Polybenzoxazole or polyimide precursor, copolymer of same, and positive photosensitive composition comprising same

Abstract

The present invention relates to a polybenzoxazole-based or polyimide-based precursor, a copolymer of the same and the like, and a positive photosensitive composition comprising the same, in which when a photosensitive composition comprising a fluorine-free polyimide precursor and a benzoxazole-based precursor copolymer resin is used, it is confirmed that the polybenzoxazole-based or polyimide-based precursor copolymer resin does not contain fluorine, and the polybenzoxazole-based or polyimide-based precursor copolymer resin does not contain fluorine. The fluorine-based photosensitive composition can present a pattern appearing degree similar to that of an existing fluorine-based photosensitive composition, and can realize a technical effect of less residue after development.

Description

[0001] Join by reference

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0141114, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to a polybenzoxazole or polyimide precursor, a copolymer thereof, and a positive photosensitive composition used in a semiconductor device or a display device made of the precursor. 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. In contrast, the negative process reacts chemically with the developer, and the reaction product is dissolved and removed. Among them, the positive process can use a photosensitive agent (Photo active compound) that absorbs light and increases solubility in the exposure step, and only the exposed part is accurately removed in the development step. Therefore, compared with the negative process, a more precise and accurate pattern can be obtained.

[0006] Conventional positive photosensitive resin compositions used in semiconductor devices or display devices utilize resins such as polyimide or polybenzoxazole because of their high heat resistance, chemical resistance, and weather resistance. However, as research into environmental pollution and human harm caused by halogenated compounds used as main materials is conducted, the demand for new materials to replace halogenated compounds is increasing.

[0007]

Prior technical literature

[0008] [Patent Literature]

[0009] (Patent Document 1) Korean Patent Publication No. 10-2010-0080344 Summary of the invention

[0010] Issues to be solved

[0011] In order to solve the above-mentioned drawbacks of the conventional technology, the present invention provides a precursor and a copolymer synthesized by introducing a monomer not containing a halogen element into the components of a polybenzoxazole-based or polyimide-based precursor and a copolymer resin.

[0012] Furthermore, the present invention aims to provide a positive photosensitive composition using the polybenzoxazole series, polyimide precursor and copolymer resin.

[0013] Furthermore, an object of the present invention is to provide a pattern or film formed using the positive photosensitive composition, and a semiconductor device or display device produced using the same.

[0014] Problem Solution

[0015] Preferably, the benzoxazole-based or polyimide-based precursor and copolymer 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.

[0016] <Chemical Formula 1-1>

[0017]

[0018] <Chemical Formula 1-2>

[0019]

[0020] In the above chemical formula 1-1 and chemical formula 1-2,

[0021] 1)* is the connected part bonded by repeating unit,

[0022] 2) X is the following chemical formula 2,

[0023] <Chemical Formula 2>

[0024]

[0025] 3) R 1 To R 10 Two of them are connecting sites with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2,

[0026] 4) The remaining R except the connecting part 1 To R 10 Independently selected from the group consisting of the following components: hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C30 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; C1~C 20 an alkoxy carbonyl group; and combinations thereof,

[0027] 5) L 1 Selected from the group consisting of: single bond; C6~C 30 an arylene 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 20 Alkylene group; C3~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; –O-, –S-, –SO2-, Si(CH3)2-, –C(SiCH3)2-C6H4-, –CO-, –NHCO-, –COO-,

[0028] 6) L 1 When it is a single bond, the adjacent R1 and R 10 ; can form a ring with R5 and R6,

[0029] 7) Y and Z are independently selected from the group consisting of the following components: C6 to C 30 an arylene 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 20 Alkylene group; C3~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20 cycloalkinylene group; and combinations thereof,

[0030] 8) Y or Z independently may further replace one or more carboxylic acid groups; or have C1~C 20 The terminal ester group,

[0031] 9) m or n is an integer greater than 1,

[0032] 10) The polymer terminal is bonded to one selected from the following chemical formulas Q-1 to Q-10:

[0033]

[0034] Preferably, the above Chemical Formula 2 is represented by the following A-1 to A-15.

[0035]

[0036]

[0037] In the above A-1 to A-15, * is a bonding site with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2.

[0038] And, preferably, the above Chemical Formula 2 is represented by the following B-1 to B-15.

[0039]

[0040] In the above B-1 to B-15, * is a bonding site with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2.

[0041] Preferably, the benzoxazole copolymer is made of diamine monomers; diacyl chloride monomers; dianhydride monomers; and anhydride monomers.

