Polyimide-based precursor and composition containing same

Abstract

The present invention relates to a polyimide-based precursor and a composition comprising the same, in which a copolymer of a monomer capable of increasing mechanical properties is introduced into a component of a polyimide-based precursor or a copolymer resin, tensile strength and elongation can be increased, a residue problem at the time of development is avoided, and an effect of maintaining pattern implementation accuracy is achieved.

Description

[0001] Join by reference

[0002] This application claims priority from Korean Patent Application Nos. 10-2023-0141249 and 10-2024-0107930, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to a polymer composition of a polyimide precursor prepared by using a polyimide precursor and used for a semiconductor device or a display device. Background Art

[0004] The photolithography process generally consists of the following steps in sequence: a coating step of coating a photoresist composition on a substrate; an exposure step of forming a pattern on the photoresist film by a light source, E-beam, etc. that penetrates a mask; a development step of removing a specific area of ​​the photoresist film engraved with the pattern, and a heat treatment (baking) step for removing the solvent from the photoresist composition or for curing the film is added between each step.

[0005] The photolithography process is generally divided into negative and positive processes. In the positive process of the development step, the exposed part reacts chemically with the developer, and the reaction product is dissolved and removed. On the contrary, the negative process reacts chemically with the developer in the non-exposed part, and the reaction product is dissolved and removed. Among them, the positive process can use a photoinitiator (Photoinitiator) that absorbs light and generates free radicals in the exposure step, and expose with less energy than the positive process. Its advantage is that it has excellent adhesion to the oxide film.

[0006] The negative photosensitive resin composition used in traditional semiconductor devices or display devices utilizes resins such as polyimide precursors or copolymers. This is because they have high heat resistance, chemical resistance, weather resistance, etc. However, since the development step uses an alkaline aqueous solution for development, the molecular weight of the polymer resin used is limited, and therefore, there are limitations in the mechanical and physical properties that can be achieved.

[0007]

Prior technical literature

[0008] [Patent Literature]

[0009] (Patent Document 1) Korean Patent Publication No. 10-2011-0041389

[0010] (Patent Document 2) Korean Patent Publication No. 10-2014-0041371 Summary of the invention

[0011] Issues to be solved

[0012] In order to solve the above-mentioned drawbacks of the conventional technology, the present invention introduces a reactive monomer into the terminal of a polymer formed from a polyimide-based precursor to improve the physical properties.

[0013] Furthermore, a negative photosensitive composition is provided by using a polymer formed from the polyimide-based precursor.

[0014] Also provided are a pattern or film formed using the negative photosensitive composition, and a semiconductor device or display device manufactured using the same.

[0015] Problem Solution

[0016] Preferably, the polyimide-based precursor of the present invention comprises a reactive terminal group represented by the following chemical formula Q.

[0017] [Chemical formula Q]

[0018]

[0019] In the above chemical formula 1,

[0020] 1) R a To R c are independently hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C1~C 30 Alkoxy group; C6~C 30 aryloxy group; C1~C 30 hydroxyacryl group; C1~C 30 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 30An alkoxy carbonyl group, or R a To R c The adjacent bases form a ring.

[0021] 2) C1 and C2 are carbon; the bond connecting C1 and C2 is a single bond or a double bond,

[0022] 3) When the bond connecting the C1 and C2 is a single bond, o and p are each independently an integer of 1 or 2; when the bond connecting the C1 and C2 is a double bond, o and p are each an integer of 1,

[0023] 4) C3 is carbon or a direct bond of C2-B2,

[0024] 5) When the C3 is carbon, q is an integer of 1 or 2,

[0025] 6) The dotted line connecting B1 and B2 indicates that there is no bond or single bond.

[0026] 7) When the dashed line connecting B1 and B2 indicates that there is no bond, B1 is hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; C1~C 20 hydroxyacryl group; C1~C 20 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 B2 is a carbon group bonded to the repeating unit of the polyimide series.

[0027] 8) When the dotted line connecting B1 and B2 is a single bond, B1 is nitrogen bonded to the polyimide repeating unit; B2 is carbon,

[0028] 9) R a To R c and the rings formed by the bonding of adjacent groups are further substituted with one or more substituents selected from the group consisting of the following components: deuterium; halogen; substituted or unsubstituted C1-C 30 Alkyl group or C6~C 30 aryl group, silane group, siloxane group, boron group, germanium group, cyano group, amino group, nitro group, C1~C 30 Alkylthio group; C1~C 30 Alkoxy group; C6~C 30 Aryl alkoxy group; C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C6~C 30 aryl group; C6~C 30 aryl group; fluorenyl group; C2~C 30 A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C3~C 30 Aliphatic ring group; C7~C 30 Aryl alkyl group; C8~C 30 and combinations thereof; or adjacent substituents may form a ring.

[0029] More preferably, the negative polyimide precursor of the present invention comprises a repeating unit selected from the group consisting of the following Chemical Formula 1-1, Chemical Formula 1-2 and a combination thereof.

[0030] [Chemical formula 1-1]

[0031]

[0032] [Chemical formula 1-2]

[0033]

[0034] In the above chemical formula 1-1 and chemical formula 1-2,

[0035] 1) * is a connecting portion bonded to the repeating unit or the reactive terminal group shown in the above chemical formula Q,

[0036] 2) R1 to R4 are the following chemical formula 2,

[0037] 3) X is the following chemical formula 3,

[0038] 4) m and n are integers from 1 to 1000,

[0039] [Chemical formula 2]

[0040]

[0041] In the above chemical formula 2,

[0042] 5) * is the bonded connected part,

[0043] 6) a is an integer from 1 to 30,

[0044] 7) R5 is hydrogen or methyl ester;

[0045] 8) Y is selected from the group consisting of: C6 to C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20cyclo alkinylene group; Chemical Formula 3; and combinations thereof,

[0046] 9) Z is selected from the group consisting of: C6~C 30 Arylene group; C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20 cyclo alkinylene group; Chemical Formula 3; and combinations thereof,

[0047] [Chemical formula 3]

[0048]

[0049] 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-,

[0050] 11) R6 to R 15 Two of them are connecting sites with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2,

[0051] 12) Except for the connecting part, the rest of R6 to R 15 independently of each other are hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 The alkoxy carbonyl group, or the adjacent R 6 and R 15 ; and R 10 and R 11 Form a ring,

[0052] 13) Y, Z, R6 to R 15 and the rings formed by the bonding of adjacent groups are further substituted with one or more substituents selected from the group consisting of the following components: deuterium; halogen; substituted or unsubstituted C1-C 30 Alkyl group or C6~C 30 aryl group, silane group, siloxane group, boron group, germanium group, cyano group, amino group, nitro group, C1~C 30 Alkylthio group; C1~C 30 Alkoxy group; C6~C 30 Aryl alkoxy group; C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C6~C 30 aryl group; C6~C30 aryl group; fluorenyl group; C2~C 30 A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C3~C 30 Aliphatic ring group; C7~C 30 Aryl alkyl group; C8~C 30 and combinations thereof; or adjacent substituents may form a ring.

[0053] The reactive terminal group represented by the above Chemical Formula Q may include compounds represented by the following Chemical Formulas Q-1 to Q-6.

[0054]

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

[0056] 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 independently hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 30 Alkyl group; C2~C 30 Alkenyl group; C2~C 30 Alkinyl group; C1~C 30 Alkoxy group; C6~C 30 aryloxy group; C1~C 30hydroxyacryl group; C1~C 30 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 30 Alkoxy carbonyl group,

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

[0058] 3) s1, s2 and u1 to u3 are integers from 1 to 2 respectively.

[0059] 4)* is the connected part of the bond.

[0060] The reactive terminal group represented by the above Chemical Formula Q may further include compounds represented by the following Chemical Formulae Q-7 to Q-10.

[0061]

[0062] The R 16 To R 18 independently of each other are hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; C1~C 20 hydroxyacryl group; C1~C 20hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 The alkoxycarbonyl group.

[0063] The precursor terminal is bonded with a chemical formula selected from the group consisting of one or a combination of the above chemical formulas Q-7 to Q-10 through an amide or imide bond.

[0064] Preferably, the polyimide-based precursor comprises a diamine monomer, a dianhydride monomer, and an anhydride monomer.

[0065] Preferably, the weight average molecular weight of the polyimide-based precursor is 5,000 to 40,000 g / mol.

[0066] In another specific example of the present invention, preferably, the polymer composition of the present invention comprises the polyimide precursor; a photoinitiator; a reactive unsaturated compound; a solvent; and an additive.

[0067] Preferably, the content of the polyimide-based precursor is 5 to 50% by weight.

[0068] Preferably, the content of the photoinitiator is 0.01 to 10 wt % in the total amount of the composition.

[0069] Preferably, the content of the reactive unsaturated compound is 1 to 40 wt % in the total amount of the composition.

[0070] Preferably, the content of the solvent is 50 to 95 wt % in the total amount of the composition.

[0071] Preferably, the content of the additive is 0.001 to 10 wt % in the total amount of the composition.

[0072] In another embodiment of the present invention, preferably, a pattern or a film prepared from the polymer composition is provided.

