KR20200064334A - Polyimide-based compound and composition including the same - Google Patents

Polyimide-based compound and composition including the same Download PDF

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KR20200064334A
KR20200064334A KR1020180150347A KR20180150347A KR20200064334A KR 20200064334 A KR20200064334 A KR 20200064334A KR 1020180150347 A KR1020180150347 A KR 1020180150347A KR 20180150347 A KR20180150347 A KR 20180150347A KR 20200064334 A KR20200064334 A KR 20200064334A
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polyimide
based compound
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integer
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KR102152075B1 (en
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도희진
허윤희
김세훈
김미애
김성현
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(주)켐이
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)

Abstract

In a polyimide-based compound and a photosensitive composition comprising the same, of the present invention, the polyimide-based compound includes a structure represented by chemical formula 1. The polyimide-based compound has excellent mechanical properties, heat resistance and chemical resistance.

Description

폴리이미드계 화합물 및 이를 포함하는 감광성 조성물{POLYIMIDE-BASED COMPOUND AND COMPOSITION INCLUDING THE SAME}A polyimide compound and a photosensitive composition comprising the same {POLYIMIDE-BASED COMPOUND AND COMPOSITION INCLUDING THE SAME}

본 발명은 폴리이미드계 화합물 및 이를 포함하는 감광성 조성물에 관한 것으로, 보다 구체적으로는 새로운 구조를 갖는 폴리이미드계 화합물 및 이를 포함하는 감광성 조성물에 관한 것이다.The present invention relates to a polyimide-based compound and a photosensitive composition comprising the same, and more particularly, to a polyimide-based compound having a new structure and a photosensitive composition comprising the same.

일반적으로, 폴리이미드는 주쇄에 헤테로 이미드 고리를 갖는 고분자로서, 테트라카르복실산과 디아민을 축중합시켜 제조된다. 폴리이미드는 우수한 광투과도를 갖고, 기계적 성질, 열적 특성 및 기질과의 접착력이 매우 우수하여 여러 기술분야에 널리 이용되고 있다. 특히, 폴리이미드는 열적 안정성이 높고 기계적 강도가 우수하여 반도체 소자의 표면보호막, 절연막으로 이용될 뿐만 아니라, TAB(tape automated bonding), CSP(chip scale package), WLP(wafer level package) 등 모듈화된 전자회로부품을 위해서도 이용되고 있으며 포토리소그래피 공정에서 감광성 고분자 화합물로도 이용되고 있다.Generally, polyimide is a polymer having a heteroimide ring in its main chain, and is prepared by condensation polymerization of tetracarboxylic acid and diamine. Polyimide has excellent light transmittance, has excellent mechanical properties, thermal properties, and adhesion to a substrate, and is widely used in various technical fields. In particular, polyimide has high thermal stability and excellent mechanical strength, and is not only used as a surface protection film or insulating film for semiconductor devices, but also modularized such as tape automated bonding (TAB), chip scale package (CSP), and wafer level package (WLP). It is also used for electronic circuit components and is used as a photosensitive polymer compound in photolithography processes.

폴리이미드를 이용하여 고분자층을 형성하는 방법으로는, 일반적인 유기용매에 용해시켜 사용하는 경우와 고분자 전구체 상태에서 유기막을 형성 후 고온의 열처리 과정을 통해 최종 고분자층을 형성하는 경우로 나눌 수 있다. 전자의 경우는 최종 고분자를 유기용매에 녹여서 바로 성막공정을 진행하여 저온의 용매 건조 과정을 통해 고분자층을 형성할 수 있으나, 용해도를 높이기 위해 도입된 고분자의 곁 사슬 등이 고분자층의 절연 특성 및 내화학성을 떨어뜨리는 단점이 있다.As a method of forming a polymer layer using polyimide, it can be divided into a case in which it is dissolved in a general organic solvent and used, and a case in which a final polymer layer is formed through a high temperature heat treatment after forming an organic film in a polymer precursor state. In the former case, the final polymer is dissolved in an organic solvent to immediately proceed with the film forming process to form a polymer layer through a low-temperature solvent drying process, but the side chains of the polymer introduced to increase the solubility and the insulating properties of the polymer layer and It has the disadvantage of deteriorating chemical resistance.

한편, 폴리이미드를 포함하는 감광성 조성물을 이용하여 패터닝된 고분자층을 제조하는 경우, 상기 감광성 조성물을 기판에 코팅하고 노광하면, 노광 부분에서 광중합이 일어나 전구체 분자 간에 가교가 형성되어 불용화되고, 다시 이를 유기용제로 현상하여 비노광부를 제거한 후 가열처리에 의해 이미드화 반응을 완결함으로써 원하는 패턴을 가진 고분자층을 수득하게 된다. On the other hand, when a patterned polymer layer is prepared by using a photosensitive composition containing polyimide, when the photosensitive composition is coated on a substrate and exposed, photopolymerization occurs in the exposed portion, crosslinking is formed between precursor molecules, and insoluble, again After developing this with an organic solvent to remove the non-exposed portion, the imidization reaction is completed by heat treatment to obtain a polymer layer having a desired pattern.

