Polyimide precursors and compositions containing the same

Abstract

To provide a polyimide precursor for improving physical properties by introducing a reactive monomer to the terminal of a polymer.SOLUTION: There is provided a polyimide precursor comprising a reactive end group represented by Formula Q. Ra to Rc are hydrogen; deuterium; a hydroxy group; a C6 to C30 aryl group or the like; C1 and C2 are carbon; C3 is carbon or a direct bond of C2-B2; the dotted line connecting B1 and B2 is a non-existent bond or single bond; when the dotted line connecting B1 and B2 is absent, B1 is hydrogen; deuterium; a hydroxy group or the like; and B2 is nitrogen connected to a polyimide repeating unit.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyimide precursor produced by using the polyimide precursor, and a polymer composition used in a semiconductor device or a display device. [Background technology]

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

[0003] The photolithography process is broadly divided into negative and positive processes, in which the exposed area reacts with the developer in the development step, and the reaction product is dissolved and removed in the positive process, and the non-exposed area reacts with the developer in the negative process, and the reaction product is dissolved and removed in the negative process. Among these, the negative process uses a photoinitiator that absorbs light and generates radicals in the exposure step, allowing exposure with a relatively small amount of energy compared to the positive process, and has the advantage of excellent adhesion to oxide films.

[0004] Conventionally, negative-type photosensitive resin compositions used in semiconductor devices and display devices have used resins such as polyimide precursors or copolymers due to their high heat resistance, chemical resistance, weather resistance, etc. However, the molecular weight of the polymer resin used is limited because development is performed using an alkaline aqueous solution in the development step, and thus there is a limit to the mechanical properties that can be achieved. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2011-0041389 [Patent Document 2] Korean Patent Publication No. 10-2014-0041371 Summary of the Invention [Problem to be solved by the invention]

[0006] In order to solve the problems of the prior art, the present invention aims to improve the physical properties by introducing a reactive monomer into the terminal of a polymer formed from a polyimide precursor.

[0007] Also, a negative-type photosensitive composition is provided using a polymer formed from the polyimide precursor.

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

[0009] The polyimide precursor according to the present invention preferably contains a reactive end group represented by the following chemical formula Q.

[0010] [ka]

[0011] In the above Chemical Formula 1,

[0012] 1) R a Or R c are independently hydrogen; deuterium; hydroxyl group; C6-C 30 aryl groups of C2-C containing at least one heteroatom of O, N, S, Si and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 30 Alkyl group; C2-C 30 Alkenyl group; C2-C30 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy groups; C1-C 30 Hydroxyacrylic group; C1-C 30 Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 30 or R a Or R c adjacent groups form a ring,

[0013] 2) C1 and C2 are carbons, and the bond connecting C1 and C2 is a single bond or a double bond;

[0014] 3) when the bond connecting C1 and C2 is a single bond, o and p are each independently an integer of 1 or 2; when the bond connecting C1 and C2 is a double bond, o and p are each an integer of 1;

[0015] 4) C3 is a carbon or a direct bond between C2 and B2;

[0016] 5) when C3 is carbon, q is an integer of 1 or 2;

[0017] 6) The dotted line connecting B1 and B2 is either no bond or a single bond;

[0018] 7) When the dotted bond connecting B1 and B2 does not exist, B1 is hydrogen; deuterium; hydroxyl group; 30 aryl groups, C2-C groups containing at least one heteroatom selected from O, N, S, Si and P; 30 Heterocyclic groups, C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring, C1-C 20 Alkyl groups, C2-C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 20 Alkoxy group; C6-C 30 Aryloxy groups; C1-C 20Hydroxyacrylic group; C1-C 20 Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 20 B2 is a nitrogen atom linked to a polyimide repeating unit;

[0019] 8) When the dotted line connecting B1 and B2 is a single bond, B1 is nitrogen connected to the polyimide repeating unit; B2 is carbon;

[0020] 9) The above R a Or R c and the ring formed by bonding adjacent groups to each other is deuterium; halogen; C1-C 30 or C6-C 30 aryl groups, substituted or unsubstituted silane groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C1-C 30 Alkylthio group; C1-C 30 Alkoxy group; C6-C 30 Arylalkoxy groups; C1-C 30 Alkyl groups of C2 to C 30 Alkenyl group; C2-C 30 Alkynyl group; C6-C 30 Aryl groups; C6-C substituted with deuterium 30 an aryl group; a fluorenyl group; a C2-C group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; 30 Heterocyclic group; C3-C 30 Aliphatic ring group; C7-C 30 Aryl alkyl group; C8-C 30 and combinations thereof, or adjacent substituents taken together form a ring.

[0021] The negative polyimide precursor according to the present invention more preferably contains a repeating unit selected from the group consisting of the following formula 1-1, formula 1-2, and a combination thereof.

[0022] [ka]

[0023] [ka]

[0024] In the above Chemical Formula 1-1 and Chemical Formula 1-2,

[0025] 1) * is a repeating unit or a portion that is connected to a reactive terminal group represented by the chemical formula Q,

[0026] 2) R1 to R4 are represented by the following formula 2:

[0027] 3) X is represented by the following chemical formula 3:

[0028] 4) m and n are integers from 1 to 1000,

[0029] [ka]

[0030] In the above Chemical Formula 2,

[0031] 5) * is the part where the bond is attached,

[0032] 6) a is an integer from 1 to 30,

[0033] 7) R5 is hydrogen or a methyl group;

[0034] 8) Y is C6~C 30 an arylene group of C2-C containing at least one heteroatom of O, N, S, Si, or 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 20Cycloalkylene group; C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 3; and combinations thereof;

[0035] 9) Z is C6~C 30 an arylene group of C2-C containing at least one heteroatom of O, N, S, Si, or 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 group; C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 3; and combinations thereof;

[0036] [ka]

[0037] 10) L 1 is selected from the group consisting of a single bond, -CH-, -CHCH-, -CHOCH-, -CH(CH)-, -C(CH)-, -O-, -CH(CF)-, -C(CF)-, -S-, -SO-, Si(CH)-, -CH, -OCHO, -CO-, -NHCO-, and -COO-;

[0038] 11) R6 or R 15 Two of them are linking sites with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2,

[0039] 12) The remaining R6 to R excluding the linking site 15 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30aryl groups of C2-C containing at least one heteroatom of 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 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 20 or adjacent R6 to R 15 ; and R 10 and R 11 forms a ring,

[0040] 13) The Y, Z, R6 to R 15 and the ring formed by bonding adjacent groups to each other are each independently deuterium; halogen; 30 or C6-C 30 aryl groups or unsubstituted silane groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C1-C 30 Alkylthio group; C1-C 30 Alkoxy group; C6-C 30 Arylalkoxy groups; C1-C 30 Alkyl group; C2-C 30 Alkenyl group; C2-C 30 Alkynyl group; C6-C 30 Aryl groups; C6-C substituted with deuterium 30 an aryl group; a fluorenyl group; a C2-C group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; 30 Heterocyclic group; C3-C 30 Aliphatic ring group; C7-C 30 Aryl alkyl group; C8-C 30 and combinations thereof, or adjacent substituents taken together form a ring.

[0041] The reactive end group represented by the formula Q may include compounds represented by the following formulas Q-1 to Q-6.