[0073] In another specific example of the present invention, preferably, a semiconductor device or a display device manufactured using the pattern or film is provided.

[0074] In another specific example of the present invention, preferably, an electronic device is provided, the electronic device including the semiconductor device or the display device and a control unit for driving the same.

[0075] Effects of the Invention

[0076] The present invention introduces reactive functional groups at the ends of polyimide-based precursor resins, which can be used to prepare polymer compositions with improved tensile strength and elongation, and can also be used to manufacture display devices or semiconductor devices. DETAILED DESCRIPTION

[0077] In the process of describing the present invention, if it is considered that the detailed description of the relevant known structure or function will confuse the main points of the present invention, the detailed description thereof may be omitted. When the present invention adopts "including", "having", "comprising", etc., other parts may be added unless "to only" is used. When the constituent elements are expressed in the singular, unless otherwise clearly stated, the case of expressing them in the plural is included.

[0078] Furthermore, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only used to distinguish the components from other components, and the nature, order, sequence or number of the components are not limited by these terms.

[0079] In the process of describing the positional relationship of constituent elements, when it is mentioned that two or more constituent elements are "connected", "combined" or "accessed", it should be understood that the two or more constituent elements can be directly "connected", "combined" or "accessed", but can also be further "carried with" the two or more constituent elements and other constituent elements to achieve "connection", "combination" or "access". Among them, the other constituent elements can include one or more of the two or more constituent elements that are "connected", "combined" or "accessed" to each other.

[0080] Furthermore, when a component such as a layer, film, region, or plate is located “on” or “over” another component, it should be understood that it includes not only the case where it is located “directly above” another component, but also the case where there is another component in between. Conversely, when a component is located “directly above” another part, it should be understood that there is no other part in between.

[0081] When describing the time flow relationship related to constituent elements, working methods, or manufacturing methods, for example, when describing the time sequence relationship or process sequence relationship such as "after", "next to", "then", "before", etc., since "immediately" or "directly" is not used, discontinuous situations can be further included.

[0082] In addition, when referring to the numerical value of a constituent element or the information corresponding thereto, even if not clearly stated separately, it should be interpreted that the numerical value or the information corresponding thereto includes: the error range caused by various factors (for example, engineering factors, internal or external impact, noise, etc.).

[0083] When interpreting the terms used in this specification and the appended claims, they should not be limited to the conventional or dictionary meanings. The inventor should interpret them as meanings and concepts that are consistent with the technical ideas described in the present invention based on the principle that the concepts of terms can be reasonably defined, so as to describe his own invention in the most preferred way.

[0084] Unless otherwise described, the term "halo" or "halogen" used in the present application includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0085] Unless otherwise described, the term "alkyl" or "alkyl group" used in this application contains 1 to 60 carbon atoms connected by single bonds, and refers to a free radical of a saturated aliphatic functional group represented by a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group, and a cycloalkyl-substituted alkyl group.

[0086] Unless otherwise described, the term "haloalkyl group" or "halogenalkyl group" used in the present application refers to an alkyl group substituted with halogen.

[0087] Unless otherwise described, the term "alkenyl" or "alkynyl" used in the present application respectively has a double bond or a triple bond, contains a straight chain or a side chain, and has 2 to 60 carbon atoms, but is not limited thereto.

[0088] Unless otherwise described, the term "cycloalkyl" used in the present application means a cyclic alkane having 3 to 60 carbon atoms, but is not limited thereto.

[0089] The term "alkoxy group" or "alkyloxy group" used in the present application refers to an alkyl group to which an oxygen radical is bonded, and unless otherwise specified, has 1 to 60 carbon atoms, but is not limited thereto.

[0090] The term "alkenoxyl group", "alkenoxygroup", "alkenyloxyl group" or "alkenyloxy group" used herein means an alkenyl group to which an oxygen radical is bonded, and unless otherwise specified, has 2 to 60 carbon atoms, but is not limited thereto.

[0091] Unless otherwise described, the terms "aryl group" and "arylene group" used in the present application have 6 to 60 carbons, respectively, but are not limited thereto. In the present application, aryl group or arylene group include monocyclic type, cyclopolymer, fused polycyclic compounds, etc. For example, the aryl group may include phenyl group, the monovalent functional group of biphenyl, the monovalent functional group of naphthalene, fluorenyl group and substituted fluorenyl group. Arylene group may include fluorenyl group and substituted fluorenyl group.

[0092] The term "ring assemblies" used in the present application is composed of two or more ring systems (single ring or fused ring systems) directly connected by a single bond or a double bond, indicating that the number of directly connected rings is less than the total number of ring systems contained in the compound by 1. The ring assemblies can be directly connected by the same or different ring systems through a single bond or a double bond.

[0093] In the present application, the aryl group includes a cyclopolymer, and thus, the aryl group includes biphenyl and terphenyl connected by a single bond to a benzene ring as a monocyclic aromatic. In addition, the aryl group also includes a compound in which an aromatic ring system combined with an aromatic monocyclic ring is connected by a single bond, and thus, for example, a compound in which an aromatic ring system combined with a benzene ring as an aromatic monocyclic ring, i.e., fluorene, is connected by a single bond.

[0094] The term "fused polycyclic ring system" used in this application refers to a fused ring that shares at least two atoms, including: a fused form of two or more hydrocarbon ring systems and a fused form of at least one heterocyclic ring system containing at least one heteroatom. The fused polycyclic ring system can be an aromatic ring, an aromatic heterocyclic ring, an aliphatic ring, or a combination of such rings. For example, an aryl group can be a naphthyl group, a phenanthrenyl group, a fluorenyl group, etc., but it is not limited thereto.

[0095] The term "spiro compound" used in the present application has a 'spiro union', which means that two rings share only one atom to form a connection. In this case, the atom shared by the two rings is called a 'spiro atom', and according to the number of spiro atoms contained in one compound, it is called a 'monospiro-', 'dispiro-', 'trispiro-' compound, respectively.

[0096] Unless otherwise described, the terms "fluorenyl group", "fluorenylene group" and "fluorene-triyl group" used in this application respectively represent monovalent, divalent or trivalent functional groups in which R, R', R" and R'" are all hydrogen in the following structures, and "substituted fluorenyl group", "substituted fluorenyl group" or "substituted fluorene-triyl group" means that at least one of the substituents R, R', R", R'" is a substituent other than hydrogen, including the case where R and R' are bonded to each other and form a spiro compound together with the carbon to which they are bonded. In this specification, the fluorenyl group, fluorenylene group and fluorene-triyl group may be named as fluorenyl group without considering the equivalent number of monovalent, divalent and trivalent.

[0097]

[0098] Furthermore, the R, R', R" and R'" may be independently selected from: 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, or a heterocyclyl group having 2 to 30 carbon atoms. For example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene or phenanthrene, and the heterocyclyl group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidone, pyridazine, pyrazine, triazine, indole, benzofuran, or the like. For example, the substituted fluorenyl group and the fluorenylene group may be monovalent or divalent functional groups of 9,9-dimethylfluorene, 9,9-diphenylfluorene, and 9,9'-spirobi [9H-fluorene], respectively.

[0099] The term "heterocyclyl group" used in this application includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group", but also non-aromatic rings. Unless otherwise described, they respectively represent rings containing one or more heteroatoms and having a carbon number of 2 to 60, but are not limited thereto. Unless otherwise described, the term "heteroatom" used in this application represents N, O, S, P or Si, and heterocyclyl group represents a monocyclic type, cyclopolymer, fused polycyclic system, spiro compound, etc. containing heteroatoms.

[0100] For example, a "heterocyclyl group" may also replace a cyclic carbon, including the following compounds, and compounds containing heteroatom terminal groups such as SO2 and P=O.

[0101]

[0102] The term "ring" used in the present application includes monocyclic and polycyclic rings, and of course, hydrocarbon rings include heterocyclic rings, the heterocyclic rings contain at least one heteroatom, and include aromatic and non-aromatic rings.

[0103] The term "polycyclic" as used in this application includes ring assemblies such as biphenyl and terphenyl and fused polycyclic systems and spiro compounds, including not only aromatic but also non-aromatic rings. Of course, hydrocarbon rings include heterocyclic rings that contain at least one heteroatom.

[0104] The term "aliphatic cyclo group" used in this application refers to cyclic hydrocarbons other than aromatic hydrocarbons, including monocyclic types, cyclopolymers, fused polycyclic systems, spiro compounds, etc., and unless otherwise specified, refers to a ring with a carbon number of 3 to 60, but is not limited thereto. For example, when fused aromatic cyclobenzene and non-aromatic cyclohexane are also equivalent to aliphatic rings.

[0105] Furthermore, when prefixes are used consecutively, it means that the substituents are arranged in the order of the description. For example, aryl alkoxy group means an alkoxy group substituted with an aryl group, alkoxy carbonyl group means a carbonyl group substituted with an alkoxy group, and aryl carbonyl alkenyl group means an alkenyl group substituted with an arylcarbonyl group, wherein aryl carbonyl group is a carbonyl group substituted with an aryl group.

