Polybenzoxazol or polyimide precursor or copolymer thereof, and positive photosensitive composition including the same

Abstract

To provide a photosensitive composition using a polyimide precursor and a benzoxazol precursor copolymer resin that does not contain fluorine.SOLUTION: It is preferable to include a repeating unit selected from the group consisting of the following formula 1-1, formula 1-2, and combinations thereof, where X is represented by the following formula 2.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polybenzoxazole-based or polyimide-based precursor, a copolymer thereof, and a positive-type photosensitive composition used in a semiconductor device or display device manufactured using the same. [Background technology]

[0002] The photolithography process is roughly divided into a coating step in which a photoresist composition is applied to a substrate, an exposure step in which a pattern is formed on the photoresist film using a light source, such as an E-beam, passing through a mask, and a development step in which specific regions of the photoresist film with the engraved pattern are removed. A baking step is added between each step to remove a solvent from the photoresist composition or to harden the film.

[0003] The photolithography process is broadly divided into negative and positive processes. In the positive process, the exposed area reacts with the developer in the development step, and the reaction product is dissolved and removed, while in the negative process, the unexposed area reacts with the developer in the development step, and the reaction product is dissolved and removed. Among them, the positive process uses a photoactive compound that absorbs light and increases its solubility in the exposure step, allowing only the exposed area to be accurately removed in the development step, resulting in a more precise and accurate pattern than the negative process.

[0004] Conventionally, as a positive-type photosensitive resin composition used in a semiconductor device or a display device, a resin such as polyimide or polybenzoxazole is used due to its high heat resistance, chemical resistance, weather resistance, etc. However, as research is being conducted on the environmental pollution and human toxicity of halogenated compounds, which are mainly used as materials, there is an increasing demand for new materials to replace halogenated compounds. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2010-0080344 Summary of the Invention [Problem to be solved by the invention]

[0006] In order to solve the problems of the prior art, the present invention provides a polybenzoxazole-based or polyimide-based precursor and a copolymer synthesized by introducing a monomer that does not contain a halogen element into a component of the copolymer resin.

[0007] The present invention also provides a positive-type photosensitive composition using the polybenzoxazole-based and polyimide precursors and copolymer resins.

[0008] The present invention also provides a pattern or film formed from the positive photosensitive composition, and a semiconductor device or display device manufactured using the same. [Means for solving the problem]

[0009] The benzoxazole-based or polyimide-based precursor and copolymer according to the present invention preferably contains a repeating unit selected from the group consisting of the following formula 1-1, formula 1-2, and combinations thereof.

[0010] [ka]

[0011] In the above Chemical Formula 1-1 and Chemical Formula 1-2, 1) * is the part where the bond is connected in the repeat unit, 2) X is represented by the following chemical formula 2:

[0012] [ka]

[0013] 3) R1 or R 10 Two of them are linking sites with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2, 4) The remaining R1 to R excluding the linking portion 10 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 aryl groups of C2-C containing at least one heteroatom of O, N, S, Si and P; 30 Heterocyclic groups; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 20 Alkoxy group; C6-C 30 Aryloxy group; Fluorenyl group; Carbonyl group; Ether group; Carboxyl group; C1-C 20 and combinations thereof; 5) Said L 1 is a single bond, C6~C 30 an arylene group of C2-C containing at least one heteroatom of O, N, S, Si, or P; 30 Heterocyclic groups; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group; C3-C 20 Cycloalkylene group; C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group selected from the group consisting of -O-, -S-, -SO2-, Si(CH3)2-, -C(SiCH3)2, -C6H4-, -CO-, -NHCO-, -COO-, 6) L 1 is a single bond, the adjacent R and R 10 and R5 and R6 can form a ring; 7) Y and Z are independently selected from the group consisting of C6 to C 30an arylene group of C2-C containing at least one heteroatom of O, N, S, Si, or P; 30 Heterocyclic groups; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group; C3-C 20 Cycloalkylene group; C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 and combinations thereof; 8) Y or Z are, independently of each other, one or more carboxylic acid groups; or C1-C 20 The ester group having a terminal end of 9) m or n is an integer of 1 or more, 10) The polymer end is bonded with one selected from the following chemical formulas Q-1 to Q-10.

[0014] [ka]

[0015] The formula 2 is preferably represented by the following A-1 to A-15.

[0016] [ka]

[0017] In A-1 to A-15, * is a linking site with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2.

[0018] In addition, the formula 2 is preferably represented by the following B-1 to B-15.

[0019] [ka]

[0020] In B-1 to B-15, * is a linking site with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2.

[0021] The benzoxazole-based copolymer is preferably prepared from a diamine monomer; a diacyl chloride monomer; a dianhydride monomer; and an anhydride monomer.

[0022] The diamines include 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) Nyl)tridecane, 4,4'-cyclohexylidine bis[2-aminophenol], 4,4'-(1,3-dimethylbutylidine)bis[2-aminophenol], 4,4'-oxybis[2-aminophenol], 4,4'-thiobis[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 3Benzamide, 4,4-diaminodiphenylmethane, 4,4'-(1-methyleneethylidine)bis[benzenamine], 4,4'-(1-ethylpropylidine)bis[benzenamine], 4,4'-(1-propylbutylidine)bis[benzenamine], It is preferable that the monomer contains one or more monomers selected from the group consisting of 4,4'-(1-butylpentylidine)bis[benzenamine], 4,4'-(1-pentylhexylidine)bis[benzenamine], 4,4'-(1-hexylheptylidine)bis[benzenamine], 4,4'-cyclohexylidinebis[benzenamine], 4,4'-(1,3-dimethylbutylidine)bis[benzenamine], 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-sulfonyldianiline, 4,4'-(bis(trimethylsilyl)methylidyne)dianiline, 4-amino-N-(4-aminophenyl)benzoamide, 4-aminophenyl-4-aminobenzoate, and combinations thereof.

