Photosensitive composition

Abstract

SOLUTION: To provide a positive photosensitive composition comprising: (A) a polybenzoxazole or polyimide-based polymer; (B) a photosensitizer; (C) a silane-based additive; and (D) a solvent, and a semiconductor device or a display device manufactured using the positive photosensitive composition.EFFECT: A pattern manufactured from a photosensitive composition including a copolymer in which a monomer capable of increasing mechanical properties is introduced into a component of a benzoxazole-based polymer resin, and a silane-based additive, has the effects of enhancing the mechanical properties and adhesion to the base material.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a positive type photosensitive composition containing polybenzoxazole or polyimide polymer and a silane additive, which is used in a semiconductor device or display device. [Background technology]

[0002] The photolithography process is broadly 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 or E-beam through a mask, and a development step in which specific areas of the photoresist film with the engraved pattern are removed. A baking step is added between each step to remove the 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 these, 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 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, since development is performed with an alkaline aqueous solution in the development stage, the molecular weight of the polymer resin used to realize a precise circuit is limited, and there is a limit to the mechanical properties that can be realized. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2006-526812 [Patent Document 2] Japanese Patent Publication No. 2007-508582 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 photosensitive composition having increased adhesion by introducing a monomer capable of increasing mechanical properties into a polybenzoxazole or polyimide polymer component and a silane additive capable of increasing adhesion to a substrate.

[0007] 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]

[0008] The positive-type photosensitive composition according to the present invention preferably comprises (A) a polybenzoxazole or polyimide-based polymer; (B) a photosensitizer; (C) a silane-based additive; and (D) a solvent.

[0009] The polymer preferably contains repeating units of Chemical Formula 1-1; Chemical Formula 1-2; Chemical Formula 1-3; Chemical Formula 1-4; or a combination thereof.

[0010] [ka]

[0011] In the above Chemical Formula 1-1 to Chemical Formula 1-4, 1) * is the part where the bond is connected in the repeat unit, 2) The * at the polymer end is the portion where the chemical formulas Q-1 to Q-10 are bonded via an amide bond or an imide bond. 3) X1 or X2 is the following chemical formula 2, 4) Y is C6~C 30 an arylene group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group, C1-C 20 Cycloalkylene groups, C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 2; and combinations thereof; 5) Z is C6~C 30 an arylene group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group, C1-C 20 Cycloalkylene groups, C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 3; and combinations thereof; 6) k, l, m, and n are integers of 1 or more,

[0012] [ka]

[0013] 7) The polymer end is bonded to a compound represented by a formula selected from the group consisting of one or a combination of formulas Q-1 to Q-10 through an amide or imide bond;

[0014] [ka]

[0015] In the above Chemical Formula 2, 8) L1 is a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-, -C(CH 13 )2-, -C(CH 10 )-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, Si(CH3)2-, -C(SiCH3)2, -CH4-, -CO-, -NHCO-, -COO-; 9) R1 or R 10 Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 10) The remaining R1 to R excluding the linking portion 10 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 an aryl group having at least one heteroatom selected from 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 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 is an alkoxycarbonyl group of the formula 11) L 1 is a single bond, the adjacent R and R 10 and R5 and R6 can form a ring;

[0016] [ka]

[0017] In the above Chemical Formula 3, 12) L 2 is a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-, -C(CH 13 )2-, -C(CH 10 )-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, Si(CH3)2-, -C(SiCH3)2, -CH4-, -CO-, -NHCO-, -COO-; 13) R 11 Or R 20 Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 14) The remaining R excluding the linking site 11 Or R 20 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 an aryl group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; 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 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 The remaining R excluding the linking portion is an alkoxycarbonyl group. 11 Or R 20 Two of them are carboxyl groups, 15) L 2 is a single bond, the adjacent R 11 and R 20 ; and R 15 and R 16 can form a ring.

[0018] The polybenzoxazole or polyimide polymer is preferably prepared from a diamine monomer, a diacyl chloride monomer, a dianhydride monomer, or an anhydride monomer.

