Photosensitive composition

Abstract

According to the present invention, the pattern is formed from a photosensitive composition containing a copolymer in which a monomer capable of increasing mechanical properties is introduced into a component of a benzoxazole copolymer resin, and a silane-based additive, thereby achieving a technical effect of improving the adhesion between the pattern and a substrate.

Description

Technical Field

[0001] The present invention relates to a positive photosensitive composition used in a semiconductor device or a display device made of a polybenzoxazole or polyimide polymer and a silane additive. Background Art

[0002] The photolithography process generally consists of the following steps, which are: coating step: coating a photoresist composition on a substrate; exposure step: using a light source or E-beam through a mask to form a pattern on the photoresist film; development step: removing a specific area of ​​the photoresist film with the pattern. In addition, a heat treatment (baking) step is added between each step: this step removes the solvent from the photoresist composition or cures the film.

[0003] The photolithography process is roughly divided into negative and positive processes. In the development step, the positive process causes the exposed part to react chemically with the developer, dissolves the reaction product and removes it. On the contrary, the negative process causes the non-exposed part to react chemically with the developer, dissolves the reaction product and removes it. Among them, the positive process uses a photosensitive agent (Photo active compound) that absorbs light and increases solubility in the exposure step, and accurately removes only the exposed part in the development step, so that a more accurate pattern can be obtained than the negative process.

[0004] Conventional semiconductor devices or display devices use positive photosensitive resin compositions. Due to their high heat resistance, chemical resistance, weather resistance, etc., the positive photosensitive resin compositions utilize resins such as polyimide or polybenzoxazole. However, in the development step, since the molecular weight of the polymer resin is limited, the polymer resin is used to develop with an alkaline aqueous solution to achieve precise circuits. Therefore, there are limitations in the mechanical properties that can be achieved.

[0005]

Prior technical literature

[0006] [Patent Literature]

[0007] (Patent Document 1) Japanese Patent Publication No. 2006-526812

[0008] (Patent Document 2) Japanese Patent Publication No. 2007-508582 Summary of the invention

[0009] Issues to be solved

[0010] In order to solve the above-mentioned disadvantages of the conventional technology, the present invention aims to provide a photosensitive composition having enhanced adhesion by introducing a monomer capable of improving mechanical properties and a silane additive capable of enhancing adhesion to a substrate into a polybenzoxazole or polyimide polymer component.

[0011] Furthermore, an object of the present invention is to provide a pattern or film formed using the positive photosensitive composition, and a semiconductor device or display device prepared using the same.

[0012] Problem Solution

[0013] Preferably, the positive photosensitive composition of the present invention comprises (A) a polybenzoxazole or polyimide polymer; (B) a photosensitizer; (C) a silane additive; and (D) a solvent.

[0014] Preferably, the polymer comprises a repeating unit consisting of Chemical Formula 1-1; Chemical Formula 1-2; Chemical Formula 1-3; Chemical Formula 1-4; or a combination thereof.

[0015] <Chemical Formula 1-1>

[0016]

[0017] <Chemical Formula 1-2>

[0018]

[0019] <Chemical Formula 1-3>

[0020]

[0021] <Chemical Formula 1-4>

[0022]

[0023] In the above Chemical Formulas 1-1 to 1-4,

[0024] 1)* is the part that makes the bond connected in a repeating unit,

[0025] 2) The * at the end of the polymer is the part to which the chemical formulas Q-1 to Q-10 are bonded via an amide bond or an imide bond,

[0026] 3) X1 or X2 is the following chemical formula 2,

[0027] 4) Y is selected from the group consisting of: C6~C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group of an aliphatic ring and an aromatic ring; C1~C 20Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkyne group; C3~C 20 cycloalkynylene group; Chemical Formula 2; and combinations thereof,

[0028] 5) Z is selected from the group consisting of: C6~C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group of an aliphatic ring and an aromatic ring; C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkyne group; C3~C 20 cycloalkynylene group; Chemical Formula 3; and combinations thereof,

[0029] 6) k, l, m, and n are integers greater than 1,

[0030] <Chemical formulas Q1 to Q10>

[0031]

[0032] 7) The polymer terminal is bonded to a chemical formula selected from one of the above chemical formulas Q-1 to Q-10 or a group consisting of a combination thereof through an amide or imide bond,

[0033] <Chemical Formula 2>

[0034]

[0035] In the above chemical formula 2,

[0036] 8) L 1 Selected from single bonds, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-、-C(C6H 13 )2-、-C(C5H 10 )-, –O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, -Si(CH3)2-, -C(SiCH3)2, -C6H4-, -CO-, -NHCO-, -COO-,

[0037] 9) R1 to R 10 Two of them are bonding sites with the amide groups shown in Chemical Formula 1-1 and Chemical Formula 1-2,

[0038] 10) In addition to the bonding site, the remaining R1 to R 10 Independently of each other: hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group (cyclogroup) of an aliphatic ring and an aromatic ring; C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 Alkoxy carbonyl group,

[0039] 11) L 1 When it is a single bond, the adjacent R1 and R 10; can form a ring with R5 and R6,

[0040] <Chemical formula 3>

[0041]

[0042] In the above chemical formula 3,

[0043] 12) L 2 Selected from single bonds, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-、-C(C6H 13 )2-、-C(C5H 10 )-, –O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, -Si(CH3)2-, -C(SiCH3)2, -C6H4-, -CO-, -NHCO-, -COO-,

[0044] 13) R 11 To R 20 Two of them are bonding sites with the amide groups shown in Chemical Formula 1-1 and Chemical Formula 1-2,

[0045] 14) In addition to the bonding site, the remaining R 11 To R 20 Independently of each other: hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group of an aliphatic ring and an aromatic ring; C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C20 However, the remaining R 11 To R 20 Two of them are carboxyl groups.

