Photocurable Binder Containing Aliphatic Polycyclic Compounds and Photosensitive Photoresist Composition

Abstract

The present invention relates to a photocurable binder useful for large-area coating and a photosensitive photoresist composition containing the same. More specifically, the invention relates to a photocurable binder containing an aliphatic polycyclic group, a photoresist composition containing the same that exhibits excellent developability and excellent solubility, thereby enabling inkjetting, and a method for manufacturing the same.

Description

Technology Field

[0001] The present invention relates to a photocurable binder usable in a composition for a photoresist and a photosensitive photoresist composition containing the same, and more specifically, to a photocurable binder containing an aliphatic polycyclic group usable in a composition for a photoresist and a photosensitive photoresist composition containing the same. Background Technology

[0003] Photoresist (PR) can be used to pattern materials used in thin-film display devices such as TFT-LCDs and OLEDs, as well as semiconductor devices, by transferring the circuit design of a mask plate onto a wafer through a photolithography process.

[0004] Photoresist has the characteristic of being able to selectively remove parts that have been exposed to light or parts that have not during the subsequent development process, because its solubility in the developer changes when exposed to light of a specific wavelength.

[0005] Here, the case where the area exposed to light dissolves well in the developer is called positive resist, and the opposite is called negative resist.

[0006] To form fine circuit patterns, such as those in liquid crystal displays or semiconductor integrated circuits, using photoresist, a photoresist composition is first uniformly coated or applied to an insulating film or a conductive metal film formed on a substrate, the coated photoresist composition is exposed to light in the presence of a mask of a predetermined shape, and the resulting structure is developed using an alkaline aqueous developer or the like to create a pattern of the desired shape.

[0007] After dry or wet etching the metal film or insulating film using the patterned photoresist film as a mask through this process, and then removing the remaining photoresist film, a microcircuit of the metal film or insulating film is formed on the substrate.

[0008] Here, in actual use, photoresist (PR) can be used by incorporating photocrosslinking agents, photopolymerization initiators, sensitizers, etc., so that the function of the polymer is suited to each application.

[0009] Recently, in the manufacturing of semiconductor devices and organic light-emitting display devices, pattern miniaturization is rapidly progressing due to advancements in lithography technology, and as a technique for this pattern miniaturization, the wavelength (high energy) of the exposure light source is being shortened.

[0010] The above photoresist material requires lithography characteristics such as sensitivity to the exposure light source and resolution capable of reproducing patterns of fine dimensions. As a resist material satisfying the above requirements, a chemically amplified resist composition is used, which contains a substrate component whose solubility in a developer changes due to the action of an acid and an acid generating agent component that generates acid upon exposure.

[0011] Generally, in chemically amplified resist compositions, a resin having multiple constituent units is used to improve lithography characteristics, etc.

[0013] As a prior art, Korean Published Patent Application No. 10-2012-0087722 discloses a tetrapolymer photoresist in which a photo-generating group of a fluoroalkyl sulfonium salt is introduced into a polymer side chain, and presents a technology that uses this to achieve high-resolution ultra-fine line widths in the photolithography process for high integration in semiconductor-related manufacturing processes such as TFT-LCDs.

[0014] Meanwhile, photosensitive photoresist compositions generally include a binder resin, a monomer, a photoinitiator, and a solvent, among which the acid value and photosensitivity of the binder play important roles. The acid value of the binder must be suitable for the development process while possessing appropriate photosensitivity; this allows for shortening the development process time or improving undercut phenomena after development.

[0015] Meanwhile, the spin coating method used for semiconductor-related processes such as semiconductor integrated circuits, as well as for the high integration of TFT-LCDs and organic light-emitting diodes, has the problem of being difficult to implement a resist layer with a uniform surface and thickness, and this problem becomes more pronounced as the area increases, so an inkjet coating method can be used to improve this.

[0016] However, in order to manufacture a resist layer by inkjet coating, it must have a low viscosity of 40 cps or less and a solid ratio of 20% or more. To satisfy these conditions, the polymer resin must have a low molecular weight and high solubility, and in addition, have high chemical resistance. Prior art literature

[0018] Korean Published Patent Application No. 10-2012-0087722 (August 7, 2012) The problem to be solved

[0019] To solve the problems associated with the prior art, the present invention aims to provide a photosensitive photoresist composition using a photosensitive binder with excellent developability by synthesizing an acrylate-based polymer exhibiting excellent developability and reacting an epoxy acrylate compound therewith.

[0020] In particular, the specific objective of the invention is to provide a photosensitive resist composition having low viscosity of 40 cps or less, high chemical resistance, low molecular weight, and a high solid ratio, which has high developability and allows for the use of an inkjet method for large-area implementation, and a method for manufacturing the same. means of solving the problem

[0022] The present invention was completed by discovering that when a polymer comprising a repeating unit (a) represented by the following structural formula 1-a or structural formula 1-b; a repeating unit (b) represented by structural formula 2; and a repeating unit (c) represented by structural formula 3 is used as a component of a photoresist composition, low viscosity, excellent developability, excellent solubility, high chemical resistance, and high solid ratio characteristics can be achieved.

[0024] More specifically, the present invention provides a polymer for a photoresist comprising a repeating unit (a) represented by the following structural formula 1-a or structural formula 1-b; a repeating unit (b) represented by structural formula 2; and a repeating unit (c) represented by structural formula 3.

[0025]

[0026] [Structural Formula 1-a] [Structural Formula 1-b]

[0027]

[0028] [Structural Formula 2] [Structural Formula 3]

[0029] In the above structural formulas 1-a and 1-b,

[0030] The above substituent R 10 The silver is any one selected from hydrogen, deuterium, and substituted or unsubstituted C1-C5 alkyl groups, and

[0031] The above A ring, B ring, and C ring are each identical or different and independently of each other, a substituted or unsubstituted six-membered aliphatic hydrocarbon ring or a substituted or unsubstituted six-membered aromatic hydrocarbon ring, and

[0032] In the case where the above A ring, B ring, and C ring are each substituted or unsubstituted aliphatic hydrocarbon rings, each aliphatic hydrocarbon ring comprises 0 to 2 double bonds, and additionally, each aliphatic hydrocarbon ring may optionally be any one of the following structural formulas F-1 to F-4.

[0033]

[0034] [Structural Formula F-1] [Structural Formula F-2] [Structural Formula F-3] [Structural Formula F-4]

[0036] In addition, where the above A ring, B ring, and C ring are each substituted or unsubstituted aliphatic hydrocarbon rings, each ring contains 0 to 1 oxygen atom, or contains 0 to 1 carbonyl group (C=O) within the ring through a double bond between the oxygen atom and a carbon atom within the aliphatic hydrocarbon ring, and

[0037] If one or more of the above A, B, and C rings are substituted or unsubstituted aromatic hydrocarbon rings, the adjacent ring is not an aromatic hydrocarbon ring, and

[0038] The above connector X is any one selected from oxygen (O), sulfur (S), N-R' and O-R6-O, and

[0039] The above R' is any one selected from hydrogen, deuterium, a substituted or unsubstituted C2-C20 alkyl group, a substituted or unsubstituted C2-C20 halogenated alkyl group, a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, and a C4-C24 heteroaryl group comprising 1 to 3 heteroatoms selected from O, N, and S as heteroatoms that are substituted or unsubstituted.

[0040] The above substituent R6 is any one selected from a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 halogenated alkylene group, a substituted or unsubstituted C2-C10 alkenylene group, a substituted or unsubstituted C2-C10 alkynylene group, a substituted or unsubstituted C1-C10 heteroalkylene group, a substituted or unsubstituted C6-C18 arylene group, a substituted or unsubstituted C7-C18 arylalkylene group, and a substituted or unsubstituted C7-C18 alkylarylene group.

[0041] The above Y is any one selected from hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 halogenated alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, a substituted or unsubstituted C6-C18 aryl group, a substituted or unsubstituted C7-C18 arylalkyl group, a substituted or unsubstituted C7-C18 alkylaryl group, a hydroxyl group, and a substituted or unsubstituted C1-C10 alkoxy group.

[0042] The above m is an integer from 0 to 4, wherein if m is 2 or greater, each Y is the same or different, and

[0043] The D ring in the above structural formula 1-a is a substituted or unsubstituted five-membered or six-membered aliphatic hydrocarbon ring, wherein the D ring has 0 to 1 double bond, or contains 0 to 1 oxygen atom, or contains 0 to 1 carbonyl group (C=O) within the ring through a double bond between the oxygen atom and a carbon atom within the ring, and

[0045] In the above structural formula 2,

[0046] The above substituent R 11 is any one selected from hydrogen, deuterium, and substituted or unsubstituted C1-C5 alkyl groups, and

[0047] The above substituent R1 is any one substituent selected from a substituted or unsubstituted C1-C40 alkyl group, a substituted or unsubstituted C1-C40 halogenated alkyl group, a substituted or unsubstituted C2-C40 alkenyl group, a substituted or unsubstituted C2-C40 alkynyl group, a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C5-C45 aliphatic polycyclic cycloalkyl group, and a substituted or unsubstituted C1-C40 alkoxy group.