종래에 알려져 있는 많은 네가티브형 감광성 폴리이미드의 경우, 포지티브형에 비해 해상력이 좋지 않고, 공정 상 패턴의 제조에 있어 불량 발생 가능성이 높으며, 고해상도 및 고감도를 위해서 분자량을 증가시키는 데에 한계가 있으며, 이로 인해 기계적 물성이 저하되는 문제점이 있다.In the case of many negative photosensitive polyimides known in the prior art, the resolution is poor compared to the positive type, the probability of occurrence of defects is high in the production of process patterns, and there is a limit in increasing the molecular weight for high resolution and high sensitivity. Due to this, there is a problem that the mechanical properties are lowered.

본 발명의 일 목적은 기계적 특성이 우수하고 내열성, 내화학성이 우수한 고분자층 제조용 폴리이미드계 화합물을 제공하는 것이다.One object of the present invention is to provide a polyimide-based compound for producing a polymer layer having excellent mechanical properties and excellent heat resistance and chemical resistance.

본 발명의 다른 목적은 상기 폴리이미드계 화합물을 포함하는 감광성 조성물을 제공하는 것이다.Another object of the present invention is to provide a photosensitive composition comprising the polyimide-based compound.

본 발명의 일 목적을 위한 폴리이미드계 화합물은 하기 화학식 1로 나타낸다. The polyimide-based compound for one purpose of the present invention is represented by Formula 1 below.

[화학식 1][Formula 1]

Figure pat00001
Figure pat00001

상기 화학식 1에서, Ra 는 하기 화학식 2로 나타내고,In Chemical Formula 1, Ra is represented by Chemical Formula 2 below,

[화학식 2][Formula 2]

Figure pat00002
Figure pat00002

Rb는 -C(=O)OH 또는 하기 화학식 3으로 나타내고,Rb is represented by -C(=O)OH or Formula 3 below,

[화학식 3][Formula 3]

Figure pat00003
Figure pat00003

상기 화학식 2 및 3에서,In Chemical Formulas 2 and 3,

R1 및 R2 는 각각 독립적으로 수소 또는 C1-6 알킬기를 나타내고,R 1 and R 2 each independently represent hydrogen or a C 1-6 alkyl group,

a, b, d 및 e는 각각 독립적으로 1 내지 5의 정수를 나타내고,a, b, d and e each independently represent an integer of 1 to 5,

W1 및 W2는 각각 독립적으로 산소원자 또는 단결합을 나타내고,W 1 and W 2 each independently represent an oxygen atom or a single bond,

상기 화학식 2의 L은 C5-10 아릴렌, C1-6 알킬렌, C3-6 알케닐렌, C3-6 알키닐렌, C3-7 헤테로아릴렌, C5-10사이클로알킬렌, C3-10 불포화탄화수소고리 또는 C3-7 불포화헤테로고리를 나타내고,L of Formula 2 is C 5-10 arylene, C 1-6 alkylene, C 3-6 alkenylene, C 3-6 alkynylene, C 3-7 heteroarylene, C 5-10 cycloalkylene, Represents a C 3-10 unsaturated hydrocarbon ring or C 3-7 unsaturated heterocycle,

상기 화학식 1에서, Q1, Q2 및 Q3는 각각 독립적으로

Figure pat00004
,
Figure pat00005
,
Figure pat00006
,
Figure pat00007
,
Figure pat00008
,
Figure pat00009
,
Figure pat00010
,
Figure pat00011
,
Figure pat00012
,
Figure pat00013
,
Figure pat00014
또는
Figure pat00015
를 나타내며,In Formula 1, Q 1 , Q 2 and Q 3 are each independently
Figure pat00004
,
Figure pat00005
,
Figure pat00006
,
Figure pat00007
,
Figure pat00008
,
Figure pat00009
,
Figure pat00010
,
Figure pat00011
,
Figure pat00012
,
Figure pat00013
,
Figure pat00014
or
Figure pat00015
Represents

Y 는

Figure pat00016
,
Figure pat00017
,
Figure pat00018
,
Figure pat00019
,
Figure pat00020
,
Figure pat00021
,
Figure pat00022
,
Figure pat00023
,
Figure pat00024
,
Figure pat00025
,
Figure pat00026
,
Figure pat00027
,
Figure pat00028
,
Figure pat00029
,
Figure pat00030
또는
Figure pat00031
를 나타내며,Y is
Figure pat00016
,
Figure pat00017
,
Figure pat00018
,
Figure pat00019
,
Figure pat00020
,
Figure pat00021
,
Figure pat00022
,
Figure pat00023
,
Figure pat00024
,
Figure pat00025
,
Figure pat00026
,
Figure pat00027
,
Figure pat00028
,
Figure pat00029
,
Figure pat00030
or
Figure pat00031
Represents

0 ≤ x ≤ 0.4이고 0.1 ≤ y ≤ 0.9이며 0 ≤ z ≤ 0.5이되, x와 z는 동시에 0이 될 수 없고, x+y+z=1 이다.0 ≤ x ≤ 0.4, 0.1 ≤ y ≤ 0.9, and 0 ≤ z ≤ 0.5, but x and z cannot be 0 at the same time, and x+y+z=1.