[0046] 15)L 2 When it is a single bond, the R adjacent to the bonding site is not 11 and R 20 ; and R 15 and R 16 Can form a ring,

[0047] Preferably, the polybenzoxazole or polyimide polymer is made of diamine monomers; diacid chloride monomers; dianhydride monomers; and acid anhydride monomers.

[0048] Preferably, the diamine comprises one or more monomers selected from the group consisting of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dihydroxybenzidine, 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'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dihydroxy-4,4'-diamino-biphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenylethoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminobenzanilide, 9,9'-bis(4-aminophenol)fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-{4-aminophenethoxyphenyl}]hexafluoropropane, 4,4'-(cyclohexane-1,1-diyl)diphenylamine, and combinations thereof.

[0049] Preferably, the diacid chloride comprises one or more monomers selected from the group consisting of 4,4'-oxydibenzoyl chloride, 1,2-cyclobutyldicarboxylic acid dichloride, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenylacetyl chloride, 1,4-naphthalene dicarboxylic acid chloride, 4,4'-dibenzoylsulfonyl chloride, 1,4-cyclohexanedicarbonyl dichloride, and combinations thereof.

[0050] Preferably, the dianhydride comprises one or more monomers selected from the group consisting of: 3,3',4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride,

[0051] 3,3'4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromethyl dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-(2,2,2-trifluoro-1-phenylethylene) diphthalic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-bisphenol A dianhydride, bicyclooctanetetracarboxylic dianhydride and combinations thereof.

[0052] Preferably, 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-norbornene-2,3-dicarboxylic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, and combinations thereof.

[0053] Preferably, the weight average molecular weight of the copolymer is 5,000 to 40,000 g / mol.

[0054] Preferably, the content of the polybenzoxazole or polyimide polymer is 5 to 50 wt % in the total amount of the composition.

[0055] Preferably, the photosensitizer comprises one or more of the following chemical formulas P-1 to P-8.

[0056]

[0057]

[0058] In P-1 to P-8, R" is hydrogen; the following chemical formula S-1; or chemical formula S-2.

[0059] <Chemical Formula S-1>

[0060]

[0061] <Chemical Formula S-2>

[0062]

[0063] Preferably, the content of the photosensitizer is 1 to 50% by weight of the composition.

[0064] The silane-based additive may be used alone or in combination with the following chemical formula T-1.

[0065]

[0066] In the above T-1 to T-2,

[0067] 1) R 21 Selected from the group consisting of: C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C3~C 30 Cycloalkyl group; C2~C 20 A heterocycloalkyl group and a combination thereof,

[0068] 2) R 22 To R 23 is selected from the group consisting of methoxy; ethoxy; acetyl; carboxyl and combinations thereof,

[0069] 3) R 24 C1~C 10 An alkyl group,

[0070] 4) R 25 To R 27 is selected from the group consisting of methoxy; ethoxy; acetyl; carboxyl and combinations thereof,

[0071] 5) Ar1 to Ar2 are selected from C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C3~C 30 Cycloalkyl group; C2~C 20 The heterocycloalkyl group is a heterocycloalkyl group.

[0072] The silane-based additive T-1 may include compounds represented by the following Chemical Formulas J-1 to J-15.

[0073]

[0074]

[0075] The silane-based additive T-2 may include compounds represented by the following chemical formulas K-1 to K-12.

[0076]

[0077] Preferably, the content of the silane additive is 0.1 to 1 wt % in the total amount of the composition.

[0078] Preferably, the solvent comprises one or more selected from the group consisting of N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, γ-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and combinations thereof.

[0079] Preferably, the content of the solvent in the total amount of the composition is 40 to 95 wt %.

[0080] Preferably, the positive photosensitive composition further comprises one or more selected from the group consisting of the following components: a surface smoothing agent; a surfactant; a crosslinking agent; and a combination thereof.

[0081] Preferably, the content of the additive is 0.001 to 10 wt % in the total amount of the composition.

[0082] In another embodiment of the present invention, preferably, a pattern or film made of the positive photosensitive composition is provided.

[0083] In another specific example of the present invention, preferably, a semiconductor device or a display device manufactured using the pattern or film is provided.

[0084] In another specific example of the present invention, preferably, an electronic device is provided, which includes the semiconductor device or the display device and a control unit for driving the same.

[0085] Effects of the Invention

[0086] The present invention adopts a photosensitive composition containing a copolymer and a silane series additive to form a pattern, thereby obtaining a technical effect of improving the adhesion between the pattern and the substrate. The copolymer introduces a monomer that can increase mechanical properties into the components of polybenzoxazole or polyimide series polymers. DETAILED DESCRIPTION

[0087] In the process of describing the present invention, if it is considered that the detailed description of the relevant known structure or function will confuse the main points of the present invention, the detailed description thereof may be omitted. When the present invention adopts "including", "having", "comprising", etc., other parts may be added unless "to only" is used. When the constituent elements are expressed in the singular, unless otherwise clearly stated, the case of expressing them in the plural is included.

[0088] Furthermore, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only used to distinguish the components from other components, and the nature, order, sequence or number of the components are not limited by these terms.

[0089] In the process of describing the positional relationship of constituent elements, when it is mentioned that two or more constituent elements are "connected", "combined" or "accessed", it should be understood that the two or more constituent elements can be directly "connected", "combined" or "accessed", but can also be further "carried with" the two or more constituent elements and other constituent elements to achieve "connection", "combination" or "access". Among them, the other constituent elements can include one or more of the two or more constituent elements that are "connected", "combined" or "accessed" to each other.

[0090] Furthermore, when a component such as a layer, film, region, or plate is located “on” or “over” another component, it should be understood that it includes not only the case where it is located “directly above” another component, but also the case where there is another component in between. Conversely, when a component is located “directly above” another part, it should be understood that there is no other part in between.

[0091] When describing the time flow relationship related to constituent elements, working methods, or manufacturing methods, for example, when describing the time sequence relationship or process sequence relationship such as "after", "next to", "then", "before", etc., since "immediately" or "directly" is not used, discontinuous situations can be further included.