[0048] In the above structural formula 3,

[0049] Substituents R9 and R 12 The groups are identical or different from each other and are each independently selected from hydrogen, deuterium, and substituted or unsubstituted C1-C5 alkyl groups, and

[0050] The above linker L is selected from single bonds, substituted or unsubstituted C1-C30 alkylene groups, and

[0051] In the above structural formulas 1-a, 1-b, 2, and 3, 'substituted' in 'substituted or unsubstituted' refers to deuterium, cyano group, halogen group, hydroxyl group, nitro group, C1-C14 alkyl group, C1-C14 halogenated alkyl group, It means being substituted with one or more substituents selected from the group consisting of C2-C14 alkenyl groups, C2-C14 alkynyl groups, C1-C14 heteroalkyl groups, C6-C18 aryl groups, C7-C19 arylalkyl groups, C7-C19 alkylaryl groups, C1-C14 alkoxy groups, C1-C14 alkylthionyl groups, C1-C14 alkylamino groups, C6-C18 arylamino groups, C1-C14 alkylsilyl groups, C6-C18 arylsilyl groups, and C6-C18 aryloxy groups. Effects of the invention

[0053] The photosensitive photoresist composition according to the present invention has a low molecular weight, high solubility, high chemical resistance, low viscosity, and a high solid ratio, making it suitable for large-area inkjet coating processes. Therefore, it can be used as a resist for high integration of devices in manufacturing processes such as semiconductor integrated circuit devices and TFT-LCDs using inkjet coating.

[0054] In addition, the polymer for photoresist in the present invention can easily control the acid value, thereby optimizing photosensitivity and developability when forming a photosensitive layer, improving photosensitivity, and facilitating the realization of fine line widths.

[0055] In addition, the photosensitive photoresist composition according to the present invention exhibits excellent developing power even in commercially available developers such as tetramethylammonium hydroxide (TMAH) and can be applied to mass production processes. Furthermore, the photosensitive photoresist composition according to the present invention ensures ultrafine line widths and high process reliability, and can be effectively utilized, particularly in large-scale semiconductor and display manufacturing processes. Specific details for implementing the invention

[0057] Unless otherwise specifically defined in this invention, technical terms used in this invention shall be interpreted in the sense generally understood by those skilled in the art to which this invention pertains, and shall not be interpreted in an overly broad or overly narrow sense.

[0058] In describing the principles of a preferred embodiment of the present invention in detail, if it is determined that a specific description of related known functions or configurations could unnecessarily obscure the essence of the present invention, such detailed description is omitted.

[0059] Specific examples of the present application are to be described in more detail. However, the contents described in the present application are provided to convey the spirit of the present application and are not limited thereto.

[0061] The present invention provides a polymer for photoresist for forming fine patterns of semiconductor devices and thin-film display devices such as TFT-LCDs and OLEDs by developing with an alkaline developer used in semiconductor processes and thin-film displays, and a photosensitive photoresist composition comprising the same.

[0062] First of all, the polymer (A) for photoresist according to the present invention is characterized by comprising a repeating unit (a) represented by the following structural formula 1-a or structural formula 1-b; a repeating unit (b) represented by structural formula 2; and a repeating unit (c) represented by structural formula 3.

[0063]

[0064] [Structural Formula 1-a] [Structural Formula 1-b]

[0065]

[0066] [Structural Formula 2] [Structural Formula 3]

[0068] The above substituent R 10 is any one selected from hydrogen, deuterium, and substituted or unsubstituted C1-C5 alkyl groups, and

[0069] The above A ring, B ring, and C ring are each identical or different and independently of each other, a substituted or unsubstituted six-membered aliphatic hydrocarbon ring or a substituted or unsubstituted six-membered aromatic hydrocarbon ring, and

[0070] In the case where the above A ring, B ring, and C ring are each substituted or unsubstituted aliphatic hydrocarbon rings, each aliphatic hydrocarbon ring comprises 0 to 2 double bonds, and additionally, each aliphatic hydrocarbon ring may optionally be any one of the following structural formulas F-1 to F-4.

[0071]

[0072] [Structural Formula F-1] [Structural Formula F-2] [Structural Formula F-3] [Structural Formula F-4]

[0074] In addition, where the above A ring, B ring, and C ring are each substituted or unsubstituted aliphatic hydrocarbon rings, each ring contains 0 to 1 oxygen atom, or contains 0 to 1 carbonyl group (C=O) within the ring through a double bond between the oxygen atom and a carbon atom within the aliphatic hydrocarbon ring, and

[0075] If one or more of the above A, B, and C rings are substituted or unsubstituted aromatic hydrocarbon rings, the adjacent ring is not an aromatic hydrocarbon ring, and

[0076] The above connector X is any one selected from oxygen (O), sulfur (S), N-R' and O-R6-O, and

[0077] The above R' is any one selected from hydrogen, deuterium, a substituted or unsubstituted C2-C20 alkyl group, a substituted or unsubstituted C2-C20 halogenated alkyl group, a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, and a C4-C24 heteroaryl group comprising 1 to 3 heteroatoms selected from O, N, and S as heteroatoms that are substituted or unsubstituted.

[0078] The above substituent R6 is any one selected from a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 halogenated alkylene group, a substituted or unsubstituted C2-C10 alkenylene group, a substituted or unsubstituted C2-C10 alkynylene group, a substituted or unsubstituted C1-C10 heteroalkylene group, a substituted or unsubstituted C6-C18 arylene group, a substituted or unsubstituted C7-C18 arylalkylene group, and a substituted or unsubstituted C7-C18 alkylarylene group.

[0079] The above Y is any one selected from hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 halogenated alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C1-C10 heteroalkyl group, a substituted or unsubstituted C6-C18 aryl group, a substituted or unsubstituted C7-C18 arylalkyl group, a substituted or unsubstituted C7-C18 alkylaryl group, a hydroxyl group, and a substituted or unsubstituted C1-C10 alkoxy group.

[0080] The above m is an integer from 0 to 4, wherein if m is 2 or greater, each Y is the same or different, and

[0081] The D ring in the above structural formula 1-a is a substituted or unsubstituted five-membered or six-membered aliphatic hydrocarbon ring, wherein the D ring has 0 to 1 double bond, or contains 0 to 1 oxygen atom, or contains 0 to 1 carbonyl group (C=O) within the ring through a double bond between the oxygen atom and a carbon atom within the ring, and

[0082] In the above structural formula 2,

[0083] The above substituent R 11 is any one selected from hydrogen, deuterium, and substituted or unsubstituted C1-C5 alkyl groups, and preferably may be a substituent selected from hydrogen, deuterium, and methyl groups, and

[0084] The above substituent R1 is any one substituent selected from a substituted or unsubstituted C1-C40 alkyl group, a substituted or unsubstituted C1-C40 halogenated alkyl group, a substituted or unsubstituted C2-C40 alkenyl group, a substituted or unsubstituted C2-C40 alkynyl group, a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C5-C45 aliphatic polycyclic cycloalkyl group, and a substituted or unsubstituted C1-C40 alkoxy group.

[0085] In the above structural formula 3,

[0086] Substituents R9 and R 12 The groups are identical or different from each other and are each independently selected from hydrogen, deuterium, and substituted or unsubstituted C1-C5 alkyl groups, and

[0087] The above linker L is selected from single bonds, substituted or unsubstituted C1-C30 alkylene groups, and

[0088] In the above structural formulas 1-a, 1-b, 2, and 3, 'substituted' in 'substituted or unsubstituted' refers to deuterium, cyano group, halogen group, hydroxyl group, nitro group, C1-C14 alkyl group, C1-C14 halogenated alkyl group, It means being substituted with one or more substituents selected from the group consisting of C2-C14 alkenyl groups, C2-C14 alkynyl groups, C1-C14 heteroalkyl groups, C6-C18 aryl groups, C7-C19 arylalkyl groups, C7-C19 alkylaryl groups, C1-C14 alkoxy groups, C1-C14 alkylthionyl groups, C1-C14 alkylamino groups, C6-C18 arylamino groups, C1-C14 alkylsilyl groups, C6-C18 arylsilyl groups, and C6-C18 aryloxy groups.

[0090] The aryl group, which is a substituent used in the organic compound described in the specification of the present invention, is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and comprises a single or fused ring system including 5 to 7 members, preferably 5 or 6 members, and additionally, when there is a substituent on the aryl group, it can fuse with neighboring substituents to form an additional ring.

[0091] Specific examples of the above aryl group include aromatic groups such as phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, terphenyl group (preferably o-terphenyl group, m-terphenyl group, p-terphenyl group), naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., and one or more hydrogen atoms of the above aryl group may be deuterium atoms, halogen atoms, hydroxyl groups, nitro groups, cyano groups, silyl groups, amino groups (-NH2, -NH(R), -N(R')(R''), where R' and R" are independently C1-C10 alkyl groups, in this case referred to as "alkylamino groups"), amido groups, hydrazine groups, hydrazone groups, carboxyl groups, It can be substituted with a sulfonic acid group, a phosphate group, a C1-C24 alkyl group, a C1-C24 halogenated alkyl group, a C2-C24 alkenyl group, a C2-C24 alkynyl group, a C1-C24 heteroalkyl group, a C6-C24 aryl group, a C7-C24 arylalkyl group, a C2-C24 heteroaryl group, or a C2-C24 heteroarylalkyl group.

[0092] The heteroaryl group, which is a substituent used in the compound of the present invention, refers to a cyclic aromatic substituent having 2 to 50 carbon atoms, preferably 2 to 24, in which one, two, or three heteroatoms selected from N, O, P, Si, S, Ge, Se, and Te are included in the aryl group and the remaining ring atom is carbon, and said rings can be fused to form a ring. And one or more hydrogen atoms of said heteroaryl group can be substituted with a substituent similar to that of said aryl group.

