Photosensitive composition

Abstract

To provide a polymer and a positive photosensitive composition which have increased mechanical properties, a cured film, a protective film, an insulating film, and a semiconductor device which are manufactured therefrom; and a method of synthesizing a polymer and a method for producing a positive photosensitive composition, for providing a display device, without use of harmful solvents.SOLUTION: A polymer is produced using only γ-butyrolactone as a single solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for preparing a polymer using only a single solvent, γ-butyrolactone, and a positive-type photosensitive composition prepared using the same and used in a semiconductor device or display device. [Background technology]

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

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

[0004] Conventionally, resins such as polyimide or polybenzoxazole have been used as positive photosensitive resin compositions for semiconductor devices and display devices because of their high heat resistance, chemical resistance, weather resistance, etc. However, the molecular weight of the polymer resin used to realize precise circuits is limited by the development using an alkaline aqueous solution in the development stage, so there is a limit to the mechanical properties that can be realized, and N-methylpyrrolidone, which is generally used in the synthesis, is harmful to the environment and human body. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 2015-0037400 [Patent Document 2] Korean Patent Publication No. 2022-0143710 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to solve the problems of the prior art by synthesizing the polymers of the following synthesis examples and practical examples using only γ-butyrolactone to solve the harmful effects on the environment and human body.

[0007] Another example is to increase the tensile strength and elongation by reducing unreacted monomers so that the mechanical properties of the polymer components can be increased.

[0008] Yet another embodiment is to use the polymer to provide a positive-sensitive composition. [Means for solving the problem]

[0009] The polymer according to the present invention preferably comprises the following formula 1-1, formula 1-2, formula 1-3, formula 1-4, or a combination thereof, and is prepared using γ-butyrolactone as a single solvent.

[0010] [ka]

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

[0012] [ka]

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

[0014] [ka]

[0015] In the above Chemical Formula 2, 8) L1 is a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-, -C(CH 13 )2-, -C(CH 10 )-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, Si(CH3)2-, -C6H4-, -CO-, -NHCO-, -COO-; 9) R1 or R 10 Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 10) The remaining R1 to R excluding the linking portion 10 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 an aryl group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 20 Alkoxy group; C6-C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 is an alkoxycarbonyl group of the formula 11) L 1 is a single bond, the adjacent R and R 10 and R5 and R6 can form a ring;

[0016] [ka]

[0017] In the above Chemical Formula 3, 12) L2 is a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-, -C(CH 13 )2-, -C(CH 10 )-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, Si(CH3)2-, -C6H4-, -CO-, -NHCO-, -COO-; 13) R 11 Or R 20 Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 14) The remaining R excluding the linking site 11 Or R 20 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 an aryl group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 20 Alkoxy group; C6-C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 The remaining R excluding the linking portion is an alkoxycarbonyl group. 11 Or R 20 Two of them are carboxyl groups, 15) L 2 is a single bond, the adjacent R 11 and R 20 ; and R 15 and R 16 can form a ring.

[0018] The polymer is preferably made from a diamine monomer; a diacyl chloride monomer; and an anhydride monomer.

[0019] The diamine preferably includes 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 combinations thereof.

[0020] The diacyl chloride preferably contains one or more monomers selected from the group consisting of 4,4'-oxybisbenzoyl chloride, 1,2-cyclobutanedicarboxylic acid dichloride, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldicarbonyl chloride, 1,4-naphthalene dicarbonyl chloride, 4,4'-sulfonyldibenzoyl chloride, 1,4-cyclohexanedicarboxylic acid dichloride, and combinations thereof.

[0021] The anhydride preferably comprises one or more monomers selected from the group consisting of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 5-novonene-2,3-dicarboxylic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, or combinations thereof.

[0022] The polymer produced by the above production method preferably has a yield of 80% or more.

[0023] The preparation method preferably further comprises the step of adding pyridine.

[0024] The weight average molecular weight of the polymer is preferably 5,000 to 40,000 g / mol.

[0025] A positive photosensitive composition prepared using the polymer resin preferably comprises the polymer; a photosensitizer; a solvent; and additives.

[0026] The photosensitizer preferably includes at least one of the following formulas P-1 to P-8.

[0027] [ka]

[0028] In the above P-1 to P-8, R″ is hydrogen; the following chemical formula S-1; or the following chemical formula S-2.

[0029] [ka]

[0030] The solvent preferably includes one or more selected from the group consisting of N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, gamma-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, or a combination thereof.

[0031] The additive preferably includes one or more selected from the group consisting of a silane coupling agent; a surface smoothing agent; a surfactant; a crosslinking agent; or a combination thereof.

[0032] The polymer is preferably contained in an amount of 5 to 50% by weight based on the total weight of the composition.

[0033] The photosensitizer is preferably contained in an amount of 1 to 50% by weight based on the total weight of the composition.

[0034] The solvent is preferably contained in an amount of 40 to 95% by weight based on the total weight of the composition.

[0035] The additives are preferably contained in an amount of 0.001 to 10% by weight based on the total weight of the composition.

[0036] In another embodiment of the present invention, it is preferable to provide a pattern or film made from the positive-sensitive composition.

[0037] As another embodiment of the present invention, it is preferable to provide a semiconductor device or a display device manufactured using the above pattern or film.