[0092] In addition, when referring to the numerical value of a constituent element or the information corresponding thereto, even if not clearly stated separately, it should be interpreted that the numerical value or the information corresponding thereto includes: the error range caused by various factors (for example, engineering factors, internal or external impact, noise, etc.).

[0093] When interpreting the terms used in this specification and the appended claims, they should not be limited to the conventional or dictionary meanings, but should be interpreted as meanings and concepts that are consistent with the technical ideas of the present invention based on the principle that the inventor can appropriately define the concepts of the terms in order to describe his own invention in the most preferred way.

[0094] Unless otherwise described, the term "halo" or "halogen" used in the present application includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0095] Unless otherwise described, the term "alkyl" or "alkyl group" used in this application contains 1 to 60 carbon atoms connected by single bonds, and refers to a free radical of a saturated aliphatic functional group represented by a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group, and a cycloalkyl-substituted alkyl group.

[0096] Unless otherwise described, the term "haloalkyl group" or "halogenalkyl group" used in the present application refers to an alkyl group substituted with halogen.

[0097] Unless otherwise described, the term "alkenyl" or "alkynyl" used in the present application respectively has a double bond or a triple bond, contains a straight chain or a side chain, and has 2 to 60 carbon atoms, but is not limited thereto.

[0098] Unless otherwise described, the term "cycloalkyl" used in the present application means a cyclic alkane having 3 to 60 carbon atoms, but is not limited thereto.

[0099] The term "alkoxy group" or "alkyloxy group" used in the present application refers to an alkyl group to which an oxygen radical is bonded, and unless otherwise specified, has 1 to 60 carbon atoms, but is not limited thereto.

[0100] The term "alkenoxyl group", "alkenoxygroup", "alkenyloxyl group" or "alkenyloxy group" used herein means an alkenyl group to which an oxygen radical is bonded, and unless otherwise specified, has 2 to 60 carbon atoms, but is not limited thereto.

[0101] Unless otherwise described, the terms "aryl group" and "arylene group" used in the present application have 6 to 60 carbons, respectively, but are not limited thereto. In the present application, aryl group or arylene group include monocyclic type, cyclopolymer, fused polycyclic compounds, etc. For example, the aryl group may include phenyl group, the monovalent functional group of biphenyl, the monovalent functional group of naphthalene, fluorenyl group and substituted fluorenyl group. Arylene group may include fluorenyl group and substituted fluorenyl group.

[0102] The term "ring assemblies" used in the present application is composed of two or more ring systems (single ring or fused ring systems) directly connected by a single bond or a double bond, indicating that the number of directly connected rings is less than the total number of ring systems contained in the compound by 1. The ring assemblies can be directly connected by the same or different ring systems through a single bond or a double bond.

[0103] In the present application, the aryl group includes a cyclopolymer, and thus, the aryl group includes biphenyl and terphenyl connected by a single bond to a benzene ring as a monocyclic aromatic. In addition, the aryl group also includes a compound in which an aromatic ring system combined with an aromatic monocyclic ring is connected by a single bond, and thus, for example, a compound in which an aromatic ring system combined with a benzene ring as an aromatic monocyclic ring, i.e., fluorene, is connected by a single bond.

[0104] The term "fused polycyclic ring system" used in this application refers to a fused ring that shares at least two atoms, including: a fused form of two or more hydrocarbon ring systems and a fused form of at least one heterocyclic ring system containing at least one heteroatom. The fused polycyclic ring system can be an aromatic ring, an aromatic heterocyclic ring, an aliphatic ring, or a combination of such rings. For example, an aryl group can be a naphthyl group, a phenanthrenyl group, a fluorenyl group, etc., but it is not limited thereto.

[0105] The term "spiro compound" used in the present application has a 'spiro union', which means that two rings share only one atom to form a connection. In this case, the atom shared by the two rings is called a 'spiro atom', and according to the number of spiro atoms contained in one compound, it is called a 'monospiro-', 'dispiro-', 'trispiro-' compound, respectively.

[0106] Unless otherwise described, the terms "fluorenyl group", "fluorenyl group" and "fluorene-triyl group" used in this application respectively represent monovalent, divalent or trivalent functional groups in which R, R', R" and R'" are all hydrogen in the following structures, and "substituted fluorenyl group", "substituted fluorenyl group" or "substituted fluorene-triyl group" means that at least one of the substituents R, R', R", R'" is a substituent other than hydrogen, including the case where R and R' are bonded to each other and form a spiro compound together with the carbon to which they are bonded. In this specification, the fluorenyl group, fluorenyl group and fluorene-triyl group may be named as fluorenyl group without considering the equivalent number of monovalent, divalent and trivalent.

[0107]

[0108] Furthermore, the R, R', R" and R'" may be independently selected from: an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclyl group having 2 to 30 carbon atoms. For example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene or phenanthrene, and the heterocyclyl group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidone, pyridazine, pyrazine, triazine, indole, benzofuran, or the like. For example, the substituted fluorenyl group and the fluorenylene group may be monovalent or divalent functional groups of 9,9-dimethylfluorene, 9,9-diphenylfluorene, and 9,9'-spirobi [9H-fluorene], respectively.

[0109] The term "heterocyclyl group" used in this application includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group", but also non-aromatic rings. Unless otherwise described, they respectively represent rings containing one or more heteroatoms and having a carbon number of 2 to 60, but are not limited thereto. Unless otherwise described, the term "heteroatom" used in this application represents N, O, S, P or Si, and heterocyclyl group represents a monocyclic type, cyclopolymer, fused polycyclic system, spiro compound, etc. containing heteroatoms.

[0110] For example, a "heterocyclyl group" may also replace a cyclic carbon, including the following compounds, and compounds containing heteroatom terminal groups such as SO2 and P=O.

[0111]

[0112] The term "ring" used in the present application includes monocyclic and polycyclic rings, and of course, hydrocarbon rings include heterocyclic rings, the heterocyclic rings contain at least one heteroatom, and include aromatic and non-aromatic rings.