[0042] Preferably, the diamine comprises one or more monomers selected from the group consisting of 4,4-methylenebis(2-aminophenol), 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-bis(3-amino-4-hydroxyphenyl)pentane, 4,4-bis(3-amino-4-hydroxyphenyl)heptane, 5,5-bis(3-amino-4-hydroxyphenyl)nonane, 6,6-bis(3-amino-4-hydroxyphenyl)dodecane, 7,7-bis(3-amino-4-hydroxyphenyl)pentane, (3-amino-4-hydroxyphenyl) tridecane, 4,4'-biphenylcyclohexane [2-aminophenol] 4,4'-(1,3-dimethylbutyl) bis [2-aminophenol], 4,4'-oxybis [2-aminophenol], 4,4'-thiol bis [2-aminophenol], bis (3-amino-4-hydroxyphenyl) sulfone, 4,4'-(bis (trimethylsilyl) methylene) bis (2-aminophenol), 4-hydroxy-N-(4-hydroxy-3λ 3 -phenyl)3-λ 3 Benzamide, 4,4-diaminodiphenylmethane, 4,4'-(1-methyleneethyl)bis[aniline], 4,4'-(1-ethylpropyl)bis[aniline], 4,4'-(1-propylbutyl)bis[aniline], 4,4'-(1-butylpentyl)bis[aniline], 4,4'-(1-pentylhexyl)bis[aniline], 4,4'-(hexylheptyl)bis[aniline], 4 ,4'-biphenylcyclohexane[aniline], 4,4'-(1,3-dimethylbutyl)bis[aniline], 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-sulfonyldiphenylamine, 4,4'-(bis(trimethylsilyl)methylene)diphenylamine, 4-amino-N-(4-aminophenol)benzamide, 4-aminophenol 4-aminobenzoate and combinations thereof.

[0043] Preferably, the diacyl chloride comprises one or more monomers selected from the group consisting of 4,4'-oxybisbenzoyl chloride, 1,2-dichlorocyclobutane dicarboxylic acid, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyl dicarboxylic acid chloride, 1,4-naphthalene dicarboxylic acid chloride, 4,4'-sulfonyl dibenzoyl chloride, 1,4-cyclohexane dicarboxylic acid dichloride, and combinations thereof.

[0044] Preferably, the dianhydride comprises one or more monomers selected from the group consisting of 4,4-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3'4'-biphenyl tetracarboxylic acid dianhydride, bicyclo[2,2,2]octa-7-yn-2,3,5,6-tetracarboxylic acid dianhydride, 4,4'-(hexafluoro isopropylidine) diphthalic anhydride, anhydride), bicyclo[2,2,2]octane-2,3,5,6-tetracarboxyl dianhydride, benzophenone tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, dicyclohexyl tetracarboxylic acid dianhydride dianhydride), 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, bicyclo octane tetracarboxyl dianhydride, and combinations thereof.

[0045] Preferably, the anhydride 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, succinic anhydride, and combinations thereof.

[0046] Preferably, the weight average molecular weight of the copolymer is 5,000 to 40,000 g / mol.

[0047] In another specific example of the present invention, preferably, the positive photosensitive composition of the present invention comprises the benzoxazole copolymer; a photosensitizer; a solvent; and an additive.

[0048] Preferably, the photosensitizer comprises one or more of the following chemical formulas P-1 to P-8.

[0049]

[0050]

[0051] In P-1 to P-8 above,

[0052] R" are each independently hydrogen; the following chemical formula S-1; or chemical formula S-2.

[0053] <Chemical Formula S-1>

[0054]

[0055] <Chemical Formula S-2>

[0056]

[0057] Preferably, the solvent comprises one or more selected from the group consisting of: N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, γ-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and combinations thereof.

[0058] Preferably, the additive comprises at least one selected from the group consisting of: a silane coupling agent; a surface smoothing agent; a surfactant; a cross-linking agent; and combinations thereof.

[0059] Preferably, the content of the benzoxazole-based copolymer is 5 to 50 wt % based on the total amount of the composition.

[0060] Preferably, the content of the photosensitizer is 1 to 50 wt % based on the total amount of the composition.

[0061] Preferably, the content of the solvent is 50 to 95 wt % based on the total amount of the composition.

[0062] Preferably, the content of the additive is 0.001 to 10 wt % based on the total amount of the composition.

[0063] In another specific example of the present invention, preferably, a pattern or film made of the positive photosensitive composition is provided.

[0064] In another specific example of the present invention, preferably, a semiconductor device or a display device manufactured using the pattern or film is provided.

[0065] In another specific example of the present invention, preferably, there is provided an electronic device including the semiconductor device or the display device and a control unit for driving the semiconductor device or the display device.

[0066] Effects of the Invention

[0067] According to the present invention, a halogen-free monomer is introduced into the components of polybenzoxazole-based and polyimide-based precursors and copolymer resins to provide a photosensitive composition containing no halogen compounds, and the composition is applied to the preparation of display devices or semiconductor devices using the same. DETAILED DESCRIPTION

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.).

[0074] 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.

[0075] Unless otherwise described, the term "halo" or "halogen" used in the present application includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0076] 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.

[0077] Unless otherwise described, the term "haloalkyl group" or "halogenalkyl group" used in the present application refers to an alkyl group substituted with halogen.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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 fluorenylene 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, fluorenyl group, fluorenylene group and fluorene-triyl group may be named as fluorenyl group without considering the equivalent number of monovalent, divalent and trivalent.