[0038] As another embodiment of the present invention, it is preferable to provide an electronic device including the semiconductor device or display device described above and a control unit for driving the same. Effect of the Invention

[0039] The polymer of the present invention is synthesized using a single solvent of γ-butyrolactone, and therefore does not contain any solvents that are harmful to the environment and human body, such as N-methylpyrrolidone, which has been used in the past. It is a polyoxazole precursor resin that significantly reduces the amount of unreacted monomers that have a negative effect on mechanical properties. Since the ratio of unreacted monomers after polymerization is low, the yield is excellent, there is no problem with residues during development, the resolution of pattern realization is high, and the physical properties of the film after heat treatment are improved to tensile strength of 10 MPa or more and elongation of 10% or more. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0040] Hereinafter, some embodiments of the present invention will be described in detail with reference to the accompanying drawings. When reference numerals are used to designate components in each drawing, the same reference numerals are used to designate the same components even if they are displayed in different drawings.

[0041] In the description of the present invention, if it is determined that a specific description of related publicly known configurations or functions may make the gist of the present invention unclear, the detailed description may be omitted. When "comprises," "has," "consists," and the like are used in this specification, other parts may be added as long as "only" is not used. When a component is expressed in the singular, it includes the plural unless otherwise expressly specified.

[0042] In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. are used to distinguish the components from other components, and the terms do not limit the nature, order, sequence, number, etc. of the components.

[0043] In describing the positional relationship of components, when two or more components are described as being "coupled," "coupled," or "connected," it should be understood that the two or more components may be directly "coupled," "coupled," or "connected," but that the two or more components may also be "coupled" or "connected" through further "intervening" components, where the other components may be included in one or more of the two or more components that are "coupled," "coupled," or "connected" to each other.

[0044] In addition, when a component such as a layer, film, region, or plate is described as being "on" or "on" another component, this should be understood to include not only the case where the component is "directly on" the other component, but also the case where there is another component in between. Conversely, when a component is described as being "directly on" another part, it should be understood to mean that there is no other part in between.

[0045] In describing a temporal sequence relating to components, methods of operation, methods of production, etc., when the temporal or flow sequence is described using, for example, "after," "following," "next to," or "before," this also includes cases where the sequence is not consecutive, unless "immediately" or "directly" is used.

[0046] On the other hand, when numerical values ​​or corresponding information for components are mentioned, even if there is no separate explicit description, the numerical values ​​or corresponding information can be interpreted as including an error range that may occur due to various factors (e.g., process factors, internal or external impacts, noise, etc.).

[0047] The terms used in this specification and the appended claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted as having a meaning and concept that is consistent with the technical idea of ​​the present invention based on the principle that an inventor can appropriately define the concept of a term in order to best describe his / her invention.

[0048] The term "halo" or "halogen" as used in this application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise stated.

[0049] The term "alkyl" or "alkyl group", as used in this application, unless otherwise specified, means the radical of a saturated aliphatic group having 1 to 60 carbons linked by a single bond, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups.

[0050] The term "haloalkyl group" or "haloalkyl group" as used herein means, unless otherwise specified, an alkyl group substituted with a halogen.

[0051] The terms "alkenyl" or "alkynyl" as used herein, unless otherwise specified, include groups having double or triple bonds, straight or branched chain groups, and having from 2 to 60 carbon atoms, but are not limited thereto.

[0052] The term "cycloalkyl" as used in this application, unless otherwise specified, means an alkyl group forming a ring having 3 to 60 carbon atoms, but is not limited thereto.

[0053] The term "alkoxy group" or "alkyloxy group" as used herein means an alkyl group having an oxygen radical attached thereto, and unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.

[0054] The terms "alkeneoxyl group," "alkenoxy group," "alkenyloxyl group," or "alkenyloxy group" as used in this application mean an alkenyl group having an oxygen radical attached thereto, and unless otherwise specified, has 2 to 60 carbon atoms, but is not limited to this.

[0055] The terms "aryl group" and "arylene group" used in this application each have 6 to 60 carbon atoms, unless otherwise specified, but are not limited thereto. In this application, the aryl group or arylene group includes a single ring, a ring assembly, a fused multiple ring system compound, etc. For example, the aryl group includes a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, and a substituted fluorenyl group, and the arylene group includes a fluorenylene group and a substituted fluorenylene group.

[0056] The term "ring assemblies" as used in this application means two or more ring systems (single ring or joined ring systems) directly linked to each other by single or double bonds, and the number of such direct connections between rings is one less than the total number of ring systems in the compound. Ring assemblies can be identical or different ring systems directly linked to each other by single or double bonds.

[0057] In the present application, the aryl group includes ring assemblies, and therefore includes biphenyl and terphenyl in which a single aromatic ring, a benzene ring, is connected by a single bond. The aryl group also includes compounds in which an aromatic ring system connected to a single aromatic ring is connected by a single bond, and therefore includes compounds in which an aromatic ring system, such as fluorene, is connected to a single aromatic ring, such as a benzene ring.

[0058] The term "fused ring system" used in this application means a fused ring form sharing at least two atoms, including a fused ring form of two or more hydrocarbon ring systems and a fused ring form of at least one heterocyclic ring system containing at least one heteroatom. Such fused ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings, or combinations of these rings. For example, in the case of an aryl group, it may be a naphthalenyl group, a phenanthrenyl group, a fluorenyl group, etc., but is not limited thereto.