[0042] [ka]

[0043] In the above chemical formulas Q-1 to Q-6,

[0044] 1) R d1 , R d2 , R e1 Or R e3 , R f1 Or R f4 , R g , R h1 , R h2 , and R i1 Or R i3 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 aryl groups of C2-C containing at least one heteroatom of O, N, S, Si and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 30 Alkyl group; C2-C 30 Alkenyl group; C2-C 30 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy groups; C1-C 30 Hydroxyacrylic group; C1-C 30 Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 30 is an alkoxycarbonyl group of the formula

[0045] 2) r and t are integers from 1 to 4;

[0046] 3) s1, s2, and u1 to u3 are each an integer of 1 or 2.

[0047] 4) * is the part where the bond is attached.

[0048] The reactive end group represented by the formula Q may also include compounds represented by the following formulas Q-7 to Q-10.

[0049] [ka]

[0050] R 16 Or R 18 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 aryl groups of C2-C containing at least one heteroatom of O, N, S, Si and P; 30 Heterocyclic 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 Aryloxy groups; C1-C 20 Hydroxyacrylic group; C1-C 20 Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 20 is an alkoxycarbonyl group.

[0051] The precursor end is bonded with a chemical formula selected from one selected from the group consisting of the chemical formulas Q-7 to Q-10 or a combination thereof via an amide or imide bond.

[0052] The polyimide precursor preferably includes a diamine monomer, a dianhydride monomer, and an anhydride monomer.

[0053] The weight average molecular weight of the polyimide precursor is preferably 5,000 to 40,000 g / mol.

[0054] In another embodiment of the present invention, the polymer composition according to the present invention preferably comprises the polyimide precursor; a photoinitiator; a reactive unsaturated compound; a solvent; and an additive.

[0055] The polyimide precursor is preferably contained in an amount of 5 to 50% by weight based on the total weight of the composition.

[0056] The photoinitiator is preferably contained in an amount of 0.01 to 10% by weight based on the total weight of the composition.

[0057] The reactive unsaturated compound is preferably contained in an amount of 1 to 40% by weight based on the total amount of the composition.

[0058] The solvent is preferably contained in an amount of 50 to 95% by weight based on the total weight of the composition.

[0059] The additives are preferably contained in an amount of 0.001 to 10% by weight based on the total weight of the composition.

[0060] In another embodiment of the present invention, it is preferred to provide a pattern or film made from the polymer composition.

[0061] 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.

[0062] 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

[0063] According to the present invention, a reactive functional group is introduced at the end of a polyimide precursor resin to produce a polymer composition having improved tensile strength and elongation, and the polymer composition can be used to produce a display device or a semiconductor device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0064] 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.

[0065] In the description of the present invention, if it is determined that a specific description of related publicly known configurations or functions may make the gist of the present invention unclear, the detailed description may be omitted. When "comprises," "has," "consists of," and the like are used in this specification, other parts may be added as long as "only" is not used. When a component is expressed in the singular, it includes the plural unless otherwise expressly specified.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.).

[0071] 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.

[0072] The term "halo" or "halogen" as used in this application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise stated.

[0073] 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.

[0074] The term "haloalkyl group" or "haloalkyl group" as used herein means, unless otherwise specified, an alkyl group substituted with a halogen.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] [ka]

[0086] 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.

[0087] 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.

[0088] 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.

[0089] [ka]

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] In addition, unless otherwise specified, in the term "substituted or unsubstituted" used in this application, "substituted" means deuterium, halogen, amino group, nitrile group, nitro group, C1-C 30 Alkyl groups, C1-C 30 Alkoxy groups, C1-C 30 Alkylamine groups, C1-C 30 Alkylthiophene groups, C6-C 30 Arylthiophene groups, C2-C 30 Alkenyl groups, C2-C 30 Alkynyl groups, C3-C 30 Cycloalkyl groups of C6 to C 30 Aryl groups, C6-C substituted with deuterium 30 Aryl groups, C8-C 30 an arylalkenyl group, a silane group, a boron group, a germanium group, and a C2-C alkyl group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; 30 The term "substituted" means that the heterocyclic group is substituted with one or more substituents selected from the group consisting of the following heterocyclic groups, but is not limited to these substituents.

[0095] 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.

[0096] Similarly, pyrimidine can be described as "pyrimidine" regardless of the valence, or as the "name of the group" of the relevant valence, such as pyrimidinyl (group) in the case of a monovalent group, pyrimidinylene (group) in the case of a divalent group, etc. Thus, when the type of ring group is described in the name of the parent compound in this application, it can mean an n-valent "group" formed by eliminating hydrogen atoms bonded to carbon atoms and / or heteroatoms of the parent compound.

[0097] 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.

[0098] 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.

[0099] [ka]

[0100] where a is an integer of 0, the substituent R 1In other words, when a is 0, it means that all the carbons forming the benzene ring are bonded to hydrogen, and in this case, the hydrogen bonded to the carbon may be omitted and the chemical formula or compound may be written. Also, when a is an integer of 1, one substituent R 1 is bonded to any one of the carbons forming a benzene ring. When a is an integer of 2 or 3, it can be bonded as shown below. When a is an integer of 4 to 6, it can be bonded to a carbon of the benzene ring in a similar manner. When a is an integer of 2 or more, R 1 may be the same as or different from each other.

[0101] [ka]

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] The polyimide precursor or polyimide precursor including polymer according to one embodiment of the present invention is preferably negative type.

[0107] The polyimide precursor according to one embodiment of the present invention is preferably a photosensitive composition.

[0108] The negative photosensitive composition can be used to manufacture insulating films, surface passivation films, and redistribution layers in semiconductor devices; and pixel defining layers (PDLs) in display devices.

[0109] In preparing a negative photosensitive composition for application to a semiconductor device or display device according to an embodiment of the present invention, the following additives may be additionally included to improve desired properties.

[0110] Additives that can be added according to an embodiment of the present invention include a surface smoothing agent to ensure a consistent thickness of the coating when coated on a substrate, a surfactant to ensure consistent coating according to the characteristics of the substrate surface, a silane coupling agent to adjust the adhesive strength with the substrate surface, and a crosslinking agent to strengthen the bond between polymers during the heat treatment step.

[0111] The elements constituting the polyimide precursor of the present invention are as follows.

[0112] (1) Polyimide precursor

[0113] The patterning resin according to an embodiment of the present invention may include a polyimide precursor.

[0114] The polyimide precursor refers to a resin including an amic acid copolymer that can be converted into a polyimide polymer by chemical or thermal treatment, and a polyimide polymer that has been subjected to chemical or thermal treatment.

[0115] The polyimide precursor may be included in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, based on the total weight of the polyimide-based composition.

[0116] The weight average molecular weight of the polyimide precursor may be 5,000 g / mol to 40,000 g / mol, preferably 5,000 g / mol to 35,000 g / mol, and more preferably 6,000 g / mol to 25,000 g / mol.

[0117] The polyimide precursor preferably contains a reactive group represented by the following chemical formula Q at its end group.