[0019] The diamines include 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dihydroxybenzidine, 4,4'-methylenebis(2-aminophenol), 4,4'-(cyclohexane-1,1-diyl)bis(2-aminophenol), 4,4'-(pentane-3,3-diyl)bis(2-aminophenol), 4,4'-(heptane-4,4-diyl)bis(2-aminophenol), 4,4'-(nonane-5,5-diyl)bis(2-aminophenol), 4,4'-(4-methylpentane-2,2-diyl)bis(2-aminophenol), 4,4'-(bis(trimethylsilyl)methylene)bis(2-aminophenol), m-tolidine, o-tolidine, 4,4'- It is preferable that the monomer contains one or more monomers selected from the group consisting of oxydianiline, 3,4'-oxydianiline, 3,3'-dihydroxy-4,4'-diamino-biphenyl, 4,4'-methylenedianiline, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminobenzanilide, 9,9'-bis(4-aminophenyl)fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-{4-aminophenoxyphenyl}]hexafluoropropane, 4,4'-(cyclohexane-1,1-diyl)dianiline, and combinations thereof.

[0020] 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.

[0021] The dianhydride preferably contains at least one monomer selected from the group consisting of 3,3',4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidine)diphthalic anhydride, 3,3'4,4'-benzophenonetetracarboxylic dianhydride, 3,3,3',4'-biphenyltetracarboxylic dianhydride, pyrromethylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-(2,2,2-trifluoro-1-phenylethylidine)diphthalic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-bisphenol A dianhydride, bicyclooctanetetracarboxylic dianhydride, and combinations thereof.

[0022] The anhydride preferably includes one or more monomers selected from the group consisting of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 5-novonene-2,3-dicarboxylic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, and combinations thereof.

[0023] The weight average molecular weight of the copolymer is preferably 5,000 to 40,000 g / mol.

[0024] The polybenzoxazole or polyimide polymer is preferably contained in an amount of 5 to 50% by weight based on the total weight of the composition.

[0025] The photosensitizer preferably includes at least one of the following formulas P-1 to P-8.

[0026] [ka]

[0027] In the above P-1 to P-8, R″ is hydrogen; the following chemical formula S-1; or the following chemical formula S-2.

[0028] [ka]

[0029] The photosensitizer is preferably contained in an amount of 1 to 50% by weight based on the total weight of the composition.

[0030] The silane-based additive may be T-1 represented by the following formula alone or a mixture of T-1 and T-2.

[0031] [ka]

[0032] In the above T-1 to T-2, 1) R21 is C6~C 30 aryl groups; C2-C containing at least one heteroatom selected from O, N, S, Si and P; 30 Heterocyclic group; C3-C 30 Cycloalkyl groups; C2-C 20 and combinations thereof; 2) R 22 Or R 23 is selected from the group consisting of a methoxy group; an ethoxy group; an acetyl group; a carboxyl group, and combinations thereof; 3) R 24 is C1~C 10 is an alkyl group of the formula 4) R 25 Or R 27 is selected from the group consisting of a methoxy group, an ethoxy group, an acetyl group, a carboxyl group, and combinations thereof; 5) Ar1-Ar2 are C6-C 30 an aryl group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic groups, C3-C 30 Cycloalkyl groups, C2-C 20 The heterocycloalkyl groups are selected from the following:

[0033] The silane-based additive T-1 may include compounds represented by the following chemical formulas J-1 to J-15.

[0034] [ka]

[0035] The silane-based additive T-2 may include compounds represented by the following chemical formulas K-1 to K-12.

[0036] [ka]

[0037] The silane additive is preferably contained in an amount of 0.1 to 1% by weight based on the total weight of the composition.

[0038] The solvent preferably 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.

[0039] The solvent is preferably contained in an amount of 40 to 95% by weight based on the total weight of the composition.

[0040] It is preferable that the positive type photosensitive composition further includes at least one selected from the group consisting of a surface smoothing agent; a surfactant; a crosslinking agent; and a combination thereof.

[0041] The additives are preferably contained in an amount of 0.001 to 10% by weight based on the total weight of the composition.

[0042] In another embodiment of the present invention, it is preferable to provide a pattern or film made from the positive-sensitive composition.

[0043] 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.