[0106] Furthermore, unless otherwise specified, in the term "substituted or unsubstituted" used in the present application, "substituted" means substituted with one or more substituents selected from the group consisting of deuterium, halogen, amino group, nitrile group, nitro group, C1-C 30 Alkyl group, C1~C 30 Alkoxy group, C1~C 30 Alkyl amine group, C1~C 30 alkyl thiophene group, C6~C 30 arylthiophene group, C2~C 30 Alkenyl group, C2~C 30 Alkinyl group, C3~C 30 Cycloalkyl group, C6~C 30 aryl group, C6~C 30 Aryl group, C8~C 30 aryl alkenyl group, silane group, boron group, germanium group and C2~C 30 The heterocyclic group, the C2~C 20 The heterocyclic group includes at least one heteroatom selected from the group consisting of O, N, S, Si and P. And, it is not limited by the substituents thereof.

[0107] In the present application, the 'functional group name' corresponding to the aryl group, arylene group, heterocyclyl group, etc. described in each label and its substituent examples can be recorded as 'functional group name reflecting valence' or as 'name of the parent compound'. For example, 'phenanthrene' as an aryl group' can be classified and recorded as the name of the 'group' according to the valence, such as recording the monovalent 'group' as 'phenanthryl (group)' and recording the divalent 'group' as 'phenanthryl (group)', etc. However, it can also be recorded as the name of the parent compound 'phenanthrene' without considering the valence.

[0108] Similarly, pyrimidone can be recorded as 'pyrimidone' regardless of the valence, or recorded as pyrimidinyl (base) when it is monovalent, and can be recorded as the 'name of the base' of the corresponding valence when it is divalent, such as pyrimidinylene (base), etc. Therefore, in the present application, when the type of substituent is recorded as the name of the parent compound, it can represent: an n-valent 'base' formed by the desorption of hydrogen atoms bonded to carbon atoms and / or heteroatoms of the parent compound.

[0109] In addition, in this specification, when recording the name of a compound or a substituent, the numerals or alphabets indicating the position may be omitted. For example, pyrido[4,3-d]pyrimidone may be recorded as pyrido pyrimidone, benzofuran[2,3-d]pyrimidone may be recorded as benzofuran pyrimidone, 9,9-dimethyl-9H-fluorene may be recorded as dimethylfluorene, etc. Therefore, benzo[g]quinoxaline or benzo[f]quinoxaline may be recorded as benzoquinoxaline.

[0110] Furthermore, unless otherwise expressly stated, the chemical formulae used in this application are also subject to the definitions of substituents according to the index definitions of the following chemical formulae.

[0111]

[0112] Wherein, when a is an integer of 0, it indicates that the substituent R 1 When a is 0, the carbon atoms forming the benzene ring are all bonded with hydrogen atoms. In this case, the symbol of the hydrogen atoms bonded with carbon atoms can be omitted and the chemical formula or compound can be recorded. 1 When a is an integer of 2 or 3, the bonding can be as follows. When a is an integer of 4 to 6, it can also be bonded to the carbon of the benzene ring by a similar method. When a is an integer of 2 or more, R 1 Can be the same or different.

[0113]

[0114] In the present application, unless otherwise described, forming a ring means that adjacent groups are bonded to each other to form a monocyclic ring or a fused polycyclic ring. The monocyclic ring and the fused polycyclic ring formed include not only hydrocarbon rings but also heterocyclic rings. The heterocyclic ring contains at least one heteroatom and may include aromatic and non-aromatic rings.

[0115] In addition, in this specification, unless otherwise described, when a condensed ring is represented, in the term "number-condensed ring", the number represents the number of condensed rings. For example, a condensed form of three rings can be represented as a 3-condensed ring, such as anthracene, phenanthrene, benzo quinozoline, etc.

[0116] In addition, unless otherwise described, the term "bridged bicyclic compound" used in the present application refers to a compound in which two rings share three or more atoms to form a ring. In this case, the shared atoms may include carbon or heteroatoms.

[0117] Hereinafter, an implementation example of the present invention will be described in detail. However, this is for illustrative purposes only and the present invention is not limited thereto. The present invention is only defined by the scope of the following claims.

[0118] According to an implementation example of the present invention, preferably, the polyimide-based precursor or the polyimide-based precursor including the polymer is of a negative type.

[0119] According to an implementation example of the present invention, preferably, the polyimide-based precursor is a photosensitive composition.

[0120] The negative photosensitive composition can be used for preparing an insulating film, a surface protection film, a rewiring layer of a semiconductor device, and a pixel definition layer (PDL) of a display device.

[0121] According to an implementation example of the present invention, when preparing a negative photosensitive composition for use in a semiconductor device or a display device, the following additives may be further included in order to improve the required properties.

[0122] According to an implementation example of the present invention, a surface leveler may be further included. The surface leveler, as an additive, can make the thickness of the coating uniform when the coating is applied to the substrate. Furthermore, a surfactant may be further included. The surfactant can make the coating uniform according to the characteristics of the substrate surface. Furthermore, in order to adjust the adhesion between the substrate surface and the substrate surface, a silane coupling agent may be further included. Furthermore, a crosslinking agent may be further included. The crosslinking agent can strengthen the bonding between polymer molecules in the heat treatment step.

[0123] The components constituting the polyimide precursor of the present invention are as follows.

[0124] (1) Polyimide Precursors

[0125] According to an embodiment of the present invention, the pattern forming resin may include a polyimide-based precursor.

[0126] The polyimide precursor refers to a resin including the following components: an amic acid copolymer that can become a polyimide precursor through chemical or thermal treatment and a polyimide copolymer that has been chemically or thermally treated.

[0127] In the total amount of the polyimide composition, the content of the polyimide precursor is 5 wt % to 50 wt %, and preferably, the content is 10 wt % to 40 wt %.

[0128] The weight average molecular weight of the polyimide-based precursor may be 5,000 g / mol to 40,000 g / mol, preferably 5,000 g / mol to 35,000 g / mol, and more preferably 6,000 g / mol to 25,000 g / mol.

[0129] Preferably, the terminal group of the polyimide-based precursor includes a reactive group represented by the following chemical formula Q.

[0130] [Chemical formula Q]

[0131]

[0132] In the above chemical formula 1,

[0133] 1) R a To R c are independently hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C1~C 30 Alkoxy group; C6~C30 aryloxy group; C1~C 30 hydroxyacryl group; C1~C 30 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 30 An alkoxy carbonyl group, or R a To R c The adjacent bases form a ring.

[0134] 2) C1 and C2 are carbon; the bond connecting C1 and C2 is a single bond or a double bond,

[0135] 3) When the bond connecting the C1 and C2 is a single bond, o and p are each independently an integer of 1 or 2; when the bond connecting the C1 and C2 is a double bond, o and p are each an integer of 1,

[0136] 4) C3 is carbon or a direct bond of C2-B2,

[0137] 5) When the C3 is carbon, q is an integer of 1 or 2,

[0138] 6) The dotted line connecting B1 and B2 indicates that there is no bond or single bond.

[0139] 7) When the dashed line connecting B1 and B2 indicates that there is no bond, B1 is hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; C1~C 20hydroxyacryl group; C1~C 20 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 B2 is a carbon group bonded to the repeating unit of the polyimide series.

[0140] 8) When the dotted line connecting B1 and B2 is a single bond, B1 is nitrogen bonded to the polyimide repeating unit; B2 is carbon,

[0141] 9) R a To R c and the rings formed by the bonding of adjacent groups are further substituted with one or more substituents selected from the group consisting of the following components: deuterium; halogen; substituted or unsubstituted C1-C 30 Alkyl group or C6~C 30 aryl group, silane group, siloxane group, boron group, germanium group, cyano group, amino group, nitro group, C1~C 30 Alkylthio group; C1~C 30 Alkoxy group; C6~C 30 Aryl alkoxy group; C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C6~C 30 aryl group; C6~C 30 aryl group; fluorenyl group; C2~C 30 A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C3~C 30 Aliphatic ring group; C7~C30 Aryl alkyl group; C8~C 30 and combinations thereof; or adjacent substituents may form a ring.

[0142] Preferably, the polyimide-based precursor includes a repeating unit selected from the group consisting of the following Chemical Formula 1-1, Chemical Formula 1-2, and a combination thereof.