[0023] The diacyl chloride preferably contains one or more monomers selected from the group consisting of 4,4'-oxybisbenzoyl chloride, 1,2-cyclobutanedicarboxylic acid dichloride, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldicarbonyl chloride, 1,4-naphthalene dicarbonyl chloride, 4,4'-sulfonyldibenzoyl chloride, 1,4-cyclohexanedicarboxylic acid dichloride, and combinations thereof.

[0024] The dianhydride is 4,4-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidine)diphthalic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, 3,3',4,4'-benzyloxydianhydride, It is preferable that the monomer contains one or more monomers selected from the group consisting of benzophenone tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, dicyclohexyl-3,4,3'4'-tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, bicyclooctane tetracarboxylic dianhydride, and combinations thereof.

[0025] The anhydride preferably comprises one or more monomers selected from the group consisting of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 5-novone-2,3-dicarboxylic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, and combinations thereof.

[0026] The weight average molecular weight of the copolymer is preferably 5,000 to 40,000 g / mol.

[0027] In another embodiment of the present invention, a positive photosensitive composition according to the present invention preferably contains the benzoxazole copolymer; a photosensitizer; a solvent; and additives.

[0028] The photosensitizer preferably includes at least one of the following formulas P-1 to P-8.

[0029] [ka]

[0030] In the above P-1 to P-8, R″ is independently hydrogen; the following formula S-1; or the following formula S-2.

[0031] [ka]

[0032] The solvent is It is preferable that the carboxylic acid ester compound includes at least one selected from the group consisting of N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, gamma-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.

[0033] The additive preferably includes at least one selected from the group consisting of a silane coupling agent, a surface smoothing agent, a surfactant, a crosslinking agent, and combinations thereof.

[0034] The benzoxazole copolymer is preferably contained in an amount of 5 to 50% by weight based on the total weight of the composition.

[0035] The photosensitizer is preferably contained in an amount of 1 to 50% by weight based on the total weight of the composition.

[0036] The solvent is preferably contained in an amount of 50 to 95% by weight based on the total weight of the composition.

[0037] The additives are preferably contained in an amount of 0.001 to 10% by weight based on the total weight of the composition.

[0038] In another embodiment of the present invention, it is preferable to provide a pattern or film produced from the positive-working photosensitive composition.

[0039] As another embodiment of the present invention, it is preferable to provide a semiconductor device or a display device manufactured using the above pattern or film.

[0040] As another embodiment of the present invention, it is preferable to provide an electronic device including the semiconductor device or display device described above and a control unit for driving the same. Effect of the Invention

[0041] According to the present invention, a halogen-free monomer is introduced into polybenzoxazole-based and polyimide-based precursors and copolymer resin components to provide a photosensitive composition that does not contain halogen compounds, and the composition can be used to manufacture a display device or semiconductor device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] Hereinafter, some embodiments of the present invention will be described in detail with reference to the accompanying drawings. When reference numerals are used to designate components in each drawing, the same reference numerals are used to designate the same components even if they are displayed in different drawings.

[0043] In the description of the present invention, if it is determined that a specific description of related publicly known configurations or functions may make the gist of the present invention unclear, the detailed description may be omitted. When "comprises," "has," "consists of," and the like are used in this specification, other parts may be added as long as "only" is not used. When a component is expressed in the singular, it includes the plural unless otherwise expressly specified.

[0044] In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. are used to distinguish the components from other components, and the terms do not limit the nature, order, sequence, number, etc. of the components.

[0045] In describing the positional relationship of components, when two or more components are described as being "coupled," "coupled," or "connected," it should be understood that the two or more components may be directly "coupled," "coupled," or "connected," but that the two or more components may also be "coupled" or "connected" through further "intervening" components, where the other components may be included in one or more of the two or more components that are "coupled," "coupled," or "connected" to each other.

[0046] In addition, when a component such as a layer, film, region, or plate is described as being "on" or "on" another component, this should be understood to include not only the case where the component is "directly on" the other component, but also the case where there is another component in between. Conversely, when a component is described as being "directly on" another part, it should be understood to mean that there is no other part in between.

[0047] In describing a temporal sequence relating to components, methods of operation, methods of production, etc., when the temporal or flow sequence is described using, for example, "after," "following," "next to," or "before," this also includes cases where the sequence is not consecutive, unless "immediately" or "directly" is used.

[0048] On the other hand, when numerical values ​​or corresponding information for components are mentioned, even if there is no separate explicit description, the numerical values ​​or corresponding information can be interpreted as including an error range that may occur due to various factors (e.g., process factors, internal or external impacts, noise, etc.).

[0049] The terms used in this specification and the appended claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted as having a meaning and concept that is consistent with the technical idea of ​​the present invention based on the principle that an inventor can appropriately define the concept of a term in order to best describe his / her invention.

[0050] The term "halo" or "halogen" as used in this application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise stated.

[0051] The term "alkyl" or "alkyl group", as used in this application, unless otherwise specified, means the radical of a saturated aliphatic group having 1 to 60 carbons linked by a single bond, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups.

[0052] The term "haloalkyl group" or "haloalkyl group" as used herein means, unless otherwise specified, an alkyl group substituted with a halogen.

[0053] The terms "alkenyl" or "alkynyl" as used herein, unless otherwise specified, include groups having double or triple bonds, straight or branched chain groups, and having from 2 to 60 carbon atoms, but are not limited thereto.

[0054] The term "cycloalkyl" as used in this application, unless otherwise specified, means an alkyl group forming a ring having 3 to 60 carbon atoms, but is not limited thereto.

[0055] The term "alkoxy group" or "alkyloxy group" as used herein means an alkyl group having an oxygen radical attached thereto, and unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.

[0056] The terms "alkeneoxyl group," "alkenoxy group," "alkenyloxyl group," or "alkenyloxy group" as used in this application mean an alkenyl group having an oxygen radical attached thereto, and unless otherwise specified, has 2 to 60 carbon atoms, but is not limited to this.