[0044] 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

[0045] According to the present invention, a pattern manufactured from a photosensitive composition including a copolymer in which a monomer capable of increasing mechanical properties is introduced into a polybenzoxazole or polyimide-based polymer component and a silane-based additive has an effect of increasing adhesion to a substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.).

[0053] 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.

[0054] The term "halo" or "halogen" as used in this application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise stated.

[0055] 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.

[0056] The term "haloalkyl group" or "haloalkyl group" as used herein means, unless otherwise specified, an alkyl group substituted with a halogen.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] [ka]

[0068] 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, benzofuran, quinazoline, 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.

[0069] 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.

[0070] 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.

[0071] [ka]

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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 groups, C3-C 30 Cycloalkyl groups of C6 to C 30 Aryl groups, C6-C substituted with deuterium 30 Aryl groups, C8-C 30 an 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.

[0077] 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.

[0078] 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) if monovalent, pyrimidinylene (group) if divalent, etc. Therefore, when the type of substituent 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 hetero atoms of the parent compound.

[0079] 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.

[0080] 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.

[0081] [ka]

[0082] Here, when a is an integer of 0, it means that the substituent R1 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 may be bonded as shown below, and when a is an integer of 4 to 6, it may be 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.

[0083] [ka]

[0084] 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.

[0085] 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.

[0086] On the other hand, the term "bridged bicyclic compound" as used in this application, unless otherwise specified, refers to a compound in which two rings share three or more atoms to form a ring, and the shared atoms include carbon or heteroatoms.

[0087] 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.

[0088] A positive photosensitive composition including a polybenzoxazole or polyimide-based polymer according to an embodiment of the present invention is used in manufacturing an insulating film, a surface passivation film, a redistribution layer of a semiconductor device, and a pixel defining layer (PDL) of a display device.

[0089] In preparing a positive 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.

[0090] 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.

[0091] The positive photosensitive composition comprises the following elements:

[0092] (1) Polybenzoxazole or polyimide polymer resin The patterning resin according to an embodiment of the present invention may include polybenzoxazole or a polyimide-based polymer.

[0093] The polybenzoxazole or polyimide polymer resin refers to a resin including a hydroxyamide-based and amic acid-based copolymer that can be converted into a benzoxazole-based and polyimide-based copolymer by chemical or thermal treatment, and a benzoxazole-based and imide-based copolymer that has been subjected to chemical or thermal treatment.

[0094] The polybenzoxazole or polyimide polymer resin may be included in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, based on the total weight of the positive type photosensitive composition.

[0095] The polybenzoxazole or polyimide polymer resin may be, but is not limited to, copolymers represented by the following formulas 1-1 to 1-4. These may be used alone or in combination of two or more. The weight average molecular weight of the polybenzoxazole or polyimide polymer resin 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.

[0096] The polybenzoxazole or polyimide polymer preferably contains a repeating unit selected from the group consisting of the following formula 1-1; formula 1-2; formula 1-3; formula 1-4; or a combination of two or more of formulas 1-1 to 1-4.

[0097] [ka]

[0098] In the above Chemical Formula 1-1 to Chemical Formula 1-4, 1) * is the part where the bond is connected in the repeat unit, 2) * at the polymer end is the part where Q-1 to Q-10 are bonded by amide bond or imide bond. 3) X1 or X2 is the following chemical formula 2, 4) Y is C6~C 30 an arylene group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group, C1-C 20 Cycloalkylene groups, C2-C20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 2; and combinations thereof; 5) Z is C6~C 30 an arylene group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group, C1-C 20 Cycloalkylene groups, C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 3; and combinations thereof; 6) k, l, m, and n are integers of 1 or more,

[0099] [ka]

[0100] 7) The polymer end is bonded to a compound represented by a formula selected from the group consisting of one or a combination of formulas Q-1 to Q-10 through an amide or imide bond;

[0101] [ka]

[0102] In the above Chemical Formula 2, 8) L 1 is a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-, -C(CH 13)2-, -C(CH 10 )-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, Si(CH3)2-, -C(SiCH3)2, -CH4-, -CO-, -NHCO-, -COO-; 9) R1 or R 10 Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 10) The remaining R1 to R excluding the linking portion 10 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 an aryl group having at least one heteroatom selected from 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 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 is an alkoxycarbonyl group of the formula 11) L 1 is a single bond, the adjacent R and R 10 and R5 and R6 can form a ring;