[0088]

[0089] 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.

[0090] 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.

[0091] 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.

[0092]

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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 recorded by classifying the valence of the 'group', 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102]

[0103] 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.

[0104]

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] According to an implementation example of the present invention, a positive photosensitive composition comprising polybenzoxazole-based and polyimide-based precursors and copolymers can be used for the preparation of insulating films, surface protection films, and rewiring layers of semiconductor devices and pixel definition layers (PDL) of display devices.

[0110] According to an implementation example of the present invention, when preparing a positive 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.

[0111] 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.

[0112] The components constituting the positive-type photosensitive composition are as follows.

[0113] (1) Polybenzoxazole and polyimide precursors and copolymer resins

[0114] According to an embodiment of the present invention, the pattern forming resin may include polybenzoxazole-based and polyimide-based precursors and copolymer resins.

[0115] The polybenzoxazole and polyimide precursors and copolymer resins refer to resins containing the following components: hydroxyamide copolymers that become polybenzoxazole copolymers through chemical or thermal treatment and polybenzoxazole copolymers that have been chemically or thermally treated; amic acid copolymers that can become polyimide copolymers and polyimide copolymers that have been chemically or thermally treated.

[0116] In the total amount of the positive photosensitive composition, the content of the polybenzoxazole-based and polyimide-based precursors and copolymer resin is 5 wt % to 50 wt %, preferably, 10 wt % to 40 wt %.

[0117] The polybenzoxazole and polyimide precursors and copolymer resins include copolymers represented by the following chemical formula 1-1 or chemical formula 1-2, but are not limited thereto. They can also be used alone or in combination of two or more. The weight average molecular weight of the polybenzoxazole and polyimide precursors and copolymer resins can be 5,000 g / mol to 40,000 g / mol, preferably 5,000 g / mol to 35,000 g / mol, and more preferably 7,000 g / mol to 25,000 g / mol.

[0118] Preferably, the benzoxazole-based copolymer includes: a repeating unit selected from the group consisting of the following Chemical Formula 1-1, Chemical Formula 1-2, and a combination thereof.

[0119] <Chemical Formula 1-1>

[0120]

[0121] <Chemical Formula 1-2>

[0122]

[0123] In the above chemical formula 1-1 and chemical formula 1-2,

[0124] 1)* is the connected part bonded by repeating unit,

[0125] 2) X is the following chemical formula 2,

[0126] <Chemical Formula 2>

[0127]

[0128] 3) R 1 To R 10Two of them are connecting sites with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2,

[0129] 4) The remaining R except the connecting part 1 To R 10 Independently selected from the group consisting of the following components: 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; C1~C 20 an alkoxy carbonyl group; and combinations thereof,

[0130] 5) L 1 Selected from the group consisting of: single bond; C6~C 30 an arylene 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 20 Alkylene group; C3~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C20 Alkinylene group; C3~C 20 Cyclo alkinylene group; –O-, –S-, –SO2-, Si(CH3)2-, –C(SiCH3)2-C6H4-, –CO-, –NHCO-, –COO-,

[0131] 6) L 1 When it is a single bond, the adjacent R1 and R 10 ; can form a ring with R5 and R6,

[0132] 7) Y and Z are independently selected from the group consisting of the following components: C6 to C 30 an arylene 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 20 Alkylene group; C3~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20 A cycloalkinylene group; and combinations thereof,

[0133] 8) Y or Z independently may further replace one or more carboxylic acid groups; or have C1~C 20 The terminal ester group,

[0134] 9) m or n is an integer greater than 1,

[0135] 10) The polymer terminal is bonded to one selected from the following chemical formulas Q-1 to Q-10,

[0136] <Chemical formulas Q1 to Q10>

[0137]

[0138] Preferably, the above Chemical Formula 2 is represented by the following A-1 to A-15.

[0139]

[0140]

[0141] In the above A-1 to A-15, * is a bonding site with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2.

[0142] And, preferably, the above Chemical Formula 2 is represented by the following B-1 to B-15.

[0143]

[0144] In the above B-1 to B-15, * is a bonding site with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2.

[0145] The weight average molecular weight of the polybenzoxazole and polyimide precursors and copolymer resins can be 5,000 to 40,000 g / mol, preferably 5,000 to 30,000 g / mol, and more preferably 7,000 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 photosensitive composition, the content of the resin 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.

[0146] (2) Photosensitizer

[0147] In order to present a negative pattern through a photolithography machine, a photo-radical initiator is required. To this end, the photosensitizer is selected with a reasonable structure according to the wavelength used, such as g-line (436nm), h-line (405nm), i-line (365nm), Deep UV (<260nm), etc., and is used separately or in combination.

[0148] The photosensitizer is a photosensitizer commonly used in positive photosensitive compositions, for example, a photosensitive diazoquinone compound, specifically, a phenol compound and a sulfonyl-based photosensitive compound represented by the following chemical formulas P-1 to P-8. Specific examples of R" include: compounds containing hydrogen, deuterium, 1,2-naphthoquinone-2-azido-5-sulfonic acid or 1,2-naphthoquinone-2-azido-4-sulfonic acid in the structure.