[0143] [Chemical formula 1-1]

[0144]

[0145] [Chemical formula 1-2]

[0146]

[0147] In the above chemical formula 1-1 and chemical formula 1-2,

[0148] 1) * is a connecting portion bonded to the repeating unit or the reactive terminal group shown in the above chemical formula Q,

[0149] 2) R1 to R4 are the following chemical formula 2,

[0150] 3) X is the following chemical formula 3,

[0151] 4) m and n are integers from 1 to 1000,

[0152] [Chemical formula 2]

[0153]

[0154] In the above chemical formula 2,

[0155] 5) * is the bonded connected part,

[0156] 6) a is an integer from 1 to 30,

[0157] 7) R5 is hydrogen or methyl ester;

[0158] 8) Y is selected from the group consisting of: C6 to C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkylene group; C1~C20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20 cyclo alkinylene group; Chemical Formula 3; and combinations thereof,

[0159] 9) Z is selected from the group consisting of: C6~C 30 Arylene group; C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20 cyclo alkinylene group; Chemical Formula 3; and combinations thereof,

[0160] [Chemical formula 3]

[0161]

[0162] 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-,

[0163] 11) R6 to R 15Two of them are connecting sites with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2,

[0164] 12) Except for the connecting part, the rest of R6 to R 15 independently of each other are hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 The alkoxy carbonyl group, or the adjacent R 6 and R 15 ; and R 10 and R 11 Form a ring,

[0165] 13) Y, Z, R6 to R 15 and the rings formed by the bonding of adjacent groups are further substituted with one or more substituents selected from the group consisting of the following components: deuterium; halogen; substituted or unsubstituted C1-C 30 Alkyl group or C6~C 30 aryl group, silane group, siloxane group, boron group, germanium group, cyano group, amino group, nitro group, C1~C 30 Alkylthio group; C1~C 30 Alkoxy group; C6~C30 Aryl alkoxy group; C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C6~C 30 aryl group; C6~C 30 aryl group; fluorenyl group; C2~C 30 A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C3~C 30 Aliphatic ring group; C7~C 30 Aryl alkyl group; C8~C 30 and combinations thereof; or adjacent substituents may form a ring.

[0166] The polyimide precursor comprises at least one of a diamine monomer, a dianhydride monomer, and an anhydride monomer.

[0167] Preferably, the diamine monomer comprises one or more monomers selected from the group consisting of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dihydroxybenzidine, 3,3'-dimethylbenzidine, 2,2'-bis(4-aminophenoxy)phenylpropane, 2,2'-bis(trifluoromethyl)benzidine, 9,9 ...3'-dihydroxybenzidine, 3,3'-dimethylbenzidine, 2,2'-bis(4-aminophenoxy)phenylpropane, 2,2'-bis(trifluoromethyl)benzidine, 9,9 (3-Fluoro-4-aminophenol)fluorene, 9,9-bis(4-aminophenol)fluorene, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-[1,1'-biphenyl]-4,4'-diamine, 4, 4'-Bis(4-aminophenoxy)biphenyl, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,4'-oxydiphenylamine, 9,9-dimethyl-9H-fluorene-2,7-diamine, 4-aminobenzoic acid-4-aminophenyl ester, [4-(4-aminobenzoyl)oxyphenyl] 4-aminobenzoate, 3,3',5,5'-tetramethylbenzidine, bis(4-aminophenyl)propane (4-aminophenol) terephthalate, 4,4-bis(3-aminophenoxy)biphenyl, N,N'-[[2,2,2-trifluoro-1-(trifluoromethyl)ethyl]bis(6-hydroxy-3,1-phenyl)bis[3-amino-benzamide], 2,2-bis(4-aminophenol)hexafluoropropane, 4,4'-benzanilide, O-tolidine, 4,4'-diaminodiphenyl sulfone and combinations thereof.

[0168] Preferably, the dianhydride monomer comprises one or more monomers selected from the group consisting of: 4,4'-oxydiphthalic anhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, pyromellitic acid dianhydride, 4,4'-phthalic anhydride, 4,4'-biphthalic anhydride, 4,4'-(hexafluoro isopropylidine) diphthalic anhydride,

[0169] 3,3',4,4'-benzophenone tetracarboxylic aciddianhydride,

[0170] 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3'4'-biphenyl tetracarboxylic aciddianhydride, 2,3,3',4'-diphenyl oxide tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 9,9-bis(3,4-decarboxyphenyl)fluorene dianhydride 1,4-bis(3,4-dicarboxy phenoxy)benzene dianhydride, and combinations thereof.

[0171] Preferably, the anhydride monomer comprises one or more monomers selected from the group consisting of dicyclo[2.2.2]octa-5-yn-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, maleic anhydride, phthalic anhydride, citraconic anhydride, succinic anhydride, and combinations thereof.

[0172] The reactive terminal group represented by the chemical formula Q may include compounds represented by the following chemical formulas Q-1 to Q-6.

[0173]

[0174] In the above chemical formulas Q-1 to Q-6,

[0175] 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 independently hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 30 Alkyl group; C2~C 30 Alkenyl group; C2~C 30 Alkinyl group; C1~C 30 Alkoxy group; C6~C 30 aryloxy group; C1~C 30 hydroxyacryl group; C1~C 30 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 30 Alkoxy carbonyl group,

[0176] 2) r and t are integers from 1 to 4,

[0177] 3) s1, s2 and u1 to u3 are integers from 1 to 2 respectively.

[0178] 4)* is the connected part of the bond.

[0179] The reactive terminal group represented by the above Chemical Formula Q may further include compounds represented by the following Chemical Formulae Q-7 to Q-10.

[0180]

[0181] The R 16 To R 18 independently of each other are hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; C1~C 20 hydroxyacryl group; C1~C 20 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 Alkoxy carbonyl group

[0182] The precursor terminal is bonded with a chemical formula selected from the group consisting of one or a combination of the above chemical formulas Q-7 to Q-10 through an amide or imide bond.

[0183] Preferably, the polyimide precursor comprises a diamine monomer, a dianhydride monomer, and an anhydride monomer.

[0184] Preferably, 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. If the weight average molecular weight of the resin is within the above range, no residue of the exposure layer will remain during development, and the film thickness loss of the non-exposure layer can be minimized to obtain a good pattern. In the total amount of the polymer composition, the content of the polymer can be 5 to 50% by weight, and more preferably, the content can be 15 to 45% by weight. When the content of the resin is within the above range, a uniform film thickness can be obtained in the coating step, and excellent sensitivity, developability and adhesion (tightness) can be obtained.

[0185] (2) Photoinitiator

[0186] In order to produce negative patterns through a photolithography machine, a photoradical initiator is required.

[0187] The photopolymerization initiator is generally used in a negative photosensitive composition, and for example, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoic acid ketone compounds, triazine compounds, oxime compounds, etc. can be used.

[0188] For example, the acetophenone compounds include: 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, etc.

[0189] For example, the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0190] For example, the thioxanthone compounds include thioxanthone, 2-chlorothiazolone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone and the like.

[0191] For example, the benzoic acid ketone-based compounds include benzoic acid ketone, benzoic acid ketone methyl ether, benzoic acid ketone ethyl ether, benzoic acid ketone isopropyl ether, benzoic acid ketone isobutyl ether, benzyl dimethyl ketal, and the like.

[0192] For example, the triazine compounds include: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, (Trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphtho-1-ol)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-ol)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl (piperonyl)-6-triazine, 2-4-trichloromethyl (4'-methoxyphenylvinyl)-6-triazine, etc.

[0193] For example, the oxime compounds include: 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoyloxime), 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-ol]ethylaniline}amino)

[0194]

[0063] 1-[(O-acetyloxy)-1-(O-acetyloxime)ethanol, 1-[ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolane)methoxybenzoyl}-9H-carbazole-3-ol]ethanol, 1-[4-[3-[4-[[2-acetyloxy]ethyl]sulfonyl]-2-methylbenzoyl]-6-[1-[(acetyloxy)imino]ethyl]-9H-carbazole-9-ol]benzene-1-(O-acetyloxime)-n-octanol, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-ol]-1-(O-acetyloxime)ethanol, and the like.

[0195] In addition to compounds, the photoinitiator may also be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a non-imidazole compound, and the like.

[0196] The photoinitiator is a free radical polymerization initiator, and may be a peroxide compound, an azobis compound, or the like.

[0197] For example, the peroxide compounds include: ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, acetylacetone peroxide, etc.; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, etc.; hydroperoxides such as 2,4,4,-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, t-butyl hydroperoxide, etc.; diisopropylbenzene peroxide, 2,5-dimethyl-2,5-di(t-butylperoxide) dialkyl peroxides such as butyl peroxy (butyl) hexane, 1,3-bis (t-butoxyisopropyl) benzene, t-butyl peroxy valerate, etc.; alkyl succinates such as 2,4,4-trimethylpentyl peroxy phenoxy acetate, α-peroxy neodecanoate cumyl, t-butyl peroxy benzoic acid, di-t-butyl peroxy trimethyl adipic acid, etc.; percarbonates such as di-3-methoxy butyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, bis-4-t-cyclohexyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, acetyl peroxy cyclohexyl sulfonyl, t-butyl peroxy carbonate, etc.

[0198] For example, the azobis compounds include: 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2,-azobis(methyl isobutyrate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), α,α'-azobis(isobutyronitrile) and 4,4'-azobis(4-cyanovaleric acid).

[0199] After the photoinitiator absorbs light and transitions to an excited state, it transfers its energy and is used together with a photosensitizer that undergoes a chemical reaction. For example, the photosensitizer includes: triethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0200] The content of the photoinitiator in the total amount of the photosensitive composition may be 0.01 to 10% by weight, for example, 0.1 to 5% by weight. When the content of the photoinitiator is within the above range, sufficient curing is induced when the pattern forming process is exposed, so that the reliability is excellent, the heat resistance, light resistance and chemical resistance of the pattern are excellent, and the clarity and adhesion are also excellent. In addition, the reduction of transmittance caused by the unreacted initiator can be prevented.