[0093] In addition, the alkyl group used as a substituent in the present invention is a substituent from which one hydrogen is removed from an alkane, and includes all of a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group, and also an alkyl group in which the straight-chain alkyl group and the cyclic alkyl group are mixed; It should be interpreted as including all alkyl groups, such as a branched alkyl group and a cyclic alkyl group. Specific examples thereof include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, ethylcyclopentyl, ethylcyclohexyl, adamantyl, dicyclopentadienyl, decahydronaphthyl, norbornyl, bornyl, isobornyl, etc., and one or more hydrogen atoms of the alkyl groups can be substituted with substituents similar to those in the case of the original aryl group.

[0094] In addition, the term "halogenated alkyl group" used in the present invention means that at least one hydrogen (H) atom bonded to a carbon atom within the alkyl group is substituted with a halogen atom, and this can be similarly applied to fluorinated alkyl groups.

[0095] The alkoxy group, which is a substituent used in the compound of the present invention, is a substituent in which an oxygen atom is bonded to the last carbon position of an alkane, and includes cases in which an oxygen atom is bonded to a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group, respectively; and should be interpreted to include cases in which an oxygen atom is bonded to an alkyl group mixed with a straight-chain alkyl group and a cyclic alkyl group, respectively; and cases in which an oxygen atom is bonded to an alkyl group mixed with a branched alkyl group and a cyclic alkyl group, respectively. Specific examples thereof include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, adamantanoxy, dicyclopentaneoxy, bornyloxy, etc., and one or more hydrogen atoms of the alkoxy group can be substituted with a substituent similar to that of the aryl group.

[0096] The alkylene group used as a substituent in the compound of the present invention is a substituent of a divalent radical from which any hydrogen atom has been additionally removed from the previously defined alkyl group, and includes all of a straight-chain alkylene group, a branched alkylene group, or a cyclic alkylene group, and also includes an alkylene group in which one cyclic alkylene group and two straight-chain alkylene groups are mixed; an alkylene group in which one straight-chain alkylene group and two cyclic alkylene groups are mixed; an alkylene group in which one branched alkylene group and two cyclic alkylene groups are mixed; and an alkylene group in which two branched alkylene groups and one cyclic alkylene group are mixed; an alkylene group in which one straight-chain alkylene group and two branched alkylene groups are mixed; and an alkylene group in which two straight-chain alkylene groups and one branched alkylene group are mixed.

[0097] The alkenyl group, which is a substituent used in the compound of the present invention, is a substituent consisting only of carbon atoms and hydrogen atoms, comprising one or two double bonds formed by removing hydrogen atoms bonded to two adjacent carbon atoms from the previously defined alkyl group, wherein the double bonds may be located at the end of the alkenyl group or at a non-end position.

[0098] In addition, the alkenyl group, which is a substituent used in the compound of the present invention, corresponds to a substituent that includes one or two triple bonds instead of a double bond in the alkenyl group.

[0099] In addition, the alkenylene group, which is a substituent used in the compound of the present invention, is a substituent consisting only of carbon atoms and hydrogen atoms, comprising one or two double bonds formed by removing hydrogen atoms bonded to two adjacent carbon atoms from the alkylene group defined above, wherein the double bonds may be located at the end of the alkenylene group or at a non-end position.

[0100] The arylalkyl group, which is a substituent used in the compound of the present invention, is a substituent in which one aryl group is bonded to an alkylene group, and specific examples thereof include phenylmethyl (benzyl), phenylethyl, phenylpropyl, naphthylmethyl, and naphthylethyl, and one or more hydrogen atoms of the arylalkyl group can be substituted with a substituent similar to that of the aryl group.

[0101] The alkylaryl group, which is a substituent used in the compound of the present invention, is a substituent in which one alkyl group is bonded to an aryl group, and specific examples thereof include ethylphenyl, propylphenyl, methylnaphthyl, and ethylnaphthyl, and one or more hydrogen atoms of the alkylaryl group can be substituted with a substituent similar to that of the aryl group.

[0102] Specific examples of silyl groups that are substituents used in the compounds of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, etc., and one or more hydrogen atoms of the silyl groups can be substituted with substituents similar to those of the aryl groups.

[0103] Meanwhile, in the present invention, the range of carbon atoms implied by expressions such as “substituted or unsubstituted C1-C20 alkyl group” and “substituted or unsubstituted C6-C50 aryl group” refers to the total number of carbon atoms constituting the alkyl portion or aryl portion when considered as unsubstituted without considering the portion where the substituent is substituted. For example, a phenyl group substituted with a butyl group at the para position should be considered as corresponding to a C6 aryl group substituted with a C4 butyl group.

[0105] In addition, as a more preferred example of “substitution” in “substituted or unsubstituted” in the present invention, this means being substituted with one or more substituents selected from the group consisting of deuterium, cyano group, halogen group, nitro group, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C2-C10 alkenyl group, C6-C12 aryl group, C7-C13 arylalkyl group, C7-C13 alkylaryl group, C1-C10 alkylsilyl group, and C6-C18 arylsilyl group.

[0106] In addition, "(meth)acryl" in (meth)acrylate, (meth)acrylamide, etc. used in the present invention means "acryl and / or methacryl."

[0108] The repeating unit represented by structural formula 1-a or structural formula 1-b in the polymer used in the photosensitive photoresist composition according to the present invention comprises three condensed six-membered rings (structural formula 1-b) and optionally comprises one five-membered or six-membered ring as an aliphatic hydrocarbon ring (structural formula 1-a), wherein the three condensed six-membered rings in structural formula 1-a and structural formula 1-b comprise 0 to 2 six-membered aromatic hydrocarbon rings, and the remaining 1 to 3 six-membered rings are composed of aliphatic hydrocarbon rings, thereby having high chemical resistance and high resistance during development according to the rigid skeletal structure of the six-membered rings, excellent plasma resistance, and the ability to minimize outgassing generated during the coating process, and the tendency for unexposed parts to dissolve well in the developer to improve resolution, thus providing desirable physical properties for providing a photosensitive photoresist composition.

[0110] Meanwhile, compounds consisting of one or two five-membered or six-membered aliphatic rings, which are used as monomers in conventional photoresist compositions, have good solubility but are highly volatile due to their low molecular weight, which can cause outgassing and have low chemical resistance, resulting in a low residual film rate. On the other hand, compounds consisting only of aromatic ring structures have high chemical resistance but have poor solubility when synthesizing acrylate polymers and preparing them as compositions, and do not dissolve well in the developer, resulting in the problem of by-products remaining during development.

[0111] The present invention was devised to solve the problems associated with the prior art, and by including a structure in which three six-membered rings are condensed, and optionally an additional five-membered or six-membered ring is condensed therein, high thermal stability and high chemical resistance are achieved due to an appropriately high molecular weight and structural rigidity. Furthermore, high structural stability, high chemical resistance, and solubility can be ensured even in cases where double bonds are partially included or aromatic rings and aliphatic rings are sequentially condensed.

[0112] That is, when one or more of the above A ring, B ring, and C ring are substituted or unsubstituted aromatic hydrocarbon rings, the adjacent ring is designed such that it does not correspond to an aromatic hydrocarbon ring.

[0113] In addition, compounds formed with three or more aromatic hydrocarbon rings that are not continuous may exhibit an overall planar molecular structure and may cause problems such as poor compatibility and inability to dissolve, so the number of aromatic rings in the present invention is designed to be 0 to 2.

[0114] In addition, the acrylic repeating unit represented by structural formula 1-a or structural formula 1-b according to the present invention may include 0 to 2 double bonds in each of the aliphatic hydrocarbon rings when the A ring, B ring, and C ring are each six-membered substituted or unsubstituted aliphatic hydrocarbon rings. That is, the substituted or unsubstituted aliphatic hydrocarbon rings may have any one structure selected from a substituted or unsubstituted cyclohexane ring, a substituted or unsubstituted cyclohexene ring, and a substituted or unsubstituted cyclohexadiene ring.

[0115] In addition, when the A ring, B ring, and C ring are each six-membered substituted or unsubstituted aliphatic hydrocarbon rings, each aliphatic hydrocarbon ring may optionally have a ring structure selected from any one of the following chemical formulas F-1 to F-4, thereby replacing any one of the aforementioned substituted or unsubstituted cyclohexane ring, substituted or unsubstituted cyclohexene ring, and substituted or unsubstituted cyclohexadiene ring.

[0116]

[0117] [Chemical Formula F-1] [Chemical Formula F-2] [Chemical Formula F-3] [Chemical Formula F-4]

[0119] In addition, when the above A ring, B ring, and C ring are each six-membered substituted or unsubstituted aliphatic hydrocarbon rings, each ring may contain 0 to 1 carbonyl group (C=O) within the ring through a double bond between an oxygen atom and a carbon atom within the ring. That is, in the above structural formula 1-a or structural formula 1-b, the A ring may contain 0 to 1 carbonyl group, the B ring may contain 0 to 1 carbonyl group, and the C ring may contain 0 to 1 carbonyl group.

[0121] Meanwhile, the 'repetitive unit represented by structural formula 1-a or structural formula 1-b' in the specification of the present invention may be described below as 'repetitive unit represented by structural formula 1' for a more concise expression.

[0123] Meanwhile, in the present invention, the photoresist polymer (A) comprising repeating units represented by structural formulas 1 to 3 is a polymer having repeating units resulting from the polymerization of at least three monomers, which may be a random copolymer, a block copolymer, an alternating copolymer, or a combination thereof, and preferably, the tripolymer may be a random copolymer without regularity of each monomer.