[0103] [ka]

[0104] In the above Chemical Formula 3, 12) L 2 is a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-, -C(CH 13 )2-, -C(CH 10)-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, Si(CH3)2-, -C(SiCH3)2, -CH4-, -CO-, -NHCO-, -COO-; 13) R 11 Or R 20 Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 14) The remaining R excluding the linking site 11 Or R 20 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 an aryl group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; 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 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 The remaining R excluding the linking portion is an alkoxycarbonyl group. 11 Or R 20 Two of them are carboxyl groups, 15) L 2 is a single bond, the adjacent R 11 and R 20 ; and R 15 and R 16 can form a ring.

[0105] 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 10 to 45 wt %, based on the total amount of the photosensitive resin composition. When the resin is included within the above range, a constant film thickness can be obtained in the coating step, and excellent sensitivity, developability, and adhesion (adhesion) can be obtained.

[0106] (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).

[0107] The photosensitizer is a photosensitizer commonly used in positive photosensitive compositions, and may be, for example, a photosensitive diazoquinone compound. Specifically, the photosensitizer may include a phenol compound and a photosensitive compound represented by the following formulas P-1 to P-8. Specific examples of R" include hydrogen; deuterium; 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-diazide-4-sulfonic acid.

[0108] [ka]

[0109] In the above P-1 to P-8, R″ is hydrogen; the following chemical formula S-1; or the following chemical formula S-2.

[0110] [ka]

[0111] In the above chemical formulas S-1 and S-2, * indicates a linking site.

[0112] The photosensitizer is preferably contained in an amount of 1 to 50% by weight based on the total weight of the composition.

[0113] (3) Silane-based additives The positive photosensitive composition may contain a silane coupling agent to improve adhesion to a substrate during coating.

[0114] The silane-based additives commonly used in the photosensitive positive photosensitive composition may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group, and specifically, may include a phenol compound and a silane-based additive represented by the following chemical formulas T-1 and T-2.

[0115] The silane additive is preferably included in an amount of 0.001 to 10 wt % based on the total weight of the composition, and more preferably included in an amount of 0.1 to 1 wt % based on the total weight of the composition.

[0116] The silane-based additive may include the following formula T-1; formula T-2, or a combination thereof.

[0117] More preferably, the silane additive comprises both of the formula T-1 and the formula T-2.

[0118] [ka]

[0119] In the above T-1 to T-2, 1) R 21 is C6~C 30 aryl groups; C2-C containing at least one heteroatom selected from O, N, S, Si and P; 30 Heterocyclic group; C3-C 30 Cycloalkyl groups; C2-C 20 and combinations thereof; 2) R 22 Or R 23 is selected from the group consisting of a methoxy group; an ethoxy group; an acetyl group; a carboxyl group, and combinations thereof; 3) R 24 is C1~C 10 is an alkyl group of the formula 4) R 25 Or R27 is selected from the group consisting of a methoxy group, an ethoxy group, an acetyl group, a carboxyl group, and combinations thereof; 5) Ar1-Ar2 are C6-C 30 an aryl group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic groups, C3-C 30 Cycloalkyl groups, C2-C 20 The heterocycloalkyl groups are selected from the following:

[0120] The silane-based additive T-1 may include compounds represented by the following chemical formulas J-1 to J-15, but is not limited thereto.

[0121] [ka]

[0122] The silane-based additive T-2 may include structures represented by the following chemical formulas K-1 to K-12, but is not limited thereto.

[0123] [ka]

[0124] (4) Solvent The solvent may be a material that is compatible with but does not react with the benzoxazole copolymer resin, the photosensitizer, and the pigment.

[0125] 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.

[0126] Also usable are high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, 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.

[0127] 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.

[0128] The solvent may be included as the remaining amount based on the total amount of the photosensitive composition, specifically, 50 to 95 wt %. When the solvent is included within this range, the positive-type photosensitive composition has an appropriate viscosity, and thus the processability during the manufacture of the pattern layer is excellent.