[0118] [ka]

[0119] In the above Chemical Formula 1,

[0120] 1) R a Or R c are independently hydrogen; deuterium; hydroxyl group; C6-C 30 aryl groups of C2-C containing at least one heteroatom of O, N, S, Si and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 30 Alkyl group; C2-C 30 Alkenyl group; C2-C 30 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy groups; C1-C 30 Hydroxyacrylic group; C1-C 30 Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 30 or R a Or R c adjacent groups form a ring,

[0121] 2) C1 and C2 are carbons, and the bond connecting C1 and C2 is a single bond or a double bond;

[0122] 3) when the bond connecting C1 and C2 is a single bond, o and p are each independently an integer of 1 or 2; when the bond connecting C1 and C2 is a double bond, o and p are each an integer of 1;

[0123] 4) C3 is a carbon or a direct bond between C2 and B2;

[0124] 5) when C3 is carbon, q is an integer of 1 or 2;

[0125] 6) The dotted line connecting B1 and B2 is either no bond or a single bond;

[0126] 7) When the dotted bond connecting B1 and B2 does not exist, B1 is hydrogen; deuterium; hydroxyl group; 30 aryl groups, C2-C groups containing at least one heteroatom selected from O, N, S, Si and P; 30 Heterocyclic groups, C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring, C1-C 20 Alkyl groups of C2 to C 20 Alkenyl group; C2-C 20 Alkynyl group; C1-C 20 Alkoxy group; C6-C 30 Aryloxy groups; C1-C 20 Hydroxyacrylic group; C1-C 20 Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 20 B2 is a nitrogen atom linked to a polyimide repeating unit;

[0127] 8) When the dotted line connecting B1 and B2 is a single bond, B1 is nitrogen connected to the polyimide repeating unit; B2 is carbon;

[0128] 9) The above Ra Or R c and the ring formed by bonding adjacent groups to each other is deuterium; halogen; C1-C 30 or C6-C 30 aryl groups, substituted or unsubstituted silane groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C1-C 30 Alkylthio group; C1-C 30 Alkoxy group; C6-C 30 Arylalkoxy groups; C1-C 30 Alkyl groups of C2 to C 30 Alkenyl group; C2-C 30 Alkynyl group; C6-C 30 Aryl groups; C6-C substituted with deuterium 30 an aryl group; a fluorenyl group; a C2-C group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; 30 Heterocyclic group; C3-C 30 Aliphatic ring group; C7-C 30 Aryl alkyl group; C8-C 30 and combinations thereof, or adjacent substituents taken together form a ring.

[0129] The polyimide precursor preferably includes a repeating unit selected from the group consisting of the following Formula 1-1, Formula 1-2, and combinations thereof.

[0130] [ka]

[0131] [ka]

[0132] In the above Chemical Formula 1-1 and Chemical Formula 1-2,

[0133] 1) * is a repeating unit or a portion that is connected to a reactive terminal group represented by the chemical formula Q,

[0134] 2) R1 to R4 are represented by the following formula 2:

[0135] 3) X is represented by the following chemical formula 3:

[0136] 4) m and n are integers from 1 to 1000,

[0137] [ka]

[0138] In the above Chemical Formula 2,

[0139] 5) * is the part where the bond is attached,

[0140] 6) a is an integer from 1 to 30,

[0141] 7) R5 is hydrogen or a methyl group;

[0142] 8) Y is C6~C 30 an arylene group of C2-C containing at least one heteroatom of O, N, S, Si, or 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 group; C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 3; and combinations thereof;

[0143] 9) Z is C6~C 30 an arylene group of C2-C containing at least one heteroatom of O, N, S, Si, or P; 30Heterocyclic 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 group; C2-C 20 Alkenylene group; C3-C 20 Cycloalkenylene group; C2-C 20 Alkynylene group; C3-C 20 a cycloalkynylene group of formula (I); Formula 3; and combinations thereof;

[0144] [ka]

[0145] 10) L 1 is selected from the group consisting of a single bond, -CH-, -CHCH-, -CHOCH-, -CH(CH)-, -C(CH)-, -O-, -CH(CF)-, -C(CF)-, -S-, -SO-, Si(CH)-, -CH, -OCHO, -CO-, -NHCO-, and -COO-;

[0146] 11) R6 or R 15 Two of them are linking sites with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2,

[0147] 12) The remaining R6 to R excluding the linking portion 15 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 aryl groups of C2-C containing at least one heteroatom of O, N, S, Si and P; 30 Heterocyclic 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 aryloxy group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 20or adjacent R6 to R 15 ; and R 10 and R 11 forms a ring,

[0148] 13) The Y, Z, R6 to R 15 and the ring formed by bonding adjacent groups to each other are each independently deuterium; halogen; 30 or C6-C 30 aryl groups or unsubstituted silane groups; siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C1-C 30 Alkylthio group; C1-C 30 Alkoxy group; C6-C 30 Arylalkoxy groups; C1-C 30 Alkyl group; C2-C 30 Alkenyl group; C2-C 30 Alkynyl group; C6-C 30 Aryl groups; C6-C substituted with deuterium 30 an aryl group; a fluorenyl group; a C2-C group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; 30 Heterocyclic group; C3-C 30 Aliphatic ring group; C7-C 30 Aryl alkyl group; C8-C 30 and combinations thereof, or adjacent substituents taken together form a ring.

[0149] The polyimide precursor may include at least one of a diamine monomer, a dianhydride monomer, and an anhydride monomer.

[0150] The diamine monomers include 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dihydroxybenzidine, 3,3'-dimethylbenzidine, 2,2'-bis(4-aminophenoxy)phenylpropane, 2,2'-bis(trifluoromethyl)benzidine, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis( 4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-[1,1'-biphenyl]-4,4'-diamine, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis It is preferable that the monomer comprises one or more monomers selected from the group consisting of (3-aminophenoxy)benzene, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,4'-oxydianiline, 9,9-dimethyl-9H-fluorene-2,7-diamine, 4-aminobenzoic acid-4-aminophenyl ester, [4-(4-aminobenzoyl)oxyphenyl]4-aminobenzoate, 3,3',5,5'-tetramethylbenzidine, bis(4-aminophenyl)terephthalate, 4,4-bis(3-aminophenoxy)biphenyl, N,N'-[[2,2,2-trifluoro-1-(trifluoromethyl)ethyllysine]bis(6-hydroxy-3,1-phenylene)bis[3-amino-benzamide], 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4-diaminobenzoanilide, O-tolidine, 4,4'-diaminodiphenylsulfone, and combinations thereof.

[0151] The dianhydride monomers include 4,4-oxydiphthalic anhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-biphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-tetracarboxydiphenyloxide dianhydride, 1,2,4, It is preferable that the monomer contains one or more monomers selected from the group consisting of 5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, bis[3,4-dicarboxylic anhydride phenyl]terephthalate, 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran)-5-carboxylate, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, and combinations thereof.

[0152] The anhydride monomer preferably comprises one or more monomers selected from the group consisting of bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 5-novone-2,3-dicarboxylic anhydride, maleic anhydride, phthalic anhydride, citraconic anhydride, succinic anhydride, and combinations thereof.

[0153] The reactive end group represented by the formula Q may include compounds represented by the following formulas Q-1 to Q-6.

[0154] [ka]

[0155] In the above chemical formulas Q-1 to Q-6,

[0156] 1) R d1 , R d2 , R e1 Or R e3 , Rf1 Or R f4 , R g , R h1 , R h2 , and R i1 Or R i3 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30 aryl groups of C2-C containing at least one heteroatom of O, N, S, Si and P; 30 Heterocyclic group; C6-C 30 A fused ring group of an aliphatic ring and an aromatic ring; C1-C 30 Alkyl group; C2-C 30 Alkenyl group; C2-C 30 Alkynyl group; C1-C 30 Alkoxy group; C6-C 30 Aryloxy groups; C1-C 30 Hydroxyacrylic group; C1-C 30 Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 30 is an alkoxycarbonyl group of the formula

[0157] 2) r and t are integers from 1 to 4;

[0158] 3) s1, s2, and u1 to u3 are each an integer of 1 or 2.