[0057] The terms "aryl group" and "arylene group" used in this application each have 6 to 60 carbon atoms, unless otherwise specified, but are not limited thereto. In this application, the aryl group or arylene group includes a single ring, a ring assembly, a fused multiple ring system compound, etc. For example, the aryl group includes a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, and a substituted fluorenyl group, and the arylene group includes a fluorenylene group and a substituted fluorenylene group.

[0058] The term "ring assemblies" as used in this application means two or more ring systems (single ring or joined ring systems) directly linked to each other by single or double bonds, and the number of such direct connections between rings is one less than the total number of ring systems in the compound. Ring assemblies can be identical or different ring systems directly linked to each other by single or double bonds.

[0059] In the present application, the aryl group includes ring assemblies, and therefore includes biphenyl and terphenyl in which a single aromatic ring, a benzene ring, is connected by a single bond. The aryl group also includes compounds in which an aromatic ring system connected to a single aromatic ring is connected by a single bond, and therefore includes compounds in which an aromatic ring system, such as fluorene, is connected to a single aromatic ring, such as a benzene ring.

[0060] The term "fused ring system" used in this application means a fused ring form sharing at least two atoms, including a fused ring form of two or more hydrocarbon ring systems and a fused ring form of at least one heterocyclic ring system containing at least one heteroatom. Such fused ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings, or combinations of these rings. For example, in the case of an aryl group, it may be a naphthalenyl group, a phenanthrenyl group, a fluorenyl group, etc., but is not limited thereto.

[0061] The term "spiro compound" as used in this application has a "spiro union", which means a union in which two rings share only one atom. In this case, the atom shared by the two rings is called a "spiro atom". Depending on the number of spiro atoms in a compound, these compounds are called "monospiro-", "dispiro-", and "trispiro-" compounds, respectively.

[0062] The terms "fluorenyl group", "fluorenylene group", and "fluorenetriyl group" used in this application mean, unless otherwise specified, a monovalent, divalent, or trivalent functional group in which R, R', R" and R'" are all hydrogen in the following structure, respectively, and "substituted fluorenyl group", "substituted fluorenylene group", or "substituted fluorenetriyl group" means that at least one of the substituents R, R', R" and R'" is a substituent other than hydrogen, and includes the case where R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded. In this specification, regardless of the valence such as monovalent, divalent, or trivalent, fluorenyl group, fluorenylene group, and fluorenetriyl group can all be named fluorene group.

[0063] [ka]

[0064] Furthermore, the R, R', R" and R'" are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. For example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene, or phenanthrene, and the heterocyclic group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, benzofuranquinazoline, or quinoxaline. For example, the substituted fluorenyl group and fluorenylene group may be a monovalent functional group or a divalent functional group of 9,9-dimethylfluorene, 9,9-diphenylfluorene, and 9,9'-spirobi[9H-fluorene], respectively.

[0065] The term "heterocyclic group" as used herein includes not only aromatic rings such as "heteroaryl groups" or "heteroarylene groups" but also non-aromatic rings, and means, but is not limited to, a ring having 2 to 60 carbon atoms and containing one or more heteroatoms, unless otherwise specified. The term "heteroatom" as used herein means N, O, S, P, or Si, unless otherwise specified, and heterocyclic group means a single ring, ring assembly, fused multiple ring system, spiro compound, etc., containing a heteroatom.

[0066] For example, the term "heterocyclic group" may include compounds that contain heteroatoms such as SO2, P=O, etc., in place of the carbons that form the ring, as in the compounds below.

[0067] [ka]

[0068] The term "ring" as used in this application includes single and multiple rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.

[0069] The term "polycyclic" as used in this application includes ring assemblies such as biphenyls, terphenyls, fused multiple ring systems, and spiro compounds, and includes aromatic as well as non-aromatic rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom.

[0070] The term "aliphatic cyclic group" used in the present application means a cyclic hydrocarbon other than aromatic hydrocarbon, including a single ring, a ring assembly, a fused multiple ring system, a spiro compound, etc., and means a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto. For example, a fusion of an aromatic ring, benzene, and a non-aromatic ring, cyclohexane, also falls under the category of an aliphatic ring.

[0071] Also, when the prefixes are named consecutively, it means that the substituents are listed in the order in which they are written, for example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group, where the arylcarbonyl group is a carbonyl group substituted with an aryl group.

[0072] In addition, unless otherwise specified, in the term "substituted or unsubstituted" used in this application, "substituted" means deuterium, halogen, amino group, nitrile group, nitro group, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylamine groups, C1-C 30 Alkylthiophene groups, C6-C 30 Arylthiophene groups, C2-C 30 Alkenyl groups, C2-C 30 Alkynyl group, C3-C 30 Cycloalkyl groups of C6 to C 30 Aryl groups, C6-C substituted with deuterium 30 Aryl groups, C8-C 30an arylalkenyl group, a silane group, a boron group, a germanium group, and a C2-C alkyl group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; 30 The term "substituted" means that the heterocyclic group is substituted with one or more substituents selected from the group consisting of the following heterocyclic groups, but is not limited to these substituents.

[0073] In this application, the "functional group name" corresponding to an aryl group, an arylene group, a heterocyclic group, etc., which are exemplified as examples of each symbol and its substituent, can be described as the "functional group name reflecting the valence" or as the "parent compound name." For example, in the case of "phenanthrene," which is a type of aryl group, the name of the group can be described by dividing the valence, such as "phenanthryl (group)" for a monovalent "group" and "phenanthrylene (group)" for a divalent group, or it can be described as the parent compound name "phenanthrene" regardless of the valence.