[0129] (5) Other additives The positive photosensitive composition may further contain additives such as malonic acid; 3-amino-1,2-propanediol; a surface smoothing agent containing a vinyl group or a (meth)acryloxy group; a surfactant; and a crosslinking agent in order to prevent stains and spots during application, improve leveling performance, and prevent the generation of residues due to undeveloped state.

[0130] The additives are preferably contained in an amount of 0.001 to 10% by weight based on the total weight of the composition.

[0131] In addition, the photosensitive composition may further include a surface smoothing agent to form a uniform film thickness during the coating step, if necessary.

[0132] 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, Efka (registered trademark) FL3741, Efka (registered trademark) FL3745, Efka (registered trademark) FL3770, etc., manufactured by BASF Corporation may be used.

[0133] 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 composition. When the surface smoothing agent is within the above range, the coating uniformity is ensured and the coating thickness can be constant.

[0134] In addition, the photosensitive composition may further include a surfactant, if necessary, to improve coating properties and prevent the generation of defects.

[0135] Examples of the surfactant include BM-1000 (registered trademark) and BM-1100 (registered trademark) manufactured by BM Chemie; Megafac F142D (registered trademark), Megafac F172 (registered trademark), Megafac F173 (registered trademark), Megafac F183 (registered trademark) manufactured by Dainippon Ink and Chemicals, Inc.; Fluorad FC-135 (registered trademark), Fluorad FC-170C (registered trademark), Fluorad FC-430 (registered trademark), Fluorad F (registered trademark) manufactured by Sumitomo 3M Limited. Surflon S-112 (registered trademark), Surflon S-113 (registered trademark), Surflon S-131, Surflon S-141, Surflon S-145, etc., available from Asahi Glass Co., Ltd.; SH-28PA (registered trademark), SH-190 (registered trademark), SH-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark), etc., available from Dray Silicon Co., Ltd. may also be used.

[0136] 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 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.

[0137] As the crosslinking agent, 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.

[0138] The crosslinking agent 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 crosslinking agent 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.

[0139] In addition, the positive photosensitive composition is not limited to the above-mentioned types of additives, and the photosensitive composition may be prepared by adding or removing an appropriate additive depending on the intended use of the composition within a range that does not impair the physical properties.

[0140] The patterned layer according to the embodiment of the present invention may have a high taper angle, for example, the patterned layer according to the embodiment of the present invention may have a taper angle of 20 degrees to 40 degrees.

[0141] 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.

[0142] Synthesis Example 1 (Synthesis of benzoxazole copolymer resin) 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), added with 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.52g of pyridine, and stirred to maintain at 40°C. 0.910g of phthalic anhydride was slowly added thereto 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 in progress, and the solution was stirred for 30 minutes while maintaining the temperature of the solution at 5°C. Then, 11.18g of 4,4'-oxybisbenzoyl chloride was slowly added and dissolved, and reacted with stirring for 12 hours.

[0143] 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 21.13 g of copolymerized polyhydroxyamide powder.

[0144] (Preparation Example 1) Preparation of Positive Photosensitive Composition 14.881 g of the benzoxazole copolymer resin obtained in Synthesis Example 1, 2.232 g of MIPHOTO TPD523 (Migen Shoji), 0.015 g of F-563 (DIC), 0.03 g to 3.33 g of T-1 or T-2 additive, and 1.0 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.

[0145] A photosensitive liquid composition was prepared according to the composition shown in Table 1 below.

[0146] [Table 1]

[0147] The method for preparing a test strip using the positive photosensitive composition is as follows.

[0148] (1) Application and coating stage The photosensitive composition prepared in the examples or comparative examples is applied to a cleaned 10cm x 10cm glass substrate with a certain thickness using a spin coater, and then a coating film is formed by removing part of the solvent using VCD (vacuum chamber dry). The coating thickness of the photosensitive composition is 11μm to 13μm after VCD.

[0149] (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).

[0150] (3) Exposure step In order to obtain a certain thickness of 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 pattern formed is a positive type 9cm x 1cm strap pattern.

[0151] (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). The substrate is then washed with ultrapure water (DI water), whereby the exposed areas are dissolved and removed, leaving only the unexposed areas to form an image pattern, with the remaining coating having a thickness of 9.0 to 11.0 μm.