[0159] 4) * is the part where the bond is attached.

[0160] The reactive end group represented by the formula Q may also include compounds represented by the following formulas Q-7 to Q-10.

[0161] [ka]

[0162] R 16 Or R 18 are each independently hydrogen; deuterium; hydroxyl group; C6-C 30aryl groups of C2-C containing at least one heteroatom of 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 Aryloxy groups; C1-C 20 Hydroxyacrylic group; C1-C 20 Hydroxymethacrylic group; fluorenyl group; carbonyl group; ether group; carboxyl group; or C1-C 20 is an alkoxycarbonyl group.

[0163] The precursor end is bonded with a chemical formula selected from one selected from the group consisting of the chemical formulas Q-7 to Q-10 or a combination thereof via an amide or imide bond.

[0164] The polyimide precursor preferably includes a diamine monomer; a dianhydride monomer; and an anhydride monomer.

[0165] The weight average molecular weight of the polyimide precursor may be 5,000 to 40,000 g / mol, preferably 5,000 to 30,000 g / mol, and more preferably 6,000 to 25,000 g / mol. When the weight average molecular weight of the resin is within the above range, no residue of the exposed layer remains during development, and the loss of thickness of the non-exposed layer is minimized, resulting in a good pattern. The polymer may be included in an amount of 5 to 50 wt %, more preferably 15 to 45 wt %, based on the total amount of the polymer 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.

[0166] (2) Photoinitiator

[0167] To achieve negative patterns in photolithography, a photoradical initiator must be used.

[0168] The photopolymerization initiator is an initiator commonly used in negative photosensitive compositions, and examples of the photopolymerization initiator that can be used include acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, and oxime-based compounds.

[0169] Examples of the acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-(morpholinophenyl)-butan-1-one, and the like.

[0170] Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0171] Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0172] Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0173] Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl) )-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth1-yl)4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl(piperonyl)-6-triazine, 2-4-trichloromethyl(4'-methoxystyryl)-6-triazine, and the like.

[0174] Examples of the oxime-based compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime), 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethylidyne}amino)oxy]-1-(O-acetyloxime)ethanone, 1-[ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]ethylidyne}amino)oxy]-1-(O-acetyloxime)ethanone, 1-[4-[3-[4-[[2-acetyloxy]ethyl[sulfonyl]-2-methylbenzoyl]-6-[1[acetyloxy(acetyl)imino]ethyl]-9H-carbazol-9-yl]phenyl-1-(O-acetyloxime)octanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, and the like.

[0175] In addition to the above compounds, the photoinitiator may be a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a non-imidazole-based compound, or the like.

[0176] The photoinitiator may be a radical polymerization initiator such as a peroxide-based compound or an azobis-based compound.

[0177] Examples of the peroxide-based compound include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, and acetylacetone peroxide; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide; hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl) hydroperoxide, and the like. peroxyhexane, 1,3-bis(t-butyloxyisopropyl)benzene, t-butylperoxyvaleric acid n-butyl ester and other dialkyl peroxides; 2,4,4-trimethylpentylperoxyphenoxyacetate, α-cumylperoxyneodecanoate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate and other alkyl peresters; di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis-4-t-butylcyclohexylperoxydicarbonate, diisopropylperoxydicarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyallylcarbonate and other percarbonates.

[0178] Examples of the azobis compounds include 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), α,α'-azobis(isobutylnitrile), and 4,4'-azobis(4-cyanovaleric acid).

[0179] The photoinitiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transfers the energy to initiate a chemical reaction. Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, etc.

[0180] The photoinitiator may be included in an amount of 0.01 to 10 wt %, for example, 0.1 to 5 wt %, based on the total amount of the photosensitive composition. When the photoinitiator is included within this range, curing occurs sufficiently upon exposure in the pattern formation process, so that excellent reliability can be obtained, and the pattern has excellent heat resistance, light resistance, and chemical resistance, excellent resolution and adhesion, and a decrease in transmittance due to unreacted initiator can be prevented.

[0181] (2) Reactive unsaturated compounds

[0182] The reactive unsaturated compound, which is essential for a negative pattern, has an ethylenically unsaturated double bond, and thereby undergoes sufficient polymerization upon exposure in the pattern formation process, thereby enabling the formation of a pattern having excellent heat resistance, light resistance and chemical resistance.

[0183] Specific examples of the reactive unsaturated compound include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, trimethylolpropane triacrylate, tripentaerythritol octaacrylate, and 4-hydroxybutyl acrylate.

[0184] Examples of commercially available products of the reactive unsaturated compounds are as follows:

[0185] Examples of the bifunctional ester of (meth)acrylic acid include Aronix M-210, M-240, M-6200, etc., manufactured by Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA, HX-220, R-604, etc., manufactured by Nippon Kayaku Co., Ltd.; and V-260, V-312, V-335HP, etc., manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0186] Examples of the trifunctional esters of (meth)acrylic acid include ARONIX M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, etc., available from Toagosei Chemical Industry Co., Ltd.; KAYARAD TMPTA, DPCA-20, DPCA-60, DPCA-120, etc., available from Nippon Kayaku Co., Ltd.; and V-295, V-300, V-360, etc., available from Osaka Organic Chemical Industry Co., Ltd.

[0187] The above products can be used alone or in combination of two or more.

[0188] The reactive unsaturated compound may be treated with an acid anhydride to provide better developability. The reactive unsaturated compound may be contained in an amount of 1 to 40% by weight, for example, 1 to 20% by weight, based on the total amount of the polymer composition. When the reactive unsaturated compound is contained within the above range, curing occurs sufficiently upon exposure in the pattern forming process, resulting in excellent reliability, and the pattern has excellent heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion.

[0189] (4) Solvent

[0190] The solvent used is a substance that is compatible with, but does not react with, the polyimide precursor or polymer, the photosensitizer, and the pigment.

[0191] 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.

[0192] Also usable are high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0193] 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.

[0194] 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 negative photosensitive composition has an appropriate viscosity, and thus has excellent processability when manufacturing a pattern layer.

[0195] (6) Other additives

[0196] The negative polymer 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.

[0197] For example, the polymer composition may further contain a 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.

[0198] 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.

[0199] The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polymer composition. When the silane coupling agent is included in the amount within the above range, the composition has excellent adhesion, storage stability, and the like.

[0200] In addition, the polymer composition may further include a surface smoothing agent, if necessary, to form a uniform film thickness during the coating step.

[0201] 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.

[0202] 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 polymer composition. When the surface smoothing agent is included within this range, the coating uniformity is ensured and the film thickness can be coated at a constant level.

[0203] Furthermore, the polymer composition may further contain a surfactant, if necessary, to improve coating properties and prevent the formation of defects.

[0204] As the surfactant, commercially available surfactants under the names of BM-1000 (registered trademark), BM-1100 (registered trademark), etc. from BM Chemie; Megafac F142D (registered trademark), F172 (registered trademark), F173 (registered trademark), F183 (registered trademark), etc. from Dainippon Ink and Chemicals Co., Ltd.; Fluorad FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark), etc. from Sumitomo 3M Limited; Surflon S-112 (registered trademark), S-113 (registered trademark), S-131, S-141, S-145, etc. from Asahi Glass Co., Ltd.; SH-28PA (registered trademark), -190 (registered trademark), -193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark), etc. from Dray Silicon Co., Ltd. may be used.

[0205] Furthermore, the polymer composition may further contain a silicon-based surfactant, if necessary.