[0113] The term "polycyclic" as used in this application includes ring assemblies such as biphenyl and terphenyl and fused polycyclic systems and spiro compounds, including not only aromatic but also non-aromatic rings. Of course, hydrocarbon rings include heterocyclic rings that contain at least one heteroatom.

[0114] The term "aliphatic cyclo group" used in this application refers to cyclic hydrocarbons other than aromatic hydrocarbons, including monocyclic types, cyclopolymers, fused polycyclic systems, spiro compounds, etc., and unless otherwise specified, refers to a ring with a carbon number of 3 to 60, but is not limited thereto. For example, when aromatic cyclobenzene and non-aromatic cyclohexane are fused, they are also equivalent to aliphatic rings.

[0115] Furthermore, when prefixes are used consecutively, it means that the substituents are arranged in the order of the description. For example, aryl alkoxy group means an alkoxy group substituted with an aryl group, alkoxy carbonyl group means a carbonyl group substituted with an alkoxy group, and aryl carbonyl alkenyl group means an alkenyl group substituted with an arylcarbonyl group, wherein aryl carbonyl group is a carbonyl group substituted with an aryl group.

[0116] Furthermore, unless otherwise specified, in the term "substituted or unsubstituted" used in the present application, "substituted" means substituted with one or more substituents selected from the group consisting of deuterium, halogen, amino group, nitrile group, nitro group, C1-C 30 Alkyl group, C1~C 30 Alkoxy group, C1~C 30 Alkyl amine group, C1~C 30 alkyl thiophene group, C6~C 30 arylthiophene group, C2~C 30 Alkenyl group, C2~C 30 Alkinyl group, C3~C 30 Cycloalkyl group, C6~C 30 aryl group, C6~C 30 Aryl group, C8~C 30 aryl alkenyl group, silane group, boron group, germanium group and C2~C 30 The heterocyclic group, the C2~C 20 The heterocyclic group includes at least one heteroatom selected from the group consisting of O, N, S, Si and P. And, it is not limited by the substituents thereof.

[0117] In the present application, the 'functional group name' corresponding to the aryl group, arylene group, heterocyclyl group, etc. described in each label and its substituent examples can be recorded as 'functional group name reflecting valence' or as 'name of the parent compound'. For example, 'phenanthrene' as an aryl group' can be classified and recorded as the name of the 'group' according to the valence, such as recording the monovalent 'group' as 'phenanthryl (group)' and recording the divalent 'group' as 'phenanthryl (group)', etc. However, it can also be recorded as the name of the parent compound 'phenanthrene' without considering the valence.

[0118] Similarly, pyrimidone can be recorded as 'pyrimidone' regardless of the valence, or recorded as pyrimidinyl (base) when it is monovalent, and can be recorded as the 'name of the base' of the corresponding valence when it is divalent, such as pyrimidinylene (base), etc. Therefore, in the present application, when the type of substituent is recorded as the name of the parent compound, it can represent: an n-valent 'base' formed by the desorption of hydrogen atoms bonded to carbon atoms and / or heteroatoms of the parent compound.

[0119] In addition, in this specification, when recording the name of a compound or a substituent, the numerals or alphabets indicating the position may be omitted. For example, pyrido[4,3-d]pyrimidone may be recorded as pyrido pyrimidone, benzofuran[2,3-d]pyrimidone may be recorded as benzofuran pyrimidone, 9,9-dimethyl-9H-fluorene may be recorded as dimethylfluorene, etc. Therefore, benzo[g]quinoxaline or benzo[f]quinoxaline may be recorded as benzoquinoxaline.

[0120] Furthermore, unless otherwise expressly stated, the chemical formulae used in this application are also subject to the definitions of substituents according to the index definitions of the following chemical formulae.

[0121]

[0122] Wherein, when a is an integer of 0, it indicates that the substituent R 1 When a is 0, the carbon atoms forming the benzene ring are all bonded with hydrogen atoms. In this case, the symbol of the hydrogen atoms bonded with carbon atoms can be omitted and the chemical formula or compound can be recorded. 1 When a is an integer of 2 or 3, the bonding can be as follows. When a is an integer of 4 to 6, it can also be bonded to the carbon of the benzene ring by a similar method. When a is an integer of 2 or more, R 1 Can be the same or different.

[0123]

[0124] In the present application, unless otherwise described, forming a ring means that adjacent groups are bonded to each other to form a monocyclic ring or a fused polycyclic ring. The monocyclic ring and the fused polycyclic ring formed include not only hydrocarbon rings but also heterocyclic rings. The heterocyclic ring contains at least one heteroatom and may include aromatic and non-aromatic rings.

[0125] In addition, in this specification, unless otherwise described, when a condensed ring is represented, in the term "number-condensed ring", the number represents the number of condensed rings. For example, a condensed form of three rings can be represented as a 3-condensed ring, such as anthracene, phenanthrene, benzo quinozoline, etc.

[0126] In addition, unless otherwise described, the term "bridged bicyclic compound" used in the present application refers to a compound in which two rings share three or more atoms to form a ring. In this case, the shared atoms may include carbon or heteroatoms.

[0127] Hereinafter, an implementation example of the present invention will be described in detail. However, this is for illustrative purposes only and the present invention is not limited thereto. The present invention is only defined by the scope of the following claims.

[0128] The positive photosensitive composition described in one embodiment of the present invention comprises polybenzoxazole or polyimide polymer, which can be used in the preparation of insulating films, surface protection films, rewiring layers, and pixel definition layers (PDL) of semiconductor devices.

[0129] When preparing the positive photosensitive composition for use in a semiconductor device or a display device according to an embodiment of the present invention, the following additives may be further included in order to improve the required characteristics.