본 발명에 따른 폴리이미드계 화합물은 하기 화학식 1a로 나타내는 단위구조를 포함한다.The polyimide-based compound according to the present invention includes a unit structure represented by Formula 1a below.

[화학식 1a][Formula 1a]

Figure pat00032
Figure pat00032

상기 화학식 1a에서, Ra 는 하기 화학식 2로 나타내고,In Chemical Formula 1a, Ra is represented by Chemical Formula 2 below,

[화학식 2][Formula 2]

Figure pat00033
Figure pat00033

상기 화학식 2에서, R1은 수소 또는 C1-6 알킬기를 나타내고, a 및 b는 각각 독립적으로 1 내지 5의 정수를 나타내고, W1는 산소원자 또는 단결합을 나타내며, L은 C5-10 아릴렌, C1-6 알킬렌, C3-6 알케닐렌, C3-6 알키닐렌, C3-7 헤테로아릴렌, C5-10사이클로알킬렌, C3-10 불포화탄화수소고리 또는 C3-7 불포화헤테로고리를 나타내고,In Formula 2, R 1 represents hydrogen or a C 1-6 alkyl group, a and b each independently represent an integer of 1 to 5, W 1 represents an oxygen atom or a single bond, and L is C 5-10 Arylene, C 1-6 alkylene, C 3-6 alkenylene, C 3-6 alkynylene, C 3-7 heteroarylene, C 5-10 cycloalkylene, C 3-10 unsaturated hydrocarbon ring or C 3 -7 represents an unsaturated heterocycle,

Q2는

Figure pat00034
,
Figure pat00035
,
Figure pat00036
,
Figure pat00037
,
Figure pat00038
,
Figure pat00039
,
Figure pat00040
,
Figure pat00041
,
Figure pat00042
,
Figure pat00043
,
Figure pat00044
또는
Figure pat00045
를 나타내며,Q 2 is
Figure pat00034
,
Figure pat00035
,
Figure pat00036
,
Figure pat00037
,
Figure pat00038
,
Figure pat00039
,
Figure pat00040
,
Figure pat00041
,
Figure pat00042
,
Figure pat00043
,
Figure pat00044
or
Figure pat00045
Represents

y는 1 이상의 정수를 나타낸다.y represents an integer of 1 or more.

일 실시예에서, 상기 폴리이미드계 화합물은 하기 화학식 1b 및 하기 화학식 1c로 나타내는 단위구조 중 적어도 어느 하나를 더 포함할 수 있다.In one embodiment, the polyimide-based compound may further include at least one of the unit structures represented by the following Chemical Formula 1b and the following Chemical Formula 1c.

[화학식 1b][Formula 1b]

Figure pat00046
Figure pat00046

[화학식 1c][Formula 1c]

Figure pat00047
Figure pat00047

상기 화학식 1b 및 1c에서, Q1 및 Q3은 각각 독립적으로

Figure pat00048
,
Figure pat00049
,
Figure pat00050
,
Figure pat00051
,
Figure pat00052
,
Figure pat00053
,
Figure pat00054
,
Figure pat00055
,
Figure pat00056
,
Figure pat00057
,
Figure pat00058
또는
Figure pat00059
를 나타내고,In Formulas 1b and 1c, Q 1 and Q 3 are each independently
Figure pat00048
,
Figure pat00049
,
Figure pat00050
,
Figure pat00051
,
Figure pat00052
,
Figure pat00053
,
Figure pat00054
,
Figure pat00055
,
Figure pat00056
,
Figure pat00057
,
Figure pat00058
or
Figure pat00059
And

상기 화학식 1b에서, Y 는

Figure pat00060
,
Figure pat00061
,
Figure pat00062
,
Figure pat00063
,
Figure pat00064
,
Figure pat00065
,
Figure pat00066
,
Figure pat00067
,
Figure pat00068
,
Figure pat00069
,
Figure pat00070
,
Figure pat00071
,
Figure pat00072
,
Figure pat00073
,
Figure pat00074
또는
Figure pat00075
를 나타내고,In the above formula 1b, Y is
Figure pat00060
,
Figure pat00061
,
Figure pat00062
,
Figure pat00063
,
Figure pat00064
,
Figure pat00065
,
Figure pat00066
,
Figure pat00067
,
Figure pat00068
,
Figure pat00069
,
Figure pat00070
,
Figure pat00071
,
Figure pat00072
,
Figure pat00073
,
Figure pat00074
or
Figure pat00075
And