[0149]

[0150]

[0151] In P-1 to P-8 above,

[0152] R" are each independently hydrogen; the following chemical formula S-1; or chemical formula S-2.

[0153] <Chemical Formula S-1>

[0154]

[0155] <Chemical Formula S-2>

[0156]

[0157] In the above chemical formula S-1 and chemical formula S-2, * represents a connecting site.

[0158] Preferably, the content of the photosensitizer is 1 to 50 wt % based on the total amount of the composition.

[0159] (3) Solvent

[0160] The solvent may be a substance that is compatible with and does not react with the benzoxazole copolymer resin, the photosensitizer, and the pigment.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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 above range, the positive photosensitive composition can have an appropriate viscosity, thereby achieving excellent processability when preparing a pattern layer.

[0165] (4) Other additives

[0166] 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 positive photosensitive resin 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 cross-linking agent.

[0167] For example, in order to improve adhesion to a substrate, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group.

[0168] 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.

[0169] The weight part of the silane coupling agent may be 0.01 parts by weight to 10 parts by weight in 100 parts by weight of the photosensitive resin composition. When the weight part of the silane coupling agent is within the above range, the adhesion and storage properties are excellent.

[0170] Furthermore, the photosensitive resin 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.

[0171] The surface leveler can be the following commercially available surface levelers: etc.; BASF FL3740, same model FL3741, same model FL3745, same model FL3770, etc.

[0172] The weight of the surface leveler can be 0.001 to 5 parts by weight in 100 parts by weight of the photosensitive resin 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.

[0173] Furthermore, the photosensitive resin composition may further include a surfactant as required to achieve the effects of improving coating properties and preventing defects from occurring.

[0174] The surfactant can be the following surfactants available on the market: etc.; Dainippon Ink & Chemicals Co., Ltd.'s Mecha Pack F Same model F Same model F Same model F 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 Same style Same style wait.

[0175] The weight of the surfactant can be 0.001 to 5 parts by weight in 100 parts by weight of the photosensitive resin 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.

[0176] The crosslinking agent may be 1,4-bis(methoxymethyl)benzene, diethyl sulfate, 3-aminopropyltriethoxysilane, N,N'-methylenebisacrylamide, etc., which may be used alone or in combination of two or more.

[0177] The weight of the crosslinking agent can be 0.001 to 5 parts by weight in 100 parts by weight of the photosensitive resin 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.

[0178] Furthermore, within the range of not damaging the physical properties, the photosensitive resin composition may be added with a certain amount of other additives. In the total amount of the composition, preferably, the content of the additives is 0.001 to 10 wt %.

[0179] 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.

[0180] (Synthesis example 1)

[0181] A 250ml 3-neck round-bottom flask is equipped with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler. Then, nitrogen is filled in, methyl pyrrolidinone (NMP) 79.2g is filled in, and then 4,4'-biphenylcyclohexane [2-aminophenol] 15g and pyridine (pyridine) 3.67g are added and stirred, and maintained at 40°C. Among them, 1.12g of phthalic anhydride is slowly added, and then stirred for a certain period of time to dissolve and react. Then, 110.742g of NMP is added to the reaction flask, and then the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 4,4' is slowly added.

[0182] 13.72 g of -oxybisbenzoyl chloride was added and stirred for 12 hours to allow it to dissolve and react.

[0183] The polyhydroxyamide solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 26.86 g of copolymer polyhydroxyamide powder.

[0184] (Synthesis example 2)

[0185] A 250ml 3-neck round-bottom flask is attached with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, methyl pyrrolidinone (NMP) 79.2g is filled, and then 4,4'-biphenylcyclohexane [aniline] 15g and pyridine (pyridine) 3.68g are added and stirred, and maintained at 40°C. Among them, 1.12g of phthalic anhydride is slowly added, and then stirred for a certain time to dissolve and react. Then, 80.67g of NMP is added to the flask in the reaction, and then the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 8.417g of 1,2-dichlorocyclobutane dicarboxylic acid is slowly added and stirred for 12 hours to dissolve and react.

[0186] The polyamic acid solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 22.08 g of copolymer polyamic acid powder.

[0187] (Synthesis example 3)

[0188] A 250ml 3-mouth round-bottom flask is attached with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, methyl pyrrolidinone (NMP) 79.2g is filled, and then 2,2-bis (3-amino-4-hydroxyphenyl) propane 15g and pyridine 3.68g are added for stirring and maintained at 40°C. Among them, 1.12g of phthalic anhydride is slowly added, and then stirred for a certain time to dissolve and react. Then, 88.06g of NMP is added to the flask in the reaction, and then the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 9.72g of 1,4-cyclohexanedicarboxylic acid dichloride is slowly added and stirred for 12 hours to dissolve and react.

[0189] The polyhydroxyamide solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 23.25 g of copolymer polyhydroxyamide powder.