[0074] Similarly, pyrimidine can be described as "pyrimidine" regardless of the valence, or as the "name of the group" of the relevant valence, such as pyrimidinyl (group) in the case of a monovalent group, pyrimidinylene (group) in the case of a divalent group, etc. Thus, when the type of ring group is described in the name of the parent compound in this application, it can mean an n-valent "group" formed by eliminating hydrogen atoms bonded to carbon atoms and / or heteroatoms of the parent compound.

[0075] In addition, in this specification, when describing the names of compounds and substituents, numbers and letters indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine may be described as pyridopyrimidine, benzofuro[2,3-d]pyrimidine as benzofuropyrimidine, 9,9-dimethyl-9H-fluorene as dimethylfluorene, etc. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline may be described as benzoquinoxaline.

[0076] In addition, unless otherwise expressly stated, the chemical formulas used in the present application are applied in the same manner as the substituent definitions according to the index definitions of the following chemical formulas.

[0077] [ka]

[0078] where a is an integer of 0, the substituent R 1 does not exist, that is, when a is 0, it means that all the carbons forming the benzene ring are bonded with hydrogen, and in this case, the hydrogen bonded to the carbon may be omitted and the chemical formula or compound may be described. When a is an integer of 1, one substituent R1 is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it can be bonded as shown below, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R 1 may be the same as or different from each other.

[0079] [ka]

[0080] Unless otherwise stated in this application, by forming a ring it is meant that adjacent groups are joined together to form a single ring or joined rings, and the single rings and joined rings formed include hydrocarbon rings as well as heterocycles containing at least one heteroatom, and include aromatic and non-aromatic rings.

[0081] In addition, unless otherwise specified in this specification, when describing a fused ring, the number in "number-fused ring" indicates the number of fused rings. For example, a form in which three rings are fused to each other, such as anthracene, phenanthrene, benzoquinazoline, etc., can be represented as a 3-fused ring.

[0082] In contrast, the term "bridged bicyclic compound" as used herein, unless otherwise specified, refers to a compound in which two rings share three or more atoms to form a ring, where the shared atoms include carbon or heteroatoms.

[0083] Hereinafter, the implementation of the present invention will be described in detail, but it should be understood that the present invention is not limited to the above embodiment, and is defined only by the scope of the claims that follow.

[0084] A positive-type photosensitive composition including polybenzoxazole-based and polyimide-based precursors and copolymers according to an embodiment of the present invention is used in manufacturing insulating films, surface protective films, and redistribution layers of semiconductor devices; and pixel defining layers (PDLs) of display devices.

[0085] In preparing a positive-type photosensitive composition for application to a semiconductor device or display device according to an embodiment of the present invention, the following additives may be further included to improve desired properties.

[0086] As additives that can be added according to an embodiment of the present invention, a surface smoothing agent may be further included to make the thickness of the coating film constant when coating the substrate. A surfactant may be further included to make the coating uniform according to the characteristics of the substrate surface, and a silane coupling agent may be further included to adjust the adhesive strength with the substrate surface. A crosslinking agent may be further included to strengthen the bond between polymers during the heat treatment step.

[0087] The positive photosensitive composition comprises the following elements:

[0088] (1) Polybenzoxazole and polyimide precursors, copolymer resins The patterning resin according to an embodiment of the present invention may include polybenzoxazole-based and polyimide-based precursors and copolymer resins.

[0089] The polybenzoxazole-based and polyimide-based precursors and copolymer resins refer to resins including hydroxyamide-based copolymers which can be converted to benzoxazole-based copolymers by chemical or thermal treatment, and polybenzoxazole-based copolymers which have been subjected to chemical or thermal treatment; amic acid-based copolymers which can be converted to polyimide-based copolymers, and polyimide-based copolymers which have been subjected to chemical or thermal treatment.

[0090] The polybenzoxazole-based and polyimide-based precursors and copolymer resins may be included in an amount of 5% by weight to 50% by weight, preferably 10% by weight to 40% by weight, based on the total amount of the positive photosensitive composition.

[0091] The polybenzoxazole-based and polyimide-based precursors and copolymer resins include, but are not limited to, copolymers represented by the following formula 1-1 or 1-2. These may be used alone or in combination of two or more. The weight average molecular weight of the polybenzoxazole-based and polyimide-based precursors and copolymer resins may 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.

[0092] The benzoxazole-based copolymer preferably contains a repeating unit selected from the group consisting of the following chemical formula 1-1, chemical formula 1-2, and combinations thereof.

[0093] [ka]

[0094] In the above Chemical Formula 1-1 and Chemical Formula 1-2, 1) * is the part where the bond is connected in the repeat unit, 2) X is represented by the following chemical formula 2:

[0095] [ka]

[0096] 3) R 1 Or R 10 Two of them are linking sites with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2, 4) The remaining R excluding the linking site 1 Or R 10 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 aryl groups of C2-C containing at least one heteroatom of O, N, S, Si and P; 30 Heterocyclic groups; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 20 Alkoxy group; C6-C 30 Aryloxy group; Fluorenyl group; Carbonyl group; Ether group; Carboxyl group; C1-C 20 and combinations thereof; 5) Said L 1 is a single bond, C6~C 30 an arylene group of C2-C containing at least one heteroatom of O, N, S, Si, or P; 30 Heterocyclic groups; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group; C3-C 20 Cycloalkylene group; C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group selected from the group consisting of -O-, -S-, -SO2-, Si(CH3)2-, -C(SiCH3)2, -C6H4-, -CO-, -NHCO-, -COO-, 6) L 1 is a single bond, the adjacent R and R 10and R5 and R6 can form a ring; 7) Y and Z are independently selected from the group consisting of C6 to C 30 an arylene group of C2-C containing at least one heteroatom of O, N, S, Si, or P; 30 Heterocyclic groups; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group; C3-C 20 Cycloalkylene group; C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 and combinations thereof; 8) Y or Z are, independently of each other, one or more carboxylic acid groups; or C1-C 20 The ester group having a terminal end of 9) m or n is an integer of 1 or more, 10) The polymer end is bonded with one selected from the following chemical formulas Q-1 to Q-10.