[0059] The term "spiro compound" as used in this application has a "spiro union", which means a union in which two rings share only one atom. In this case, the atom shared by the two rings is called a "spiro atom". Depending on the number of spiro atoms in a compound, these compounds are called "monospiro-", "dispiro-", and "trispiro-" compounds, respectively.

[0060] The terms "fluorenyl group", "fluorenylene group", and "fluorenetriyl group" used in this application mean, unless otherwise specified, a monovalent, divalent, or trivalent functional group in which R, R', R" and R'" are all hydrogen in the following structure, respectively, and "substituted fluorenyl group", "substituted fluorenylene group", or "substituted fluorenetriyl group" means that at least one of the substituents R, R', R" and R'" is a substituent other than hydrogen, and includes the case where R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded. In this specification, regardless of the valence such as monovalent, divalent, or trivalent, fluorenyl group, fluorenylene group, and fluorenetriyl group can all be named fluorene group.

[0061] [ka]

[0062] Furthermore, the R, R', R" and R'" are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. For example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene, or phenanthrene, and the heterocyclic group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, benzofuranquinazoline, or quinoxaline. For example, the substituted fluorenyl group and fluorenylene group may be a monovalent functional group or a divalent functional group of 9,9-dimethylfluorene, 9,9-diphenylfluorene, and 9,9'-spirobi[9H-fluorene], respectively.

[0063] The term "heterocyclic group" as used herein includes not only aromatic rings such as "heteroaryl groups" or "heteroarylene groups" but also non-aromatic rings, and means, but is not limited to, a ring having 2 to 60 carbon atoms and containing one or more heteroatoms, unless otherwise specified. The term "heteroatom" as used herein means N, O, S, P, or Si, unless otherwise specified, and heterocyclic group means a single ring, ring assembly, fused multiple ring system, spiro compound, etc., containing a heteroatom.

[0064] For example, the term "heterocyclic group" may include compounds that contain heteroatoms such as SO2, P=O, etc., in place of the carbons that form the ring, as in the compounds below.

[0065] [ka]

[0066] The term "ring" as used in this application includes single and multiple rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.

[0067] The term "polycyclic" as used in this application includes ring assemblies such as biphenyls, terphenyls, fused multiple ring systems, and spiro compounds, and includes aromatic as well as non-aromatic rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom.

[0068] The term "aliphatic cyclic group" used in the present application means a cyclic hydrocarbon other than aromatic hydrocarbon, including a single ring, a ring assembly, a fused multiple ring system, a spiro compound, etc., and means a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto. For example, a fusion of an aromatic ring, benzene, and a non-aromatic ring, cyclohexane, also falls under the category of an aliphatic ring.

[0069] Also, when the prefixes are named consecutively, it means that the substituents are listed in the order in which they are written, for example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group, where the arylcarbonyl group is a carbonyl group substituted with an aryl group.

[0070] In addition, unless otherwise specified, in the term "substituted or unsubstituted" used in this application, "substituted" means deuterium, halogen, amino group, nitrile group, nitro group, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylamine groups, C1-C 30 Alkylthiophene group, C6-C 30 Arylthiophene groups, C2-C 30 Alkenyl groups, C2-C 30 Alkynyl groups, C3-C 30 Cycloalkyl groups of C6 to C 30 Aryl groups, C6-C substituted with deuterium 30 Aryl groups, C8-C 30 an arylalkenyl group, a silane group, a boron group, a germanium group, and a C2-C alkyl group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; 30 The term "substituted" means that the heterocyclic group is substituted with one or more substituents selected from the group consisting of the following heterocyclic groups, but is not limited to these substituents.

[0071] In this application, the "functional group name" corresponding to an aryl group, an arylene group, a heterocyclic group, etc., which are exemplified as examples of each symbol and its substituent, can be described as the "functional group name reflecting the valence" or as the "parent compound name." For example, in the case of "phenanthrene," which is a type of aryl group, the name of the group can be described by dividing the valence, such as "phenanthryl (group)" for a monovalent "group" and "phenanthrylene (group)" for a divalent group, or it can be described as the parent compound name "phenanthrene" regardless of the valence.

[0072] Similarly, pyrimidine can be described as "pyrimidine" regardless of the valence, or as the "name of the group" of the relevant valence, such as pyrimidinyl (group) if monovalent, pyrimidinylene (group) if divalent, etc. Therefore, when the type of substituent is described in the name of the parent compound in this application, it can mean an n-valent "group" formed by eliminating hydrogen atoms bonded to carbon atoms and / or hetero atoms of the parent compound.

[0073] In addition, in this specification, when describing the names of compounds and substituents, numbers and letters indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine may be described as pyridopyrimidine, benzofuro[2,3-d]pyrimidine as benzofuropyrimidine, 9,9-dimethyl-9H-fluorene as dimethylfluorene, etc. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline may be described as benzoquinoxaline.

[0074] In addition, unless otherwise expressly stated, the chemical formulas used in the present application are applied in the same manner as the substituent definitions according to the index definitions of the following chemical formulas.