[0201] (3) Reactive unsaturated compounds

[0202] The reactive unsaturated compound is an essential component of the negative pattern and has an ethylene unsaturated double bond. Therefore, when the pattern forming process is exposed, it can initiate sufficient polymerization to form a pattern with excellent heat resistance, light resistance and chemical resistance.

[0203] Specific examples of the reactive unsaturated compound 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, 4-hydroxybutyl acrylate, etc.

[0204] Commercially available products of the reactive unsaturated compound are, for example, the following.

[0205] For example, the difunctional esters of (meth)acrylic acid include: aronyx M-210, M-240, M-6200, etc. from Toa Synthetic Chemical Industry Co., Ltd.; KAYARAD HDDA, HX-220, R-604, etc. from Nippon Chemical Co., Ltd.; V-260, V-312, V-335HP, etc. from Osaka Organic Chemical Industry Co., Ltd.

[0206] For example, the trifunctional esters of (meth)acrylic acid include: aronyx M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, etc. of Toa Synthetic Chemical Industry Co., Ltd.; KAYARAD TMPTA, DPCA-20, DPCA-60, DPCA-120, etc. of Nippon Chemical Co., Ltd.; V-295, V-300, V-360, etc. of Osaka Organic Chemical Industry Co., Ltd.

[0207] The above products can be used alone or in combination of two or more.

[0208] In order to have a better developability, the reactive unsaturated compound may be used after being treated with an acid anhydride. The content of the reactive unsaturated compound in the total amount of the polymer composition may be 1 to 40% by weight, for example, 1 to 20% by weight. When the content of the reactive unsaturated compound is within the above range, sufficient curing is induced when the pattern forming process is exposed, so that the reliability is excellent, the heat resistance, light resistance and chemical resistance of the pattern are excellent, and the clarity and adhesion are also excellent.

[0209] (4) Solvent

[0210] The solvent may be a substance that is compatible with and does not react with the polyimide precursor or polymer, the photosensitizer, and the pigment.

[0211] For example, the solvent includes: alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, anisole, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethyl acetate glycol ethers such as methoxyethyl acetate, ethoxyethyl acetate, and diethoxyethyl acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol Propylene glycol alkyl ether acetates such as methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-di-n-amyl ketone, 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, methyl oxyacetate, butyl oxyacetate; methoxy Alkoxyacetic acid alkyl esters such as methyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; 3-oxopropionic acid alkyl esters such as methyl 3-oxopropionate, ethyl 3-oxopropionate, etc.; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-oxopropionic acid alkyl esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, etc.; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, etc. 2-alkoxypropionic acid alkyl esters such as ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl 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 hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate; keto acid esters such as ethyl pyruvate, etc.

[0212] In addition, high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol phenyl acetate can be used.

[0213] Taking into account the compatibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether (ethylene glycolmonoethyl ether); ethylene glycol acetate alkoxy ethers such as ethoxyethyl acetate; ethers such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

[0214] In the total amount of the photosensitive composition, the solvent may be included as a balance, specifically, the content may be 50 to 95% by weight. When the content of the solvent is included in the range, the negative type photosensitive composition may have an appropriate viscosity, thereby achieving excellent processability when preparing a pattern layer.

[0215] (5) Other additives

[0216] In order to prevent the occurrence of marks or spots, improve the flatness and prevent the generation of residues due to undevelopment when coating the negative polymer composition, the composition may further include additives such as malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing a vinyl or (meth)acryloxy group; a surface leveler; a surfactant; and a crosslinking agent.

[0217] For example, in order to improve adhesion to a substrate, the polymer composition may further include a coupling agent, wherein the silane coupling agent has a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group.

[0218] For example, the silane coupling agent includes trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltrioxysilane, γ-glycidyloxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, and KBM-502, KBM-602, KBM-573, KBE-9007N and other silane coupling agents available on the market from Shinetsusilicon, which can be used alone or in combination of two or more.

[0219] The weight part of the silane coupling agent can be 0.01 parts by weight to 10 parts by weight in 100 parts by weight of the polymer composition. When the weight part of the silane coupling agent is within the above range, the adhesion and storage properties are excellent.

[0220] Furthermore, the polymer composition may further include a surface smoothener as required, and the surface smoothener is used to form a uniform film thickness in the coating step.

[0221] The surface leveler can be the following commercially available surface levelers: etc.; BASF FL3740, same model FL3741, same model FL3745, same model FL3770, etc.

[0222] The weight of the surface leveler can be 0.001 to 5 parts by weight in 100 parts by weight of the polymer composition. When the weight of the surface leveler is within the above range, the uniformity of the coating can be ensured and the film thickness of the coating can be uniform.

[0223] Furthermore, the polymer composition may further include a surfactant as required to achieve the effects of improving coating properties and preventing defects from occurring.

[0224] The surfactant can be the following commercially available surfactant: etc.; Dainippon Ink & Chemicals Co., Ltd.'s mecha package Same style Same style Same style etc.; Lard from Sumitomo 3M Co. Same style Same style Same style etc.; Saffron from Asahi Glass Co., Ltd. Same style Same style Same style Same style etc.; Toray Silicon Corporation wait.

[0225] Furthermore, the polymer composition may further contain a silane-based surfactant as needed.

[0226] The silane surfactant can be the following commercially available silane surfactants: S-101, S-201, S-301, S-601, S-701, S-801RS-55, RS-56, etc. from DIC; 3030, 3034, 3886, etc.; 3030, 3085, 3236, etc. from AFCONA; BYK-378, BYK-3550, BYK-3751, BYK-3754, etc. silane-based surfactants on sale.

[0227] The weight of the surfactant can be 0.001 to 5 parts by weight in 100 parts by weight of the polymer composition. When the weight of the surfactant is within the above range, the coating uniformity can be ensured, no spots will occur, and the wettability of the glass substrate is excellent.

[0228] The crosslinking agent may be 1,4-bis(methoxymethyl)benzene, diethyl sulfate, 3-aminopropyltriethoxysilane, N,N'-methylenebisacrylamide, N,N'-dicyclohexylcarbodiimide, etc., which may be used alone or in combination of two or more.

[0229] The weight of the crosslinking agent can be 0.001 to 5 parts by weight in 100 parts by weight of the polymer composition. When the crosslinking agent is included in the above range, it is beneficial to reasonably impart physical properties to the cured coating film, for example, mechanical physical properties such as tensile strength.

[0230] Furthermore, within the range not impairing the physical properties, a certain amount of other additives may be added to the polymer composition.

[0231] Hereinafter, the synthesis examples and examples of the present invention will be described in detail, but the synthesis examples and examples of the present invention are not limited thereto.

[0232] (Synthesis example 1)

[0233] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen gas inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled, and 141.87 g of N-methylpyrrolidinone (NMP) was added, and then 22.22 g of 3,3',4,4'-benzophenone tetracarboxylic dianhydride was added and stirred, and the temperature was kept at 25°C. Among them, 19.86 g of 4-hydroxybutyl acrylate was added, and then 11.17 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 35.54 g of N,N'-dicyclohexylcarbodiimide and 71.07 g of N-methylpyrrolidone (NMP) was slowly added and stirred for 3 hours.

[0234] (Solution B) A 500 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was introduced, and 62.09 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25° C. Then, 15 g of 3,3'-dimethylbenzidine was added and stirred until it was completely dissolved, and then 0.52 g of phthalic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10° C. and maintained.

[0235] (Polymerization reaction) Solution A was dripped into solution B maintained at -10°C using a metering pump and stirred for 1 hour. Then, the temperature was raised for 1 hour until 25°C, and then, the reaction was maintained for 2 hours, and then, the solution was dripped into 2275 g of distilled water to precipitate. The solid obtained was rinsed twice with distilled water, and then, vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0236] (Synthesis example 2)

[0237] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen gas inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled, and 141.87 g of N-methylpyrrolidone (NMP) was added, and then 22.22 g of 3,3',4,4'-benzophenone tetracarboxylic dianhydride was added and stirred, and kept at 25°C. Among them, 19.86 g of 4-hydroxybutyl acrylate was added, and then 11.17 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 35.54 g of N,N'-dicyclohexylcarbodiimide and 71.07 g of N-methylpyrrolidone (NMP) was slowly added and stirred for 3 hours.

[0238] (Solution B) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen gas inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 61.58 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25°C. Then, 15 g of 3,3'-dimethylbenzidine was added and stirred until it was completely dissolved, and then 0.52 g of phthalic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10°C and maintained. Then, 0.40 g of citraconic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10°C and maintained.

[0239] (Polymerization reaction) Solution A was dripped into solution B maintained at -10°C using a metering pump and stirred for 1 hour. Then, the temperature was raised for 1 hour until 25°C, and then, the reaction was maintained for 2 hours, and then, the solution was dripped into 2272 g of distilled water to precipitate. The solid obtained was rinsed twice with distilled water, and then, vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0240] (Synthesis example 3)

[0241] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled, and 141.87 g of N-methylpyrrolidone (NMP) was added, and then 22.22 g of 3,3',4,4'-benzophenone tetracarboxylic dianhydride was added and stirred, and kept at 25°C. Among them, 19.86 g of 4-hydroxybutyl acrylate was added, and then 11.17 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 35.53 g of N,N'-dicyclohexylcarbodiimide and 71.07 g of N-methylpyrrolidone (NMP) was slowly added and stirred for 3 hours.

