Photosensitive composition

Abstract

The present invention relates to a method for synthesizing a polymer and a method for preparing a positive photosensitive composition for providing a polymer and a positive photosensitive composition having increased mechanical properties, and a cured film, a protective film, an insulating film and a semiconductor device prepared therefrom. A display device.

Description

Technical Field

[0001] The invention relates to a method for preparing a polymer by using only a single solvent, gamma-butyrolactone, and a positive photosensitive composition used in a semiconductor device or a display device prepared by using the method. 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 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, and N-methylpyrrolidone commonly used for synthesis is harmful to the environment and the human body.

[0005]

Prior technical literature

[0006] [Patent Literature]

[0007] (Patent Document 1) Korean Patent Publication No. 2015-0037400

[0008] (Patent Document 2) Korean Patent Publication No. 2022-0143710 Summary of the invention

[0009] Issues to be solved

[0010] In order to solve the above-mentioned drawbacks of the conventional technology, the purpose of the present invention is to use only γ-butyrolactone as the polymer described in the following synthesis examples and implementation examples to implement synthesis, so as to solve the problem of being harmful to the environment and human body.

[0011] In yet another embodiment, the present invention aims to reduce unreacted monomers to increase tensile strength and elongation, thereby increasing the mechanical properties of the polymer.

[0012] In yet another embodiment, the present invention aims to provide a positive photosensitive composition using the polymer.

[0013] Problem Solution

[0014] The polymer of the present invention comprises the following Chemical Formula 1-1; Chemical Formula 1-2; Chemical Formula 1-3; Chemical Formula 1-4; or a combination thereof, and is preferably prepared by using γ-butyrolactone as a single solvent.

[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 formula 1-1; chemical formula 1-2; chemical formula 1-3; chemical formula 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 a portion to which 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 30A 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; or a combination 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; or a combination 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 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,

[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-, -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 1When 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-, -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 30aryloxy 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.

[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 polymer is made from a diamine monomer; a diacid chloride monomer; and an anhydride monomer.

[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) or a combination 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 or a combination thereof.

[0050] 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 or a combination thereof.

[0051] Preferably, the yield of the polymer prepared by the preparation method is above 80%.

[0052] Preferably, the preparation method further comprises the use of pyridine for preparation.

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

[0054] The positive photosensitive composition is made of the polymer resin, and preferably comprises the polymer; a photosensitizer; a solvent; and an additive.

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

[0056]

[0057] In P-1 to P-8, R" is hydrogen; the following chemical formula S-1; or chemical formula S-2.

[0058] <Chemical Formula S-1>

[0059]

[0060] <Chemical Formula S-2>

[0061]

[0062] Preferably, the solvent comprises one or more selected from the group consisting of N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, 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 or a combination thereof.

[0063] Preferably, the additive comprises at least one selected from the group consisting of the following components: a silane coupling agent; a surface smoothing agent; a surfactant; a cross-linking agent; or a combination thereof.

[0064] Preferably, the content of the polymer is 5 to 50 wt % based on the total weight of the composition.

[0065] Preferably, the content of the photosensitizer is 1 to 50% by weight in the total amount of the composition.

[0066] Preferably, the content of the solvent in the total amount of the composition is 40 to 95 wt %.

[0067] Preferably, the content of the additive is 0.001 to 10 wt % in the total amount of the composition.

[0068] In another embodiment of the present invention, preferably, a pattern or film made of the positive photosensitive composition is provided.

[0069] In another specific example of the present invention, preferably, a semiconductor device or a display device manufactured using the pattern or film is provided.

[0070] 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.

[0071] Effects of the Invention

[0072] The polymer of the present invention is synthesized by using only a single solvent, γ-butyrolactone, and does not contain solvents such as N-methylpyrrolidone that are harmful to the environment and human body, which are used in traditional technologies. As a polyoxazole precursor resin, it significantly reduces the unreacted monomers that have a negative impact on mechanical properties. Since the unreacted monomer ratio after the polymerization reaction is low, the yield is excellent. In addition, there is no residue problem during development, the clarity of the displayed pattern is high, and the tensile strength of the film after post-baking treatment is above 10MPa, and the elongation is above 10%, which has the effect of improving physical properties. DETAILED DESCRIPTION

[0073] Hereinafter, some embodiments of the present invention will be described in detail with reference to the schematic diagrams. When components of each drawing are denoted by reference symbols, the same components are given the same symbols as much as possible even if they are shown in other drawings.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.).