[0075] [ka]

[0076] Here, when a is an integer of 0, it means that the substituent R1 does not exist, that is, when a is 0, it means that all the carbons forming the benzene ring are bonded with hydrogen, and in this case, the hydrogen bonded to the carbon may be omitted and the chemical formula or compound may be described. When a is an integer of 1, one substituent R1 is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it may be bonded as follows, for example, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, and when a is an integer of 2 or more, R1 may be the same or different from each other.

[0077] [ka]

[0078] Unless otherwise stated in this application, by forming a ring it is meant that adjacent groups are joined together to form a single ring or joined rings, and the single rings and joined rings formed include hydrocarbon rings as well as heterocycles containing at least one heteroatom, and include aromatic and non-aromatic rings.

[0079] In addition, unless otherwise specified in this specification, when describing a fused ring, the number in "number-fused ring" indicates the number of fused rings. For example, a form in which three rings are fused to each other, such as anthracene, phenanthrene, benzoquinazoline, etc., can be represented as a 3-fused ring.

[0080] In contrast, the term "bridged bicyclic compound" as used herein, unless otherwise specified, refers to a compound in which two rings share three or more atoms to form a ring, where the shared atoms include carbon or heteroatoms.

[0081] Hereinafter, the implementation of the present invention will be described in detail, but it should be understood that the present invention is not limited to the above embodiment, and is defined only by the scope of the claims that follow.

[0082] A positive photosensitive composition including a polymer and a precursor according to an embodiment of the present invention is used in manufacturing insulating films, surface passivation films, and redistribution layers of semiconductor devices; and pixel defining layers (PDLs) of display devices.

[0083] In preparing a positive photosensitive composition for application to a semiconductor device or display device according to an embodiment of the present invention, the composition may further include the following additives to improve desired properties.

[0084] As additives that can be added according to an embodiment of the present invention, a surface smoothing agent may be further included to make the thickness of the coating film constant when coating the substrate. A surfactant may be further included to make the coating uniform according to the characteristics of the substrate surface, and a silane coupling agent may be further included to adjust the adhesive strength with the substrate surface. A crosslinking agent may be further included to strengthen the bond between polymer molecules during the heat treatment step.

[0085] The positive photosensitive composition comprises the following elements:

[0086] (1) Polymer The patterning resin according to an embodiment of the present invention may include a polymer.

[0087] The polymer refers to a resin that contains a hydroxyamide-based precursor that can be formed into a polymer by chemical or thermal treatment.

[0088] The polymer may be included in an amount of 5% to 50% by weight, preferably 10% to 45% by weight, based on the total weight of the positive-type photosensitive composition.

[0089] The polymer may be a precursor represented by the following formula 1-1, 1-2, 1-3, or 1-4, but is not limited thereto, which may be used alone or in combination of two or more.

[0090] The polymer preferably contains a repeating unit selected from the group consisting of the following formula 1-1; formula 1-2; formula 1-3; formula 1-4; or a combination of two or more of formulas 1-1 to 1-4.

[0091] [ka]

[0092] In the group consisting of 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, 1) * is the part where the bond is connected in the repeat unit, 2) * at the end of the polymer is the portion where Q-1 to Q-10 are bonded by an amide bond or an imide bond. 3) X1 or X2 is the following chemical formula 2, 4) Y is C6~C 30 an arylene group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group, C1-C 20 Cycloalkylene groups, C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 2; or a combination thereof; 5) Z is C6~C 30 an arylene group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkylene group, C1-C 20 Cycloalkylene groups, C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 3; or a combination thereof; 6) k, l, m, and n are integers of 1 or more,

[0093] [ka]

[0094] 7) The polymer end is bonded to a compound represented by a formula selected from the group consisting of one selected from the formulas Q-1 to Q-10 or a combination thereof through an amide or imide bond;

[0095] [ka]

[0096] In the above Chemical Formula 2, 8) L1 is a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-, -C(CH 13 )2-, -C(CH 10 )-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, Si(CH3)2-, -C6H4-, -CO-, -NHCO-, -COO-; 9) R1 or R 10 Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 10) The remaining R1 to R excluding the linking portion 10 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 an aryl group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkyl group; C2-C 20Alkenyl group; C2-C 20 Alkynyl group; C1-C 20 Alkoxy group; C6-C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 is an alkoxycarbonyl group of the formula 11) L 1 is a single bond, the adjacent R and R 10 and R5 and R6 can form a ring;

[0097] [ka]

[0098] In the above Chemical Formula 3, 12) L2 is a single bond, -CH2-, -CH2CH2-, -CH2OCH2-, -CH(CH3)-, -C(CH3)2-, -C(C2H5)2-, -C(C3H7)2-, -C(C4H9)2-, -C(C5H 11 )2-, -C(CH 13 )2-, -C(CH 10 )-, -O-, -CH(CF3)-, -C(CF3)2-, -S-, -SO2-, Si(CH3)2-, -C6H4-, -CO-, -NHCO-, -COO-; 13) R 11 Or R 20 Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 14) The remaining R excluding the linking site 11 Or R 20 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 an aryl group having at least one heteroatom selected from O, N, S, Si, and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 Alkyl group; C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C20 Alkoxy group; C6-C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or a C1-C 20 The remaining R excluding the linking portion is an alkoxycarbonyl group. 11 Or R 20 Two of them are carboxyl groups, 15) L 2 is a single bond, the adjacent R 11 and R 20 ; and R 15 and R 16 can form a ring.