상기 화학식 1c의 Rb는 -C(=O)OH 또는 하기 화학식 3으로 나타내고,Rb of Formula 1c is represented by -C(=O)OH or Formula 3 below,

[화학식 3][Formula 3]

Figure pat00076
Figure pat00076

상기 화학식 3에서, W2는 산소원자 또는 단결합을 나타내고, In Chemical Formula 3, W 2 represents an oxygen atom or a single bond,

d 및 e는 각각 독립적으로 1 내지 5의 정수를 나타내고,d and e each independently represent an integer of 1 to 5,

x 및 z는 각각 독립적으로 1 이상의 정수를 나타낸다.x and z each independently represent an integer of 1 or more.

일 실시예에서, 상기 폴리이미드계 화합물에서 x:y=1:9 내지 4:6이고, y:z=1:9 내지 5:5이며, x:z=4:6 내지 5:5일 수 있다.In one embodiment, in the polyimide-based compound, x:y=1:9 to 4:6, y:z=1:9 to 5:5, and x:z=4:6 to 5:5. have.

일 실시예에서, 상기 화학식 1a로 나타내는 단위구조는 하기 화학식 A로 나타내고, 상기 화학식 1c로 나타내는 단위구조는 하기 화학식 B 및 하기 화학식 D 중 적어도 어느 하나를 나타낼 수 있다.In one embodiment, the unit structure represented by Formula 1a is represented by Formula A, and the unit structure represented by Formula 1c can represent at least one of Formula B and Formula D below.

[화학식 A] [Formula A]

Figure pat00077
Figure pat00077

[화학식 B][Formula B]

Figure pat00078
Figure pat00078

[화학식 D][Formula D]

Figure pat00079
Figure pat00079

상기 화학식 A, B 및 D에서 n은 각각 독립적으로 1 이상의 정수를 나타낸다.In Formulas A, B, and D, each independently represents an integer of 1 or more.

본 발명에 따른 감광성 조성물은 상기에서 설명한 폴리이미드계 화합물, 폴리아믹산 및 이미드화 촉매를 포함한다.The photosensitive composition according to the present invention includes the polyimide-based compound, polyamic acid and imidation catalyst described above.

일 실시예에서, 상기 이미드화 촉매는 피리딘(pyridine), 이소퀴놀린(isoquinoline), β퀴놀린(β, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, N-비닐피롤리돈, N-메틸카프로락탐, 디메틸술폭시드, 테트라메틸요소, 피리딘, 디메틸술폰, 헥사메틸술폭시드, m-크레졸, γ-부티로락톤, 에틸셀로솔브, 부틸셀로솔브, 에틸카르비톨, 부틸카르비톨, 에틸카르비톨 아세테이트, 부틸카르비톨 아세테이트, 에틸렌글리콜, 프로필렌글리콜 모노메틸 에테르 아세테이트(PGMEA), 젖산에틸, 젖산부틸, 시클로헥사논, 및 시클로펜타논 중에서 선택된 1종 이상을 포함할 수 있다.In one embodiment, the imidization catalyst is pyridine, isoquinoline, β-quinoline (β, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N -Vinylpyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, At least one selected from ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone. It may include.

일 실시예에서, 상기 감광성 조성물은 1,8-다이아자바이사이클로[5,4,0]운덱-7-엔(1,8-Diazabicyclo[5,4,0]undec-7-ene), 1,5-다이아자바이사이클로(4,3,0)-논-5-엔(1,5-Diazabicyclo(4,3,0)-non-5-ene), 트리에틸아민(trimethylamine), N-메틸이미다졸(Nmethylimidazole) 및 다이아이소프로필에틸렌아민(diisopropylethylamine)중에서 선택된 1종 이상의 반응촉매를 더 포함할 수 있다.In one embodiment, the photosensitive composition is 1,8-diazabicyclo[5,4,0]undec-7-ene (1,8-Diazabicyclo[5,4,0]undec-7-ene), 1, 5-diazabicyclo(4,3,0)-non-5-ene (1,5-Diazabicyclo(4,3,0)-non-5-ene), triethylamine, N-methyl It may further include at least one reaction catalyst selected from midazole (Nmethylimidazole) and diisopropylethylamine.

상기에서 설명한 본 발명의 폴리이미드계 화합물 및 이를 포함하는 감광성 조성물에 따르면, 본 발명의 폴리이미드계 화합물은 광에 대한 고해상도 및 고감도를 가질 뿐만 아니라, 기계적, 화학적으로 우수한 제반 물성을 가지며, 특히 광학적으로 투명성이 우수하면서도 저온 경화성이 우수하다. According to the polyimide-based compound of the present invention described above and the photosensitive composition comprising the same, the polyimide-based compound of the present invention not only has high resolution and high sensitivity to light, but also has excellent mechanical and chemical properties, especially optical As it is excellent in transparency, it is also excellent in low temperature curing properties.