[0130] Regarding the additives that can be added in one implementation example of the present invention, a surface leveler can be further included, and when coating is performed on a substrate, the surface leveler can make the coating film have a constant thickness. In order to obtain a smooth coating according to the characteristics of the substrate surface, a surfactant can be further included. In order to adjust the adhesion between the substrate surface, a silane coupling agent can be further included. In order to enhance the bonding between polymer molecules in the heat treatment step, a cross-linking agent can be further included.

[0131] The components of the positive photosensitive composition are as follows.

[0132] (1) Polybenzoxazole or polyimide polymer resin

[0133] According to an embodiment of the present invention, the pattern forming resin may include polybenzoxazole or polyimide-based polymer.

[0134] The polybenzoxazole or polyimide polymer resin refers to a resin containing hydroxyamide and amic acid copolymers; and benzoxazole and imide copolymers. The hydroxyamide and amic acid copolymers can be formed into benzoxazole and polyimide copolymers through chemical or thermal treatment, while the benzoxazole and imide copolymers have been chemically or thermally treated.

[0135] The content of the polybenzoxazole or polyimide polymer resin in the total amount of the positive photosensitive composition may be 5 wt % to 50 wt %, preferably, 10 wt % to 40 wt %.

[0136] The polybenzoxazole or polyimide polymer resin includes copolymers represented by the following chemical formulas 1-1 to 1-4, etc., but is not limited thereto. They can be used alone or in combination of two or more. The weight average molecular weight of the polybenzoxazole or polyimide polymer resin can be 5,000 g / mol to 40,000 g / mol, preferably 5,000 g / mol to 35,000 g / mol, and more preferably 7,000 g / mol to 25,000 g / mol.

[0137] Preferably, the polybenzoxazole or polyimide-based polymer includes a repeating unit selected from the group consisting of the following Chemical Formula 1-1; Chemical Formula 1-2; Chemical Formula 1-3; Chemical Formula 1-4; or a combination of two or more of Chemical Formulas 1-1 to 1-4.

[0138] <Chemical Formula 1-1>

[0139]

[0140] <Chemical Formula 1-2>

[0141]

[0142] <Chemical Formula 1-3>

[0143]

[0144] <Chemical Formula 1-4>

[0145]

[0146] In the above Chemical Formulas 1-1 to 1-4,

[0147] 1)* is the part that makes the bond connected in a repeating unit,

[0148] 2) The * at the end of the polymer is the part to which the chemical formulas Q-1 to Q-10 are bonded via an amide bond or an imide bond,

[0149] 3) X1 or X2 is the following chemical formula 2,

[0150] 4) Y is selected from the group consisting of: C6~C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group of an aliphatic ring and an aromatic ring; C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkyne group; C3~C 20 cycloalkynylene group; Chemical Formula 2; and combinations thereof,

[0151] 5) Z is selected from the group consisting of: C6~C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group of an aliphatic ring and an aromatic ring; C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkyne group; C3~C 20cycloalkynylene group; Chemical Formula 3; and combinations thereof,

[0152] 6) k, l, m, and n are integers greater than 1,

[0153] <Chemical formulas Q1 to Q10> 1)

[0154]

[0155] 7) The polymer terminal is bonded with a chemical formula selected from one or a combination of the above chemical formulas Q-1 to Q-10 through an amide or imide bond,

[0156] <Chemical Formula 2>

[0157]

[0158] In the above chemical formula 2,

[0159] 8) L 1 Selected from single bonds, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-、-C(C6H 13 )2-、-C(C5H 10 )-, –O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, -Si(CH3)2-, -C(SiCH3)2, -C6H4-, -CO-, -NHCO-, -COO-,

[0160] 9) R1 to R 10 Two of them are bonding sites with the amide groups shown in Chemical Formula 1-1 and Chemical Formula 1-2,

[0161] 10) In addition to the bonding site, the remaining R1 to R 10 Independently of each other: hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group (cyclogroup) of an aliphatic ring and an aromatic ring; C1~C 20 Alkyl group; C2~C 20alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 Alkoxy carbonyl group,

[0162] 11) L 1 When it is a single bond, the adjacent R1 and R 10 ; can form a ring with R5 and R6,

[0163] <Chemical formula 3>

[0164]

[0165] In the above chemical formula 3,

[0166] 12) L 2 Selected from single bonds, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-、-C(C6H 13 )2-、-C(C5H 10 )-, –O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, -Si(CH3)2-, -C(SiCH3)2, -C6H4-, -CO-, -NHCO-, -COO-,

[0167] 13) R 11 To R 20 Two of them are bonding sites with the amide groups shown in Chemical Formula 1-1 and Chemical Formula 1-2,

[0168] 14) In addition to the bonding site, the remaining R 11 To R 20 Independently of each other: hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30heterocyclic group; C6~C 30 A condensed ring group of an aliphatic ring and an aromatic ring; C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 However, the remaining R 11 To R 20 Two of them are carboxyl groups.

[0169] 15)L 2 When it is a single bond, the R adjacent to the bonding site is not 11 and R 20 ; and R 15 and R 16 A ring can be formed.

[0170] If the weight average molecular weight of the resin is within the range, no residue of the exposure layer remains during development, the film thickness loss of the non-exposure layer is reduced to a minimum, and a good pattern can be obtained. In the total amount of the photosensitive composition, the content of the resin is 5 to 50% by weight, and more preferably, the content can be 10 to 45% by weight. When the content of the resin is within the range, a constant film thickness, excellent sensitivity, developability and adhesion (tightness) can be obtained in the coating step.

[0171] (2) Photosensitizer

[0172] In order to present a positive pattern through a photolithography machine, a photo-radical initiator is required. The photosensitive agent can be selected according to the wavelength used, such as g-line (436nm), h-line (405nm), i-line (365nm), Deep UV (<260nm), etc., and used separately or in combination.

[0173] The photosensitizer is a photosensitizer commonly used in positive photosensitive compositions, for example, a photosensitive diazoquinone compound, etc. Specifically, it can include a phenol compound and a photosensitive compound represented by the following chemical formula P-1 to chemical formula P-8. Specific examples of R" include: a compound containing hydrogen; deuterium; 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid in the structure.