[0099] The polymer according to one embodiment of the present invention is produced using γ-butyrolactone as a single solvent, and therefore is less harmful to the environment and human body, and has an excellent yield of the reactant (polymer).

[0100] The yield of the polymer produced by the above production method is preferably 80% or more, and more preferably 82.5% or more.

[0101] It is preferred that pyridine is further added in the preparation method, since pyridine increases the compatibility of γ-butyrolactone and the monomer and acts as a catalyst for the polymerization reaction, so that the polymerization reaction can occur more efficiently.

[0102] The weight average molecular weight of the polymer resin may be 5,000 g / mol to 30,000 g / mol, preferably 5,000 g / mol to 40,000 g / mol, more preferably 7,000 g / mol to 25,000 g / mol. When the weight average molecular weight of the resin is within the above range, no residue of the exposed layer remains during development, and the loss of the thickness of the non-exposed layer is minimized, so that a good pattern can be obtained. The resin may be included in an amount of 5 to 50 wt %, more preferably 10 to 45 wt %, based on the total amount of the photosensitive composition. When the resin is included within the above range, a constant thickness can be obtained in the coating step, and excellent sensitivity, developability, and adhesion (adhesion) can be obtained.

[0103] (2) Photosensitizer The photosensitizer is a photosensitizer commonly used in positive photosensitive compositions, and may be, for example, a photosensitive diazoquinone compound. Specifically, the photosensitizer may include a phenol compound and a photosensitive compound represented by the following formulas P-1 to P-8. Specific examples of R" include hydrogen, deuterium, and compounds having 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-diazide-4-sulfonic acid in their structures.

[0104] [ka]

[0105] In the above P-1 to P-8, R″ is hydrogen; the following chemical formula S-1; or the following chemical formula S-2.

[0106] [ka]

[0107] In the above chemical formulas S-1 and S-2, * indicates a linking site.

[0108] The photosensitizer may be included in an amount of 1 to 50% by weight based on the total weight of the composition.

[0109] (3) Solvent The solvent may be any material that is compatible with, but does not react with, the polymer resin, the photosensitizer, and the pigment.

[0110] Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethyl glycol monomethyl ester, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4- Ketones such as methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate;2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; and ketone acid esters such as ethyl pyruvate.

[0111] Also usable are high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0112] Among the above solvents, in consideration of compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate may be used.

[0113] The solvent may be included as the remaining amount based on the total amount of the photosensitive composition, specifically, 50 to 95 wt %. When the solvent is included within this range, the positive type photosensitive composition has an appropriate viscosity, and thus has excellent processability when manufacturing a pattern layer.

[0114] (4) Other additives The positive photosensitive resin composition may further contain additives such as malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing a vinyl group or a (meth)acryloxy group; a surface smoothing agent; a surfactant; and a crosslinker in order to prevent stains and spots during application, improve leveling performance, and prevent the generation of residues due to undeveloped state.

[0115] For example, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion to a substrate.

[0116] Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, gamma methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, gamma isocyanate propyl triethoxysilane, gamma glycidoxypropyl trimethoxysilane, beta epoxy cyclohexylethyl trimethoxysilane, and silane-based coupling agents commercially available under the names of KBM-502, KBM-602, KBM-573, and KBE-9007N from Shinetsu Silicon Co., Ltd., and these may be used alone or in combination of two or more kinds.

[0117] The silane coupling agent may be contained in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the composition has excellent adhesion, storage stability, and the like.

[0118] In addition, the photosensitive resin composition may further include a surface smoothing agent, if necessary, to form a uniform film thickness during the coating step.

[0119] As the surface smoothing agent, surface smoothing agents commercially available under the names of F-554 (registered trademark), F-556 (registered trademark), F-557 (registered trademark), F-559 (registered trademark), F-560 (registered trademark), F-563 (registered trademark), RS-72-K (registered trademark), R-40 (registered trademark), R-41 (registered trademark), R-43 (registered trademark), etc., manufactured by DIC Corporation; Efka (registered trademark) FL3740, FL3741, FL3745, FL3770, etc., manufactured by BASF Corporation may be used.

[0120] The surface smoothing agent may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surface smoothing agent is within the above range, the coating uniformity is ensured and the film thickness can be coated at a constant level.

[0121] In addition, the photosensitive resin composition may further include a surfactant, if necessary, to improve coating properties and prevent the generation of defects.

[0122] The surfactants include BM Surfactants commercially available under the names of BM-1000 (registered trademark), BM-1100 (registered trademark) and the like from Chemie; Megafac F142D (registered trademark), F172 (registered trademark), F173 (registered trademark), F183 (registered trademark) and the like from Dainippon Ink and Chemicals Co., Ltd.; Fluorad FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark) and the like from Sumitomo 3M Co., Ltd.; Surflon S-112 (registered trademark), S-113 (registered trademark), S-131, S-141, S-145 and the like from Asahi Glass Co., Ltd.; SH-28PA (registered trademark), S-190 (registered trademark), S-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark) and the like from Dray Silicon Co., Ltd. may also be used.

[0123] The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within this range, coating uniformity is ensured, spots are not generated, and the wetting property to the glass substrate is excellent.