[0097] [ka]

[0098] The formula 2 is preferably represented by the following A-1 to A-15.

[0099] [ka]

[0100] In A-1 to A-15, * is a linking site with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2.

[0101] In addition, the formula 2 is preferably represented by the following B-1 to B-15.

[0102] [ka]

[0103] In B-1 to B-15, * is a linking site with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2.

[0104] The weight average molecular weight of the polybenzoxazole-based and polyimide-based precursors and copolymer resins may 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. When the weight average molecular weight of the resin is within the above range, no residue of the exposed layer remains during development, and the loss of thickness of the non-exposed layer is minimized, resulting in a good pattern. The resin may be included in an amount of 5 to 50 wt %, more preferably 15 to 45 wt %, based on the total amount of the photosensitive composition. When the resin is included within the above range, a constant thickness can be obtained in the coating step, and excellent sensitivity, developability, and adhesion (adhesion) can be obtained.

[0105] (2) Photosensitizer To realize a positive pattern in photolithography, a photoradical initiator must be used. The photosensitizer can be used individually or in combination by selecting an appropriate structure according to the wavelength used, such as g-line (436 nm), h-line (405 nm), i-line (365 nm), or deep UV (<260 nm).

[0106] The photosensitizer is a photosensitizer commonly used in positive-type photosensitive compositions, and examples thereof include photosensitive diazoquinone compounds. Specifically, the photosensitizer may include a phenol compound and a sulfonyl-based photosensitive compound represented by the following formulas P-1 to P-8. Specific examples of R″ include hydrogen; deuterium; and compounds having 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid in their structures.

[0107] [ka]

[0108] In the above P-1 to P-8, R″ is independently hydrogen; the following formula S-1; or the following formula S-2.

[0109] [ka]

[0110] In the above chemical formulas S-1 and S-2, * indicates a linking site.

[0111] The photosensitizer is preferably contained in an amount of 1 to 50% by weight based on the total weight of the composition.

[0112] (3) Solvent The solvent used is a substance that is compatible with, but does not react with, the benzoxazole copolymer resin, the photosensitizer, and the pigment.

[0113] Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethyl glycol monomethyl ester, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4- Ketones such as methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate;2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and 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 esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; and ketone acid esters such as ethyl pyruvate.

[0114] Also usable are high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0115] Among the above solvents, in consideration of compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate may be used.

[0116] The solvent may be contained in an amount of the remainder based on the total amount of the photosensitive composition, specifically, 50 to 95% by weight. When the solvent is contained within the above range, the positive photosensitive composition has an appropriate viscosity, and thus has excellent processability during the manufacture of the pattern layer.

[0117] (4) Other additives The positive photosensitive resin composition may further contain additives such as malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing a vinyl group or a (meth)acryloxy group; a surface smoothing agent; a surfactant; and a crosslinker in order to prevent stains and spots during application, improve leveling performance, and prevent the generation of residues due to undeveloped state.

[0118] For example, 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 in order to improve adhesion to a substrate.

[0119] Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, gamma methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, gamma isocyanate propyl triethoxysilane, gamma glycidoxypropyl trimethoxysilane, beta epoxy cyclohexylethyl trimethoxysilane, and silane-based coupling agents commercially available under the names of KBM-502, KBM-602, KBM-573, and KBE-9007N from Shinetsu Silicon Co., Ltd., and these may be used alone or in combination of two or more kinds.

[0120] The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included in the amount within the above range, the composition has excellent adhesion, storage stability, and the like.

[0121] In addition, the photosensitive resin composition may further include a surface smoothing agent, if necessary, to form a uniform film thickness during the coating step.

[0122] As the surface smoothing agent, surface smoothing agents commercially available under the names of F-554 (registered trademark), F-556 (registered trademark), F-557 (registered trademark), F-559 (registered trademark), F-560 (registered trademark), F-563 (registered trademark), RS-72-K (registered trademark), R-40 (registered trademark), R-41 (registered trademark), R-43 (registered trademark), etc., manufactured by DIC Corporation; Efka (registered trademark) FL3740, FL3741, FL3745, FL3770, etc., manufactured by BASF Corporation may be used.

[0123] The surface smoothing agent may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surface smoothing agent is included within this range, the uniformity of the coating can be ensured and the film thickness can be uniformly coated.

[0124] In addition, the photosensitive resin composition may further include a surfactant, if necessary, to improve coating properties and prevent the generation of defects.

[0125] Examples of the surfactant include BM-1000 (registered trademark) and BM-1100 (registered trademark) manufactured by BM Chemie; Megafac F142D (registered trademark), F172 (registered trademark), F173 (registered trademark), F183 (registered trademark) manufactured by Dainippon Ink and Chemicals, Inc.; Fluorad FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), and FC-431 (registered trademark) manufactured by Sumitomo 3M Limited. Surflon S-112 (registered trademark), S-113 (registered trademark), S-131 (registered trademark), S-141 (registered trademark), S-145 (registered trademark), etc., available from Asahi Glass Co., Ltd.; SH-28PA (registered trademark), S-190 (registered trademark), S-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark), etc., available from Dray Silicon Co., Ltd. may also be used.

[0126] The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within this range, coating uniformity is ensured, spots are not generated, and wetting to the glass substrate is excellent.

[0127] As the crosslinker, 1,4-bis(methoxymethyl)benzene, diethyl sulfate, 3-aminopropyltriethoxysilane, N,N'-methylenebisacrylamide, etc. may be used, and these may be used alone or in combination of two or more kinds.

[0128] The crosslinker may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive composition. When the crosslinker is contained within the above range, it is advantageous for imparting suitable physical properties, such as mechanical properties such as tensile strength, to the cured coating film.