[0125] In addition, in the present invention, the mole fraction of each repeating unit in the polymer comprising the repeating unit represented by structural formula 1-a or structural formula 1-b; the repeating unit represented by structural formula 2; and the repeating unit represented by structural formula 3 may be in the range of 0.01 to 0.85 based on the total polymer content as 1, preferably in the range of 0.02 to 0.80, and preferably in the range of 0.03 to 0.75.

[0126] In addition, the polymer in the present invention may additionally include a repeating unit represented by the structural formula 4 below.

[0127]

[0128] [Structural Formula 4]

[0129] Here, the repeating unit represented by the above structural formula 4 can generate the repeating unit represented by structural formula 3 through a reaction with an acrylic compound represented by the following chemical formula A.

[0130] That is, the repeating unit represented by the above structural formula 3 can be produced by a reaction between the repeating unit represented by the following structural formula 4 and the acrylic compound represented by chemical formula A.

[0131] In order to produce a polymer according to the present invention, a polymer comprising a repeating unit (a) represented by structural formula 1-a or structural formula 1-b; a repeating unit (b) represented by structural formula 2; and a repeating unit (c) represented by structural formula 4 is first prepared by polymerizing an acrylic monomer corresponding to each of these, and then a repeating unit represented by structural formula 3 may be produced by a reaction between the repeating unit represented by structural formula 4 and an acrylic compound represented by the following chemical formula A, wherein a repeating unit of structural formula 3 having a hydroxyl group may be produced by the carboxylic acid in structural formula 4 reacting with an epoxy group in chemical formula A, so that the oxygen atom of the carboxylic acid bonds with the terminal carbon atom of the epoxy group and the ring is simultaneously unraveled.

[0132]

[0133] [Structural Formula 4] [Chemical Formula A]

[0134] In the above structural formula 4 and chemical formula A, the linker L, substituents R9 and R 12 It is the same as previously defined.

[0135] In addition, the repeating unit represented by structural formula 4 in the photoresist polymer (A) may optionally be included to replace about 20 to 60%, preferably 30 to 50%, of the repeating unit represented by structural formula 3 in the photoresist polymer (A), which is desirable in terms of the developability of the composition.

[0136] In this case, the acid value range of the polymer (A) for the photoresist is preferably 20 to 100 (KOH mg / g). When the acid value is within the above range, solubility in the developer is improved, so that the non-exposed area dissolves easily and sensitivity increases, and as a result, the pattern of the exposed area remains during development, thereby improving the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can typically be obtained by titrating using an aqueous potassium hydroxide solution.

[0137] In addition, as a preferred embodiment of the present invention, the weight average molecular weight of the polymer for the photoresist is 1,000 ≤ M w It may be in the range ≤ 30,000, and preferably 2,000 ≤ M w It may be in the range ≤ 25,000, and more preferably 3,000 ≤ M w It may be in the range of ≤ 20,000, and through this, a composition with excellent solubility in a solvent during the lithography process can be provided.

[0138] As one embodiment, the mole fraction of the repeating unit represented by structural formula 1 in the polymer may be in the range of 0.01 to 0.30, the mole fraction of the repeating unit represented by structural formula 2 may be in the range of 0.20 to 0.85, and the mole fraction of the repeating unit represented by structural formula 3 may be in the range of 0.05 to 0.60; preferably, the mole fraction of the repeating unit represented by structural formula 1 in the polymer may be in the range of 0.02 to 0.20, the mole fraction of the repeating unit represented by structural formula 2 may be in the range of 0.30 to 0.80, and the mole fraction of the repeating unit represented by structural formula 3 may be in the range of 0.10 to 0.50.

[0139] As one embodiment, a repeating unit represented by structural formula 1-a or structural formula 1-b; a repeating unit represented by structural formula 2; a repeating unit represented by structural formula 3; and substituents R9 to R 1２ Each can be hydrogen, deuterium, or a methyl group.

[0140] In one embodiment, R1 in the structural formula 2 may preferably be a substituted or unsubstituted C4-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C25 arylalkyl group, a substituted or unsubstituted C6-C43 aliphatic polycyclic cycloalkyl group, or a substituted or unsubstituted C1-C35 alkoxy group, and more preferably may be any one selected from a substituted or unsubstituted C5-C25 alkyl group, a substituted or unsubstituted C7-C20 arylalkyl group, a substituted or unsubstituted C7-C40 aliphatic polycyclic cycloalkyl group, or a substituted or unsubstituted C1-C30 alkoxy group.

[0141] In one embodiment, the A ring, B ring, and C ring within the repeating unit (a) represented by structural formula 1-a or structural formula 1-b may each be a substituted or unsubstituted aliphatic hydrocarbon ring containing 0 to 1 double bond.

[0142] In one embodiment, at least one of the A ring, B ring, and C ring within the repeating unit (a) represented by the structural formula 1-a or structural formula 1-b may be any one of the rings selected from the chemical formulas F-1 to F-4.

[0143] As one embodiment, within the above structural formula 1-a The D ring may be a substituted or unsubstituted six-membered or five-membered aliphatic hydrocarbon ring, and when the D ring is a five-membered ring, it may preferably be a substituted or unsubstituted cyclopentane or a substituted or unsubstituted cyclopentene, and in this case, the substituent corresponding to the 'substitution' may preferably be substituted or unsubstituted cyclopentane, or selected from a C1-C10 alkyl group, a C1-C10 alkenyl group, a carbonyl group, or a C1-C10 halogenated alkyl group.

[0144] As one embodiment, the repeating unit represented by structural formula 1-a or structural formula 1-b may be produced by the polymerization of an acrylic compound derived from any one compound selected from linestrenol, dihydroepiandrosterone, allylestrenol, methylandrostenodiol, pregnenolone, kerenol, cholesterol, ergosterol, beta-sitosterol, lanosterol, 24-methylenecholesterol, campesterol, carnosol, 12-methyl ether of carnosic acid, rosmanol, and 20-deoxocarnosol.

[0145] Here, the meaning of 'acrylic compound derived from compound A' refers to a compound in which only an acrylic substituent is added or substituted to compound A, or an acrylic substituent is added or substituted to a structure in which a double bond is simply created or eliminated without a change in the skeleton of the matrix structure within the molecule, or an acrylic substituent is added or substituted by changing one or two substituents at the ends of the matrix structure, or an acrylic substituent is added or substituted to an intermediate in which the matrix structure is modified by a process of one or two steps from compound A.

[0146] As one embodiment, in the above structural formulas 1-a and 1-b, m may be an integer from 0 to 3, and preferably may be an integer from 0 to 2.

[0147] As one embodiment, the repeating unit represented by the structural formula 1-a or structural formula 1-b may be formed by the polymerization of any one of the compounds selected from <Compound 1> to <Compound 39> below, but the present invention is not limited thereto.

[0149]

[0150] <Compound 1> <Compound 2> <Compound 3>

[0151]

[0152] <Compound 4> <Compound 5> <Compound 6>

[0153]

[0154] <Compound 7> <Compound 8> <Compound 9>

[0155]

[0156] <Compound 10> <Compound 11> <Compound 12>

[0157]

[0158] <Compound 13> <Compound 14> <Compound 15>

[0159]

[0160] <Compound 16> <Compound 17> <Compound 18>

[0161]

[0162] <화합물 19> <화합물 20> <화합물 21>

[0163]

[0164] <화합물 22> <화합물 23> <화합물 24>

[0165]

[0166] <화합물 25> <화합물 26> <화합물 27>

[0167]

[0168] <화합물 28> <화합물 29> <화합물 30>

[0169]

[0170] <화합물 31> <화합물 32> <화합물 33>

[0171]

[0172] <화합물 34> <화합물 35> <화합물 36>

[0173]

[0174] <화합물 37> <화합물 38> <화합물 39>

[0176] As one embodiment, the repeating unit represented by Structural Formula 2 is propyl(meth)acrylate, butyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, cyclohexyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate, dodecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, isobornyl(meth)acrylate, icosyl(meth)acrylate, butycosyl(meth)acrylate, adamantyl(meth)acrylate, dicyclofentanyl(meth)acrylate, benzyl(meth)acrylate, phenoxybenzyl(meth)acrylate, 2-methoxyethyl(meth)acrylate, It may be formed by the polymerization of any one compound selected from 2-ethoxyethyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, and 2-dodecylhexadecyl (meth)acrylate.

[0177] As one example, the compound represented by the formula A may be any one selected from glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate glycidyl, α-n-propylacrylate glycidyl, α-n-butylacrylate glycidyl, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, β-ethylglycidyl acrylate, β-ethylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, and α-ethylacrylate-6,7-epoxyheptyl.

[0179] Meanwhile, the method for preparing the polymer for photoresist in the present invention may include: a) a step of preparing a polymer comprising repeating units represented by structural formula 1-a or structural formula 1-b; repeating units represented by structural formula 2; and repeating units represented by structural formula 4 by polymerizing the following compounds a or b; compounds c; and compounds d; in the presence or absence of a solvent; and b) a step of reacting the polymer obtained in step a) with an acrylic compound represented by the following chemical formula A, thereby producing repeating units represented by structural formula 3 by the reaction between the repeating units represented by structural formula 4 in the polymer obtained in step a) and the acrylic compound represented by chemical formula A.