본 발명은 산가(Acid value)를 가지는 다양한 무수물을 도입하여 산가가 있는 구조를 포함하기 때문에 알칼리 현상액에 탁월한 현상성을 가진다. Since the present invention includes a structure having an acid value by introducing various anhydrides having an acid value, it has excellent developability in an alkali developer.

본 발명은 위와 같은 탁월한 현상성으로 인해 고해상도, 고감도 패턴 형성이 가능하다. The present invention is capable of forming a high resolution and high sensitivity pattern due to the excellent developability as described above.

본 출원에서 사용한 용어는 단지 특정한 실시 예를 설명하기 위해 사용된 것으로서 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terms used in the present application are only used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "include" or "have" are intended to indicate the presence of features, steps, actions, components, parts or combinations thereof described in the specification, one or more other features or steps. It should be understood that it does not preclude the existence or addition possibility of the operation, components, parts or combinations thereof.

다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. Terms, such as those defined in a commonly used dictionary, should be interpreted as having meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. Does not.

본 발명의 고분자 화합물은 서로 다른 2 이상의 단위구조들이 중합된 중합체를 의미하는 것으로, 단위구조 A와 단위구조의 공중합체인 "-(A)x-(B)y-" 표현은 -(A-A-A-B-B-B)- 등과 같은 순차적 결합 공중합체뿐만 아니라, -(A-B-A-A-B-A)-, -(A-A-B-B)-, -(A-A-A-B-A-A-B)- 등 다양한 형태로 랜덤하게 공중합된 것도 포함하는 것으로 정의한다. 이때, -(A)x-(B)y- 에서 x, y는 A와 B의 비율을 의미한다. 상기에서는 단위구조 A, B를 일례로 들었으나, A, B, C, D 등을 포함하는 경우에도 동일한 의미를 가지므로, 중복되는 상세한 설명은 생략한다.The polymer compound of the present invention means a polymer in which two or more different unit structures are polymerized, and the expression "-(A)x-(B)y-", which is a copolymer of unit structure A and unit structure, is -(AAABBB)- It is defined as including not only sequential binding copolymers such as, but also randomly copolymerized in various forms such as -(ABAABA)-, -(AABB)-, -(AAABAAB)-. At this time, x, y in -(A)x-(B)y- means the ratio of A and B. In the above, the unit structures A and B have been exemplified, but the same detailed meaning is also included when A, B, C, D, etc. are included, and thus, detailed descriptions thereof will be omitted.

본 발명에서 사용하는 용어인 "C1", "C2" 등은 탄소수를 의미하는 것으로서, 예를 들어 "C1-5의 알킬기"는 탄소수 1 내지 5를 갖는 알킬기를 의미한다.The terms "C 1 ", "C 2 ", and the like used in the present invention mean carbon number, and for example, "C 1-5 alkyl group" means an alkyl group having 1 to 5 carbon atoms.

본 발명에서, 알킬기는 선형(linear) 포화탄화수소기 또는 분지형(branched) 포화탄화수소기를 의미하는 것으로, 메틸, 에틸, n-프로필, 이소프로필, n-부틸, sec-부틸, 이소부틸, tert-부틸 등을 포함한다.In the present invention, the alkyl group means a linear saturated hydrocarbon group or a branched saturated hydrocarbon group, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- Butyl and the like.

본 발명에서, 알킬렌은 상기와 같이 정의된 알킬기로부터 유도된 2가의 작용기를 의미하는 것이다.In the present invention, alkylene means a divalent functional group derived from an alkyl group defined as above.

본 발명에서, 아릴기는 일환 방향족 또는 다환 방향족과, 일환 또는 다환 방향족에 포화탄화수소 고리가 융합된 구조도 포함한다. 아릴기는 페닐기, 나프탈렌일, 테트라하이드로나프탈렌일, 바이페닐 등을 포함한다.In the present invention, the aryl group also includes a monocyclic or polycyclic aromatic and a structure in which a saturated hydrocarbon ring is fused to a monocyclic or polycyclic aromatic. The aryl group includes a phenyl group, naphthalenyl, tetrahydronaphthalenyl, biphenyl, and the like.