[0080] 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.

[0081] Unless otherwise described, the term "halo" or "halogen" used in the present application includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0082] 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.

[0083] Unless otherwise described, the term "haloalkyl group" or "halogenalkyl group" used in the present application refers to an alkyl group substituted with halogen.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] Unless otherwise specified, the terms "aryl group" and "arylene group" used in this application have 6 to 60 carbon atoms, respectively, but are not limited thereto. In this application, aryl groups or arylene groups include monocyclic types, cyclopolymers, and fused polycyclic compounds. For example, the aryl group may include a phenyl group, a monovalent functional group of biphenyl, a naphthalene group, a cyclopentane ...

[0089] The arylene group may include a monovalent functional group of naphthalene, a fluorenyl group and a substituted fluorenyl group. The arylene group may include a fluorenylene group and a substituted fluorenylene group.

[0090] The term "ringassemblies" used in this application is composed of two or more ring systems (single ring or combined 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 ringassemblies can be directly connected by the same or different ring systems through a single bond or a double bond.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] Unless otherwise described, the terms "fluorenyl group", "fluorenylene group" and "fluorene-triyl group" used in this application respectively represent monovalent, divalent or trivalent functional groups in which R, R', R" and R'" are all hydrogen in the following structures, and "substituted fluorenyl group", "substituted fluorenyl group" or "substituted fluorene-triyl group" means that at least one of the substituents R, R', R", R'" is a substituent other than hydrogen, including the case where R and R' are bonded to each other and form a spiro compound together with the carbon to which they are bonded. In this specification, the fluorenyl group, fluorenylene group and fluorene-triyl group may be named as fluorenyl group without considering the equivalent number of monovalent, divalent and trivalent.

[0095]

[0096] 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 selected from: The substituted fluorenyl group and the fluorenyl group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidone, pyridazine, pyrazine, triazine, indole, benzofuran, quinazoline or quinoxaline. For example, the substituted fluorenyl group and the fluorenyl group may be monovalent or divalent functional groups of 9,9-dimethylfluorene, 9,9-diphenylfluorene and 9,9'-spirobi [9H-fluorene], respectively.

[0097] 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.

[0098] 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.

[0099]

[0100] 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.

[0101] The term "polycyclic" 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. Of course, hydrocarbon rings include heterocyclic rings that contain at least one heteroatom.

[0102] 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.

[0103] Furthermore, when prefixes are used consecutively, it means that the substituents are arranged in the order of the description. For example, arylalkoxy group means an alkoxy group substituted with an aryl group, alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group, wherein arylcarbonyl group is a carbonyl group substituted with an aryl group.

[0104] 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 30 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.

[0105] 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.

[0106] 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.

[0107] 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 pyridopyrimidone, benzofuran[2,3-d]pyrimidone may be recorded as benzofuranpyrimidone, 9,9-dimethyl-9H-fluorene may be recorded as dimethylfluorene, etc. Therefore, benzo[g]quinoxaline or benzo[f]quinoxaline may be recorded as benzoquinoxaline.

[0108] 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.

[0109]

[0110] 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 greater than 2, R1 can be the same or different.

[0111]

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] The positive photosensitive composition described in one embodiment of the present invention comprises a polymer and a precursor, and can be used in the preparation of an insulating film, a surface protection film, a rewiring layer, and a pixel definition layer (PDL) of a semiconductor device.

[0117] 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.

[0118] 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.

[0119] The components of the positive photosensitive composition are as follows.

[0120] (1) Polymer

[0121] According to an embodiment of the present invention, the pattern forming resin may include a polymer.

[0122] The polymer refers to a resin containing a hydroxyamide precursor, and the hydroxyamide can be formed into a polymer by chemical or thermal treatment.