[0242] (Solution B) A 500 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was introduced, and 61.61 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25°C. Then, 15 g of 3,3'-dimethylbenzidine was added and stirred until it was completely dissolved, and then 0.40 g of glutamine anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10°C and maintained.

[0243] (Polymerization reaction) Solution A was dripped into solution B maintained at -10°C using a metering pump and stirred for 1 hour. Then, the temperature was raised for 1 hour until 25°C, and then, the reaction was maintained for 2 hours, and then, the solution was dripped into 2272 g of distilled water to precipitate. The solid obtained was rinsed twice with distilled water, and then, vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0244] (Synthesis Example 4)

[0245] A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled, and 205.32 g of N-methylpyrrolidone (NMP) was added, and then 22.22 g of 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 0.52 g of phthalic anhydride were added and stirred, and kept at 25°C. Among them, 20.37 g of 4-hydroxybutyl acrylate was added, and then 11.46 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 36.46 g of N,N'-dicyclohexylcarbodiimide and 72.89 g of N-methylpyrrolidone (NMP) was slowly dripped and stirred for 3 hours. Then, the internal temperature was cooled to -10°C, and 15 g of 3,3'-dimethylbenzidine was dripped and stirred for 30 minutes. Then, the temperature was raised to 25°C for 1 hour, and then the reaction was maintained for 2 hours, and then the mixture was dropped into 2305 g of distilled water to precipitate. The solid was washed twice with distilled water, and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0246] (Synthesis Example 5)

[0247] A 500ml heat medium circulation jacketed reactor is attached with a stirrer, a nitrogen gas inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, and 204.81g of N-methylpyrrolidone (NMP) is filled, and then 22.22g of 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 0.40g of citraconic anhydride are added for stirring, and the mixture is kept at 25°C. Among them, 20.37g of 4-hydroxybutyl acrylate is added, and then 11.45g of pyridine is slowly added to react. Then, the internal temperature of the reactor during the reaction is maintained at -10°C, and a solution of 36.45g of N,N'-dicyclohexylcarbodiimide and 72.89g of N-methylpyrrolidone (NMP) is slowly dripped in and stirred for 3 hours. Then, the internal temperature is cooled to -10°C, and 15g of 3,3'-dimethylbenzidine is dripped in with stirring, and the stirring and dripping time is 30 minutes. Then, the temperature was raised to 25°C for 1 hour, and then the reaction was maintained for 2 hours, and then the mixture was dropped into 2301 g of distilled water to precipitate the mixture. The solid was washed twice with distilled water, and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0248] (Synthesis Example 6)

[0249] A 500ml heat medium circulation jacketed reactor is attached with a stirrer, a nitrogen gas inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, and 204.84g of N-methylpyrrolidone (NMP) is filled, and then 22.22g of 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 0.40g of glutamine anhydride are added and stirred, and kept at 25°C. Among them, 20.37g of 4-hydroxybutyl acrylate is added, and then 11.46g of pyridine is slowly added to react. Then, the internal temperature of the reactor during the reaction is maintained at -10°C, and a solution of 36.45g of N,N'-dicyclohexylcarbodiimide and 72.89g of N-methylpyrrolidone (NMP) is slowly dripped and stirred for 3 hours. Then, the internal temperature is cooled to -10°C, and 15g of 3,3'-dimethylbenzidine is dripped and stirred for 30 minutes. Then, the temperature was raised to 25°C for 1 hour, and then the reaction was maintained for 2 hours, and then the mixture was dropped into 2302 g of distilled water to precipitate. The solid was washed twice with distilled water, and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0250] (Synthesis Example 7)

[0251] (Solution A) A 500 ml heat medium circulation jacketed reactor is provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen is charged, and 256.4 g of N-methylpyrrolidone (NMP) is filled, and then 22.31 g of 4,4'-oxydiphthalic anhydride and 5.29 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride are added for stirring, and the mixture is kept at 35°C. Among them, 25.91 g of () is added, and then 29.15 g of pyridine is slowly added to react. Next, the internal temperature of the reactor during the reaction is maintained at -10°C, and a solution of 37.09 g of N,N'-dicyclohexylcarbodiimide and 74.190 g of γ-butyrolactone is slowly added and stirred for 3 hours.

[0252] (B solution) A 1000 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 93.11 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25° C. Then, 20 g of 4,4'-oxydiphenylamine was added and stirred until it was completely dissolved, and then 3.28 g of 5-norbornene-2,3-dicarboxylic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10° C. and maintained.

[0253] (Polymerization reaction) Using a quantitative pump, solution A is dripped into solution B maintained at -10°C and stirred, and the dripping and stirring time is 1 hour. Then, it is heated for 1 hour until 25°C, then, it is kept reacting for 2 hours, then, 40g of ethanol is added, stirred for 1 hour, and maintained. Then, filter paper is used for filtration, and 1417g of ethanol is added to the filtered filtrate to precipitate solids. The solid is dissolved in 56.68g of THF and dripped into 6802g of distilled water to precipitate it. Among them, the solid obtained by rinsing twice with distilled water is then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0254] (Synthesis Example 8)

[0255] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled in, and 258.4 g of N-methylpyrrolidone (NMP) was added, and then 13.94 g of 4,4'-oxydiphthalic anhydride and 13.22 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride were added and stirred, and the temperature was maintained at 35°C. 25.91 g of 4-hydroxybutyl acrylate was added, and then 29.15 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 37.09 g of N,N'-dicyclohexylcarbodiimide and 74.190 g of γ-butyrolactone was slowly added and stirred for 3 hours.

[0256] (B solution) A 1000 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 93.11 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25° C. Then, 20 g of 4,4'-oxydiphenylamine was added and stirred until it was completely dissolved, and then 3.28 g of 5-norbornene-2,3-dicarboxylic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10° C. and maintained.

[0257] (Polymerization reaction) Using a quantitative pump, solution A is dripped into solution B maintained at -10°C and stirred, and the dripping and stirring time is 1 hour. Then, it is heated for 1 hour until 25°C, then, it is kept to react for 2 hours, then, 40g of ethanol is added, stirred for 1 hour, then, 7.6g of mandelic acid is added, stirred for 2 hours and kept. Then, filter paper is used for filtration, and 1417g of ethanol is added to the filtered filtrate to precipitate solids. The solid is dissolved in 56.68g of THF and dripped into 6802g of distilled water to precipitate it. Among them, the solid obtained by rinsing twice with distilled water is then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0258] (Synthesis Example 9)

[0259] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen gas inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled in, and 254.8 g of N-methylpyrrolidone (NMP) was added, and then 5.57 g of 4,4'-oxydiphthalic anhydride and 21.16 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride were added and stirred, and the temperature was maintained at 35°C. Among them, 25.91 g of 4-hydroxybutyl acrylate was added, and then 29.15 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 37.09 g of N,N'-dicyclohexylcarbodiimide and 74.190 g of γ-butyrolactone was slowly added and stirred for 3 hours.

[0260] (B solution) A 1000 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 93.11 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25° C. Then, 20 g of 4,4'-oxydiphenylamine was added and stirred until it was completely dissolved, and then 3.28 g of 5-norbornene-2,3-dicarboxylic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10° C. and maintained.

[0261] (Polymerization reaction) Using a quantitative pump, solution A was dripped into solution B maintained at -10°C and stirred for 1 hour. Then, the temperature was raised for 1 hour until 25°C, then the reaction was maintained for 2 hours, then 40g of ethanol was added, stirred for 1 hour, and then filtered using filter paper. 1417g of ethanol was added to the filtered filtrate to precipitate a solid. The solid was dissolved in 56.68g of THF and dripped into 6802g of distilled water to precipitate it. Among them, the solid obtained by rinsing twice with distilled water was then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0262] (Synthesis Example 10)

[0263] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled in, and 149.04 g of N-methylpyrrolidone (NMP) was added, and then 8.01 g of 4,4'-oxydiphthalic anhydride and 7.60 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride were added and stirred, and the temperature was maintained at 35°C. Among them, 14.89 g of 4-hydroxybutyl acrylate was added, and then 16.75 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 21.31 g of N,N'-dicyclohexylcarbodiimide and 42.62 g of γ-butyrolactone was slowly added and stirred for 3 hours.

[0264] (B solution) A 1000 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 87.54 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25° C. Then, 20 g of 9,9-bis(4-aminophenol)fluorene was added and stirred until it was completely dissolved, and then 1.88 g of 5-norbornene-2,3-dicarboxylic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10° C. and maintained.