[0190] (Synthesis Example 4)

[0191] A 250 ml 3-neck round bottom flask is attached with a stirrer, a nitrogen gas inlet, a dropping funnel, a thermostat and a cooler, and then filled with nitrogen, filled with methyl pyrrolidinone (NMP) 79.18g, then added with 4,4'-(1-methyleneethyl)bis[aniline] 15g and pyridine 2.48g, stirred, and maintained at 40°C. Among them, 5-norbornene-2,3-dicarboxylic anhydride 0.75g is slowly added, and then stirred for a certain period of time to dissolve and react. Then, NMP 90.80g is added to the flask in the reaction, and then the solution is stirred for 30 minutes while the temperature is maintained at 5°C. Then, 8.67 g of 1,4-cyclohexanedicarboxylic acid dichloride and 1.15 g of bicyclo[2,2,2]octa-7-yn-2,3,5,6-tetracarboxylic acid dianhydride were slowly added, and the mixture was stirred for 12 hours to allow dissolution and reaction to proceed.

[0192] The polyamic acid solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 20.75 g of copolymer polyamic acid powder.

[0193] (Synthesis Example 5)

[0194] A 250 ml 3-neck round bottom flask is attached with a stirrer, a nitrogen gas inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, methyl pyrrolidinone (NMP) 79.18g is filled, and then 4,4'-(bis(trimethylsilyl)methylene)bis(2-aminophenol) 15g and pyridine (pyridine) 3.68g are added and stirred, and maintained at 40°C. Among them, 5-norbornene-2,3-dicarboxylic anhydride 1.41g is slowly added, and then stirred for a certain time to dissolve and react. Then, NMP 89.72g is added to the flask in the reaction, and then the temperature of the solution is kept at 5°C and stirred for 30 minutes. Then, 7.70 g of 1,4-cyclohexanedicarboxylic acid dichloride and 2.31 g of bicyclo[2,2,2]octa-7-yn-2,3,5,6-tetracarboxylic acid dianhydride were slowly added, and the mixture was stirred for 12 hours to allow dissolution and reaction to proceed.

[0195] The polyhydroxyamide solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 20.90 g of copolymer polyhydroxyamide powder.

[0196] (Synthesis Example 6)

[0197] A 250 ml 3-neck round bottom flask was attached with a stirrer, a nitrogen gas inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen was filled in, methyl pyrrolidinone (NMP) 79.18 g was added, and then 4,4'-sulfonyl diphenylamine 15 g and pyridine 2.94 g were added and stirred, and the temperature was maintained at 40°C. Among them, 0.72 g of dicyclo [2.2.2] octa-5-yn-2,3-dicarboxylic anhydride was slowly added, and then stirred for a certain period of time to dissolve and react. Then, 84.5 g of NMP was added to the flask in the reaction, and then the solution was stirred for 30 minutes while the temperature was maintained at 5°C. Then, 9.46 g of bicyclo[2,2,2]octa-7-yn-2,3,5,6-tetracarboxylic acid dianhydride was slowly added, and the mixture was stirred for 12 hours to allow dissolution and reaction to proceed.

[0198] The polyamic acid solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 21.05 g of copolymer polyamic acid powder.

[0199] (Synthesis Example 7)

[0200] A 250ml 3-mouth round-bottom flask is attached with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, methyl pyrrolidinone (NMP) 79.18g is filled, and then 4,4-bis (3-amino-4-hydroxyphenyl) heptane 15g and pyridine 3.18g are added for stirring and maintained at 40°C. Among them, 1.44g of maleic anhydride is slowly added, and then stirred for a certain time to dissolve and react. Then, 92.48g of NMP is added to the flask in the reaction, and then the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 10.48g of 1,4-cyclohexanedicarboxylic acid dichloride is slowly added and stirred for 12 hours to dissolve and react.

[0201] The polyhydroxyamide solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 19.41 g of copolymer polyhydroxyamide powder.

[0202] (Synthesis Example 8)

[0203] A 250ml 3-mouth round-bottom flask is attached with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen is charged, methyl pyrrolidinone (NMP) 79.18g is filled, and then 4-amino-N-(4-aminophenol) benzamide cinnamylamine 15g and pyridine 2.87g are added for stirring and maintained at 40°C. Among them, 1.48g of maleic anhydride is slowly added, and then stirred for a certain period of time to dissolve and react. Then, 91.42g of NMP is added to the flask in the reaction, and then the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 10.62 g of bicyclo[2,2,2]octa-7-yn-2,3,5,6-tetracarboxylic acid dianhydride was slowly added, and the mixture was stirred for 12 hours to allow dissolution and reaction to proceed.

[0204] The polyamic acid solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 22.15 g of copolymer polyamic acid powder.