[0123] The content of the polymer in the total amount of the positive photosensitive composition is 5 wt % to 50 wt %, preferably, 10 wt % to 45 wt %.

[0124] The polymers include precursors represented by the following chemical formulas 1-1, 1-2, 1-3, and 1-4, but are not limited thereto. These can be used alone or in combination of two or more.

[0125] Preferably, the 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.

[0126] <Chemical Formula 1-1>

[0127]

[0128] <Chemical Formula 1-2>

[0129]

[0130] <Chemical Formula 1-3>

[0131]

[0132] <Chemical Formula 1-4>

[0133]

[0134] In the above 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,

[0135] 1)* is the part that makes the bond connected in a repeating unit,

[0136] 2) The * at the end of the polymer is a portion to which chemical formulas Q-1 to Q-10 are bonded via an amide bond or an imide bond,

[0137] 3) X1 or X2 is the following chemical formula 2,

[0138] 4) Y is selected from the group consisting of: C6~C 30 an arylene group; a C2-C 30heterocyclic 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; or a combination thereof,

[0139] 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; or a combination thereof,

[0140] 6) k, l, m, and n are integers greater than 1,

[0141] <Chemical formulas Q1 to Q10>

[0142]

[0143] 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,

[0144] <Chemical Formula 2>

[0145]

[0146] In the above chemical formula 2,

[0147] 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-, -C6H4-, -CO-, -NHCO-, -COO-,

[0148] 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,

[0149] 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,

[0150] 11) L 1 When it is a single bond, the adjacent R1 and R 10 ; can form a ring with R5 and R6,

[0151] <Chemical formula 3>

[0152]

[0153] In the above chemical formula 3,

[0154] 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-, -C6H4-, -CO-, -NHCO-, -COO-,

[0155] 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,

[0156] 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 30aryloxy 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.

[0157] 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.

[0158] The polymer described in one embodiment of the present invention is prepared by using a single solvent, γ-butyrolactone, which has little harm to the environment and human body and has an excellent yield of the reactant (polymer).

[0159] The yield of the polymer prepared by the preparation method is 80% or more, preferably 82.5% or more.

[0160] Preferably, the preparation method further adds pyridine. When pyridine is added, the compatibility between γ-butyrolactone and the monomer can be increased, and since pyridine is used as a catalyst for the polymerization reaction, the efficiency of the polymerization reaction can be further improved.

[0161] The weight average molecular weight of the polymer resin is 5,000 g / mol to 30,000 g / mol, preferably 5,000 g / mol to 40,000 g / mol, and more preferably 7,000 g / mol to 25,000 g / mol. If the weight average molecular weight of the resin is within the range, no residue of the exposure layer remains during development, and the film thickness loss of the non-exposure layer is reduced to a minimum, so that 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.

[0162] (2) Photosensitizer

[0163] 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.

[0164]

[0165]

[0166] In P-1 to P-8, R" is hydrogen; the following chemical formula S-1; or chemical formula S-2.

[0167] <Chemical Formula S-1>

[0168]

[0169] <Chemical Formula S-2>

[0170]

[0171] In the above chemical formula S-1 and chemical formula S-2, * represents a bonding site.

[0172] Preferably, the content of the photosensitizer is 1 to 50% by weight in the total amount of the composition.

[0173] (3) Solvent

[0174] The solvent may be a substance that is compatible with and does not react with the polymer resin, the photosensitizer, and the pigment.

[0175] 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.

[0176] In addition, high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic 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.

[0177] 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.

[0178] 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.

[0179] (4) Other additives

[0180] In order to prevent the occurrence of marks or spots, improve the flatness and prevent the generation of residues due to undevelopment when coating the positive photosensitive resin composition, the composition may further contain additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent containing a vinyl or (meth)acryloxy group, a surface leveler, a surfactant and a cross-linking agent.

[0181] For example, in order to improve adhesion to a substrate, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group.