[0152] (5) Post-heat treatment stage In order to obtain an image pattern obtained by the above development, the coating film obtained is cured by carrying out post baking in an oven at 300 to 320° C. for 30 to 120 minutes.

[0153] (6) Adhesion evaluation After forming 100 cut surfaces using a cross-cut on the test piece produced in the above manufacturing process, NICHIBAN's peeling tape (CT-24) was applied to the cut surfaces without creating any air bubbles. The tape peeling was performed using Coretec Korea's UTM (QM100S) equipment, which was fixed to a 90° jig, and peeled at a constant force at a speed of 300mm / min. The number of peeled pieces on the cut surfaces after peeling was measured compared to before the peel test to confirm adhesion.

[0154] (7) Taper angle measurement The taper angle of each of the test pieces of the embodiment and the comparative example obtained in the post-heat treatment step was confirmed by measuring the cross section of the pattern using a JEOL scanning electron microscope, JSM-IT800.

[0155] [Table 2]

[0156] As a result of the development test shown in Table 2, the accuracy of pattern realization was confirmed using a 10 μm hole mask in all of Examples 1 to 8 and Comparative Examples 1 and 2. It was confirmed that the patterns were accurately realizable with an error of within 0.2 μm in all cases.

[0157] As a result of the adhesion evaluation, in Table 1, Examples 1 to 8 had 20 or less film peelings, while Comparative Examples 1 to 2 had 40 or more. Comparing the taper angles of Examples 1 to 8 and Comparative Examples 1 and 2, it can be seen that the taper angle is lower when the silane additive is not included. Therefore, it was confirmed that the silane additive according to the present invention has an effect of improving adhesion to the substrate, and that the taper angle of the pattern is affected depending on the content of the silane additive.

[0158] The present invention is not limited to the above embodiments and may be implemented in many different forms.

[0159] The above description is merely illustrative of the present invention, and various modifications can be made by a person having ordinary knowledge in the technical field to which the present invention pertains without departing from the essential characteristics of the present invention.

[0160] 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 positive-type photosensitive composition comprising: (A) a polybenzoxazole or polyimide-based polymer; (B) a photosensitizer; (C) a silane-based additive; and (D) a solvent.

2. The positive type photosensitive composition according to claim 1, wherein the polybenzoxazole or polyimide-based polymer comprises a repeating unit selected from the group consisting of the following Formula 1-1; Formula 1-2; Formula 1-3; Formula 1-4; or a combination thereof. 【Chemistry 1】 In the above Chemical Formula 1-1 to Chemical Formula 1-4, 1) * is the part where the bond is connected in the repeat unit, 2) * at the polymer end is the portion where Q-1 to Q-10 of the chemical formula are bonded via an amide bond or an imide bond; 3) X １ Or X ２ is represented by the following chemical formula 2, 4) Y is C ６ ~C ３０ an arylene group having at least one heteroatom selected from O, N, S, Si and P; 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 １ ~C ２０ a cycloalkylene group of C 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 of formula (I); formula (II); and combinations thereof; 5) Z is C ６ ~C ３０ an arylene group having at least one heteroatom selected from O, N, S, Si and P; 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 １ ~C ２０ a cycloalkylene group of C 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 cycloalkynylene groups of the formula: 6) k, l, m, and n are integers of 1 or more; 【Chemistry 2】 7) The polymer end is bonded to a compound represented by a formula selected from the group consisting of one or a combination of formulas Q-1 to Q-10 through an amide or imide bond; 【Chemistry 3】 In the above Chemical Formula 2, 8) L １ is a single bond, -CH ２ --, --CH ２ CH ２ --, --CH ２ OCH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, -C(C ２ H ５ ) ２ -, -C(C ３ H ７ ) ２ -, -C(C ４ H ９ ) ２ -, -C(C ５ H １１ ) ２ -, -C(C ６ H １３ ) ２ -, -C(C ５ H １０ )-, -O-, -CH(CF ３ ) -, -C(CF ３ ) ２ -, -S-, -SO ２ -, Si(CH ３ ) ２ -, -C(SiCH ３ ) ２、 -C ６ H ４－ -CO-, -NHCO-, -COO-, 9) R １ Or R １０ Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 10) The remaining R excluding the linking site １ Or R １０ are each independently hydrogen; deuterium; a hydroxyl group; ６ ~C ３０ an aryl 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 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; or C １ ~C ２０ is an alkoxycarbonyl group of the formula 11) L １ is a single bond, the adjacent R １ and R １０ and R ５ and R ６ can form a ring, 【Chemistry 4】 In the above Chemical Formula 3, 12) L ２ is a single bond, -CH ２ --, --CH ２ CH ２ --, --CH ２ OCH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, -C(C ２ H ５ ) ２ -, -C(C ３ H ７ ) ２ -, -C(C ４ H ９ ) ２ -, -C(C ５ H １１ ) ２ -, -C(C ６ H １３ ) ２ -, -C(C ５ H １０ )-, -O-, -CH(CF ３ ) -, -C(CF ３ ) ２ -, -S-, -SO ２ -, Si(CH ３ ) ２ -, -C(SiCH ３ ) ２ , -C ６ H ４－ -CO-, -NHCO-, -COO-, 13) R １１ Or R ２０ Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 14) The remaining R excluding the linking portion １１ Or R ２０ are each independently hydrogen; deuterium; a hydroxyl group; ６ ~C ３０ an aryl 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 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; or C １ ~C ２０ The remaining R excluding the linking portion is an alkoxycarbonyl group. １１ Or R ２０ Two of them are carboxyl groups, 15) L ２ is a single bond, the adjacent R １１ and R ２０ and R １５ and R １６ can form a ring.