[0180]

[0181] <Compound a> <Compound b>

[0182]

[0183] <Compound c> <Compound d>

[0184]

[0185] [Structural Formula 4] [Chemical Formula A]

[0187] Here, the above compounds a to d, the A to D rings in structural formula 4 and formula A, X, Y, m, linker L, R1, R9 to R12 are the same as defined in structural formula 1-a, structural formula 1-b, and structural formula 2 to 4, and the mole fraction of the compound represented by compound a or compounds b to d is in the range of 0.01 to 0.85 with respect to the polymer for the photoresist composition as 1.

[0188] That is, the polymer according to the present invention can produce repeating units represented by structural formula 1-a or structural formula 1-b; repeating units represented by structural formula 2; and repeating units represented by structural formula 4 by polymerizing compound a or compound b; compound c; and compound d; as monomers in a solvent. Among these, repeating units represented by structural formula 3 can be produced by a reaction between the repeating unit represented by structural formula 4 and an acrylic compound represented by chemical formula A. This is because the carboxylic acid in structural formula 4 reacts with the epoxy group in chemical formula A, and the oxygen atom of the carboxylic acid bonds with the terminal carbon atom of the epoxy group while the ring is released, thereby producing repeating units of structural formula 3 having hydroxyl groups.

[0189] Here, a photoresist polymer (A) comprising a repeating unit represented by structural formula 1-a; a repeating unit represented by structural formula 1-b; a repeating unit represented by structural formula 2; and a repeating unit represented by structural formula 3 according to the present invention can be obtained by polymerizing the monomers in the presence of a polymerization initiator in the presence or absence of an organic solvent.

[0191] At this time, known existing radical polymerization initiators may be used as the type of polymerization initiator; examples include azo compounds, peroxide compounds, and redox compounds, and in particular, 2,2'-azobis-2,4-dimethyl valeronitrile, dimethyl-2,2'-azobis-isobutyrate, 2,2'-azobis-isobutyronitrile, 2,2'-azobis(4-methoxyvaleronitrile), peroxide, lauroyl peroxide, succinate peroxide, disinnamyl peroxide, di-n-propylperoxydicarbonate, t-butylperoxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, ammonium persulfate, etc. It may be used, but if it corresponds to a polymerization initiator capable of forming repeating units represented by the above structural formulas 1 to 3, it may be used without limitation of type.

[0193] Meanwhile, the present invention may provide a photosensitive photoresist composition comprising the photoresist polymer (A) according to the present invention described above; a photogenerator or photoinitiator; and a polymerizable compound comprising at least one double bond.

[0194] That is, the photosensitive photoresist composition according to the present invention may comprise an acrylate-based polymer (A) comprising a repeating unit represented by structural formula 1-a or a repeating unit represented by structural formula 1-b; a repeating unit represented by structural formula 2; and a repeating unit represented by structural formula 3; a photoinitiator or a photogenerator; and an additional polymerizable compound comprising at least one double bond.

[0195] Here, the photo acid generator (PAG) is a compound that generates acid in response to external energy or light, and in particular, any compound that generates acid by high-energy irradiation can be used without limitation in type, and preferably includes sulfonium salts, iodinium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generators, etc., and these can be used alone or in a mixture of two or more types.

[0197] In addition, the above photogenerative agent must have high thermal stability, that is, be stable up to at least 140°C, so that it does not deteriorate during photolithography pretreatment.

[0198] As a photogenerator usable in the photosensitive photoresist composition according to the present invention, the following group of compounds is included, but is not limited thereto.

[0199] (1) Sulfonium salts include triphenylsulfonium perfluoromethanesulfonate (triphenylsulfonium trilate), triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluoropentanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, tris(t-butylphenyl)sulfonium perfluorooctanesulfonate, diphenylethylsulfonium chloride, and phenacyldimethylsulfonium chloride, etc.;

[0200] (2) Halonium salts, specifically iodonium salts, include diphenyliodonium perfluoromethanesulfonate (diphenyliodonium trilate), diphenyliodonium perfluorobutanesulfonate, diphenyliodonium perfluoropentanesulfonate, diphenyliodonium perfluorooctanesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis-(t-butylphenyl)iodonium trilate, and bis-(t-butylphenyl)-iodonium campanylsulfonate, etc.;

[0201] (3) As α,α'-bis-sulfonyl-diazomethanes, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyl diazomethane, 1-cyclohexylsulfonyl-1-(1,1-dimethylethylsulfonyl) diazomethane, and bis(cyclohexylsulfonyl) diazomethane, etc.;

[0202] (4) Trifluoromethanesulfonate esters of imides and hydroxyimides, e.g., α-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-tin-2,3-dicarboxyimide (MDT);

[0203] (5) Nitrobenzyl sulfonate esters include 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, and 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate, etc.;

[0204] (6) Sulfonyloxynaphthalimides, including N-camphorsulfonyloxynaphthalimide and N-pentafluorophenylsulfonyloxynaphthalimide;

[0205] (7) Pyrogallol derivatives (e.g., trimesylate of pyrogallol);

[0206] (8) Naphthoquinone-4-diazides;

[0207] (9) alkyl disulfones;

[0208] (10) s-triazine derivatives, described in U.S. Patent No. 4,189,323; and

[0209] (11) Miscellaneous sulfonic acid generators include t-butylphenyl-α-(p-toluenesulfonyloxy)-acetate, t-butyl-α-(p-toluenesulfonyloxy)acetate, N-hydroxy-naphthalimide dodecane sulfonate (DDSN), and benzoin tosylate.

[0210] Other suitable photocatalysts are disclosed in Reichmanis et al., Chemistry of Materials 3:395 (1991) and U.S. Patent No. 5,679,495 (inventors Yamachika et al.).

[0211] Meanwhile, the photoacid generator according to the present invention may be mixed into the polymer itself of the photosensitive photoresist composition. In the region exposed to ultraviolet light, the PAG mixed with the polymer will be photochemically converted, for example, into a sulfonic acid group mixed with the polymer. Suitable monomers having PAG substituents are well known in the literature.

[0212] In addition, as a polymerization initiator usable in the photosensitive photoresist composition according to the present invention, a photoinitiator or a thermal initiator capable of performing a photocurable reaction may be used, for example.

[0213] The above thermal polymerization initiator may be an azo-based, peroxy-based, etc., and the photoinitiator may be selected from benzoin-based, triazine-based, acetophenone-based, benzophenone-based, anthracunone-based, ketal-based, thioxanthone-based, benzophenone-based, phosphine oxide-based, and oxime-based, used alone or in a mixture of two or more types.

[0214] The above thermal initiator may represent organic peroxides or hydroperoxides, azo compounds, redox compounds, etc., and any one of these selected may be used alone or two or more may be used in combination. In addition, a photoinitiator and a thermal initiator may be used in combination.

[0215] Herein, specific examples of the polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin sobutyl ether, etc.; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], etc. Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; thioxantones such as 2,4-diethylthioxantone, 2-isopropylthioxantone, 2-chlorothioxantone; ketal types such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4,4'-bismethylaminobenzophenone; Examples include phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide. One or more initiators selected from the above polymerization initiators may be used alone or in combination of two or more, but are not limited to the above polymerization initiators.

[0216] The photogenerator or photoinitiator in the photoresist composition according to the present invention may be included in an amount of 0.1 to 30 weight% based on the total composition as 100, preferably in an amount of 0.1 to 25 weight%, more preferably in an amount of 0.1 to 20 weight%, more preferably in an amount of 0.2 to 10 weight%, and even more preferably in an amount of 0.2 to 5 weight%. In this case, when an organic solvent is used, the content of the photogenerator or photoinitiator in the photosensitive photoresist composition is calculated by excluding its content from the total composition.

[0218] In addition, the polymerizable compound in the photosensitive photoresist composition according to the present invention may be used without limitation in type as long as it is a compound in which radicals are generated by UV of the photogenerative agent or photoinitiator and crosslinked or polymerized by the generated radicals, and preferably, a compound containing one, two, three, or four functional groups selected from acrylic groups, methacrylic groups, and vinyl groups in the molecule may be used.

[0219] Specific examples of the above polymerizable compounds include alkyl acrylates such as hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tetradecyl (meth)acrylate, and hexadecyl (meth)acrylate; or one or more selected from the group consisting of alkyl methacrylate, ethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, acrylic acid, methacrylic acid, glycidyl acrylate, and styrene.

[0220] In this case, the content of the polymerizable compound excludes the content when an organic solvent is used, and may include 1 to 90 parts by weight based on the total composition as 100, preferably 2 to 85 parts by weight, and more preferably 3 to 80 parts by weight, and is calculated by excluding the content of the polymerizable compound in the total composition when an organic solvent is used.

[0222] Meanwhile, the present invention may optionally include an organic solvent to dissolve the photosensitive photoresist composition, which is used to control viscosity and improve coating characteristics; it is preferable to use a hydrocarbon or a hydrocarbon organic solvent containing oxygen atoms as such a solvent.