[0182] For example, the silane coupling agent includes trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltrioxysilane, γ-glycidyloxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, KBM-502, KBM-602, KBM-573, KBE-9007N produced by Shinetsu silicon, and the like, which can be used alone or in combination of two or more.

[0183] The weight part of the silane coupling agent may be 0.01 parts by weight to 10 parts by weight in 100 parts by weight of the photosensitive resin composition. When the weight part of the silane coupling agent is within the above range, the adhesion and storage properties are excellent.

[0184] Furthermore, in order to form a constant film thickness in a coating step, the photosensitive resin composition may further include a surface leveler as needed.

[0185] The surface leveler can be made from DIC etc.; BASF FL3740, FL3741, FL3745, FL3770 and other surface levelers are on sale.

[0186] 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 resin 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.

[0187] Furthermore, in order to improve coating properties and prevent defects, the photosensitive resin composition may further contain a surfactant as needed.

[0188] The surfactant can be the following commercially available surfactant: etc.; Dainippon Ink & Chemicals Co., Ltd.'s Mecha Pack F Same model F Same model F Same model F etc.; Lard from Sumitomo 3M Co. Same style Same style Same style etc.; Saffron from Asahi Glass Co., Ltd. Same style Same style Same style Same style etc.; Toray Silicon Corporation Same style Same style wait.

[0189] The amount of the surfactant can be 0.001 to 5 parts by weight in 100 parts by weight of the photosensitive resin composition. When the weight of the surfactant is within the above range, the coating uniformity can be ensured, no spots will occur, and the wettability of the glass substrate is excellent.

[0190] The crosslinking agent, 1,4-bis(methoxymethyl)benzene, dimethyl sulfate, 3-aminopropyltriethoxysilane, N,N'-methylenebisacrylamide, etc., can be used alone or in combination of two or more.

[0191] The amount of the crosslinking agent can be 0.001 to 5 parts by weight in 100 parts by weight of the photosensitive resin composition. When the weight of the crosslinking agent is within the above range, it is beneficial to impart physical properties to the cured coating film, for example, mechanical properties such as tensile strength.

[0192] Furthermore, a certain amount of other additives may be added to the photosensitive resin composition within a range that does not impair physical properties.

[0193] 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.

[0194] Synthesis example 1:

[0195] A 250ml 3-neck round-bottom flask is attached with a stirrer, a nitrogen injection device, a dropping funnel, a thermostat and a cooler, and then filled with nitrogen and filled with 120.47g of γ-butyrolactone (GBL), and then 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.58g 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, the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 10.58g of 4,4'-oxydibenzoyl chloride is slowly added to dissolve it, and stirred for 12 hours to react.

[0196] 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 copolymerized polyhydroxyamide powder with a yield of 87.56%.

[0197] Synthesis example 2:

[0198] A 250ml 3-necked round-bottom flask was attached with a stirrer, a nitrogen injection device, a dropping funnel, a thermostat and a cooler. Then, nitrogen was filled and filled with 65.7g of γ-butyrolactone (GBL). Then, 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.52g of pyridine were added and stirred, and the mixture was kept at 40°C. Among them, 0.910g of phthalic anhydride was slowly added, and then stirred for a certain period of time to dissolve and react. Then, 52.70g of GBL and 2.06g of pyridine were added to the flask in the reaction, and the temperature of the solution was kept at 5°C and stirred for 30 minutes. Then, 8.76g of 4,4'-biphenyl dicarboxylic acid chloride was slowly added to dissolve it, and stirred for 12 hours to react.

[0199] 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 copolymerized polyhydroxyamide powder with a yield of 85.47%.

[0200] Synthesis example 3

[0201] A 250ml 3-neck round bottom flask was attached with a stirrer, a nitrogen injection device, a dropping funnel, a thermostat and a cooler. Then, nitrogen was filled and filled with 65.7g of γ-butyrolactone (GBL). Then, 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.52g of pyridine were added and stirred, and the temperature was kept at 40°C. Among them, 1.54g of 5-norbornene-2,3-dicarboxylic anhydride was slowly added, and then stirred for a certain time to dissolve and react. Then, 52.70g of GBL and 2.06g of pyridine were added to the flask in the reaction, and the temperature of the solution was kept at 5°C and stirred for 30 minutes. Then, 9.48g of 4,4'-oxydibenzoyl chloride was slowly added to dissolve it, and stirred for 12 hours to react.