[0174]

[0175] In P-1 to P-8, R" is hydrogen; the following chemical formula S-1; or chemical formula S-2.

[0176] <Chemical Formula S-1>

[0177]

[0178] <Chemical Formula S-2>

[0179]

[0180] In the above chemical formula S-1 and chemical formula S-2, * represents a bonding site.

[0181] Preferably, the content of the photosensitizer is 1 to 50% by weight in the total amount of the composition.

[0182] (3) Silane additives

[0183] In order to improve the adhesion performance with the substrate, the positive photosensitive resin composition may include a silane coupling agent.

[0184] Silane additives are generally used in the photosensitive positive photosensitive composition, and may further include a silane coupling agent, which has a reactive substituent such as a vinyl group, a carboxyl group, a methacrylic group, an isocyanate group, an epoxy group, etc. Specifically, it may include a phenol compound and a silane additive represented by the following chemical formulas T-1 to T-2.

[0185] Preferably, the content of the silane additive is 0.001 to 10 wt % of the total amount of the composition. More preferably, the content of the silane additive is 0.1 to 1 wt % of the total amount of the composition.

[0186] The silane-based additive may include the following Chemical Formula T-1; Chemical Formula T-2 or a combination thereof.

[0187] More preferably, the silane-based additive includes both Chemical Formula T-1 and Chemical Formula T-2.

[0188]

[0189] In the above T-1 to T-2,

[0190] 1) R 21 Selected from the group consisting of: C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C3~C 30 Cycloalkyl group; C2~C 20 A heterocycloalkyl group and a combination thereof,

[0191] 2) R 22 To R 23 is selected from the group consisting of methoxy; ethoxy; acetyl; carboxyl and combinations thereof,

[0192] 3) R 24 C1~C 10 An alkyl group,

[0193] 4) R 25 To R 27 is selected from the group consisting of methoxy; ethoxy; acetyl; carboxyl and combinations thereof,

[0194] 5) Ar1 to Ar2 are selected from C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C3~C 30 Cycloalkyl group; C2~C 20 The heterocycloalkyl group is a heterocycloalkyl group.

[0195] The silane-based additive T-1 may include structures represented by the following chemical formulas J-1 to J-15, but is not limited thereto.

[0196]

[0197] 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.

[0198]

[0199] (4) Solvent

[0200] The solvent may be a substance that is compatible with and does not react with the benzoxazole copolymer resin, the photosensitizer, and the pigment.

[0201] For example, the solvent includes: alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, anisole, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethyl acetate glycol ethers such as methoxyethyl acetate, ethoxyethyl acetate, and diethoxyethyl acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol Propylene glycol alkyl ether acetates such as methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-di-n-amyl ketone, 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, methyl oxyacetate, butyl oxyacetate; methoxy Alkoxyacetic acid alkyl esters such as methyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; 3-oxopropionic acid alkyl esters such as methyl 3-oxopropionate, ethyl 3-oxopropionate, etc.; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-oxopropionic acid alkyl esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, etc.; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, etc. 2-alkoxypropionic acid alkyl esters such as ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate; keto acid esters such as ethyl pyruvate, etc.

[0202] In addition, high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol phenyl acetate can be used.

[0203] Taking into account the compatibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether (ethylene glycolmonoethyl ether); ethylene glycol acetate alkoxy ethers such as ethoxyethyl acetate; ethers such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

[0204] In the total amount of the photosensitive composition, the solvent may be included as a balance, specifically, the content may be 50 to 95% by weight. When the content of the solvent is included in the range, the positive photosensitive resin composition may have an appropriate viscosity, thereby achieving excellent processability when preparing a pattern layer.

[0205] (5) Other additives

[0206] In order to prevent the occurrence of marks or spots, improve the leveling performance and prevent the generation of residues due to undevelopment when coating the positive photosensitive composition, the composition may further contain additives such as malonic acid, 3-amino-1,2-propanediol, a surface leveler containing a vinyl group or a (meth)acryloxy group, a surfactant, and a cross-linking agent.

[0207] Preferably, the content of the additive is 0.001 to 10 wt % in the total amount of the composition.

[0208] Also, in order to form a constant film thickness in a coating step, the photosensitive composition may further include a surface leveler as needed.

[0209] The surface leveler can be made from DIC etc.; BASF FL3740, FL3741, FL3745, FL3770 and other surface levelers are on sale.

[0210] The surface leveler may be used in an amount of 0.001 to 5 parts by weight in 100 parts by weight of the photosensitive composition. When the surface leveler is used in an amount within the above range, coating uniformity can be ensured, and a coating with a constant film thickness can be formed.

[0211] Furthermore, in order to improve coating properties and prevent defects, the photosensitive composition may further include a surfactant as needed.

[0212] The surfactant can be the following commercially available surfactant: etc.; Dainippon Ink & Chemicals Co., Ltd.'s Mecha Pack F Mecha Pack F Mecha Pack F Mecha Pack F etc.; Lard from Sumitomo 3M Co. lard lard lard etc.; Saffron from Asahi Glass Co., Ltd. Saffron Saffron Saffron Saffron etc.; Toray Silicon Corporation wait.

[0213] The amount of the surfactant can be 0.001 to 5 parts by weight in 100 parts by weight of the photosensitive composition. When the weight of the surfactant is within the above range, the coating uniformity can be ensured, no spots will occur, and the wettability of the glass substrate is excellent.

[0214] The crosslinking agent may be 1,4-bis(methoxymethyl)benzene, dimethyl sulfate, 3-aminopropyltriethoxysilane, N,N'-methylenebisacrylamide, etc., which may be used alone or in combination of two or more.

[0215] The amount of the crosslinking agent can be 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive composition. When the weight of the crosslinking agent is within the above range, it is beneficial to appropriately impart physical properties to the cured coating film, for example, mechanical properties such as tensile strength.