[0206] As the silicone surfactant, commercially available silicone surfactants under the names of S-101, S-201, S-301, S-601, S-701, S-801, RS-55, RS-56, etc., from DIC; EFKA (registered trademark) 3030, EFKA (registered trademark) 3034, EFKA (registered trademark) 3886, etc., from BASF; 3030, 3085, 3236, etc., from AFCONA; and BYK-378, BYK-3550, BYK-3751, BYK-3754, etc., may be used.

[0207] The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the polymer composition. When the surfactant is included within this range, coating uniformity is ensured, spots are not generated, and wetting to glass substrates is excellent.

[0208] As the crosslinker, 1,4-bis(methoxymethyl)benzene, diethyl sulfate, 3-aminopropyltriethoxysilane, N,N'-methylenebisacrylamide, N,N'-dicyclohexylcarbodiimide, etc. may be used, and these may be used alone or in combination of two or more kinds.

[0209] The crosslinker may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the polymer composition. When the crosslinker is contained within the above range, it is advantageous for imparting suitable physical properties, such as mechanical properties such as tensile strength, to the cured coating film.

[0210] In addition, the polymer composition may contain other additives in a certain amount within a range that does not impair the physical properties.

[0211] 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.

[0212] (Synthesis Example 1)

[0213] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 141.87g of N-methylpyrrolidone (NMP), added with 22.22g of 3,3',4,4'-benzophenonetetracarboxylic anhydride, and stirred and maintained at 25°C. 19.86g of 4-hydroxybutyl acrylate was added thereto, and then 11.17g of pyridine was slowly added and reacted. The internal temperature of the reactor during the reaction was then maintained at -10°C, and a solution of 35.54g of N,N'-dicyclohexylcarbodiimide and 71.07g of N-methylpyrrolidone (NMP) was slowly added dropwise and stirred for 3 hours.

[0214] (Solution B) A 500 ml heat medium circulation jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 62.09 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 15 g of 3,3'-dimethylbenzidine was added and stirred until completely dissolved, and 0.52 g of phthalic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0215] (Polymerization reaction) Solution A was added dropwise to solution B, which was kept at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which the solution was added dropwise to 2275 g of distilled water for precipitation. The solid thus obtained was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0216] (Synthesis Example 2)

[0217] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 141.87g of N-methylpyrrolidone (NMP), added with 22.22g of 3,3',4,4'-benzophenonetetracarboxylic anhydride, and stirred and maintained at 25°C. 19.86g of 4-hydroxybutyl acrylate was added thereto, and then 11.17g of pyridine was slowly added and reacted. The internal temperature of the reactor during the reaction was then maintained at -10°C, and a solution of 35.54g of N,N'-dicyclohexylcarbodiimide and 71.07g of N-methylpyrrolidone (NMP) was slowly added dropwise and stirred for 3 hours.

[0218] (Solution B) A 500 ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 61.58 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 15 g of 3,3'-dimethylbenzidine was added and stirred until completely dissolved, and 0.40 g of citraconic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0219] (Polymerization reaction) Solution A was added dropwise to solution B, which was kept at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which the solution was added dropwise to 2272 g of distilled water for precipitation. The solid thus obtained was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0220] (Synthesis Example 3)

[0221] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 141.87g of N-methylpyrrolidone (NMP), added with 22.22g of 3,3',4,4'-benzophenonetetracarboxylic anhydride, and stirred and maintained at 25°C. 19.86g of 4-hydroxybutyl acrylate was added thereto, and then 11.17g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 35.53g of N,N'-dicyclohexylcarbodiimide and 71.07g of N-methylpyrrolidone (NMP) was slowly added dropwise and stirred for 3 hours.

[0222] (Solution B) A 500 ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 61.61 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 15 g of 3,3'-dimethylbenzidine was added and stirred until completely dissolved, and 0.40 g of glutaric anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0223] (Polymerization reaction) Solution A was added dropwise to solution B, which was kept at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which the solution was added dropwise to 2272 g of distilled water for precipitation. The solid thus obtained was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0224] (Synthesis Example 4)

[0225] A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 205.32g of N-methylpyrrolidone (NMP), then added 22.22g of 3,3',4,4'-benzophenonetetracarboxylic anhydride and 0.52g of phthalic anhydride, and stirred and maintained at 25°C. 20.37g of 4-hydroxybutyl acrylate was added thereto, and then 11.46g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 36.46g of N,N'-dicyclohexylcarbodiimide and 72.89g of N-methylpyrrolidone (NMP) was slowly added dropwise and stirred for 3 hours. The internal temperature was then cooled to -10°C, and 15g of 3,3'-dimethylbenzidine was added dropwise with stirring for 30 minutes. The temperature was then raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which it was added dropwise to 2305g of distilled water to cause precipitation. The solid thus obtained was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0226] (Synthesis Example 5)

[0227] A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 204.81g of N-methylpyrrolidone (NMP), then added 22.22g of 3,3',4,4'-benzophenonetetracarboxylic anhydride and 0.40g of citraconic anhydride, and stirred and maintained at 25°C. 20.37g of 4-hydroxybutyl acrylate was added thereto, and then 11.45g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 36.45g of N,N'-dicyclohexylcarbodiimide and 72.89g of N-methylpyrrolidone (NMP) was slowly added dropwise and stirred for 3 hours. Then, the internal temperature was cooled to -10°C, and 15g of 3,3'-dimethylbenzidine was added dropwise with stirring for 30 minutes. The temperature was then raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which it was added dropwise to 2301g of distilled water to cause precipitation. The solid thus obtained was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0228] (Synthesis Example 6)

[0229] A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 204.84g of N-methylpyrrolidone (NMP), then added 22.22g of 3,3',4,4'-benzophenonetetracarboxylic anhydride and 0.40g of glutaric anhydride, and stirred and maintained at 25°C. 20.37g of 4-hydroxybutyl acrylate was added thereto, and then 11.46g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 36.45g of N,N'-dicyclohexylcarbodiimide and 72.89g of N-methylpyrrolidone (NMP) was slowly added dropwise and stirred for 3 hours. The internal temperature was then cooled to -10°C, and 15g of 3,3'-dimethylbenzidine was added dropwise with stirring for 30 minutes. The temperature was then raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which the mixture was added dropwise to 2302g of distilled water to cause precipitation. The solid thus obtained was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0230] (Synthesis Example 7)

[0231] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 256.4g of N-methylpyrrolidone (NMP), then added 22.31g of 4,4'-oxydiphthalic anhydride and 5.29g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and stirred and maintained at 35°C. 25.91g was added, and then 29.15g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 37.09g of N,N'-dicyclohexylcarbodiimide and 74.190g of γ-butyrolactone was slowly added dropwise and stirred for 3 hours.

[0232] (Solution B) A 1000 ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 93.11 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 20 g of 4,4'-oxydianiline was added and stirred until completely dissolved, and 3.28 g of 5-novone-2,3-dicarboxylic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0233] (Polymerization reaction) Solution A was added dropwise to solution B, which was maintained at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which 40g of ethanol was added and stirred for 1 hour. Then, 1417g of ethanol was added to the filtrate, which was filtered using filter paper, to precipitate a solid. This solid was dissolved in 56.68g of THF and added dropwise to 6802g of distilled water to precipitate. The solid obtained here was washed twice with distilled water and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0234] (Synthesis Example 8)

[0235] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 258.4g of N-methylpyrrolidone (NMP), then added 13.94g of 4,4'-oxydiphthalic anhydride and 13.22g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and stirred and maintained at 35°C. 25.91g of 4-hydroxybutyl acrylate was added thereto, and then 29.15g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 37.09g of N,N'-dicyclohexylcarbodiimide and 74.190g of γ-butyrolactone was slowly added dropwise and stirred for 3 hours.