[0129] In addition, the photosensitive resin composition may contain other additives in a certain amount within a range that does not impair the physical properties. The additives are preferably contained in an amount of 0.001 to 10% by weight based on the total amount of the composition.

[0130] Synthesis examples and examples according to the present invention will be specifically described below, but the synthesis examples and examples of the present invention are not limited thereto.

[0131] (Synthesis Example 1) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.2g of N-methylpyrrolidone (NMP), added with 15g of 4,4'-cyclohexylidinebis[2-aminophenol] and 3.67g of pyridine, and stirred and maintained at 40°C. 1.12g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 110.742g of NMP was added to the flask in which the reaction was proceeding, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 13.72g of 4,4'-oxybisbenzoyl chloride was slowly added and dissolved and reacted while stirring for 12 hours.

[0132] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 26.86 g of copolymerized polyhydroxyamide powder.

[0133] (Synthesis Example 2) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.2g of N-methylpyrrolidone (NMP), added with 15g of 4,4'-cyclohexylidinebis[benzenamine] and 3.68g of pyridine, and stirred and maintained at 40°C. 1.12g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 80.67g of NMP was added to the flask in which the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 8.417g of 1,2-cyclobutanedicarboxylic acid dichloride was slowly added and dissolved and reacted while stirring for 12 hours.

[0134] The polyamic acid solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 22.08 g of a copolymerized polyamic acid powder.

[0135] (Synthesis Example 3) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.2g of N-methylpyrrolidone (NMP), added with 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)propane and 3.68g of pyridine, and stirred and maintained at 40°C. 1.12g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 88.06g of NMP was added to the flask in which the reaction was proceeding, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 9.72g of 1,4-cyclohexanedicarboxylic acid dichloride was slowly added and dissolved and reacted while stirring for 12 hours.

[0136] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 23.25 g of copolymerized polyhydroxyamide powder.

[0137] (Synthesis Example 4) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.18g of N-methylpyrrolidone (NMP), added with 15g of 4,4'-(1-methyleneethyllysine)bis[benzenamine] and 2.48g of pyridine, and stirred and maintained at 40°C. 0.75g of 5-novone-2,3-dicarboxylic anhydride was slowly added thereto, and stirred for a certain period of time to dissolve and react. After that, 90.80g of NMP was added to the flask in which the reaction was proceeding, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 8.67g of 1,4-cyclohexanedicarboxylic acid dichloride and 1.15g of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride were slowly added, and dissolved and reacted while stirring for 12 hours.

[0138] The polyamic acid solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 20.75 g of a copolymerized polyamic acid powder.

[0139] (Synthesis Example 5) A 250ml 3-neck round bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.18g of N-methylpyrrolidone (NMP), then added with 15g of 4,4'-(bis(trimethylsilyl)methylene)bis(2-aminophenol) and 3.68g of pyridine, stirred and maintained at 40°C. 1.41g of 5-novone-2,3-dicarboxylic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 89.72g of NMP was added to the flask during the reaction, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Thereafter, 7.70 g of 1,4-cyclohexanedicarboxylic acid dichloride and 2.31 g of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride were slowly added, and the mixture was stirred for 12 hours to dissolve and react.

[0140] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 20.90 g of copolymerized polyhydroxyamide powder.

[0141] (Synthesis Example 6) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.18g of N-methylpyrrolidone (NMP), added with 15g of 4,4'-sulfonyldianiline and 2.94g of pyridine, and stirred and maintained at 40°C. 0.72g of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 84.5g of NMP was added to the flask in which the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 9.46g of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride was slowly added and dissolved and reacted while stirring for 12 hours.

[0142] The polyamic acid solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried at 60° C. in vacuum for 12 hours to obtain 21.05 g of a copolymerized polyamic acid powder.

[0143] (Synthesis Example 7) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.18g of N-methylpyrrolidone (NMP), added with 15g of 4,4-bis(3-amino-4-hydroxyphenyl)heptane and 3.18g of pyridine, and stirred and maintained at 40°C. 1.44g of maleic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 92.48g of NMP was added to the flask in which the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 10.48g of 1,4-cyclohexanedicarboxylic acid dichloride was slowly added and stirred for 12 hours to dissolve and react.

[0144] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 19.41 g of a copolymerized polyhydroxyamide powder.

[0145] (Synthesis Example 8) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.18g of N-methylpyrrolidone (NMP), then added 15g of 4-amino-N-(4-aminophenyl)benzoamide and 2.87g of pyridine, stirred and maintained at 40°C. 1.48g of maleic anhydride was slowly added thereto, and stirred for a certain period of time to dissolve and react. After that, 91.42g of NMP was added to the flask in which the reaction was proceeding, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 10.62g of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride was slowly added and dissolved and reacted while stirring for 12 hours.

[0146] The polyamic acid solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 22.15 g of a copolymerized polyamic acid powder.

[0147] (Synthesis Example 9) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.18g of N-methylpyrrolidone (NMP), then added 15g of bis(3-amino-4-hydroxyphenyl)sulfone and 4.84g of pyridine, stirred and maintained at 40°C. 2.84g of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride was slowly added thereto, and stirred for a certain period of time to dissolve and react. After that, 91.58g of NMP was added to the flask in which the reaction was proceeding, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 13.93g of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride was slowly added and dissolved and reacted while stirring for 12 hours.

[0148] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 23.82 g of copolymerized polyhydroxyamide powder.

[0149] (Synthesis Example 10) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.18g of N-methylpyrrolidone (NMP), added with 15g of 4,4'-diaminodiphenyl sulfide and 4.12g of pyridine, and stirred and maintained at 40°C. 3.84g of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride was slowly added and stirred for a certain period of time to dissolve and react. Then, 95.62g of NMP was added to the flask in which the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 9.98g of 4,4'-benzophenonetetracarboxylic dianhydride was slowly added and dissolved and reacted while stirring for 12 hours.