[0216] Furthermore, the additives that can be added to the positive photosensitive composition are not limited to the above-mentioned types. The photosensitive composition can be prepared by adding or excluding appropriate additives in a range that does not impair the physical properties according to the purpose of use of the composition.

[0217] The pattern layer of the embodiment of the present invention may have a relatively high taper angle. For example, the taper angle of the pattern layer of the embodiment of the present invention may be 20° to 40°.

[0218] Hereinafter, the synthesis examples and examples of the present invention will be described in detail, but the synthesis examples and examples of the present invention are not limited thereto.

[0219] Synthesis Example 1: (Synthesis of benzoxazole copolymer resin)

[0220] A 250ml 3-neck round bottom flask is attached with a stirrer, a nitrogen injection device, a dropping funnel, a thermostat and a cooler. Then, nitrogen is filled and filled with 65.7g of N-methylpyrrolidone (NMP). Then, 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.52g of pyridine are added and stirred, and maintained at 40°C. Among them, 0.910g of phthalic anhydride is slowly added, and then stirred for a certain time to dissolve and react. Then, 52.70g of NMP is added to the reacting flask, the temperature of the solution is maintained at 5°C, and stirred for 30 minutes. Then, 11.18g of 4,4'-oxydibenzoyl chloride is slowly added, dissolved, and stirred for 12 hours to react.

[0221] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid powder was vacuum dried at 60° C. for 12 hours to obtain 21.13 g of copolymerized polyhydroxyamide powder.

[0222] (Preparation Example 1) Preparation of positive photosensitive composition

[0223] 14.881 g of the benzoxazole copolymer resin obtained in Synthesis Example 1, 32.232 g of MIPHOTO TPD52 (Mihara Trading Co., Ltd.), 0.015 g of F-563 (DIC Corporation), 0.03 g to 3.33 g of T-1 or T-2 additive, 1.0 g of 1,4-bis(methoxymethyl)benzene, and 32.5 g of γ-butyrolactone were stirred at room temperature for 12 hours. Then, the composition was filtered three times to remove impurities, thereby preparing a photosensitive composition.

[0224] A photosensitive composition liquid was prepared according to the composition described in Table 1 below.

[0225]

Table 1

[0226]

[0227]

[0228] The method for preparing a test piece using the positive photosensitive composition is as follows.

[0229] (1) Coating and coating steps

[0230] On a cleaned 10 cm*10 cm glass substrate, the photosensitive composition prepared in the embodiment or comparative example is coated with a constant thickness using a spin coater, and then a portion of the solvent is removed using a vacuum chamber dry (VCD) to form a coating film. The thickness of the coating of the photosensitive composition after VCD is 11 μm to 13 μm.

[0231] (2) Pre-baking step

[0232] The obtained coating film is heated at 100°C to 140°C for 50 to 200 seconds on a hot plate to remove the solvent contained in the obtained coating film. This process removes a certain amount of solvent so that after the next process (exposure) is implemented, a coating film with a constant thickness can be obtained even in the development step.

[0233] (3) Exposure Step

[0234] In order to obtain the required constant thickness of the coating film obtained above, 190nm to 600nm actinic rays are irradiated by an exposure machine, preferably, a metal or LED light source with ghi-line is irradiated to form a pattern. The exposure amount of the irradiation is 50 to 500mJ / cm 2 The pattern formed is a positive 9cm*1cm strip pattern.

[0235] (4) Development step

[0236] After the exposure step, a certain amount of TMAH (tetramethylhydroxyammonium) 2.38wt% developer was used to wet the substrate at 23±2°C by a puddle method, and the substrate was left for a certain period of time (minutes) and developed. After development, the substrate was rinsed with deionized water (DI water) to dissolve and remove the exposed part, leaving only the non-exposed part, to form an image pattern. The thickness of the residual coating was 9.0 to 11.0μm.

[0237] (5) Post-baking step

[0238] In order to obtain the image pattern obtained by the development, post baking is performed in an oven at 300 to 320° C. for 30 to 120 minutes, and then the obtained coating film is cured.

[0239] (6) Adhesion test

[0240] On the test pieces obtained through the above-mentioned preparation process, 100 cutting surfaces were formed using the cross-cut method, and then, the peeling tape (CT-24) of NICHIBAN Co., Ltd. was pasted on the cutting surfaces without air bubbles. When peeling the tape, using the UTM (QM 100S) equipment of Korea Koto Co., Ltd., it was fixed on a 90° jig, and then peeled at a speed of 300 mm / min with a constant force. By comparing the number of tears on the cutting surface before and after the peeling test, the tightness was confirmed.

[0241] (7) Taper angle detection

[0242] The test pieces of the examples and comparative examples obtained after the baking treatment step of the test pieces were taken out, and the cross-sections of the patterns were detected using the scanning electron microscope JSM-IT800 of JEOL Ltd., and the taper angle was confirmed.

[0243]

Table 2

[0244]

[0245]

[0246] As shown in the development test results recorded in Table 2 above, Examples 1 to 8 and Comparative Examples 1 to 2 all used a 10 μm Hole mask to confirm the accuracy of the developed pattern. From the results, it was confirmed that the error was within 0.2 μm, and the pattern was developed precisely.

[0247] Regarding the number of film peelings in the evaluation results of tightness, the number of Examples 1 to 8 in Table 1 above was 20 or less, and the number of Comparative Examples 1 to 2 was 40 or more. By comparing the taper angles (Taper angle) of Examples 1 to 8 and Comparative Examples 1 to 2, it can be seen that when the silane additive was not included, the taper angle (Taper angle) decreased. From this, it can be confirmed that the silane additive of the present invention can improve the adhesion force with the substrate, and the content of the silane-based additive has an impact on the taper angle (Taper angle) of the pattern.

[0248] The present invention is not limited by the above-mentioned examples and can be prepared in various different forms.