[0265] (Polymerization reaction) Using a quantitative pump, solution A was dripped into solution B maintained at -10°C and stirred for 1 hour. Then, the temperature was raised for 1 hour until 25°C, then the reaction was maintained for 2 hours, then 40g of ethanol was added, stirred for 1 hour and maintained, then filtered using filter paper, 917g of ethanol was added to the filtered filtrate to precipitate solids. The solid was dissolved in 36.70g of THF and dripped into 6802g of distilled water to precipitate it. Among them, the solid obtained by rinsing twice with distilled water was then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0266] (Synthesis Example 11)

[0267] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen gas inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled in, and 176.52 g of N-methylpyrrolidone (NMP) was added, and then 9.55 g of 4,4'-oxydiphthalic anhydride and 9.06 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride were added and stirred, and the temperature was kept at 35°C. Among them, 17.75 g of 4-hydroxybutyl acrylate was added, and then 19.97 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 25.41 g of N,N'-dicyclohexylcarbodiimide and 50.80 g of γ-butyrolactone was slowly added and stirred for 3 hours.

[0268] (B solution) A 1000 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 88.98 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25° C. Then, 20 g of 1,4-bis(4-aminophenoxy)benzene was added and stirred until it was completely dissolved, and then 2.25 g of 5-norbornene-2,3-dicarboxylic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10° C. and maintained.

[0269] (Polymerization reaction) Using a quantitative pump, solution A was dripped into solution B maintained at -10°C and stirred for 1 hour. Then, the temperature was raised for 1 hour until 25°C, then the reaction was maintained for 2 hours, then 40g of ethanol was added, stirred for 1 hour and maintained, then filtered using filter paper, 1045g of ethanol was added to the filtered filtrate to precipitate a solid. The solid was dissolved in 56.68g of THF and dripped into 5019g of distilled water to precipitate it. Among them, the solid obtained by rinsing twice with distilled water was then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0270] (Synthesis Example 12)

[0271] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled, and 118.6 g of N-methylpyrrolidone (NMP) was added, and then 4.76 g of 4,4'-oxydiphthalic anhydride and 8.38 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride were added and stirred, and the temperature was maintained at 35°C. Among them, 12.64 g of 4-hydroxybutyl acrylate was added, and then 14.22 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 18.09 g of N,N'-dicyclohexylcarbodiimide and 36.18 g of γ-butyrolactone was slowly added and stirred for 3 hours.

[0272] (B solution) A 1000 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 86.40 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25°C. Then, 20 g of 2,2'-bis(4-aminophenoxy)phenylpropane was added and stirred until it was completely dissolved, and then 1.60 g of 5-norbornene-2,3-dicarboxylic anhydride was added and reacted for 5 hours, and then the internal temperature was cooled to -10°C and maintained.

[0273] (Polymerization reaction) Using a quantitative pump, solution A was dripped into solution B maintained at -10°C and stirred for 1 hour. Then, it was heated for 1 hour until 25°C, then, it was kept reacting for 2 hours, then, 40g of ethanol was added, stirred for 1 hour and kept, then, it was filtered using filter paper, and 815g of ethanol was added to the filtered filtrate to precipitate solids. The solid was dissolved in 32.61g of THF and dripped into 3913g of distilled water to precipitate it. Among them, the solid obtained by rinsing twice with distilled water was then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0274] (Synthesis Example 13)

[0275] (Solution A) A 500 ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen gas inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled, and 141.87 g of N-methylpyrrolidone (NMP) was added, and then 22.22 g of 3,3',4,4'-benzophenone tetracarboxylic dianhydride was added and stirred, and kept at 25°C. Among them, 19.86 g of 4-hydroxybutyl acrylate was added, and then 11.17 g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 35.54 g of N,N'-dicyclohexylcarbodiimide and 71.07 g of N-methylpyrrolidone (NMP) was slowly added and stirred for 3 hours.

[0276] (Solution B) A 500 ml heat medium circulation jacketed reactor was provided with a stirrer, a nitrogen gas introduction device, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 61.41 g of N-methylpyrrolidone (NMP) was added, and then stirred at 25° C. Then, 15 g of 3,3'-dimethylbenzidine was added and stirred until it was completely dissolved, and then 0.35 g of succinic anhydride was added, and the mixture was reacted for 5 hours, and then the internal temperature was cooled to -10° C. and maintained.

[0277] (Polymerization reaction) Solution A was dripped into solution B maintained at -10°C using a metering pump and stirred for 1 hour. Then, the temperature was raised for 1 hour until 25°C, and then the reaction was maintained for 2 hours. Then, 1563 g of distilled water and 782 g of ethanol were added to precipitate the solution. The solid was rinsed twice with distilled water and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0278] (Synthesis Example 14)

[0279] A 500ml heat medium circulation jacketed reactor was attached with a stirrer, a nitrogen inlet device, a dropping funnel, a thermostat and a cooler, and then nitrogen was charged, and 281.4g of N-methylpyrrolidone (NMP) was added, and then 10.84g of 4,4'-oxydiphthalic anhydride and 19.10g of 3,3'4,4'-biphenyltetracarboxylic dianhydride were added for stirring, and the temperature was kept at 35°C. 28.80g of 4-hydroxybutyl acrylate was added, and then 32.39g of pyridine was slowly added to react. Then, the internal temperature of the reactor during the reaction was kept at -10°C, and a solution of 41.21g of N,N'-dicyclohexylcarbodiimide and 82.42g of γ-butyrolactone was slowly added and stirred for 3 hours. Next, 80 g of N-methylpyrrolidone (NMP) was added to the reactor, and then 20 g of 4,4'-oxydiphenylamine was added in portions over one hour, and stirred until the mixture was completely dissolved, and then allowed to react for 5 hours.

[0280] Then, it was heated for 1 hour until 25 ° C, then, it was kept reacting for 2 hours, then, 40g of ethanol was added, and it was kept stirring for 1 hour. Then, filter paper was used for filtration, and 1492g of ethanol was added to the filtered filtrate to precipitate solid. The solid was dissolved in 59.69g of THF and dropped into 7162g of distilled water to precipitate it. Among them, the solid obtained by rinsing twice with distilled water was then dried in vacuum at 25 ° C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0281] (Preparation Example 1) Preparation of negative photosensitive composition

[0282] 14.88 g of the polyimide precursor obtained in Synthesis Examples 1 to 7, 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), 1.0 g of 1,4-bis(methoxymethyl)benzene, and propylene glycol methyl ether (PGMEA) were mixed.

[0283] Then, the composition was filtered three times to remove impurities, thereby preparing a composition.

[0284] The photosensitive composition solution was prepared using the components in Table 1 below.

[0285]

Table 1

[0286]

[0287]

[0288] The method for preparing a test piece for UTM (Universal Testing Machine) using the negative photosensitive composition is as follows.

[0289] (1) Coating and coating steps

[0290] On a cleaned and metal-evaporated 10cm*10cm substrate, a photosensitive composition is coated with a constant thickness using a spin coater, and then a vacuum drying chamber (VCD, vacuum chamber dry) is used to remove part of the solvent to form a coating. The thickness of the coating of the photosensitive composition after VCD is 3.5 microns to 3.3 microns. The photosensitive composition is a low-viscosity liquid sample. After coating with the substrate, a spin coater or a slit coater is used to make the coating uniform. The faster the spin coater rotates, the smaller the thickness. Its advantage is that the deviation of flatness in the area becomes smaller. If you want to coat a large area substrate, it is preferred to use a slit coater rather than a spin coater. After coating, due to the residual solvent, the surface has fluidity, and thus it has the disadvantage of reduced flatness. In order to overcome this disadvantage, VCD (vacuum chamber dry) is used to remove part of the solvent, thereby reducing the fluidity of the surface.

[0291] (2) Pre-baking step

[0292] This process uses a hot plate or oven to heat the substrate of the coating at a certain temperature and time to remove the solvent contained in the coating film. If the surface or deep part of the coating film is not dry, it will cause photomask contamination when it is exposed during the next process, and it will cause poor curing of the exposed part when irradiated with ultraviolet light. If it is not cured, the pattern cannot be formed in the development process and it will be removed.

[0293] (3) Exposure Step

[0294] After the pre-baking step is completed, the process uses a photomask with a pattern to irradiate actinic rays (ultraviolet rays) to solidify the formed film. The types of lamps that generate actinic rays include LED lamps or metal (mercury), and the wavelengths are g-line (436nm), h-line (405nm), i-line (365nm), and Deep UV (<260nm), which can be used separately or in combination.

[0295] (4) Development step

[0296] When irradiating actinic rays in the exposure step, since the photomask is divided into an exposed part and a non-exposed part, when it is a positive type, the exposed part is melted by the developer, and the non-exposed part can be supported in the developer, leaving a pattern. When it is a negative type, the exposed part is solidified, generating resistance to the developer, and the non-exposed part is developed. The composition described in the present invention is a negative type, which is divided into an exposed part (solidified) and a non-exposed part (developed) to form a pattern.

[0297] (5) Post-baking step

[0298] The process heats the developed substrate at a high temperature of 210°C or above to remove residual solvent and fume. If the process does not completely remove the solvent and fume, degassing will occur in the process after post-baking, which will affect the components and thus affect black spots or shrinkage.

[0299] (6) Test piece peeling

[0300] In order to obtain an undamaged UTM test piece on the substrate after the post-baking step, the substrate is dipped in a 2% fluoric acid aqueous solution at 23±2°C for a certain period of time (minutes), and then the separated test piece is rinsed with deionized water (DI water) and placed in a vacuum chamber at room temperature for drying to obtain a UTM test piece.