[0124] As the crosslinker, 1,4-bis(methoxymethyl)benzene, diethyl sulfate, 3-aminopropyltriethoxysilane, N,N'-methylenebisacrylamide, etc. may be used, and these may be used alone or in combination of two or more kinds.

[0125] The crosslinker may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the crosslinker is used within the above range, it is advantageous for imparting suitable physical properties, such as mechanical properties such as tensile strength, to the cured coating film.

[0126] The photosensitive resin composition may contain other additives in a certain amount within a range that does not impair the physical properties.

[0127] Synthesis examples and examples according to the present invention will be specifically described below, but the synthesis examples and examples of the present invention are not limited thereto.

[0128] Synthesis Example 1 A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, and then filled with nitrogen and 120.47g of γ-butyrolactone (GBL). Then, 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.58g of pyridine were added and stirred while maintaining the temperature at 40°C. 0.910g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. The solution was then stirred for 30 minutes while maintaining the temperature at 5°C. Then, 10.58g of 4,4'-oxybisbenzoyl chloride was slowly added and dissolved, and reacted while stirring for 12 hours.

[0129] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain a copolymerized polyhydroxyamide powder with a yield of 87.56%.

[0130] Synthesis Example 2 A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, and then filled with nitrogen and 65.7g of γ-butyrolactone (GBL). 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.52g of pyridine were added and stirred while maintaining the temperature at 40°C. 0.910g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 52.70g of GBL and 2.06g of pyridine were added to the flask where the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 8.76g of 4,4'-biphenyldicarbonyl chloride was slowly added and dissolved, and the reaction was allowed to proceed with stirring for 12 hours.

[0131] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain a copolymerized polyhydroxyamide powder with a yield of 85.47%.

[0132] Synthesis Example 3 A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, and then filled with nitrogen and 65.7g of gamma-butyrolactone (GBL). 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.52g of pyridine were added and stirred to maintain the temperature at 40°C. 1.54g of 5-novone-2,3-dicarboxylic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 52.70g of GBL and 2.06g of pyridine were added to the flask in which the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 9.48g of 4,4'-oxybisbenzoyl chloride was slowly added and dissolved, and the reaction was stirred for 12 hours.

[0133] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain a copolymerized polyhydroxyamide powder in a yield of 87.23%.

[0134] Synthesis Example 4 A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, and then filled with nitrogen and 65.7g of γ-butyrolactone (GBL). 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)propane and 0.52g of pyridine were added and stirred to maintain the temperature at 40°C. 0.91g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 52.70g of GBL and 2.06g of pyridine were added to the flask where the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 11.95g of 1,4-4,4'-oxybisbenzoyl chloride was slowly added and dissolved, and the reaction was stirred for 12 hours.

[0135] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain a copolymerized polyhydroxyamide powder with a yield of 84.77%.

[0136] Comparative Example 1 A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, red-brown funnel, temperature controller and cooler, and then filled with nitrogen and 65.7g of N-methylpyrrolidone (NMP). 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.52g of pyridine were added and stirred to maintain the temperature at 40°C. 0.910g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 54.77g of NMP and 2.06g of pyridine were added to the flask in which the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 10.58g of 4,4'-oxybisbenzoyl chloride was slowly added and dissolved, and the reaction was carried out with stirring for 12 hours.

[0137] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain a copolymerized polyhydroxyamide powder with a yield of 76.42%.

[0138] Comparative Example 2 A 250ml three-neck round-bottom flask was equipped with a stirrer, nitrogen injector, red-brown funnel, temperature controller and cooler, and then filled with nitrogen and 65.7g of N-methylpyrrolidone (NMP). 15g of 2,2'-bis(3-amino-4-hydroxyphenyl)propane and 0.52g of pyridine were added and stirred to maintain the temperature at 40°C. 0.910g of phthalic anhydride was slowly added and stirred for a certain period of time to dissolve and react. After that, 54.77g of NMP and 2.06g of pyridine were added to the flask in which the reaction was in progress, and the solution was stirred for 30 minutes while maintaining the temperature at 5°C. Then, 11.95g of 4,4'-oxybisbenzoyl chloride was slowly added and dissolved, and the reaction was stirred for 12 hours.

[0139] The polyhydroxyamide solution was stirred at room temperature for 1 hour, and then precipitated with methanol. The precipitated solid was dried in vacuum at 60° C. for 12 hours to obtain a copolymerized polyhydroxyamide powder with a yield of 73.82%.

[0140] [Table 1]

[0141] As a result of the synthesis test shown in Table 1, it was confirmed that the results were obtained in a yield of more than 84% in all of Examples 1 to 4, which is 8% higher than that of Comparative Examples 1 and 2. In addition, it was confirmed that the ratio of unreacted monomer remained in Comparative Examples 1 and 2 by 5% or more compared to Synthesis Examples 1 to 4.

[0142] (Preparation Example 1) Preparation of Positive Photosensitive Composition 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 TPD52 (Migen Shoji Co., Ltd.), 0.013 g of F-563 (DIC Co., Ltd.), 1.7 g of KBM-573 (Shinetsu Silicon Co., Ltd.), and 1.2 g of 1,4-bis(methoxymethyl)benzene were stirred with 32.5 g of γ-butyrolactone at room temperature for 12 hours. Then, the composition was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

[0143] A photosensitive composition solution was prepared according to the composition shown in Table 2 below.