[0223] As a preferred type of organic solvent for this purpose, propylene glycol alkyl ether acetates such as propylene glycol monoethylpropionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol dimethyl ether; and propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone;or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-ethyl hydroxypropionate, 2-methyl hydroxy2-methylpropionate, 2-ethyl hydroxy2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetate butyl hydroxyacetate, methyl lactic acid, ethyl lactic acid, propyl lactic acid, butyl lactic acid, 3-methyl hydroxypropionate, 3-ethyl hydroxypropionate, 3-propyl hydroxypropionate, 3-butyl hydroxypropionate, 2-methyl 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxyacetate butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxyacetate butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxyacetate butyl ethoxyacetate, methyl propoxyacetate, Ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methyl methoxypropionate, 2-ethyl methoxypropionate, 2-propyl methoxypropionate, 2-butyl methoxypropionate, 2-methyl ethoxypropionate, 2-ethyl ethoxypropionate, 2-propyl ethoxypropionate, 2-butyl ethoxypropionate, 2-methyl methoxypropionate, 2-ethyl ethoxypropionate, 2-propyl ethoxypropionate, 2-butyl ethoxypropionate, 2-methyl methoxypropionate, 2-ethyl methoxypropionate, 2-propyl methoxypropionate, 2-butyl methoxypropionate, 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-propyl methoxypropionate, 3-methyl methoxypropionate, Esters such as ethyl ethoxypropionate, propyl ethoxypropionate, butyl ethoxypropionate, methyl propoxypropionate, ethyl ethoxypropionate, propyl ethoxypropionate, butyl propoxypropionate, methyl butoxypropionate, ethyl butoxypropionate, propyl butoxypropionate, methyl butoxypropionate, ethyl butoxypropionate, propyl butoxypropionate, and butyl butoxypropionate may be used. Specifically, propylene glycol alkyl ether acetates such as propylene glycol monoethylpropionate, propylene glycol methyl etherpropionate, propylene glycol ethyl etherpropionate, propylene glycol propyl etherpropionate, and propylene glycol butyl etherpropionate may be used, which have solubility, reactivity with each component, and facilitate the formation of a coating film.

[0224] In this case, the content of the organic solvent may be 0 to 300 parts by weight based on the total content excluding the organic solvent of the coating solution composition being 100, and preferably 10 to 150 parts by weight when an organic solvent is used, and if necessary, two or more types of organic solvents may be used alone or mixed.

[0225] As exemplary conditions for preparing the acrylate-based polymer according to the present invention, ethylene glycol dimethyl ether (EGDE) may be used as an organic solvent, and 2,2'-asobis-2,4-dimethylvaleronitrile (V65) may be used as a polymerization initiator.

[0226] At this time, the polymerization conditions may be carried out under a nitrogen or argon atmosphere at a temperature range of, for example, 0 to 80 ℃, preferably 20 to 70 ℃.

[0228] In addition, as a preferred embodiment of the present invention, the photosensitive photoresist composition may be used in an exposure process using KrF, ArF, or an electron beam.

[0229] In addition, the photoresist composition provided in the present invention may have a viscosity of 40 cps or less and a solid ratio of 20% or more.

[0231] In addition, as a preferred embodiment of the present invention, the photosensitive photoresist composition may be used in any one of the following devices: a TFT-LCD, a color filter, an organic light-emitting diode (OLED), a lighting device, a metal sensor, a solar cell, an integrated circuit, an organic field-effect transistor (O-FET), and an organic thin-film transistor (O-TFT).

[0233] The present invention is explained in more detail by the following examples, which are intended to aid in understanding the invention and should not be interpreted as limiting the scope of the invention.

[0235] Preparation Example: Preparation of an acrylate compound represented by Structural Formula 1

[0236] Synthesis Example 1: Synthesis of Compound 3

[0237]

[0238] 100 g (480 mmol) of compound 3-1 was dissolved in 400 mL of dichloromethane in a 3 L reactor, and after cooling the internal temperature to 0 ℃, 72.9 g (720 mmol) of triethylamine and 65.2 g (624 mmol) of methacryl chloride were slowly added dropwise, and the mixture was stirred for 2 hours while maintaining the temperature. The reaction mixture was filtered through a filter filled with Celite to remove the generated salt, and then 1 L of distilled water was added to the filtrate to wash it. The organic layer was dried with anhydrous magnesium sulfate and concentrated to obtain an organic material, which was then column-processed with a mixture of ethyl acetate and normal hexane to obtain 77.0 g (yield: 58%) of the target compound 3 as a clear liquid.

[0239] 1 H NMR (δ ppm; DMSO- d 6 ): 6.38~6.30(m, 2H), 3.81(m, 1H), 1.91(s, 3H), 1.70~1.41(m, 4H), 1.33~1.17(m, 18H)

[0240] MS( m / e ) : 276.2.

[0243] Synthesis Example 2: Synthesis of Compound 13

[0245]

[0246] 75.6 g (yield: 62%) of the white solid target compound 13 was obtained using 100.0 g (406 mmol) of compound 13-1, 61.6 g (60.9 mmol) of triethylamine, 47.8 g (528 mmol) of acryl chloride, and 400 mL of dichloromethane in the same manner as in Synthesis Example 1.

[0247] 1 H NMR (δ ppm; DMSO- d6 ): 6.20~6.17(m, 2H), 5.95(m, 1H), 5.49~5.39(m,2H), 4.33(m, 1H), 2.00~1.88(m, 3H), 1.83~1.11(m, 19H)

[0248] MS( m / e ) : 300.2

[0250] Synthesis Example 3: Synthesis of Compound 36

[0252]

[0253] 71.1 g (yield: 60%) of the white solid target compound 36 was obtained using 100 g (259 mmol) of compound 36-1, 39.3 g (388 mmol) of triethylamine, 35.1 g (336 mmol) of methacryl chloride, and 400 mL of dichloromethane in the same manner as in Synthesis Example 1.

[0254] 1 H NMR (δ ppm; DMSO- d 6 ): 6.38(m, 1H), 6.30(m, 1H), 5.27(m, 1H), 3.89(m, 1H), 2.23(m, 2H), 1.98~1.69(m, 5H), 1.65~0.94(m, 30H), 0.86~0.81(m, 9H)

[0255] MS( m / e ) : 454.4

[0257] Synthesis Example 4: Synthesis of Polymer 1 for Photoresist

[0258]

[0259] o : 0.07, p : 0.63, q : 30

[0261] Synthesis Example 4-1: Synthesis of Acrylate-based Polymer 1

[0262] 15.0 g (54 mmol) of compound 3, 166.0 g (588 mmol) of compound [4-1], 22.0 g (255 mmol) of compound [4-2], and 20 mL of ethylene glycol dimethyl ether were dissolved in a 1 L reactor under a nitrogen atmosphere, and 0.6 g of polymerization initiator V65 (2,2'-azobis(2,4-dimethylvaleronitrile)) was added dropwise and reacted at 45 °C for 24 hours. After cooling the reaction mixture to room temperature, the reaction precipitate was filtered. The filtered precipitate was dissolved in a small amount of tetrahydrofuran and then precipitated in acetone. The resulting compound was vacuum dried for 48 hours to obtain 39.9 g of polymer (1). The average molecular weight (Mw) of the copolymer prepared in this way was confirmed to be 7,051, and the degree of dispersion was 1.6.

[0264] Synthesis Example 4-2: Synthesis of Polymer 1 for Photoresist

[0265] 39.9 g of acrylate-based polymer 1 prepared according to Synthesis Example 4-1, 9.1 g of glycidyl methacrylate, 0.15 g of tetrabutylammonium chloride, and 12 mL of dipropylene glycol methyl ether were added to a reactor, and the reaction was carried out at 70 °C for 2 hours under a nitrogen atmosphere to obtain polymer (binder) 1 for photoresist.

[0266] Polymer acid value: 82 mg KOH / g

[0268] Synthesis Example 5: Synthesis of Polymer 2 for Photoresist

[0269]

[0270] o : 0.07, p : 0.63, q : 30

[0272] Synthesis Example 5-1: Synthesis of Acrylate-based Polymer 2

[0273] In the same manner as in Synthesis Example 4, 32.0 g (50 mmol) of compound 13, 152.7 g (541 mmol) of compound [4-1], 20.2 g (235 mmol) of compound [4-2], 30 mL of ethylene glycol dimethyl ether, and 0.6 g of initiator V65 were used to obtain 36.2 g of acrylate-based polymer 2. The average molecular weight (Mw) of the copolymer prepared in this way was confirmed to be 8,471, and the degree of dispersion was 1.7.

[0275] Synthesis Example 5-2: Synthesis of Polymer 2 for Photoresist

[0276] 36.2 g of acrylate-based polymer 2, 8.3 g of glycidyl methacrylate, 0.14 g of tetrabutylammonium chloride, and 12 mL of dipropylene glycol methyl ether were added to a reactor, and the reaction was carried out at 70 °C for 2 hours under a nitrogen atmosphere to obtain polymer (binder) 2.

[0277] Polymer acid value: 74 mg KOH / g

[0279] Synthesis Example 6: Synthesis of Photoresist Polymer 3

[0280]

[0281] o : 0.07, p : 0.63, q : 30

[0283] Synthesis Example 6-1: Synthesis of Acrylate-based Polymer 3

[0284] In the same manner as in Synthesis Example 4, 29.0 g of acrylate-based polymer 3 was obtained using 15.0 g (33 mmol) of compound 36, 131.0 g (357 mmol) of compound [6-1], 13.3 g (155 mmol) of compound [4-2], 30 mL of ethylene glycol dimethyl ether, and 0.5 g of initiator V65. The average molecular weight (Mw) of the copolymer prepared in this way was confirmed to be 9,981, and the degree of dispersion was 1.8.

[0286] Synthesis Example 6-2: Synthesis of Polymer 3 for Photoresist

[0287] 29.0 g of the above acrylate-based polymer 1, 5.5 g of glycidyl methacrylate, 0.09 g of tetrabutylammonium chloride, and 12 mL of dipropylene glycol methyl ether were added to a reactor, and the reaction was carried out at 70 °C for 2 hours under a nitrogen atmosphere to obtain polymer 3.