[0205] (Synthesis Example 9)

[0206] A 250 ml 3-necked round-bottom flask is provided with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler. Then, nitrogen is introduced, and 79.18 g of methyl pyrrolidinone (NMP) is added. Then, 15 g of bis(3-amino-4-hydroxyphenyl)sulfone and 4.84 g of pyridine are added, stirred and maintained at 40°C. 2.84 g of dicyclo[2.2.2]octa-5-yn-2,3-dicarboxylic anhydride is slowly added, and then stirred for a certain period of time to dissolve and react. Then, 91.58 g of NMP is added to the reacting flask, and then, the solution is stirred for 30 minutes while the temperature is maintained at 5°C. Then, slowly add

[0207] 13.93 g of bicyclo[2,2,2]octa-7-yn-2,3,5,6-tetracarboxylic acid dianhydride was added and stirred for 12 hours to allow dissolution and reaction to proceed.

[0208] The polyhydroxyamide solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 23.82 g of copolymer polyhydroxyamide powder.

[0209] (Synthesis Example 10)

[0210] A 250 ml 3-neck round bottom flask is attached with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, methyl pyrrolidinone (NMP) 79.18g is added, and then 4,4'-diaminodiphenyl sulfide 15g and pyridine 4.12g are added and stirred, and maintained at 40°C. Among them, dicyclo [2.2.2] octa-5-yn-2,3-dicarboxylic anhydride 3.84g is slowly added, and then stirred for a certain time to dissolve and react. Then, NMP 95.62g is added to the flask in the reaction, and then the solution temperature is kept at 5°C and stirred for 30 minutes. Then, 9.98 g of 4,4′-benzophenone tetracarboxylic acid dianhydride was slowly added and stirred for 12 hours to allow the mixture to dissolve and react.

[0211] The polyamic acid solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 21.05 g of copolymer polyamic acid powder.

[0212] (Synthesis Example 11)

[0213] A 250ml 3-mouth round-bottom flask is attached with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, methyl pyrrolidinone (NMP) 79.18g is filled, and then 4,4'-oxybis[2-aminophenol] 15g and pyridine (pyridine) 3.66g are added for stirring and maintained at 40°C. Among them, 1.12g of phthalic anhydride is slowly added, and then stirred for a certain time to dissolve and react. Then, 87.52g of NMP is added to the flask in the reaction, and then the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 13.25g of 1,4-cyclohexanedicarboxylic acid dichloride is slowly added and stirred for 12 hours to dissolve and react.

[0214] The polyhydroxyamide solution was stirred at room temperature for one hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 20.11 g of copolymer polyhydroxyamide powder.

[0215] (Synthesis Example 12)

[0216] A 250ml 3-mouth round-bottom flask is attached with a stirrer, a nitrogen inlet, a dropping funnel, a thermostat and a cooler, and then nitrogen is filled, methyl pyrrolidinone (NMP) 65.7g is filled, and then 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 15g and pyridine (pyridine) 0.52g are added for stirring and maintained at 40°C. Among them, 0.910g of phthalic anhydride is slowly added, and then stirred for a certain time to dissolve and react. Then, 52.70g of NMP is added to the flask in the reaction, and then the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 11.18g of 4,4'-oxybisbenzoyl chloride is slowly added and stirred for 12 hours to dissolve and react.

[0217] The polyhydroxyamide solution was stirred at room temperature for one hour, and then precipitated with 1506 g of methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 21.13 g of copolymer polyhydroxyamide powder.

[0218] (Preparation Example 1) Preparation of positive photosensitive composition

[0219] 14.881 g of the benzoxazole copolymer resin obtained in Synthesis Examples 1 to 7, 32.232 g of MIPHOTO TPD52 (Mihara Trading Co., Ltd.), 0.004 g of F-563 (DIC Corporation), 0.223 g of KBM-573 (Shinetsu Silicon Corporation), 0.149 g of 1,4-bis(methoxymethyl)benzene, and 32.5 g of γ-butyrolactone were stirred at room temperature for 12 hours. Then, the composition was filtered three times to remove impurities to prepare a photosensitive composition.

[0220] The photosensitive composition solution was prepared using the components in Table 1 below.

[0221]

Table 1

[0222]

[0223]

[0224] The process of forming a cured film on a silicon wafer using the positive photosensitive composition is as follows.

[0225] (1) Coating and coating steps

[0226] On a cleaned 200 mm silicon wafer, the photosensitive composition prepared in the embodiment or comparative example is coated at a constant thickness using a spin coater, and then a portion of the solvent is removed using a vacuum chamber dry (VCD) to form a coating film. The thickness of the coating of the photosensitive composition formed by VCD is 5 μm to 10 μm.

[0227] (2) Pre-baking step

[0228] The obtained coating film is heated at 100° C. to 140° C. for 50 to 200 seconds on a hot plate to remove the solvent contained in the obtained coating film. This process removes a certain amount of solvent, so that a coating film of constant thickness can be obtained in the development step after the next process (exposure).

[0229] (3) Exposure Step

[0230] In order to obtain the required constant thickness of the coating film obtained above, 190nm to 600nm actinic rays are irradiated by an exposure machine. Preferably, a metal or LED light source with ghi-line can be irradiated to form a pattern. The exposure amount of the irradiation is 50 to 500mJ / cm 2 The pattern formed is a negative type of Hole and Line and Space pattern of different sizes in μm.