3. 2. The positive type photosensitive composition of claim 1, wherein the silane additive comprises the following formula T-1: 【Chemistry 5】 In the above T-1 to T-2, 1) R ２１ is C ６ ~C ３０ aryl groups of the formula: ２ ~C ３０ Heterocyclic group of C ３ ~C ３０ A cycloalkyl group represented by the formula: ２ ~C ２０ and combinations thereof; 2) R ２２ Or R ２３ is selected from the group consisting of a methoxy group; an ethoxy group; an acetyl group; a carboxyl group, and combinations thereof; 3) R ２４ is C １ ~C １０ is an alkyl group of the formula 4) R ２５ Or R ２７ is selected from the group consisting of a methoxy group, an ethoxy group, an acetyl group, a carboxyl group, and combinations thereof; 5) Ar １ ~Ar ２ is C ６ ~C ３０ an aryl group of the formula: ２ ~C ３０ a heterocyclic group of ３ ~C ３０ a cycloalkyl group of C ２ ~C ２０ The heterocycloalkyl groups are selected from the following:

4. 4. The positive type photosensitive composition of claim 3, wherein the compound represented by Formula T-1 includes compounds represented by Formulas J-1 to J-15 below. 【Chemistry 6】

5. 4. The positive type photosensitive composition of claim 3, wherein the compound represented by Formula T-2 includes compounds represented by Formulas K-1 to K-12 below. 【Chemistry 7】

6. 2. The positive type photosensitive composition of claim 1, wherein the silane additive is present in an amount of 0.1 to 1% by weight based on the total weight of the composition.

7. 2. The positive type photosensitive composition of claim 1, wherein the polybenzoxazole or polyimide polymer is contained in an amount of 5 to 50% by weight based on the total weight of the composition.

8. 2. The positive type photosensitive composition of claim 1, wherein the photosensitizer comprises at least one of the following formulas P-1 to P-8: 【Chemistry 8】 In the above P-1 to P-8, R″ is hydrogen; the following formula S-1; or the following formula S-2. 【Chemistry 9】

9. 2. The positive-type photosensitive composition of claim 1, wherein the photosensitizer is contained in an amount of 1 to 50% by weight based on the total weight of the composition.

10. 2. The positive type photosensitive composition of claim 1, 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.

11. 2. The positive photosensitive composition of claim 1, wherein the solvent is present in an amount of 40 to 95% by weight based on the total weight of the composition.

12. A pattern or film made from the positive-working photosensitive composition of claim 1.

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

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

Images