본 발명에서 헤테로아릴기는 상기 아릴기에서 적어도 1개 이상의 탄소원자가 질소(N), 산소(O) 또는 황(S)으로 치환된 일환 또는 다환의 헤테로 고리를 의미하는 것이다. 헤테로아릴기는, 피리딘일, 퓨란일, 피롤릴, 티오펜일, 티아졸릴, 이소티아졸릴, 이미다졸릴, 트리아졸릴, 테트라졸릴, 피라졸릴, 옥사졸일, 이소옥사졸일, 피라진일, 피리다진일, 피리미딘일, 이소퀴놀린일, 카바졸릴, 벤조옥사졸일, 벤조다이옥솔일, 벤조다이옥사졸일, 벤조다이옥신일, 벤조티아졸릴, 벤조이미다졸릴, 디하이드로벤조티오펜일, 벤조티오펜일, 퀴놀린일, 인돌릴, 벤조퓨란일, 디하이드로벤조퓨란일, 퓨린일, 인돌리진일, 크로만일, 크로멘일, 디하이드로벤조다이옥신일 등을 포함한다.In the present invention, the heteroaryl group means a monocyclic or polycyclic heterocycle in which at least one carbon atom is substituted with nitrogen (N), oxygen (O) or sulfur (S) in the aryl group. Heteroaryl groups are pyridinyl, furanyl, pyrrolyl, thiophyl, thiazolyl, isothiazolyl, imidazolyl, triazolyl, tetrazolyl, pyrazolyl, oxazolyl, isooxazolyl, pyrazinyl, pyridazinyl , Pyrimidinyl, isoquinolinyl, carbazolyl, benzooxazolyl, benzodioxolyl, benzodioxazolyl, benzodioxinyl, benzothiazolyl, benzoimidazolyl, dihydrobenzothiophenyl, benzothiophenyl, Quinolinyl, indolyl, benzofuranyl, dihydrobenzofuranyl, purinyl, indolizinyl, chromanyl, chromanyl, dihydrobenzodioxinyl, and the like.

본 발명에서, 아릴렌 및 헤테로아릴렌 각각은 상기와 같이 정의된 아릴기, 헤테로아릴기로부터 유도된 2가의 작용기를 의미하는 것이다.In the present invention, each of arylene and heteroarylene refers to an aryl group as defined above and a divalent functional group derived from a heteroaryl group.

본 발명에서, 사이클로알킬렌은 고리를 포함하는 명시된 수의 탄소원자를 일반적으로 갖는 포화탄화수소 고리인 사이클로알킬에서 유도된 2가의 작용기를 의미하는 것으로, 일환 및 다환을 모두 포함하는 의미이다. 사이클로알킬기는, 사이클로헥실, 사이클로헵탄일, 사이클로옥탄일, 테트라하이드로나프탈렌일 등을 포함하고, 사이클로알킬렌은 이들로부터 유도된 2가의 작용기를 말한다.In the present invention, cycloalkylene refers to a divalent functional group derived from cycloalkyl, which is a saturated hydrocarbon ring generally having a specified number of carbon atoms including a ring, which includes both monocyclic and polycyclic. Cycloalkyl groups include cyclohexyl, cycloheptanyl, cyclooctanyl, tetrahydronaphthalenyl, and the like, and cycloalkylene refers to divalent functional groups derived therefrom.

본 발명에서, 불포화탄화수소고리는 상기에서 정의한 아릴기와 사이클로알킬기를 제외하고, 적어도 1개 이상의 탄소 사이의 이중결합 또는 삼중결합을 포함하는 2가의 고리를 의미하는 것이다. 불포화탄화수소고리의 예로서는, 사이클로프로펜, 사이클로부텐, 사이클로헥센 등에서 유도된 2가의 작용기인 사이클로알케닐렌, 사이클로헥사인 등에서 유도된 2가의 작용기인 사이클로알카인렌 등을 들 수 있다.In the present invention, an unsaturated hydrocarbon ring means a divalent ring including a double bond or a triple bond between at least one or more carbons, except for the aryl group and cycloalkyl group defined above. Examples of the unsaturated hydrocarbon ring include cycloalkenylene, a divalent functional group derived from cyclopropene, cyclobutene, cyclohexene, etc., cycloalkaneene, which is a divalent functional group derived from cyclohexanine, and the like.

본 발명에서, 불포화헤테로고리는 상기 불포화탄화수소고리에서 적어도 1개 이상의 탄소원자가 N, O 또는 S으로 치환된 고리를 의미하는 것으로, 2가의 작용기를 의미하는 것이다.In the present invention, the unsaturated heterocyclic ring means a ring in which the at least one carbon atom is substituted with N, O or S in the unsaturated hydrocarbon ring, and refers to a divalent functional group.

폴리이미드계 화합물Polyimide compound

본 발명에 따른 폴리이미드계 화합물은 하기 화학식 1a로 나타내는 단위구조를 포함한다.The polyimide-based compound according to the present invention includes a unit structure represented by Formula 1a below.

[화학식 1a][Formula 1a]

Figure pat00080
Figure pat00080

상기 화학식 1a에서, Ra 는 하기 화학식 2로 나타낸다.In the above formula 1a, Ra is represented by the following formula (2).