[0231] (4) Development step

[0232] After the exposure step, a certain amount of TMAH (tetramethylhydroxyammonium) 2.38wt% developer solution is taken to immerse the substrate at 23±2°C by a puddle method, and then development is performed after a certain time (minutes). After development, the substrate is rinsed with deionized water (DI water) to dissolve and remove the exposed part, leaving only the non-exposed part to form an image pattern. The thickness of the residual coating is 4.0 to 9.0μm.

[0233] (5) Post-baking step

[0234] In order to obtain the image pattern obtained by the development, post baking is performed in an oven at 300 to 320° C. for 30 to 120 minutes, and then the obtained coating film is cured.

[0235] (6) FE-SEM testing

[0236] On the substrate after the post-bake process, a sample was taken without damaging the pattern, and the hole and line and space patterns were observed using a scanning electron microscope JSM-IT800 of JEOL.

[0237]

Table 2

[0238] <![CDATA[Residue after development * > Hole pattern accuracy (10μm) Resolution(μm) Example 1 X 9.9576 3 Example 2 X 9.9742 3 Example 3 X 9.9365 2 Example 4 X 9.9554 3 Example 5 X 9.9778 3 Example 6 X 10.0325 2 Example 7 X 9.9485 3 Example 8 X 9.9352 2 Example 9 X 9.9482 3 Example 10 X 9.9768 3 Embodiment 11 X 9.9876 3 Comparative Example 1 △ 9.9334 3

[0239] *: X has five residues, △ has some residues, ○ has a lot of residues

[0240] After the development process and post-baking treatment described in Table 2 above were performed, the Hole and Line and Space patterns were observed using a scanning electron microscope. It was confirmed that no residue remained after development in Examples 1 to 11. In contrast, it was confirmed that a small amount of residue remained at the bottom of the Hole pattern in Comparative Example 1.

[0241] Furthermore, the realization of the 10 μm hole pattern was observed to confirm the accuracy of the hole realization. As a result, Examples 1 to 11 and Comparative Example 1 all realized the pattern accurately within a deviation of 0.1 μm. It was confirmed that the minimum resolution achieved by Examples 1 to 11 and Comparative Example 1 was 2 to 3 μm.

[0242] According to the test results of the present invention, it is confirmed that when a polyimide-based precursor and a polybenzoxazole-based precursor that do not contain fluorine are used, performance similar to that of existing fluorine-based materials can be exhibited, and the residue after development also exhibits more excellent technical effects.

[0243] The present invention is not limited to the above embodiments, but can be prepared in a variety of different forms.

[0244] 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.

[0245] 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 benzoxazole copolymer, characterized in that: The benzoxazole copolymer comprises: 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 the connected part bonded by repeating unit, 2) X is the following chemical formula 2, <Chemical Formula 2> 3) R 1 To R 10 Two of them are connecting sites with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2, 4) The remaining R except the connecting part 1 To R 10 Independently selected from the group consisting of the following components: 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; C1~C 20 an alkoxy carbonyl group; and combinations thereof, 5) L 1 Selected from the group consisting of: single bond; C6~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; C3~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; –O-, –S-, –SO2-, Si(CH3)2-, –C(SiCH3)2-C6H4-, –CO-, –NHCO-, –COO-, 6) L 1 When it is a single bond, the adjacent R1 and R 10 ; can form a ring with R5 and R6, 7) Y and Z are independently selected from the group consisting of the following components: 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; C3~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkinylene group; C3~C 20 cycloalkinylene group; and combinations thereof, 8) Y or Z independently may further replace one or more carboxylic acid groups; or have C1~C 20 The terminal ester group, 9) m or n is an integer greater than 1, 10) The polymer terminal is bonded to one selected from the following chemical formulas Q-1 to Q-10, <Chemical formulas Q1 to Q10> 2. The benzoxazole copolymer according to claim 1, characterized in that: The chemical formula 2 represents the following A-1 to A-15, In A-1 to A-15, * is a connecting portion with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2.

3. The imide copolymer according to claim 1, characterized in that: The chemical formula 2 is represented by the following B-1 to B-15, In B-1 to B-15, * is the connecting site with the amide group shown in Chemical Formula 1-1 or Chemical Formula 1-2.

4. The benzoxazole copolymer according to claim 1, characterized in that: The copolymer is prepared from diamine monomers, diacyl chloride monomers, dianhydride monomers, and anhydride monomers.