[0236] (Solution B) A 1000 ml heat medium circulation jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 93.11 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 20 g of 4,4'-oxydianiline was added and stirred until completely dissolved, and 3.28 g of 5-novone-2,3-dicarboxylic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0237] (Polymerization reaction) Solution A was added dropwise to solution B, which was maintained at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours. Then, 40g of ethanol was added and stirred for 1 hour, and 7.6g of mandelic acid was added and stirred for 2 hours. Then, 1417g of ethanol was added to the filtrate, which was filtered using filter paper, to precipitate a solid. This solid was dissolved in 56.68g of THF and dropped into 6802g of distilled water to precipitate. The solid obtained here was washed twice with distilled water and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0238] (Synthesis Example 9)

[0239] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 254.8g of N-methylpyrrolidone (NMP), then added 5.57g of 4,4'-oxydiphthalic anhydride and 21.16g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and stirred and maintained at 35°C. 25.91g of 4-hydroxybutyl acrylate was added thereto, and then 29.15g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 37.09g of N,N'-dicyclohexylcarbodiimide and 74.190g of γ-butyrolactone was slowly added dropwise and stirred for 3 hours.

[0240] (Solution B) A 1000 ml heat medium circulation jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 93.11 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 20 g of 4,4'-oxydianiline was added and stirred until completely dissolved, and 3.28 g of 5-novone-2,3-dicarboxylic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0241] (Polymerization reaction) Solution A was added dropwise to solution B, which was maintained at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which 40g of ethanol was added and stirred for 1 hour. Then, 1417g of ethanol was added to the filtrate, which was filtered using filter paper, to precipitate a solid. This solid was dissolved in 56.68g of THF and added dropwise to 6802g of distilled water to precipitate. The solid obtained here was washed twice with distilled water and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0242] (Synthesis Example 10)

[0243] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 149.04g of N-methylpyrrolidone (NMP), then added 8.01g of 4,4'-oxydiphthalic anhydride and 7.60g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and stirred and maintained at 35°C. 14.89g of 4-hydroxybutyl acrylate was added thereto, and then 16.75g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 21.31g of N,N'-dicyclohexylcarbodiimide and 42.62g of γ-butyrolactone was slowly added dropwise and stirred for 3 hours.

[0244] (Solution B) A 1000 ml heat medium circulation jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 87.54 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 20 g of 9,9-bis(4-aminophenyl)fluorene was added and stirred until completely dissolved, and 1.88 g of 5-novone-2,3-dicarboxylic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0245] (Polymerization reaction) Solution A was added dropwise to solution B, which was maintained at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which 40g of ethanol was added and stirred for 1 hour. Then, 917g of ethanol was added to the filtrate, which was filtered using filter paper, to precipitate a solid. This solid was dissolved in 36.70g of THF and added dropwise to 6802g of distilled water to precipitate. The solid obtained here was washed twice with distilled water and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0246] (Synthesis Example 11)

[0247] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 176.52g of N-methylpyrrolidone (NMP), then added 9.55g of 4,4'-oxydiphthalic anhydride and 9.06g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and stirred and maintained at 35°C. 17.75g of 4-hydroxybutyl acrylate was added thereto, and then 19.97g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 25.41g of N,N'-dicyclohexylcarbodiimide and 50.80g of γ-butyrolactone was slowly added dropwise and stirred for 3 hours.

[0248] (Solution B) A 1000 ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 88.98 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 20 g of 1,4-bis(4-aminophenoxy)benzene was added and stirred until completely dissolved, and 2.25 g of 5-novone-2,3-dicarboxylic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0249] (Polymerization reaction) Solution A was added dropwise to solution B, which was maintained at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which 40g of ethanol was added and stirred for 1 hour. Then, the solution was filtered using filter paper, and 1045g of ethanol was added to the filtrate to precipitate a solid. This solid was dissolved in 56.68g of THF and added dropwise to 5019g of distilled water to precipitate. The solid obtained here was washed twice with distilled water and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0250] (Synthesis Example 12)

[0251] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 118.6g of N-methylpyrrolidone (NMP), then added 4.76g of 4,4'-oxydiphthalic anhydride and 8.38g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and stirred and maintained at 35°C. 12.64g of 4-hydroxybutyl acrylate was added thereto, and then 14.22g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 18.09g of N,N'-dicyclohexylcarbodiimide and 36.18g of γ-butyrolactone was slowly added dropwise and stirred for 3 hours.

[0252] (Solution B) A 1000 ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 86.40 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 20 g of 2,2'-bis(4-aminophenoxy)phenylpropane was added and stirred until completely dissolved, and 1.60 g of 5-novone-2,3-dicarboxylic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0253] (Polymerization reaction) Solution A was added dropwise to solution B, which was maintained at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which 40g of ethanol was added and stirred for 1 hour. Then, 815g of ethanol was added to the filtrate, which was filtered using filter paper, to precipitate a solid. This solid was dissolved in 32.61g of THF and added dropwise to 3913g of distilled water to precipitate. The solid obtained here was washed twice with distilled water and then vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0254] (Synthesis Example 13)

[0255] (Solution A) A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 141.87g of N-methylpyrrolidone (NMP), added with 22.22g of 3,3',4,4'-benzophenonetetracarboxylic anhydride, and stirred and maintained at 25°C. 19.86g of 4-hydroxybutyl acrylate was added thereto, and then 11.17g of pyridine was slowly added and reacted. The internal temperature of the reactor during the reaction was then maintained at -10°C, and a solution of 35.54g of N,N'-dicyclohexylcarbodiimide and 71.07g of N-methylpyrrolidone (NMP) was slowly added dropwise and stirred for 3 hours.

[0256] (Solution B) A 500 ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, and filled with 61.41 g of N-methylpyrrolidone (NMP), and stirred at 25° C. Then, 15 g of 3,3'-dimethylbenzidine was added and stirred until completely dissolved, and 0.35 g of succinic anhydride was added and reacted for 5 hours, after which the internal temperature was cooled to -10° C. and maintained.

[0257] (Polymerization reaction) Solution A was added dropwise to solution B, which was kept at -10°C, with stirring for 1 hour using a metering pump. After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which the solution was added dropwise to 1563g of distilled water and 782g of ethanol for precipitation. The solid thus obtained was washed twice with distilled water and then vacuum-dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0258] (Synthesis Example 14)

[0259] A 500ml heat medium circulation type jacketed reactor was equipped with an agitator, nitrogen injector, dropping funnel, temperature controller and cooler, then filled with nitrogen, filled with 281.4g of N-methylpyrrolidone (NMP), then added 10.84g of 4,4'-oxydiphthalic anhydride and 19.10g of 3,3'4,4'-biphenyltetracarboxylic dianhydride, and stirred and maintained at 35°C. 28.80g of 4-hydroxybutyl acrylate was added thereto, and then 32.39g of pyridine was slowly added and reacted. Then, the internal temperature of the reactor during the reaction was maintained at -10°C, and a solution of 41.21g of N,N'-dicyclohexylcarbodiimide and 82.42g of γ-butyrolactone was slowly added dropwise and stirred for 3 hours. Thereafter, 80 g of N-methylpyrrolidone (NMP) was added to the reactor, and 20 g of 4,4'-oxydianiline was added in portions every hour. The mixture was stirred until completely dissolved, and then reacted for 5 hours.