[0150] The polyamic acid solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried at 60° C. in vacuum for 12 hours to obtain 21.05 g of a copolymerized polyamic acid powder.

[0151] (Synthesis Example 11) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 79.18g of N-methylpyrrolidone (NMP), added with 15g of 4,4'-oxybis[2-aminophenol] and 3.66g of pyridine, and stirred and maintained at 40°C. 1.12g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 87.52g of NMP was added to the flask in which the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 13.25g of 1,4-cyclohexanedicarboxylic acid dichloride was slowly added and dissolved and reacted while stirring for 12 hours.

[0152] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain 20.11 g of copolymerized polyhydroxyamide powder.

[0153] (Synthesis Example 12) A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 65.7g of N-methylpyrrolidone (NMP), then added 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.52g of pyridine, stirred and maintained at 40°C. 0.910g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 52.70g of NMP was added to the flask in which the reaction was proceeding, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 11.18g of 4,4'-oxybisbenzoyl chloride was slowly added and dissolved and reacted while stirring for 12 hours.

[0154] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with 1506 g of methanol. The precipitated solid was dried at 60° C. in vacuum for 12 hours to obtain 21.13 g of copolymerized polyhydroxyamide powder.

[0155] (Production Example 1) Production of positive-type photosensitive composition 14.881 g of the benzoxazole copolymer resin obtained from Synthesis Examples 1 to 7, 2.232 g of MIPHOTO TPD523 (Migen Shoji Co., Ltd.), 0.004 g of F-563 (DIC Corporation), 0.223 g of KBM-573 (Shinetsu Silicon Co., Ltd.), and 0.149 g of 1,4-bis(methoxymethyl)benzene were stirred with 32.5 g of gamma-butyrolactone at room temperature for 12 hours. Then, the composition was filtered three times to remove impurities, thereby preparing a photosensitive composition.

[0156] A photosensitive liquid composition was prepared according to the composition shown in Table 1 below.

[0157] [Table 1]

[0158] The process of forming a cured film on a silicon wafer using the positive photosensitive composition is as follows.

[0159] (1) Application and coating stage The photosensitive composition prepared in the examples or comparative examples is applied to a cleaned 200 mm silicon wafer with a certain thickness using a spin coater, and then a coating film is formed by removing a part of the solvent using VCD (vacuum chamber dry). The coating thickness of the photosensitive composition is 5 μm to 10 μm after VCD.

[0160] (2) Pre-bake stage In order to remove the solvent contained in the obtained coating film, the film is heated on a hot plate at 100°C to 140°C for 50 to 200 seconds. By removing a certain amount of the solvent in this process, a coating film of a certain thickness can be obtained even in the development step after the next process (exposure).

[0161] (3) Exposure stage In order to obtain a certain thickness required for the obtained coating film, a pattern can be formed by irradiating the film with an actinic ray of 190 nm to 600 nm, preferably with a light source of a metal or LED lamp having a ghi-line. The exposure dose is 50 to 500 mJ / cm. 2 The formed patterns are positive type hole and line and space patterns with sizes in μm units.

[0162] (4) Development stage Following the exposure step, the substrate is developed using a puddle method in which a certain amount of 2.38 wt% TMAH (tetramethylammonium hydroxide) developer is applied to the substrate at 23±2°C and left for a certain time (minutes), and then washed with ultrapure water (DI water). This dissolves and removes the non-exposed areas, leaving only the non-exposed areas to form an image pattern, with the remaining coating having a thickness of 4.0 to 9.0 μm.

[0163] (5) Post-heat treatment stage In order to obtain an image pattern obtained by the above phenomenon, the coating film obtained is cured by post-baking in an oven at 300 to 320° C. for 30 to 120 minutes.

[0164] (6)FE-SEM Measurement After the post-heat treatment, the substrate was sampled without damaging the pattern, and the hole and line and space patterns were observed using a JEOL scanning electron microscope JSM-IT800.

[0165] [Table 2]

[0166] After performing the development process and post-heat treatment shown in Table 2, the hole and line and space patterns were observed using a scanning electron microscope. It was confirmed that no development that left residues after development occurred in Examples 1 to 11. In contrast, in Comparative Example 1, it was confirmed that a small amount of residues remained under the hole pattern.

[0167] In addition, the accuracy of hole realization was confirmed by observing the realization of a 10 μm hole pattern, and it was confirmed that the pattern was accurately realized with an error of 0.1 μm or less in all of Examples 1 to 11 and Comparative Example 1. It was confirmed that the minimum resolution realized in all of Examples 1 to 11 and Comparative Example 1 was 2 to 3 μm.

[0168] According to the test results of the present invention, it was confirmed that the use of fluorine-free polyimide-based precursors and polybenzoxazole-based precursors showed similar performance to existing fluorine-based materials and showed even better results in terms of residue after development.

[0169] The above description is merely illustrative of the present invention, and various modifications may be made by those having ordinary skill in the art to which the present invention pertains without departing from the essential characteristics of the present invention.

[0170] Therefore, the embodiments disclosed in this specification are for illustrative purposes only and are not intended to limit the present invention, and the spirit and scope of the present invention are not limited by such embodiments. The scope of protection of the present invention should be interpreted by the claims, and all technologies within the scope equivalent thereto should be interpreted as being included in the scope of the present invention.