[0144] [Table 2]

[0145] The method for preparing the UTM test piece using the positive type photosensitive resin composition is as follows.

[0146] (1) Application and coating stage The photosensitive composition prepared in the examples or comparative examples is applied to a cleaned 10cm x 10cm glass substrate with a certain thickness using a spin coater, and then a coating film is formed by removing part of the solvent using VCD (vacuum chamber dry). The coating thickness of the photosensitive composition is 11μm to 13μm after VCD.

[0147] (2) Pre-bake stage In order to remove the solvent contained in the obtained coating film, the film is heated on a hot plate at 100°C to 140°C for 50 to 200 seconds. By removing a certain amount of the solvent in this process, a coating film of a certain thickness can be obtained even in the development step after the next process (exposure).

[0148] (3) Exposure step In order to obtain the necessary pattern formation and a certain thickness for the obtained coating film, a pattern can be formed by irradiating the film with an actinic ray of 190 nm to 600 nm, preferably with a light source of a metal or LED lamp having a ghi-line. The exposure dose is 50 to 500 mJ / cm. 2 The pattern formed is a positive type 9cm x 1cm strap pattern.

[0149] (4) Development stage Following the exposure step, the substrate is developed using a puddle method in which a certain amount of 2.38 wt% TMAH (tetramethylammonium hydroxide) developer is applied to the substrate at 23±2°C and left for a certain time (minutes). The substrate is then washed with ultrapure water (DI water), whereby the exposed areas are dissolved and removed, leaving only the unexposed areas to form an image pattern, with the remaining coating having a thickness of 9.0 to 11.0 μm.

[0150] (5) Post-heat treatment stage In order to obtain an image pattern obtained by the above development, the coating film obtained is cured by carrying out post baking in an oven at 300 to 320° C. for 30 to 120 minutes.

[0151] (6) Peeling off the test piece In order to obtain UTM specimens without damage from the substrates that had undergone the post-heat treatment step, the substrates were dipped in a 2% hydrofluoric acid solution at 23±2°C for a certain time (minutes), and the separated specimens were washed using ultrapure water (DI water) and then dried in a vacuum chamber at room temperature to obtain UTM specimens.

[0152] (7) UTM measurement The tensile strength and elongation of the test pieces of the examples and comparative examples were measured using a universal material testing machine QM100S from QMESYS Co., Ltd. The measurement conditions were a measurement temperature of 25° C., a tensile speed of 5 mm / min, and a gauge length of 20 mm.

[0153] (8) NMP content measurement In addition, in order to analyze the NMP content of the prepared composition, the composition was subjected to Headspace GC / MS analysis by SGS Korea, an accredited testing organization, to measure the NMP content, and the LDL was 5 ppm.

[0154] [Table 3]

[0155] As a result of the development test shown in Table 2, it was confirmed that no development that left residues after development occurred in any of Examples 1 to 4 except for the Comparative Example. In addition, when comparing Example 1 and Comparative Example 3, and Example 4 and Comparative Example 4, which were synthesized with the same composition but different solvents, it was confirmed that the elongation rate and tensile strength of Examples 1 and 4 were 10% and 10 MPa higher, respectively, and that the physical properties of the Examples with a low content of unreacted monomers were better. In addition, it was confirmed that a pattern was realized with excellent resolution compared to the Comparative Example. As a result of analyzing the NMP content, it was confirmed that NMP was not detected in any of Examples 1 to 4, and that 150 ppm and 158 ppm of NMP were detected in Comparative Examples 1 and 2, respectively. Recently, regulations have been strengthened to remove or not use NMP, which is harmful to the human body, from display and semiconductor materials, and it is possible to produce a composition that does not contain NMP using the synthesis method presented in this patent.

[0156] The present invention is not limited to the above embodiments and may be implemented in many different forms.

[0157] The above description is merely illustrative of the present invention, and various modifications may be made by those having ordinary skill in the art to which the present invention pertains without departing from the essential characteristics of the present invention.

[0158] Therefore, the embodiments disclosed in this specification are for illustrative purposes only and are not intended to limit the present invention, and the spirit and scope of the present invention are not limited by such embodiments. The scope of protection of the present invention should be interpreted by the claims, and all technologies within the scope equivalent thereto should be interpreted as being included in the scope of the present invention.