[0249] The above description only illustrates the present invention. As long as those of ordinary skill in the technical field to which the present invention pertains, various modifications can be made without departing from the essential characteristics of the present invention.

[0250] Therefore, the embodiments disclosed in this specification are used to describe the present invention, rather than to limit the present invention, and the idea and scope of the present invention are not limited by such embodiments. The scope of the claims of the present invention should be interpreted according to the following claims, and should be interpreted as including all technologies within the scope equivalent thereto falling within the scope of the claims of the present invention.

Claims

1. A positive photosensitive composition, characterized in that: The invention comprises (A) a polybenzoxazole or polyimide polymer; (B) a photosensitizer; (C) a silane additive; and (D) a solvent.

2. The positive photosensitive composition according to claim 1, characterized in that: The polybenzoxazole or polyimide polymer comprises a repeating unit selected from the group consisting of the following chemical formula 1-1; chemical formula 1-2; chemical formula 1-3; chemical formula 1-4; or a combination thereof, <Chemical Formula 1-1> <Chemical Formula 1-2> <Chemical Formula 1-3> <Chemical Formula 1-4> In the above Chemical Formulas 1-1 to 1-4, 1)* is the part that makes the bond connected in a repeating unit, 2) The * at the end of the polymer is the part to which 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 selected from the group consisting of: C6~C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group of an aliphatic ring and an aromatic ring; C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkyne group; C3~C 20 cycloalkynylene group; Chemical formula 2; and combinations thereof, 5) Z is selected from the group consisting of: C6~C 30 an arylene group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group of an aliphatic ring and an aromatic ring; C1~C 20 Alkylene group; C1~C 20 Cycloalkylene group; C2~C 20 alkenylene group; C3~C 20 Cycloalkenylene group; C2~C 20 Alkyne group; C3~C 20 cycloalkynylene group; Chemical Formula 3; and combinations thereof, 6) k, l, m, and n are integers greater than 1, <Chemical formulas Q1 to Q10> 7) The polymer terminal is bonded to a chemical formula selected from one of the above chemical formulas Q-1 to Q-10 or a group consisting of a combination thereof through an amide or imide bond, <Chemical Formula 2> In the above chemical formula 2, 8) L 1 Selected from single bonds, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-、-C(C6H 13 )2-、-C(C5H 10 )-, –O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, -Si(CH3)2-, -C(SiCH3)2, -C6H4-, -CO-, -NHCO-, -COO-, 9) R1 to R 10 Two of them are bonding sites with the amide groups shown in Chemical Formula 1-1 and Chemical Formula 1-2, 10) In addition to the bonding site, the remaining R1 to R 10 Independently of each other: hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group (cyclogroup) of an aliphatic ring and an aromatic ring; C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 Alkoxy carbonyl group, 11) L 1 When it is a single bond, the adjacent R1 and R 10 ; can form a ring with R5 and R6, <Chemical formula 3> In the above chemical formula 3, 12) L 2 Selected from single bonds, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-、-C(C6H 13 )2-、-C(C5H 10 )-, –O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, -Si(CH3)2-, -C(SiCH3)2, -C6H4-, -CO-, -NHCO-, -COO-, 13) R 11 To R 20 Two of them are bonding sites with the amide groups shown in Chemical Formula 1-1 and Chemical Formula 1-2, 14) In addition to the bonding site, the remaining R 11 To R 20 Independently of each other: hydrogen; deuterium; hydroxyl group; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A condensed ring group (cyclogroup) of an aliphatic ring and an aromatic ring; C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1~C 20 However, the remaining R 11 To R 20 Two of them are carboxyl groups. 15)L 2 When it is a single bond, the R adjacent to the bonding site is not 11 and R 20 ; and R 15 and R 16 A ring can be formed.

3. The positive photosensitive composition according to claim 1, characterized in that: The silane additive comprises the following chemical formula T-1; or a combination of chemical formulas T-1 and T-2, In the above T-1 to T-2, 1) R 21 Selected from the group consisting of: C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C3~C 30 Cycloalkyl group; C2~C 20 A heterocycloalkyl group and a combination thereof, 2) R 22 To R 23 is selected from the group consisting of methoxy; ethoxy; acetyl; carboxyl and combinations thereof, 3) R 24 C1~C 10 An alkyl group, 4) R 25 To R 27 is selected from the group consisting of methoxy; ethoxy; acetyl; carboxyl and combinations thereof, 5) Ar1 to Ar2 are selected from C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C3~C 30 Cycloalkyl group; C2~C 20 The heterocycloalkyl group is a heterocycloalkyl group.

4. The silane-based additive according to claim 3, characterized in that: The chemical formula T-1 includes compounds represented by the following chemical formulas J-1 to J-15:

5. The silane-based additive according to claim 3, characterized in that: The chemical formula T-2 comprises the compounds represented by the following chemical formulas K-1 to K-12:

6. The positive photosensitive composition according to claim 1, characterized in that: The content of the silane additive is 0.1 to 1 weight % in the total amount of the composition.

7. The positive photosensitive composition according to claim 1, characterized in that: The content of the polybenzoxazole or polyimide polymer is 5 to 50 weight % in the total weight of the composition.

8. The positive photosensitive composition according to claim 1, characterized in that: The photosensitizer comprises one or more of the following chemical formulas P-1 to P-8: In P-1 to P-8, R" is hydrogen; the following chemical formula S-1; or chemical formula S-2, <Chemical Formula S-1> <Chemical Formula S-2> 9. The positive photosensitive composition according to claim 1, characterized in that: The content of the photosensitizer in the total amount of the composition is 1 to 50 weight %.

10. The positive photosensitive composition according to claim 1, characterized in that: The solvent comprises one or more selected from the group consisting of N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, γ-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and combinations thereof.

11. The positive photosensitive composition according to claim 1, characterized in that: The content of the solvent in the total amount of the composition is 40 to 95 weight %.

12. A pattern or film made from the positive photosensitive composition according to claim 1.

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

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

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