[화학식 2][Formula 2]

Figure pat00081
Figure pat00081

상기 화학식 2에서, R1은 수소 또는 C1-6 알킬기를 나타내고, a 및 b는 각각 독립적으로 1 내지 5의 정수를 나타내고, W1는 산소원자 또는 단결합을 나타내며, L은 C5-10 아릴렌, C1-6 알킬렌, C3-6 알케닐렌, C3-6 알키닐렌, C3-7 헤테로아릴렌, C5-10사이클로알킬렌, C3-10 불포화탄화수소고리 또는 C3-7 불포화헤테로고리를 나타낸다.In Formula 2, R 1 represents hydrogen or a C 1-6 alkyl group, a and b each independently represent an integer of 1 to 5, W 1 represents an oxygen atom or a single bond, and L is C 5-10 Arylene, C 1-6 alkylene, C 3-6 alkenylene, C 3-6 alkynylene, C 3-7 heteroarylene, C 5-10 cycloalkylene, C 3-10 unsaturated hydrocarbon ring or C 3 -7 It represents an unsaturated heterocycle.

L은 적어도 1개 이상의 이중 결합을 포함하되 2가의 불포화탄화수소 결합부를 의미하는 것으로, 선형 구조뿐만 아니라 고리형 구조를 포함할 수 있다. L의 구체적인 예로서는, 페닐렌, 에틸렌 등을 들 수 있다.L includes at least one double bond, but refers to a divalent unsaturated hydrocarbon bond, and may include a cyclic structure as well as a linear structure. Examples of L include phenylene, ethylene, and the like.

상기 화학식 1a에서, Q2는 산무수물 또는 그 유도체로부터 유도되는 4가의 유기기를 의미하는 것으로,

Figure pat00082
,
Figure pat00083
,
Figure pat00084
,
Figure pat00085
,
Figure pat00086
,
Figure pat00087
,
Figure pat00088
,
Figure pat00089
,
Figure pat00090
,
Figure pat00091
,
Figure pat00092
또는
Figure pat00093
를 나타낸다.In Formula 1a, Q 2 refers to a tetravalent organic group derived from an acid anhydride or a derivative thereof,
Figure pat00082
,
Figure pat00083
,
Figure pat00084
,
Figure pat00085
,
Figure pat00086
,
Figure pat00087
,
Figure pat00088
,
Figure pat00089
,
Figure pat00090
,
Figure pat00091
,
Figure pat00092
or
Figure pat00093
Indicates.

상기 화학식 1a로 나타내는 단위구조를 포함함으로써 본 발명에 따른 폴리이미드계 화합물을 이용한 감광성 조성물로 패턴을 형성할 때 노광 후 현상 공정에서 알칼리 현상액에 대한 우수한 현상성을 확보할 수 있다. When the pattern is formed of a photosensitive composition using the polyimide-based compound according to the present invention by including the unit structure represented by Formula 1a, it is possible to secure excellent developability for an alkali developer in a post-exposure development process.

일 실시예에서 본 발명에 따른 폴리이미드계 화합물은 화학식 1a로 나타내는 단위구조와 함께, 하기 화학식 1b로 나타내는 단위구조 및 하기 화학식 1c로 나타내는 단위구조 중 적어도 어느 하나를 더 포함할 수 있다.In one embodiment, the polyimide-based compound according to the present invention may further include at least one of a unit structure represented by the following formula 1b and a unit structure represented by the following formula 1c together with the unit structure represented by Formula 1a.

[화학식 1b][Formula 1b]

Figure pat00094
Figure pat00094

[화학식 1c][Formula 1c]

Figure pat00095
Figure pat00095

상기 화학식 1b 및 1c에서, Q1 및 Q3은 각각 독립적으로

Figure pat00096
,
Figure pat00097
,
Figure pat00098
,
Figure pat00099
,
Figure pat00100
,
Figure pat00101
,
Figure pat00102
,
Figure pat00103
,
Figure pat00104
,
Figure pat00105
,
Figure pat00106
또는
Figure pat00107
를 나타낸다.In Formulas 1b and 1c, Q 1 and Q 3 are each independently
Figure pat00096
,
Figure pat00097
,
Figure pat00098
,
Figure pat00099
,
Figure pat00100
,
Figure pat00101
,
Figure pat00102
,
Figure pat00103
,
Figure pat00104
,
Figure pat00105
,
Figure pat00106
or
Figure pat00107
Indicates.