[0202] 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 copolymerized polyhydroxyamide powder with a yield of 87.23%.

[0203] Synthesis example 4

[0204] A 250ml 3-necked round-bottom flask was attached with a stirrer, a nitrogen injection device, a dropping funnel, a thermostat and a cooler. Then, nitrogen was filled and filled with 65.7g of γ-butyrolactone (GBL). Then, 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)propane and 0.52g of pyridine were added and stirred, and the mixture was kept at 40°C. Among them, 0.91g of phthalic anhydride was slowly added, and then stirred for a certain period of time to dissolve and react. Then, 52.70g of GBL and 2.06g of pyridine were added to the flask in the reaction, and the temperature of the solution was kept at 5°C and stirred for 30 minutes. Then, 11.95g of 1,4-4,4'-oxydibenzoyl chloride was slowly added, dissolved, and stirred for 12 hours to react.

[0205] 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 copolymerized polyhydroxyamide powder with a yield of 84.77%.

[0206] Comparative Example 1

[0207] 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, 54.77g of NMP and 2.06g of pyridine are added to the flask in the reaction, and the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 10.58g of 4,4'-oxydibenzoyl chloride is slowly added to dissolve it, and stirred for 12 hours to react.

[0208] 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 copolymerized polyhydroxyamide powder with a yield of 76.42%.

[0209] Comparative Example 2

[0210] 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)propane 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, 54.77g of NMP and 2.06g of pyridine are added to the flask in the reaction, and the temperature of the solution is maintained at 5°C and stirred for 30 minutes. Then, 11.95g of 4,4'-oxydibenzoyl chloride is slowly added to dissolve it, and stirred for 12 hours to react.

[0211] 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 copolymerized polyhydroxyamide powder with a yield of 73.82%.

[0212]

Table 1

[0213] Yield (%) Unreacted monomer ratio (%) Synthesis example 1 87.56 2.48 Synthesis example 2 85.47 2.95 Synthesis example 3 87.23 1.74 Synthesis example 4 84.77 2.26 Comparative Example 1 76.42 5.54 Comparative Example 2 73.82 6.15

[0214] From the synthesis test results recorded in Table 1 above, it can be seen that in Examples 1 to 4, the yield of the product can exceed 84%, which is confirmed to be 8% higher than that of Comparative Examples 1 to 2. In addition, it has been confirmed that the unreacted monomer ratio is compared with that of Synthesis Examples 1 to 4, and the residual of Comparative Examples 1 to 2 exceeds 5%.

[0215] (Preparation Example 1) Preparation of positive photosensitive composition

[0216] 13.759 g of the polymer resin obtained in Synthesis Examples 1 to 4 and Comparative Examples 1 to 2, 2.052 g of MIPHOTO TPD523 (Mihara Trading Co., Ltd.), 0.013 g of F-563 (DIC Corporation), 1.7 g of KBM-573 (Shinetsu Silicon Corporation), and 1.2 g of 1,4-bis(methoxymethyl)benzene were stirred at room temperature for 12 hours with 32.5 g of γ-butyrolactone. Then, the composition was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

[0217] A photosensitive composition liquid was prepared according to the composition described in Table 2 below.

[0218]

Table 2

[0219]

[0220] The method for preparing a UTM test piece using the positive photosensitive resin composition is as follows.

[0221] (1) Coating and coating steps

[0222] 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.

[0223] (2) Pre-baking step

[0224] 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.

[0225] (3) Exposure Step

[0226] 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.

[0227] (4) Development step

[0228] 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 a certain time (minutes) was waited for development. 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 11.0 μm.

[0229] (5) Post-baking step

[0230] 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.