[0260] After that, the temperature was raised to 25°C over 1 hour, and the reaction was maintained for 2 hours, after which 40g of ethanol was added and stirred for 1 hour. Then, 1492g of ethanol was added to the filtrate filtered through filter paper to precipitate a solid. This solid was dissolved in 59.69g of THF and added dropwise to 7162g of distilled water to precipitate. The solid obtained here was washed twice with distilled water and vacuum dried at 25°C for 48 hours to obtain a copolymerized polyimide precursor powder.

[0261] (Production Example 1) Production of negative photosensitive composition

[0262] 14.88 g of the polyimide precursor obtained from Synthesis Examples 1 to 7, 0.45 g of PBG-304 (Tronly), 7.3 g of Miramer M600, 0.015 g of F-563 (DIC), 1.5 g of KBM-573 (Shinetsu Silicon), and 1.0 g of 1,4-bis(methoxymethyl)benzene were stirred with 53.4 g of propylene glycol methyl ether acetate (PGMEA) at room temperature for 12 hours. Then, the composition was filtered three times to remove impurities, thereby preparing a photosensitive composition.

[0263] A photosensitive liquid composition was prepared according to the composition shown in Table 1 below.

[0264] [Table 1]

[0265] A method for preparing a test piece for a universal testing machine (UTM) using the negative photosensitive composition is as follows.

[0266] (1) Application and coating stage

[0267] The photosensitive composition is a low-viscosity liquid sample, and a spin coater or slit coater is used to coat the substrate at a consistent thickness after application. The faster the spin coater rotates, the less the thickness is, but the greater the reduction in the flatness deviation over the surface area, making a slit coater more preferable for coating large substrates. After coating, the surface becomes fluid due to the remaining solvent, which can cause poor flatness. To overcome this, a vacuum chamber dry (VCD) is used to remove part of the solvent, reducing the fluidity of the surface.

[0268] (2) Pre-bake stage

[0269] This is a process in which the coated substrate is heated at a certain temperature and time on a hot plate or in an oven to remove some of the solvent contained in the coating film. If the surface or deep part of the coating film is not dried, contamination of the photomask occurs during exposure in the next process, and the exposed part does not harden well when irradiated with ultraviolet light, and the uncured part is removed without forming a pattern in the development process.

[0270] (3) Exposure stage

[0271] After the pre-baking process is completed, the formed film is cured by irradiating actinic rays (ultraviolet rays) using a patterned photomask. The types of lamps that generate actinic rays include LED lamps and metal (mercury) lamps, and the wavelengths are g-line (436nm), h-line (405nm), i-line (365nm), and deep UV (<260nm), which can be used individually or in combination.

[0272] (4) Development stage

[0273] In the exposure step, the exposed and non-exposed areas are separated by a photomask when irradiated with actinic radiation. In the case of a positive type, the exposed areas are dissolved by a developer, while the non-exposed areas are resistant to the developer, leaving a pattern. In the case of a negative type, the exposed areas are hardened and resistant to the developer, while the non-exposed areas are developed. The composition of the present invention is a negative type, and is divided into an exposed area (hardened) and a non-exposed area (developed) to form a pattern.

[0274] (5) Post-heat treatment stage

[0275] This is a process in which the developed substrate is heated at a high temperature of over 210℃ to remove the remaining solvent and fumes. If the solvent and fumes are not completely removed in this process, outgassing will occur in the post-heat treatment process, which will affect the device, resulting in dark spots or shrinkage.

[0276] (6) Peeling off the test piece

[0277] In order to obtain UTM specimens without damage from the substrates after 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 with ultrapure water (DI water) and then dried in a vacuum chamber at room temperature to obtain UTM specimens.

[0278] (7) UTM measurement

[0279] The tensile strength and elongation of the UTM specimens of the examples and comparative examples obtained in the test specimen peeling step 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.

[0280] [Table 2]

[0281] As a result of the development test shown in Table 2, it was confirmed that no residue remained after development in any of Examples 1 to 12 and Comparative Examples 1 and 2. As a result of checking the accuracy of pattern realization using a 30 μm hole mask, it was confirmed that the patterns were accurately realized within an error of 0.4 μm in any of Examples 1 to 6 and Comparative Example 1, and that the patterns were accurately realized within an error of 0.2 μm in any of Examples 7 to 12 and Comparative Example 2.

[0282] As a result of the UTM measurement, the tensile strength was 4.41 MPa or more in Examples 1 to 6 in Table 2, and 3.16 MPa was measured in Comparative Example 1. In addition, the elongation was 62% or more in Examples 1 to 6, and 51.6% in Comparative Example 1. This confirms that the introduction of reactive groups to the ends of the polyimide precursor according to the present invention is effective in improving the tensile strength and elongation.

[0283] The present invention is not limited to the above embodiments and may be implemented in many different forms.

[0284] The above description is merely illustrative of the present invention, and various modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention.

[0285] 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 polyimide precursor comprising a reactive end group represented by the chemical formula Q: 【Chemistry 1】 In the above Chemical Formula 1, 1) R ａ Or R ｃ are each independently hydrogen; deuterium; a hydroxyl group; C ６ ~C ３０ aryl groups of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ３０ an alkyl group of C ２ ~C ３０ an alkenyl group of C ２ ~C ３０ an alkynyl group of C １ ~C ３０ an alkoxy group of C ６ ~C ３０ an aryloxy group of C １ ~C ３０ Hydroxyacrylic group of C １ ~C ３０ a hydroxymethacrylic group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or C １ ~C ３０ or R ａ Or R ｃ adjacent groups form a ring, 2) C １ and C ２ is carbon, C １ and C ２ The bond connecting the is a single bond or a double bond, 3) The above C １ and C ２ When the bond connecting C is a single bond, o and p each independently represent an integer of 1 or 2; １ and C ２ When the bond connecting the groups is a double bond, o and p each represent an integer of 1; 4) C ３ is carbon or C ２ -B ２ is a direct bond of 5) The above C ３ is carbon, q is an integer of 1 or 2; 6) B １ and B ２ The dotted lines connecting the are no bonds or a single bond, 7) B １ and B ２ If there is no dotted bond connecting B １ is hydrogen; deuterium; hydroxyl group; C ６ ~C ３０ aryl groups of the formula: ２ ~C ３０ a heterocyclic group of ６ ~C ３０ a fused ring group of an aliphatic ring and an aromatic ring, １ ~C ２０ Alkyl groups 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 of C １ ~C ２０ Hydroxyacrylic group of C １ ~C ２０ a hydroxymethacrylic group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or C １ ~C ２０ and B is an alkoxycarbonyl group of the formula ２ is a nitrogen atom linked to a polyimide repeat unit, 8) The above B １ and B ２ If the dotted line connecting B is a single bond, １ is a nitrogen atom linked to a polyimide repeating unit; B ２ is carbon, 9) The R ａ Or R ｃ and the ring formed by bonding adjacent groups to each other is deuterium; halogen; １ ~C ３０ or C ６ ~C ３０ aryl group-substituted or unsubstituted silane group; siloxane group; boron group; germanium group; cyano group; amino group; nitro group; C １ ~C ３０ an alkylthio group of C １ ~C ３０ an alkoxy group of C ６ ~C ３０ an arylalkoxy group of C １ ~C ３０ Alkyl groups of C ２ ~C ３０ an alkenyl group of C ２ ~C ３０ an alkynyl group of C ６ ~C ３０ aryl groups of the formula: ６ ~C ３０ an aryl group of the formula: ２ ~C ３０ Heterocyclic group of C ３ ~C ３０ an aliphatic ring group represented by C ７ ~C ３０ Aryl alkyl group of C ８ ~C ３０ and combinations thereof, or adjacent substituents taken together form a ring.