[0288] Polymer acid value: 71 mg KOH / g

[0290] It is obvious to those skilled in the art that the above synthesis examples 1 to 6 describe specific examples and do not limit the synthesis method of the present invention.

[0292] Solid-phase ratio evaluation and resist evaluation: Photosensitive photoresist compositions for Examples 1 and 2 and Comparative Example 1 were prepared as shown in Tables 1 and 2 below and evaluated.

[0293] (A) Acrylate-based polymer polymerization

[0294] Acrylate-based polymer Structural Formula 1 Structural Formula 2 Structural Formula 4 Example A-1 Compound 3(7) Tetradecyl methacrylate (63) methacrylic acid (30) Example A-2 Compound 13(7) Tetradecyl methacrylate (63) methacrylic acid (30) Comparative Example E-1 Pheanthren-9-yl-methacrylate (7) Tetradecyl methacrylate (63) methacrylic acid (30)

[0296] (B) Synthesis of photoresist polymer

[0297] Polymer for photoresist Acrylate-based polymer Compound of chemical formula A Example B-1 Example A-1 (39.9 g) Glycidyl methacrylate (9.1 g) Example B-2 Example A-2 (36.2 g) Glycidyl methacrylate (8.3 g) Comparative Example F-1 Comparative Example E-1 (38.4 g) Glycidyl methacrylate (8.1 g)

[0299] (C) Polymerizable compound

[0300] Dipentaerythritol hexaacrylate (Compound C)

[0301]

[0303] (D) Photoinitiator

[0304] Oxime-based initiator (Irgacure OXE-01)

[0305]

[0307] Examples 1 and 2: Preparation of photoresist compositions

[0308] A polymer for photoresist (B-1) or a polymer for photoresist (B-2); (B) a polymerizable compound; and (C) a photoinitiator (Irgacure OXE-01); were added, and PGMEA was added as a solvent to achieve a viscosity of 35 cps, and the mixture was stirred at room temperature for 12 hours to prepare a photoresist composition according to the present invention.

[0310] Comparative Example 1

[0311] A photoresist composition was prepared using a photosensitive polymer (F-1) in the same manner as in Example 1.

[0312] The components and viscosity of the compositions according to Examples 1 and 2 and Comparative Example 1 are shown in Table 3 below.

[0314] composition Photosensitive binder (%) Photopolymerizable Compounds (%) Photoinitiator Irgacure OXE-01 (%) Solvent PGMEA (%) Viscosity (cps) To 25℃ Example 1 Example B-1 (20) Compound C (25) 1.35 53.65 38.2 Example 2 Example B-2 (15) Compound C (24) 1.17 59.83 39.5 Comparative Example 1 Comparative Example F-1(7) Compound C(10) 0.51 82.49 39.9

[0316] Experimental Example 1: Evaluation of Solid-Phase Ratio

[0317] The previously prepared photoresist composition was placed in an aluminum dish and subjected to soft baking (100℃ / 10 min), followed by exposure (1,000 mJ / ㎠), and then hard baking (100℃ / 30 min). The solid ratio was measured three times based on the weight ratio before / after heating and is shown in Table 4 below.

[0319] Sample Al dish Sample weight Total weight 100 o Total weight after heating at C / 30 minutes 100 o Sample weight after heating at C / 30 minutes Solid Content Example 1 1 time 1.1206 5.0063 6.1269 2.9329 1.8123 36.2 2nd time 1.1457 5.0403 6.1860 3.0005 1.8548 36.8 3 times 1.1674 5.1057 6.2731 3.0310 1.8636 36.5 average 5.0508 6.1953 2.9881 1.8436 36.5 Example 2 1 time 1.1407 5.0173 6.1580 3.0372 1.8965 37.8 2nd time 1.1299 5.0351 6.1650 2.9979 1.8680 37.1 3 times 1.1301 4.9983 6.1284 3.0045 1.8744 37.5 average 5.0169 6.1505 3.0132 1.8796 37.5 Comparative Example 1 1 time 1.1315 5.0298 6.1613 1.6647 0.5332 10.6 2nd time 1.1547 5.0625 6.2172 1.6863 0.5316 10.5 3 times 1.1298 5.0072 6.1370 1.6355 0.5057 10.1 average 5.0332 6.1718 1.6622 0.5235 10.4

[0321] Experimental Example 2: Photoresist Evaluation

[0322] 1) Residual film rate

[0323] After applying the photoresist composition according to the examples and comparative examples onto a substrate using a spin coater, the substrate was heated at 100°C for 2 minutes, exposed to 1000 mJ at 365 nm, and then developed in a 2.38% TMAH aqueous solution. A hard bake was performed at 250°C for 30 minutes, and the thickness ratio (%) of the photoresist film before and after the hard bake was measured.

[0325] 2) Transmittance

[0326] After applying the above photoresist composition onto a substrate using a spin coater, it was pre-baked at 100°C for 2 minutes, exposed to 1000 mJ at 365 nm, and then developed in a 2.38% TMAH aqueous solution. After hard-baking at 250°C for 30 minutes, the transmittance was measured at 400 nm using a UV-vis spectrophotometer.

[0328] The photoresist compositions prepared according to Examples 1 to 2 and Comparative Example 1 above were evaluated on a glass substrate, and performance evaluations such as residual film rate and transmittance of the photoresist compositions were performed, and the results are shown in Table 5 below.

[0330] Examples Residual film rate (%) Transmittance (%) Example 1 92 98 Example 2 95 98 Comparative Example 2 65 71

[0331] As can be seen from the results of Tables 2 and 3 above, the photoresist composition of the present invention shows superior physical properties of solid phase ratio, residual film rate, and transmittance compared to conventional photoresist compositions.

[0332] In addition, generally, to be used as an inkjet ink, it must have a viscosity of 50 cps or less, and preferably 40 cps or less. Also, it must have a solid-phase ratio of 20% or more to possess high chemical resistance and enable the realization of fine lines. In the above examples and comparative examples, the monomer responsible for chemical resistance has an aromatic structure, but the comparative example, which lacks a structure that improves solubility, has a viscosity of 39.9 cps, and since the dissolution rate is inevitably low, the residual film rate during development is low.

[0333] The comparative example, which exhibits significantly lower solubility in the solid-phase ratio shown in Table 2, shows a lower residual film rate than the example. Consequently, the uniformity of the thin film is reduced, and as shown in Table 3, it exhibits a lower transmittance. These results offer the advantage of improved productivity in photoresists utilizing large-area inkjet technology during the exposure and hard-baking processes in semiconductor manufacturing.

[0335] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also included within the scope of the present invention.