Claims

1. A method for producing a polymer comprising the following formula 1-1; formula 1-2; formula 1-3; formula 1-4; or a combination thereof, the polymer being produced using γ-butyrolactone as a single solvent. 【Chemistry 1】 In the above Chemical Formula 1-1 to Chemical Formula 1-4, 1) * is the part where the bond is connected in the repeat unit, 2) The * at the end of the polymer represents the portion where Q-1 to Q-10 are bonded via an amide bond or an imide bond. 3) X １ Or X ２ is the following chemical formula 2, 4) Y is C ６ ~C ３０ an arylene group having at least one heteroatom selected from O, N, S, Si and P; ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkylene group of C １ ~C ２０ a cycloalkylene group of C ２ ~C ２０ an alkenylene group represented by the formula C ３ ~C ２０ A cycloalkenylene group represented by the formula: ２ ~C ２０ An alkynylene group represented by the formula: ３ ~C ２０ a cycloalkynylene group of formula (I); formula (II); or a combination thereof; 5) Z is C ６ ~C ３０ an arylene group having at least one heteroatom selected from O, N, S, Si and P; ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkylene group of C １ ~C ２０ a cycloalkylene group of C ２ ~C ２０ an alkenylene group represented by the formula C ３ ~C ２０ A cycloalkenylene group represented by the formula: ２ ~C ２０ An alkynylene group represented by the formula: ３ ~C ２０ a cycloalkynylene group of formula (I); formula (II); or a combination thereof; 6) k, l, m, and n are integers of 1 or more; 【Chemistry 2】 7) The polymer end is bonded to a compound represented by a formula selected from the group consisting of one or a combination of formulas Q-1 to Q-10 through an amide or imide bond; 【Chemistry 3】 In the above Chemical Formula 2, 8) L １ is a single bond, -CH ２ --, --CH ２ CH ２ --, --CH ２ OCH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, -C(C ２ H ５ ) ２ -, -C(C ３ H ７ ) ２ -, -C(C ４ H ９ ) ２ -, -C(C ５ H １１ ) ２ -, -C(C ６ H １３ ) ２ -, -C(C ５ H １０ )-, -O-, -CH(CF ３ ) -, -C(CF ３ ) ２ -, -S-, -SO ２ -, Si(CH ３ ) ２ -, -C ６ H ４ selected from the group consisting of -, -CO-, -NHCO-, and -COO-; 9) R １ Or R １０ Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 10) The remaining R excluding the linking site １ Or R １０ are each independently hydrogen; deuterium; a hydroxyl group; ６ ~C ３０ an aryl group of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkyl group of C ２ ~C ２０ an alkenyl group of C ２ ~C ２０ an alkynyl group of C １ ~C ２０ an alkoxy group of C ６ ~C ３０ an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or C １ ~C ２０ is an alkoxycarbonyl group of the formula 11) L １ is a single bond, the adjacent R １ and R １０ and R ５ and R ６ can form a ring, 【Chemistry 4】 In the above Chemical Formula 3, 12) L ２ is a single bond, -CH ２ --, --CH ２ CH ２ --, --CH ２ OCH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, -C(C ２ H ５ ) ２ -, -C(C ３ H ７ ) ２ -, -C(C ４ H ９ ) ２ -, -C(C ５ H １１ ) ２ -, -C(C ６ H １３ ) ２ -, -C(C ５ H １０ )-, -O-, -CH(CF ３ ) -, -C(CF ３ ) ２ -, -S-, -SO ２ -, Si(CH ３ ) ２ -, -C ６ H ４ selected from the group consisting of -, -CO-, -NHCO-, and -COO-; 13) R １１ Or R ２０ Two of them are linking sites with the amide groups of Chemical Formula 1-1 and Chemical Formula 1-2, 14) The remaining R excluding the linking portion １１ Or R ２０ are each independently hydrogen; deuterium; a hydroxyl group; ６ ~C ３０ an aryl group of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkyl group of C ２ ~C ２０ an alkenyl group of C ２ ~C ２０ an alkynyl group of C １ ~C ２０ an alkoxy group of C ６ ~C ３０ an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or C １ ~C ２０ The remaining R excluding the linking portion is an alkoxycarbonyl group. １１ Or R ２０ Two of them are carboxyl groups, 15) L ２ is a single bond, the adjacent R １１ and R ２０ and R １５ and R １６ can form a ring.

2. 2. The method for producing a polymer according to claim 1, wherein the yield of the polymer produced by the method is 80% or more.

3. The method for producing the polymer according to claim 1, further comprising the step of:

4. 2. The method of claim 1, wherein the polymer is made from a diamine monomer; a diacyl chloride monomer; an anhydride monomer; or a combination thereof.

5. 5. The method for producing a polymer according to claim 4, wherein 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. 5. The polymer according to claim 4, wherein the diacyl chloride comprises one or more monomers selected from the group consisting of 4,4'-oxybisbenzoyl chloride, 1,2-cyclobutanedicarboxylic acid dichloride, terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldicarbonyl chloride, 1,4-naphthalene dicarbonyl chloride, 4,4'-sulfonyldibenzoyl chloride, 1,4-cyclohexanedicarboxylic acid dichloride, and combinations thereof.

7. 5. The method for producing a polymer according to claim 4, wherein the anhydride comprises one or more monomers selected from the group consisting of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 5-novonene-2,3-dicarboxylic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, or a combination thereof.

8. A positive photosensitive composition comprising the polymer of claim 1; a photosensitizer; a solvent; and an additive.

9. 9. The positive photosensitive composition of claim 8, wherein the photosensitizer comprises at least one of the following formulas P-1 to P-8: 【Chemistry 5】 In the above P-1 to P-8, R″ is hydrogen; the following formula S-1; or the following formula S-2. 【Chemistry 6】

10. 9. The positive photosensitive composition of claim 8, wherein the solvent comprises at least one selected from the group consisting of N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, gamma-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, or a combination thereof.

11. 9. The positive photosensitive composition of claim 8, wherein the additive comprises at least one selected from the group consisting of a silane coupling agent; a surface smoothing agent; a surfactant; a crosslinking agent; or a combination thereof.

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

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

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

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