2. The polyimide precursor according to claim 1, comprising a repeating unit selected from the group consisting of the following formula 1-1, formula 1-2, and combinations thereof: 【Chemistry 2】 【Chemistry 3】 In the above Chemical Formula 1-1 and Chemical Formula 1-2, 1) * is a repeating unit or a portion that is connected to a reactive terminal group represented by chemical formula Q in claim 1, 2) R １ Or R ４ is represented by the following chemical formula 2, 3) X is represented by the following formula 3: 4) m and n are integers from 1 to 1000; 【Chemistry 4】 In the above Chemical Formula 2, 5) * is the part where the bond is connected, 6) a is an integer from 1 to 30; 7) R ５ is hydrogen or a methyl group, 8) Y is C ６ ~C ３０ an arylene group of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkylene group of C １ ~C ２０ A cycloalkylene group represented by the formula: ２ ~C ２０ an alkenylene group represented by the formula C ３ ~C ２０ A cycloalkenylene group represented by the formula: ２ ~C ２０ An alkynylene group represented by the formula: ３ ~C ２０ cycloalkynylene groups of the formula: 9) Z is C ６ ~C ３０ an arylene group of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkylene group of C １ ~C ２０ A cycloalkylene group represented by the formula: ２ ~C ２０ an alkenylene group represented by the formula C ３ ~C ２０ A cycloalkenylene group represented by the formula: ２ ~C ２０ An alkynylene group represented by the formula: ３ ~C ２０ cycloalkynylene groups of the formula: 【Chemistry 5】 10) L １ is a single bond, -CH ２ --, --CH ２ CH ２ --, --CH ２ OCH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, -O-, -CH(CF ３ ) -, -C(CF ３ ) ２ -, -S-, -SO ２ -, Si(CH ３ ) ２ -, -C ６ H ４ , -OC ６ H ４ selected from the group consisting of O, —CO—, —NHCO—, and —COO—; 11) R ６ Or R １５ Two of them are linking sites with the amide group of Chemical Formula 1-1 or Chemical Formula 1-2, 12) The remaining R excluding the linking portion ６ Or R １５ are each independently hydrogen; deuterium; a hydroxyl group; ６ ~C ３０ aryl groups of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkyl group of C ２ ~C ２０ an alkenyl group of C ２ ~C ２０ an alkynyl group of C １ ~C ２０ an alkoxy group of C ６ ~C ３０ an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or C １ ~C ２０ or an adjacent R ６ Or R １５ and R １０ and R １１ forms a ring, 13) The Y, Z, and R ６ Or R １５ and the ring formed by bonding adjacent groups to each other are each independently deuterium; halogen; １ ~C ３０ or an alkyl group of ６ ~C ３０ silane groups substituted or unsubstituted with aryl groups of the formula: siloxane groups; boron groups; germanium groups; cyano groups; amino groups; nitro groups; C １ ~C ３０ an alkylthio group of C １ ~C ３０ an alkoxy group of C ６ ~C ３０ an arylalkoxy group of C １ ~C ３０ an alkyl group of C ２ ~C ３０ an alkenyl group of C ２ ~C ３０ an alkynyl group of C ６ ~C ３０ aryl groups of the formula: ６ ~C ３０ an aryl group of the formula: ２ ~C ３０ Heterocyclic group of C ３ ~C ３０ an aliphatic ring group represented by C ７ ~C ３０ Aryl alkyl group of C ８ ~C ３０ and combinations thereof, or adjacent substituents taken together form a ring.

3. The polyimide precursor according to claim 1, wherein the compound represented by the chemical formula Q includes compounds represented by the following Q-1 to Q-6: 【Chemistry 6】 In the above formulas Q-1 to Q-6, 1) R ｄ１ , R ｄ２ , R ｅ１ Or R ｅ３ , R ｆ１ Or R ｆ４ , R ｇ , R ｈ１ , R ｈ２ , and R ｉ１ Or R ｉ３ are each independently hydrogen; deuterium; a hydroxyl group; C ６ ~C ３０ aryl groups of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ３０ an alkyl group of C ２ ~C ３０ an alkenyl group of C ２ ~C ３０ an alkynyl group of C １ ~C ３０ an alkoxy group of C ６ ~C ３０ an aryloxy group of C １ ~C ３０ Hydroxyacrylic group of C １ ~C ３０ a hydroxymethacrylic group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or C １ ~C ３０ is an alkoxycarbonyl group of the formula 2) r and t are integers from 1 to 4; 3) s １ , s ２ and u １ Nai u ３ are each an integer of 1 or 2. 4) * is the part where the bond is attached.

4. The polyimide precursor according to claim 1, wherein the compound represented by the chemical formula Q includes compounds represented by the following Q-7 to Q-10: <Chemical Formulas Q-7 to Q-10> 【Chemistry 7】 The R １６ Or R １８ are each independently hydrogen; deuterium; a hydroxyl group; ６ ~C ３０ aryl groups of the formula: ２ ~C ３０ Heterocyclic group of C ６ ~C ３０ A fused ring group of an aliphatic ring and an aromatic ring; １ ~C ２０ an alkyl group of C ２ ~C ２０ an alkenyl group of C ２ ~C ２０ an alkynyl group of C １ ~C ２０ an alkoxy group of C ６ ~C ３０ an aryloxy group of C １ ~C ２０ Hydroxyacrylic group of C １ ~C ２０ a hydroxymethacrylic group; a fluorenyl group; a carbonyl group; an ether group; a carboxyl group; or C １ ~C ２０ is an alkoxycarbonyl group. The precursor end is bonded with a formula selected from the group consisting of one selected from the formulas Q-7 to Q-10 or a combination thereof through an amide or imide bond.

5. The polyimide precursor of claim 1 , comprising at least one of a diamine monomer; a dianhydride monomer; and an anhydride monomer.

6. The polyimide precursor of claim 1, wherein the polyimide precursor has a weight average molecular weight of 5,000 to 40,000 g / mol.

7. The polyimide precursor of claim 6 , wherein the composition further comprises: a photoinitiator; a reactive unsaturated compound; a solvent; and an additive.

8. 7. The polyimide precursor according to claim 6, wherein the polyimide polymer is contained in an amount of 5 to 50% by weight based on the total weight of the composition.

9. 7. The polyimide precursor according to claim 6, wherein the photoinitiator is contained in an amount of 0.01 to 10% by weight based on the total amount of the polyimide precursor.

10. 7. The polyimide precursor according to claim 6, wherein the reactive unsaturated compound is contained in an amount of 1 to 40% by weight based on the total amount of the polyimide precursor.

11. 7. The polyimide precursor according to claim 6, wherein the solvent is contained in an amount of 50 to 95% by weight based on the total weight of the composition.

12. 7. The polyimide precursor according to claim 6, wherein the additive is contained in an amount of 0.001 to 10% by weight based on the total weight of the composition.

13. A pattern or film produced from the polyimide precursor of claim 6.

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

15. A display device manufactured using the pattern or film of claim 13.

16. An electronic device comprising: the display device of claim 15 and a control unit for driving the display device.

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