[0231] (6) Test piece peeling

[0232] In order to obtain a UTM test piece without damage from the substrate that has completed the post-baking step, the substrate is immersed (dipping) in a 2% hydrofluoric acid aqueous solution at 23±2°C for a certain period of time (minutes), then rinsed with deionized water (DI water), and then dried in a vacuum chamber at room temperature to obtain a UTM test piece.

[0233] (7) UTM detection

[0234] The UTM test pieces obtained in the test piece peeling step were used to test the tensile strength and elongation of the test pieces in the embodiment and the comparative example using a universal material testing machine QM100S from QMESYS. The testing conditions are as follows: the testing temperature is 25°C, the tensile speed is 5mm / min, and the gauge length is 20mm.

[0235] (8) NMP content detection

[0236] Furthermore, in order to analyze the NMP content of the composition prepared above, SGS Korea, a national certified testing company, was commissioned to perform Headspace GC / MS analysis on the composition and detect the NMP content, and the LDL was 5 ppm.

[0237]

Table 3

[0238] Post-development residue Resolution(μm) Elongation(%) Tensile strength(MPa) NMP content (PPM) Example 1 X 5 56.8±0.2 140 ND Example 2 X 5 56.4±0.3 138 ND Example 3 X 6 57.0±0.3 142 ND Example 4 X 6 57.1±0.4 142 ND Comparative Example 3 O 10 46.9±0.3 130 150 Comparative Example 4 O 12 43.8±0.4 134 158

[0239] From the development test results recorded in Table 2 above, it is confirmed that, except for the comparative example, there is no residue left in Examples 1 to 4 after development. In addition, Example 1 and Comparative Example 3, and Example 4 and Comparative Example 4 have the same synthetic components and only different solvents. After comparison, it is found that the elongation of Example 1 and Example 4 is 10%, and the tensile strength is more than 10MPa higher. It is confirmed that the examples with less unreacted monomer content show better physical properties. It is also confirmed that the clarity of the pattern is better than the comparative example. The analysis results of the NMP content show that no NMP was detected in Examples 1 to 4, while the NMP detected in Comparative Examples 1 to 2 were 150ppm and 158ppm, respectively. Recently, the control of display and semiconductor materials has become stricter, requiring the removal or non-use of NMP that is harmful to the human body. The synthesis method inspired by this patent can prepare a composition that does not contain NMP.

[0240] The present invention is not limited to the above-mentioned embodiments and can be prepared into various different forms.

[0241] The above description is merely an example of the present invention, and a person skilled in the art in the art to which the present invention belongs can make various modifications without departing from the essential characteristics of the present invention.

[0242] 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 method for preparing a polymer, characterized in that: The composition comprises the following chemical formula 1-1; chemical formula 1-2; chemical formula 1-3; chemical formula 1-4; or a combination thereof, and is prepared using a single solvent, γ-butyrolactone, <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 a portion to which 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; or a combination 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; or a combination thereof, 6) k, l, m, and n are integers greater than 1, <Chemical formulas Q1 to Q10> 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, <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-, -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-, -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.

2. The method for preparing a polymer according to claim 1, characterized in that: The yield of the polymer prepared by the preparation method is more than 80%.

3. The method for preparing a polymer according to claim 1, characterized in that: Further comprising pyridine.

4. The polymer according to claim 1, characterized in that: The polymer is made of diamine monomers; diacid chloride monomers; acid anhydride monomers; or a combination thereof.

5. The polymer according to claim 4, characterized in that: 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) or a combination thereof.

6. The polymer according to claim 4, characterized in that: 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, or a combination thereof.

7. The polymer according to claim 4, characterized in that: 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, or a combination thereof.

8. A positive photosensitive composition comprising the polymer according to claim 1; a photosensitizer; a solvent; and additives.

9. The positive photosensitive composition according to claim 8, 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> 10. The positive photosensitive composition according to claim 8, 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, 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 or a combination thereof.

11. The positive photosensitive composition according to claim 8, characterized in that: The additive comprises at least one selected from the group consisting of the following components: a silane coupling agent; a surface smoothing agent; a surfactant; a cross-linking agent; or a combination thereof.

12. A pattern or film made from the positive photosensitive composition of claim 8 at 300°C to 400°C.

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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