Claims

1. A benzoxazole-based copolymer comprising a repeating unit selected from the group consisting of the following Chemical Formula 1-1, Chemical Formula 1-2, and a combination thereof: 【Chemistry 1】 In the above Chemical Formula 1-1 and Chemical Formula 1-2, 1) * is the part where the bond is connected in the repeat unit, 2) X is represented by the following chemical formula 2: 【Chemistry 2】 3) R １ Or R １０ Two of them are linking sites with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2, 4) The remaining R excluding the linking site １ Or R １０ are each independently hydrogen; deuterium; a hydroxyl group; ６ ~C ３０ aryl groups of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkyl group of C ２ ~C ２０ an alkenyl group of C ２ ~C ２０ an alkynyl group of C １ ~C ２０ an alkoxy group of C ６ ~C ３０ an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; １ ~C ２０ and combinations thereof; 5) Said L １ is a single bond, C ６ ~C ３０ an arylene group of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkylene group of C ３ ~C ２０ A cycloalkylene group represented by the formula: ２ ~C ２０ an alkenylene group represented by the formula C ３ ~C ２０ A cycloalkenylene group represented by the formula: ２ ~C ２０ An alkynylene group represented by the formula: ３ ~C ２０ a cycloalkynylene group represented by the formula: ２ -, Si(CH ３ ) ２ -, -C(SiCH ３ ) ２, -C ６ H ４ selected from the group consisting of -, -CO-, -NHCO-, and -COO-; 6) L １ is a single bond, the adjacent R １ and R １０ and R ５ and R ６ can form a ring, 7) Y and Z are each independently C ６ ~C ３０ an arylene group of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkylene group of C ３ ~C ２０ A cycloalkylene group represented by the formula: ２ ~C ２０ an alkenylene group represented by the formula C ３ ~C ２０ A cycloalkenylene group represented by the formula: ２ ~C ２０ An alkynylene group represented by the formula: ３ ~C ２０ and combinations thereof; 8) Y or Z are, independently of each other, one or more carboxylic acid groups; or C １ ~C ２０ The ester group having a terminal end of 9) m or n is an integer of 1 or more, 10) The polymer end is bonded to one selected from the following chemical formulas Q-1 to Q-10. 【Chemistry 3】

2. The benzoxazole copolymer according to claim 1, wherein the formula 2 is represented by the following A-1 to A-15. 【Chemistry 4】 In A-1 to A-15, * is a linking site with the amide group of Formula 1-1 or Formula 1-2.

3. The benzoxazole copolymer according to claim 1, wherein the formula 2 is represented by the following B-1 to B-15. 【Chemistry 5】 In B-1 to B-15, * is a linking site with the amide group of Formula 1-1 or Formula 1-2.

4. 2. The benzoxazole-based copolymer according to claim 1, wherein the copolymer is prepared from a diamine monomer; a diacyl chloride monomer; a dianhydride monomer; and an anhydride monomer.

5. The diamine is 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) nyl)tridecane, 4,4'-cyclohexylidine bis[2-aminophenol], 4,4'-(1,3-dimethylbutylidine)bis[2-aminophenol], 4,4'-oxybis[2-aminophenol], 4,4'-thiobis[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-methyleneethylidine)bis[benzenamine], 4,4'-(1-ethylpropylidine)bis[benzenamine], 4,4'-(1-propylbutylidine)bis[benzenamine], 5. The benzoxazole copolymer according to claim 4, comprising at least one monomer selected from the group consisting of 4,4'-(1-butylpentylidine)bis[benzenamine], 4,4'-(1-pentylhexylidine)bis[benzenamine], 4,4'-(1-hexylheptylidine)bis[benzenamine], 4,4'-cyclohexylidinebis[benzenamine], 4,4'-(1,3-dimethylbutylidine)bis[benzenamine], 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-sulfonyldianiline, 4,4'-(bis(trimethylsilyl)methylidyne)dianiline, 4-amino-N-(4-aminophenyl)benzoamide, 4-aminophenyl-4-aminobenzoate, and combinations thereof.

6. The benzoxazole copolymer according to claim 4, wherein the diacyl chloride comprises one or more monomers selected from the group consisting of 4,4'-oxybisbenzoyl chloride, 1,2-cyclobutanedicarboxylic acid dichloride, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldicarbonyl chloride, 1,4-naphthalene dicarbonyl chloride, 4,4'-sulfonyldibenzoyl chloride, 1,4-cyclohexanedicarboxylic acid dichloride, and combinations thereof.

7. The dianhydride is, for example, 4,4-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidine)diphthalic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 5. The benzoxazole copolymer according to claim 4, characterized in that it contains one or more monomers selected from the group consisting of benzoic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, dicyclohexyl-3,4,3'4'-tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, and combinations thereof.

8. The benzoxazole copolymer according to claim 4, wherein the anhydride comprises one or more monomers selected from the group consisting of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 5-novone-2,3-dicarboxylic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, or a combination thereof.

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

10. A positive-type photosensitive composition comprising the benzoxazole copolymer of claim 1; a photosensitizer; a solvent; and an additive.

11. 11. The positive photosensitive composition of claim 10, wherein the photosensitizer comprises at least one of the following formulas P-1 to P-8: 【Chemistry 6】 In the above P-1 to P-8, R″ is each independently hydrogen; the following formula S-1; or the following formula S-2. 【Chemistry 7】

12. 11. The positive photosensitive composition of claim 10, wherein the solvent comprises at least one selected from the group consisting of N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, gamma-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. 11. The positive photosensitive composition according to claim 10, wherein the additive comprises at least one selected from the group consisting of a silane coupling agent; a surface smoothing agent; a surfactant; a crosslinking agent; and combinations thereof.

14. 11. The positive photosensitive composition of claim 10, wherein the benzoxazole copolymer is contained in an amount of 5 to 50% by weight based on the total weight of the composition.

15. 11. The positive photosensitive composition of claim 10, wherein the photosensitizer is contained in an amount of 1 to 50% by weight based on the total amount of the composition.

16. 11. The positive photosensitive composition of claim 10, wherein the solvent is contained in an amount of 50 to 95% by weight based on the total weight of the composition.

17. 11. The positive photosensitive composition according to claim 10, wherein the additive is contained in an amount of 0.001 to 10% by weight based on the total weight of the composition.

18. A pattern or film made from the positive-working photosensitive composition of claim 10.

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

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

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