z, R ６ R １５ The rings formed by the bonding of adjacent groups to each other are, respectively, deuterium; halogen; and C. １ ~C ３０ alkyl group or C ６ ~C ３０ Silane groups substituted or unsubstituted with aryl groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C １ ~C ３０ alkylthio group; C １ ~C ３０ alkoxy group of; C ６ ~C ３０ arylalkoxy group; C １ ~C ３０ alkyl group; C ２ ~C ３０ alkenyl group of C ２ ~C ３０ Alkynyl group of C ６ ~C ３０ aryl group; deuterium-substituted C ６ ~C ３０ An aryl group; a fluorenyl group; and a carbon atom containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P. ２ ~C ３０ heterocyclic group; C ３ ~C ３０ aliphatic ring group of; C ７ ~C ３０ arylalkyl groups; C ８ ~C ３０ The aryl alkenyl group; further substituted with one or more substituents selected from the group consisting of combinations thereof, or adjacent substituents forming a ring.

5. The negative-type photosensitive composition according to claim 1, characterized in that the polyimide precursor comprises a repeating unit and a reactive end group represented by the following chemical formula Q that is bonded to the end of the polyimide repeating unit: 【Transformation 7】 In the aforementioned chemical formula Q, 1) R ａ R ｃ These are, independently, hydrogen; deuterium; hydroxyl group; and C. ６ ~C ３０ The aryl group of; C containing at least one heteroatom of O, N, S, Si, and P. ２ ~C ３０ heterocyclic group; C ６ ~C ３０ A fusion ring group of an aliphatic ring and an aromatic ring; C １ ~C ３０ alkyl group; C ２ ~C ３０ alkenyl group of C ２ ~C ３０ Alkynyl group of C １ ~C ３０ alkoxy group of; C ６ ~C ３０ aryloxy group; C １ ~C ３０ hydroxyacrylic group of; C １ ~C ３０ Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C １ ~C ３０ It is an alkoxycarbonyl group of; or R ａ R ｃ The adjacent groups form a ring, 2) C １ and C ２ is carbon; C １ and C ２ The double dotted lines connecting them represent single or double bonds. 3) The above C １ and C ２ If the double dotted line connecting them is a single connection, then o and p are each independently integers of 1 or 2; the C １ and C ２ If the double dotted line connecting them is a double bond, then o and p are each integers of 1. 4) C ３ Is it carbon or C ２ -B ２ It is a direct combination of, 5) The above C ３ If carbon is the element, then q is an integer of 1 or 2. 6) B １ and B ２ The dotted lines connecting them indicate that there is no connection or that there is a single connection. 7) The above B １ and B ２ If there is no dotted line connecting B １ is hydrogen; deuterium; hydroxyl group; C ６ ~C ３０ The aryl group of; C containing at least one heteroatom of O, N, S, Si, and P. ２ ~C ３０ heterocyclic group; C ６ ~C ３０ A fusion ring group of an aliphatic ring and an aromatic ring; C １ ~C ２０ alkyl group; C ２ ~C ２０ alkenyl group of C ２ ~C ２０ Alkynyl group of C １ ~C ２０ alkoxy group of; C ６ ~C ３０ aryloxy group; C １ ~C ２０ hydroxyacrylic group of; C １ ~C ２０ Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C １ ~C ２０ It is an alkoxycarbonyl group; B ２ This is a carbon atom linked to a polyimide repeating unit. 8) The above B １ and B ２ If the dotted line connecting them is a single connection, then B １ This is nitrogen linked to a polyimide repeating unit, and B ２ It is carbon, 9) The R ａ R ｃ The rings formed by the bonding of adjacent groups to each other are, respectively, deuterium; halogen; and C. １ ~C ３０ alkyl group or C ６ ~C ３０ Silane groups substituted or unsubstituted with aryl groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C １ ~C ３０ alkylthio group; C １ ~C ３０ alkoxy group of; C ６ ~C ３０ arylalkoxy group; C １ ~C ３０ alkyl group; C ２ ~C ３０ alkenyl group of C ２ ~C ３０ Alkynyl group of C ６ ~C ３０ aryl group; deuterium-substituted C ６ ~C ３０ An aryl group; a fluorenyl group; and a carbon atom containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P. ２ ~C ３０ heterocyclic group; C ３ ~C ３０ aliphatic ring group of; C ７ ~C ３０ arylalkyl groups; C ８ ~C ３０ The aryl alkenyl group; further substituted with one or more substituents selected from the group consisting of combinations thereof, or adjacent substituents forming a ring.

6. The negative-type photosensitive composition according to claim 5, characterized in that the compound represented by the chemical formula Q includes the compounds represented by Q-1 to Q-6 below: 【Transformation 8】 In the aforementioned chemical formulas Q-1 to Q-6, 1) R ｄ１ , R ｄ２ , R ｅ１ R ｅ３ , R ｆ１ R ｆ４ , R ｇ , R ｈ１ , R ｈ２ , and R ｉ１ R ｉ３ These are, independently, hydrogen; deuterium; hydroxyl group; and C. ６ ~C ３０ The aryl group of; C containing at least one heteroatom of O, N, S, Si, and P. ２ ~C ３０ heterocyclic group; C ６ ~C ３０ A fusion ring group of an aliphatic ring and an aromatic ring; C １ ~C ３０ alkyl group; C ２ ~C ３０ alkenyl group of C ２ ~C ３０ Alkynyl group of C １ ~C ３０ alkoxy group of; C ６ ~C ３０ aryloxy group; C １ ~C ３０ hydroxyacrylic group of; C １ ~C ３０ Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C １ ~C ３０ It is an alkoxycarbonyl group, 2) r and t are integers from 1 to 4, 3) s １ s ２ and u １ or u ３ Each of these is an integer, either 1 or 2.

7. The negative-type photosensitive composition according to claim 1, characterized in that the repeating units of the polyimide precursor include a diamine monomer; a dianhydride monomer; and an anhydride monomer.

8. The negative-type photosensitive composition according to claim 1, characterized in that the weight-average molecular weight of the polyimide precursor is 5,000 to 40,000 g / mol.

9. The negative-type photosensitive composition according to claim 1, further comprising a reactive unsaturated compound; a solvent; and other additives.

10. The negative-type photosensitive composition according to claim 1, characterized in that the initiator is contained in an amount of 0.01 to 10% by weight relative to the total amount.

11. The negative-type photosensitive composition according to claim 1, characterized in that the polyimide precursor is contained in an amount of 5 to 50% by weight relative to the total amount of the composition.

12. A film manufactured from the negative-type photosensitive composition of claim 1.

13. A semiconductor device manufactured using the film of claim 12.

14. A display device manufactured using the film of claim 12.

15. An electronic device comprising a display device according to claim 14 and a control unit for driving the same.

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