5. The benzoxazole copolymer according to claim 4, characterized in that: The diamine comprises one or more monomers selected from the group consisting of: 4,4-methylenebis(2-aminophenol), 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-bis(3-amino-4-hydroxyphenyl)pentane, 4,4-bis(3-amino-4-hydroxyphenyl)heptane, 5,5-bis(3-amino-4-hydroxyphenyl)nonane, 6,6-bis(3-amino-4-hydroxyphenyl)dodecane, 7,7-bis(3-amino-4-hydroxyphenyl)tridecane, 4,4'-biphenylcyclohexane[2-aminophenol]4,4'-(1,3-dimethylbutyl)bis[2-aminophenol], 4,4'-oxybis[2-aminophenol], 4,4'-thiolbis[2-aminophenol], bis(3-amino-4-hydroxyphenyl)sulfone, 4,4'-(bis(trimethylsilyl)methylene)bis(2-aminophenol), 4-hydroxy-N-(4-hydroxy-3λ 3 -phenyl)3-λ 3 Benzamide, 4,4-diaminodiphenylmethane, 4,4'-(1-methyleneethyl)bis[aniline], 4,4'-(1-ethylpropyl)bis[aniline], 4,4'-(1-propylbutyl)bis[aniline], 4,4'-(1-butylpentyl)bis[aniline], 4,4'-(1-pentylhexyl)bis[aniline], 4,4'-(hexylheptyl)bis[aniline], 4 ,4'-biphenylcyclohexane[aniline], 4,4'-(1,3-dimethylbutyl)bis[aniline], 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-sulfonyldiphenylamine, 4,4'-(bis(trimethylsilyl)methylene)diphenylamine, 4-amino-N-(4-aminophenol)benzamide, 4-aminophenol 4-aminobenzoate and combinations thereof.

6. The benzoxazole copolymer according to claim 4, characterized in that: The diacyl chloride comprises one or more monomers selected from the group consisting of 4,4'-oxybisbenzoyl chloride, 1,2-dichlorocyclobutane dicarboxylic acid, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyl dicarboxylic acid chloride, 1,4-naphthalene dicarboxylic acid chloride, 4,4'-sulfonyl dibenzoyl chloride, 1,4-cyclohexane dicarboxylic acid dichloride, and combinations thereof.

7. The benzoxazole copolymer according to claim 4, characterized in that: The dianhydride comprises one or more monomers selected from the group consisting of: 4,4-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride、2,3,3'4'-biphenyl tetracarboxylic acid dianhydride、 Bicyclo[2,2,2]octa-7-yn-2,3,5,6-tetracarboxylic acid dianhydride, 4,4' -(hexafluoroisopropylidene)diphthalic anhydride isoPropylidine)diphthalic anhydride), dicyclic [2,2,2]octane-2,3,5,6-tetracarboxyl dianhydride), 3,3',4,4'-benzophenone tetracarboxylicacid dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, Cyclobutane-1,2,3,4-tetracarboxylic aciddianhydride, Cyclohexane-1,2,4,5-tetracarboxylic aciddianhydride, dicyclohexyl tetracarboxylic aciddianhydride, 1,4,5,8-naphthalene tetracarboxylic aciddianhydride, and combinations thereof.

8. The polymer according to claim 4, characterized in that: The anhydride comprises one or more monomers selected from the group consisting of dicyclo[2.2.2]octa-5-yn-2,3-dicarboxylic anhydride. anhydride), 5-norbornene-2,3-dicarboxylic anhydride (5-norbornene-2,3-dicarboxylic anhydride), maleic anhydride, phthalic anhydride, succinic anhydride or a combination thereof.

9. The benzoxazole copolymer according to claim 1, characterized in that: The weight average molecular weight of the copolymer is 5,000 to 40,000 g / mol.

10. A positive photosensitive composition comprising the benzoxazole copolymer according to claim 1; a photosensitizer; a solvent; and an additive.

11. The positive photosensitive composition according to claim 10, characterized in that: The photosensitizer comprises one or more of the following chemical formulas P-1 to P-8: In P-1 to P-8 above, R" are each independently hydrogen; the following chemical formula S-1; or chemical formula S-2, <Chemical Formula S-1> <Chemical Formula S-2> 12. The positive photosensitive composition according to claim 10, characterized in that: The solvent comprises one or more selected from the group consisting of N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, γ-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and combinations thereof.

13. The positive photosensitive composition according to claim 10, characterized in that: The additive includes at least one selected from the group consisting of the following components: a silane coupling agent; a surface smoothing agent; a surfactant; a crosslinking agent; and combinations thereof.

14. The positive photosensitive composition according to claim 10, characterized in that: The benzoxazole-based copolymer is present in an amount of 5 to 50% by weight based on the total amount of the composition.

15. The positive photosensitive composition according to claim 10, characterized in that: The content of the photosensitizer is 1 to 50% by weight in the total amount of the composition.

16. The positive photosensitive composition according to claim 10, characterized in that: The content of the solvent is 50 to 95% by weight in the total amount of the composition.

17. The positive photosensitive composition according to claim 10, characterized in that: The additive is contained in an amount of 0.001 to 10% by weight in the total amount of the composition.

18. A pattern or film made from the positive photosensitive composition according to claim 10.

19. A semiconductor device manufactured using the pattern or film according to claim 18.

20. A display device manufactured using the pattern or film according to claim 18.

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