Claims

Claim 1 A polymer for photoresist comprising a repeating unit (a) represented by the following structural formula 1-a or structural formula 1-b; a repeating unit (b) represented by structural formula 2; and a repeating unit (c) represented by structural formula 3. [Structural Formula 1-a] [Structural Formula 1-b] [Structural Formula 2] [Structural Formula 3] In the above structural formulas 1-a and 1-b, the substituent R 10 The ring is selected from hydrogen, deuterium, and substituted or unsubstituted C1 to C5 alkyl groups, and the A ring, B ring, and C ring are each identical or different and independently of each other a substituted or unsubstituted six-membered aliphatic hydrocarbon ring or a substituted or unsubstituted six-membered aromatic hydrocarbon ring, and when the A ring, B ring, and C ring are each substituted or unsubstituted aliphatic hydrocarbon rings, each aliphatic hydrocarbon ring comprises 0 to 2 double bonds, and additionally, each aliphatic hydrocarbon ring may optionally be any one of the rings selected from structural formulas F-1 to F-4 below. [Structural Formula F-1] [Structural Formula F-2] [Structural Formula F-3] [Structural Formula F-4] Furthermore, where the A ring, B ring, and C ring are each substituted or unsubstituted aliphatic hydrocarbon rings, each ring contains 0 to 1 oxygen atom, or contains 0 to 1 carbonyl group (C=O) within the ring through a double bond between the oxygen atom and a carbon atom within the aliphatic hydrocarbon ring; where one or more of the A ring, B ring, and C ring are substituted or unsubstituted aromatic hydrocarbon rings, the adjacent ring is not an aromatic hydrocarbon ring; and the linker X is any one selected from oxygen (O), sulfur (S), N-R', and O-R6-O, wherein R' is hydrogen, deuterium, a substituted or unsubstituted C2-C20 alkyl group, a substituted or unsubstituted C2-C20 halogenated alkyl group, or a substituted or unsubstituted Any one selected from a C6-C24 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, and a C4-C24 heteroaryl group comprising 1 to 3 heteroatoms selected from O, N, and S as heteroatoms, wherein the substituent R6 is any one selected from a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C1-C10 halogenated alkylene group, a substituted or unsubstituted C2-C10 alkenylene group, a substituted or unsubstituted C2-C10 alkynylene group, a substituted or unsubstituted C1-C10 heteroalkylene group, a substituted or unsubstituted C6-C18 arylene group, a substituted or unsubstituted C7-C18 arylalkylene group, or a substituted or unsubstituted C7-C18 alkylarylene group, and wherein Y is hydrogen, deuterium, Substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C1-C10 halogenated alkyl groups, substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted C2-C10 alkynyl groups, substituted or unsubstituted C1-C10 heteroalkyl groups, substituted or unsubstituted C6-C18 aryl groups, substituted or unsubstituted C7-C18 arylalkyl groups,Any one selected from substituted or unsubstituted C7-C18 alkylaryl groups, hydroxyl groups, or substituted or unsubstituted C1-C10 alkoxy groups, wherein m is an integer from 0 to 4, and when m is 2 or more, each Y is the same or different, and the D ring in the above structural formula 1-a is a substituted or unsubstituted 5-membered or 6-membered aliphatic hydrocarbon ring, wherein the D ring has 0 to 1 double bond, or contains 0 to 1 oxygen atom, or contains 0 to 1 carbonyl group (C=O) within the ring through a double bond between the oxygen atom and a carbon atom within the ring, and in the above structural formula 2, the substituent R, 11 is any one selected from hydrogen, deuterium, and substituted or unsubstituted C1-C5 alkyl groups, and the substituent R1 is any one selected from substituted or unsubstituted C1-C40 alkyl groups, substituted or unsubstituted C1-C40 halogenated alkyl groups, substituted or unsubstituted C2-C40 alkenyl groups, substituted or unsubstituted C2-C40 alkynyl groups, substituted or unsubstituted C6-C24 aryl groups, substituted or unsubstituted C7-C30 arylalkyl groups, substituted or unsubstituted C5-C45 aliphatic polycyclic cycloalkyl groups, and substituted or unsubstituted C1-C40 alkoxy groups, and in the above structural formula 3, substituents R9 and R 12 The groups are identical or different from each other and are each independently selected from hydrogen, deuterium, and substituted or unsubstituted C1-C5 alkyl groups; the linker L is selected from single bonds and substituted or unsubstituted C1-C30 alkylene groups; the mole fraction of the repeating unit represented by structural formula 1-a or structural formula 1-b in the polymer is in the range of 0.02 to 0.20, the mole fraction of the repeating unit represented by structural formula 2 is in the range of 0.30 to 0.80, and the mole fraction of the repeating unit represented by structural formula 3 is in the range of 0.10 to 0.50; and the 'substituted' in 'substituted or unsubstituted' in structural formulas 1-a, 1-b, 2, and 3 refers to deuterium, cyano group, halogen group, hydroxyl group, C1-C14 alkyl group, or C1-C14 halogenated group. It means being substituted with one or more substituents selected from the group consisting of alkyl groups, C2-C14 alkenyl groups, C6-C18 aryl groups, C7-C19 arylalkyl groups, C7-C19 alkylaryl groups, C1-C14 alkoxy groups, C1-C14 alkylsilyl groups, C6-C18 arylsilyl groups, and C6-C18 aryloxy groups. Claim 2 A polymer for photoresist according to claim 1, characterized in that the polymer additionally comprises a repeating unit represented by the following structural formula 4. [Structural Formula 4] In the above structural formula 4, substituent R12 is the same as defined in claim 1 above. Claim 3 delete Claim 4 A polymer for photoresist according to claim 1, characterized in that the repeating unit represented by structural formula 3 is produced by a reaction between the repeating unit represented by structural formula 4 below and an acrylic compound represented by chemical formula A. [Structural Formula 4] [Chemical Formula A] In the above Structural Formula 4 and Chemical Formula A, the linker L, substituents R9 and R 12 It is the same as defined in the first paragraph above. Claim 5 In claim 1, the weight average molecular weight of the polymer for the photoresist is 1,000 ≤ M w A polymer for photoresist characterized by having a range of ≤ 30,000. Claim 6 delete Claim 7 A polymer for photoresist according to claim 1, wherein R1 in structural formula 2 is selected from any one of a substituted or unsubstituted C4-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C25 arylalkyl group, a substituted or unsubstituted C6-C43 aliphatic polycyclic cycloalkyl group, or a substituted or unsubstituted C1-C35 alkoxy group. Claim 8 A polymer for photoresist according to claim 1, characterized in that the A ring, B ring, and C ring within the repeating unit (a) represented by structural formula 1-a or structural formula 1-b are each substituted or unsubstituted aliphatic hydrocarbon rings containing 0 to 1 double bond. Claim 9 A polymer for photoresist according to claim 1, characterized in that at least one of the A ring, B ring, and C ring within the repeating unit (a) represented by structural formula 1-a or structural formula 1-b is any one of the rings selected from structural formulas F-1 to F-4. Claim 10 A polymer for photoresist according to claim 1, characterized in that the D ring in structural formula 1-a is a substituted or unsubstituted six-membered or five-membered aliphatic hydrocarbon ring. Claim 11 In claim 1, the repeating unit represented by the above structural formula 1-a or structural formula 1-b; the repeating unit represented by structural formula 2; the repeating unit represented by structural formula 3; and the substituents R9 to R 1２ A polymer for photoresist characterized by each being hydrogen, deuterium, or a methyl group. Claim 12 A polymer for a photoresist according to claim 1, wherein the repeating unit represented by structural formula 1-a or structural formula 1-b is formed by the polymerization of an acrylic compound derived from any one compound selected from linestrenol, dihydroepiandrosterone, allylestrenol, methylandrostenediol, pregnenolone, kerenol, cholesterol, ergosterol, beta-sitosterol, lanosterol, 24-methylenecholesterol, campesterol, carnosol, 12-methyl ether of carnosic acid, rosmanol, and 20-deoxocarnosol. Claim 13 A polymer for photoresist according to claim 1, wherein the repeating unit represented by structural formula 1-a or structural formula 1-b is formed by the polymerization of any one of the compounds selected from <Compound 1> to <Compound 39> below. <Compound 1> <Compound 2> <Compound 3> <Compound 4> <Compound 5> <Compound 6> <Compound 7> <Compound 8> <Compound 9> <Compound 10> <Compound 11> <Compound 12> <Compound 13> <Compound 14> <Compound 15> <Compound 16> <Compound 17> <Compound 18> <Compound 19> <Compound 20> <Compound 21> <Compound 22> <Compound 23> <Compound 24> <Compound 25> <Compound 26> <Compound 27> <Compound 28> <Compound 29> <Compound 30> <Compound 31> <Compound 32> <Compound 33> <Compound 34> <Compound 35> <Compound 36> <Compound 37> <Compound 38> <Compound 39> Claim 14 In claim 1, the repeating unit represented by the above structural formula 2 is propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isobornyl (meth)acrylate, icosyl (meth)acrylate, butycosyl (meth)acrylate, adamanthyl (meth)acrylate, dicyclofentanyl (meth)acrylate, benzyl (meth)acrylate, phenoxybenzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, A polymer for photoresist characterized by being formed by the polymerization of any one compound selected from 2-ethoxyethyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, and 2-dodecylhexadecyl (meth)acrylate. Claim 15 A polymer for a photoresist according to claim 4, characterized in that the compound represented by the above chemical formula A is selected from any one of glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate, α-n-propylacrylate, α-n-butylacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, β-ethylglycidyl acrylate, β-ethylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, and α-ethylacrylate-6,7-epoxyheptyl. Claim 16 A photoresist composition comprising: a polymer for photoresist according to any one of claims 1, 2, 4, 5, 7 to 15; a photogenerator or photoinitiator; and a polymerizable compound comprising at least one double bond. Claim 17 A photoresist composition according to claim 16, characterized in that the photogenerator or photoinitiator in the photoresist composition comprises 0.1 to 30 weight% based on the total composition as 100. Claim 18 In claim 16, the polymerizable compound in the photoresist composition is an alkyl acrylate such as hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tetradecyl (meth)acrylate, and hexadecyl (meth)acrylate; A photoresist composition characterized by using one or more selected from the group consisting of alkyl methacrylate, ethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, acrylic acid, methacrylic acid, glycidyl acrylate, and styrene. Claim 19 A photoresist composition according to claim 16, characterized in that the content of the polymerizable compound comprises 1 to 90 parts by weight based on the total composition as 100. Claim 20 A photoresist composition comprising according to claim 16 may include an organic solvent, wherein the content of the organic solvent is 0 to 300 parts by weight based on the total content excluding the organic solvent being 100. Claim 21 A photoresist composition according to claim 16, characterized in that the photoresist composition has a viscosity of 40 cps or less and a solid ratio of 20% or more. Claim 22 In claim 16, the photoresist composition is characterized by being used in any one of the following devices selected from TFT-LCDs, color filters, organic light-emitting diodes (OLEDs), lighting devices, metal sensors, solar cells, integrated circuits, organic field-effect transistors (O-FETs), and organic thin-film transistors (O-TFTs). Claim 23 a) a step of polymerizing the following compounds a or b; compounds c; and compounds d; in the presence or absence of a solvent to produce a polymer comprising repeating units represented by structural formula 1-a or structural formula 1-b according to claim 1; repeating units represented by structural formula 2; and repeating units represented by structural formula 4 according to claim 2; and b) a step of reacting the polymer obtained in step a) with an acrylic compound represented by the following chemical formula A, wherein repeating units represented by structural formula 3 are produced by the reaction between the repeating units represented by structural formula 4 in the polymer obtained in step a) and the acrylic compound represented by chemical formula A. <Compound a> <Compound b> <Compound c> <Compound d> [Structural Formula 4] [Chemical Formula A] Here, compounds a to d, rings A to D, X, Y, m, linker L, R1, R9 to R12 in structural formula 4 and chemical formula A are the same as defined in structural formula 1-a, structural formula 1-b, and structural formulas 2 to 4 in claims 1 and 2.

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