[0301] (7) UTM detection

[0302] The UTM test pieces of the embodiment and the comparative example obtained in the test piece peeling step were tested for tensile strength and elongation using a universal material testing machine QM100S from QMESYS. The testing conditions were as follows: the testing temperature was 25°C, the elongation speed was 5mm / min, and the marking distance was 20mm.

[0303]

Table 2

[0304]

[0305]

[0306] From the development test results described in Table 2 above, it can be seen that no residues appeared after development in Examples 1 to 12 and Comparative Examples 1 and 2. The results of confirming the pattern display accuracy using a 30μm Hole mask showed that Examples 1 to 6 and Comparative Example 1 all accurately displayed patterns with a deviation within 0.4μm, and Examples 7 to 12 and Comparative Example 2 all accurately displayed patterns with a deviation within 0.2μm.

[0307] According to the UTM test results, in Table 1 above, the tensile strength of Examples 1 to 6 is 4.41 MPa or more, and that of Comparative Example 1 is 3.16 MPa. In addition, the elongation of Examples 1 to 6 is 62% or more, and that of Comparative Example 1 is 51.6%, which confirms that the introduction of reactive groups into the ends of the polyimide precursor of the present invention has an effect on improving the tensile strength and elongation.

[0308] The present invention is not limited to the above-mentioned embodiments and can be prepared in various forms.

[0309] The substrates obtained in the post-process of the post-baking step were tested and compared for the amount of moisture generated. From Comparative Examples 1 to 6 in Table 2 above, it can be confirmed that the post-baking temperature is low, so even if the post-baking time is increased, the moisture content after the post-baking is above 50 ppm. It has been confirmed that when the moisture content after the post-baking increases, black spots will be generated during component driving. Reference Examples 1 to 12 can confirm that when the moisture content after the post-baking is below 50 ppm, black spots and life problems will not occur.

[0310] The above description is merely an example of the present invention, and a person skilled in the art in the art to which the present invention belongs can make various modifications without departing from the essential characteristics of the present invention.

[0311] Therefore, the embodiments disclosed in this specification are used to describe the present invention, rather than to limit the present invention, and the idea and scope of the present invention are not limited by such embodiments. The scope of the claims of the present invention should be interpreted according to the following claims, and should be interpreted as including all technologies within the scope equivalent thereto falling within the scope of the claims of the present invention.

Claims

1. A polyimide precursor, characterized in that: Contains a reactive terminal group represented by the chemical formula Q: [Chemical formula Q] In the above chemical formula 1, 1) R a To R c are independently hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 Heterocyclyl group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C1~C 30 Alkoxy group; C6~C 30 aryloxy group; C1~C 30 hydroxyacryl group; C1~C 30 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 30 An alkoxy carbonyl group, or R a To R c The adjacent bases form a ring. 2) C1 and C2 are carbon; the bond connecting C1 and C2 is a single bond or a double bond, 3) When the bond connecting the C1 and C2 is a single bond, o and p are each independently an integer of 1 or 2; when the bond connecting the C1 and C2 is a double bond, o and p are each an integer of 1, 4) C3 is carbon or a direct bond of C2-B2, 5) When the C3 is carbon, q is an integer of 1 or 2, 6) The dotted line connecting B1 and B2 indicates that there is no bond or single bond. 7) When the dashed line connecting B1 and B2 indicates that there is no bond, B1 is hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; C1~C 20 hydroxyacryl group; C1~C 20 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 B2 is a carbon group bonded to the repeating unit of the polyimide series. 8) When the dotted line connecting B1 and B2 is a single bond, B1 is nitrogen bonded to the polyimide repeating unit; B2 is carbon, 9) R a To R c and the rings formed by the bonding of adjacent groups are further substituted with one or more substituents selected from the group consisting of the following components: deuterium; halogen; substituted or unsubstituted C1-C 30 Alkyl group or C6~C 30 aryl group, silane group, siloxane group, boron group, germanium group, cyano group, amino group, nitro group, C1~C 30 Alkylthio group; C1~C 30 Alkoxy group; C6~C 30 Aryl alkoxy group; C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C6~C 30 aryl group; C6~C 30 aryl group; fluorenyl group; C2~C 30 A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C3~C 30 Aliphatic ring group; C7~C 30 Aryl alkyl group; C8~C 30 and combinations thereof; or adjacent substituents may form a ring.

2. The polyimide precursor according to claim 1, characterized in that: The polyimide-based precursor includes a repeating unit selected from the group consisting of the following Chemical Formula 1-1, Chemical Formula 1-2, and a combination thereof: [Chemical formula 1-1] [Chemical formula 1-2] In the above chemical formula 1-1 and chemical formula 1-2, 1) * is a connecting portion bonded to the repeating unit or the reactive terminal group represented by the chemical formula Q according to claim 1, 2) R1 to R4 are the following chemical formula 2, 3) X is the following chemical formula 3, 4) m and n are integers from 1 to 1000, [Chemical formula 2] In the above chemical formula 2, 5) * is the bonded connected part, 6) a is an integer from 1 to 30, 7) R5 is hydrogen or methyl ester; 8) Y is selected from the group consisting of: C6 to C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20 cyclo alkinylene group; Chemical Formula 3; and combinations thereof, 9) Z is selected from the group consisting of: Arylene group; C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20 cyclo alkinylene group; Chemical Formula 3; and combinations thereof, [Chemical formula 3] 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-, 11) R6 to R 15 Two of them are connecting sites with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2, 12) Except for the connecting part, the rest of R6 to R 15 independently of each other are hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 The alkoxy carbonyl group, or the adjacent R 6 and R 15 ; and R 10 and R 11 Form a ring, 13) Y, Z, R6 to R 15 and the rings formed by the bonding of adjacent groups are further substituted with one or more substituents selected from the group consisting of the following components: deuterium; halogen; substituted or unsubstituted C1-C 30 Alkyl group or C6~C 30 aryl group, silane group, siloxane group, boron group, germanium group, cyano group, amino group, nitro group, C1~C 30 Alkylthio group; C1~C 30 Alkoxy group; C6~C 30 Aryl alkoxy group; C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C6~C 30 aryl group; C6~C 30 aryl group; fluorenyl group; C2~C 30 A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C3~C 30 Aliphatic ring group; C7~C 30 Aryl alkyl group; C8~C 30 and combinations thereof; or adjacent substituents may form a ring.

3. The polyimide precursor according to claim 1, characterized in that: The compound represented by the above chemical formula Q includes compounds represented by the following chemical formulas Q-1 to Q-6, In the above chemical formulas Q-1 to Q-6, 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 independently hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 30 Alkyl group; C2~C 30 Alkenyl group; C2~C 30 Alkinyl group; C1~C 30 Alkoxy group; C6~C 30 aryloxy group; C1~C 30 hydroxyacryl group; C1~C 30 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 30 Alkoxy carbonyl group, 2) r and t are integers from 1 to 4, 3) s1, s2 and u1 to u3 are integers from 1 to 2 respectively, 4)* is the connected part of the bond.

4. The polyimide precursor according to claim 1, characterized in that: The compound represented by the above chemical formula Q includes compounds represented by the following chemical formulae Q-7 to Q-10, <Chemical formulas Q-7 to Q-10> The R 16 To R 18 independently of each other are hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; C1~C 20 hydroxyacryl group; C1~C 20 hydroxymethaacryl group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 Alkoxy carbonyl group, The precursor terminal is bonded with a chemical formula selected from the group consisting of one or a combination of the above chemical formulas Q-7 to Q-10 through an amide or imide bond.

5. The polyimide precursor according to claim 1, characterized in that: The polyimide precursor comprises at least one of a diamine monomer, a dianhydride monomer, and an anhydride monomer.

6. The polyimide precursor according to claim 1, characterized in that: The weight average molecular weight of the polyimide-based precursor is 5,000 to 40,000 g / mol.

7. The polyimide precursor according to claim 6, characterized in that: The composition further comprises a photoinitiator; a reactive unsaturated compound; a solvent; and an additive.

8. The polyimide precursor according to claim 6, characterized in that: The content of the polyimide polymer is 5 to 50 weight % in the total amount of the composition.

9. The polyimide precursor according to claim 6, characterized in that: The photoinitiator is contained in an amount of 0.01 to 10 wt % in the total amount thereof.

10. The polyimide precursor according to claim 6, characterized in that: The reactive unsaturated compound is contained in an amount of 1 to 40% by weight in the total amount thereof.

11. The polyimide precursor according to claim 6, characterized in that: The content of the solvent is 50 to 95% by weight of the total weight of the composition.

12. The polyimide precursor according to claim 6, characterized in that: The content of the additive is 0.001 to 10% by weight of the total amount of the composition.

13. A pattern or film prepared from the polyimide-based precursor according to claim 6.

14. A semiconductor device manufactured using the pattern or film according to claim 13.

15. A display device prepared using the pattern or film according to claim 13. 16 . A display device comprising the display device according to claim 15 and a control unit for driving the display device.

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