상기 화학식 1b에서, Y 는

Figure pat00108
,
Figure pat00109
,
Figure pat00110
,
Figure pat00111
,
Figure pat00112
,
Figure pat00113
,
Figure pat00114
,
Figure pat00115
,
Figure pat00116
,
Figure pat00117
,
Figure pat00118
,
Figure pat00119
,
Figure pat00120
,
Figure pat00121
,
Figure pat00122
또는
Figure pat00123
를 나타낸다.In the above formula 1b, Y is
Figure pat00108
,
Figure pat00109
,
Figure pat00110
,
Figure pat00111
,
Figure pat00112
,
Figure pat00113
,
Figure pat00114
,
Figure pat00115
,
Figure pat00116
,
Figure pat00117
,
Figure pat00118
,
Figure pat00119
,
Figure pat00120
,
Figure pat00121
,
Figure pat00122
or
Figure pat00123
Indicates.

상기 화학식 1c의 Rb는 -C(=O)OH 또는 하기 화학식 3으로 나타낸다.Rb of Formula 1c is represented by -C(=O)OH or Formula 3 below.

[화학식 3][Formula 3]

Figure pat00124
Figure pat00124

상기 화학식 3에서, W2는 산소원자 또는 단결합을 나타내고, d 및 e는 각각 독립적으로 1 내지 5의 정수를 나타낸다.In Chemical Formula 3, W 2 represents an oxygen atom or a single bond, and d and e each independently represent an integer of 1 to 5.

상기 화학식 1b로 나타내는 단위구조는 폴리이미드 구조의 범용 골격구조로서, 상기 화학식 1b로 나타내는 단위구조를 포함함으로써 본 발명에 따른 폴리이미드계 화합물이 전체적으로 범용 폴리이미드 구조 및 물성을 가질 수 있다.The unit structure represented by Formula 1b is a general-purpose skeleton structure of a polyimide structure, and the polyimide-based compound according to the present invention may have a general-purpose polyimide structure and physical properties by including the unit structure represented by Formula 1b.

또한, 상기 화학식 1c로 나타내는 단위구조는 상기 화학식 1c로 나타내는 단위구조에서 상기 화학식 1a로 나타내는 단위구조로 유도할 때 일부가 잔류하는 경우 본 발명에 따른 폴리이미드계 화합물에 포함될 수 있다.In addition, the unit structure represented by the formula (1c) may be included in the polyimide-based compound according to the present invention when a portion of the unit structure represented by the formula (1c) is derived from the unit structure represented by the formula (1a).

본 발명에서의 상기 화학식 1a, 1b 및 1c로 나타내는 단위구조들을 포함하는 폴리이미드계 화합물은 화학식 1로 나타내는 구조를 포함한다.The polyimide-based compound comprising the unit structures represented by Formulas 1a, 1b, and 1c in the present invention includes a structure represented by Formula 1.

[화학식 1][Formula 1]

Figure pat00125
Figure pat00125

상기 화학식 1에서의 Q1 내지 Q3, Y, Ra 및 y는 각각 상기 화학식 1a, 1b 및 1c에서 설명한 것과 실질적으로 동일하다. 따라서, 중복되는 상세한 설명은 생략한다.In Formula 1, Q 1 to Q 3 , Y, Ra and y are substantially the same as those described in Formulas 1a, 1b, and 1c, respectively. Therefore, detailed description of overlapping is omitted.

상기 화학식 1에서, x+y+z=1이되, 0 ≤ x ≤ 0.4이고 0.1 ≤ y ≤ 0.9이며 0 ≤ z ≤ 0.5이되, x와 z는 동시에 0이 될 수 없다.In Chemical Formula 1, x+y+z=1, but 0 ≤ x ≤ 0.4, 0.1 ≤ y ≤ 0.9, and 0 ≤ z ≤ 0.5, but x and z cannot be simultaneously 0.

일 실시예에서, Q1 내지 Q3은 서로 동일할 수 있다.In one embodiment, Q 1 to Q 3 may be the same as each other.

이와 달리, Q1 내지 Q3이 서로 다를 수 있다.Alternatively, Q 1 to Q 3 may be different.

상기 화학식 1에서, 상기 화학식 1a로 나타내는 단위구조가 필수 구조이고, 0.1 ≤ y ≤ 0.9 조건에서 알칼리 현상액에 탁원한 현상성을 구현할 수 있다. 또한, 상기 화학식 1b로 나타내는 단위구조가 0 ≤ x ≤ 0.4 조건을 만족함으로써 범용 폴리이미드의 고유의 구조 및 물성을 유지할 수 있다.In the formula (1), the unit structure represented by the formula (1a) is an essential structure, and in 0.1 ≤ y ≤ 0.9 conditions, it is possible to implement excellent developability in an alkaline developer. In addition, the unit structure represented by Chemical Formula 1b satisfies the condition of 0 ≤ x ≤ 0.4, thereby maintaining the inherent structure and physical properties of the general-purpose polyimide.

일 실시예에서, 상기 화학식 1로 나타내는 구조를 갖는 화합물은, 하기 화학식 4로 나타내는 구조를 포함할 수 있다.In one embodiment, the compound having a structure represented by Formula 1 may include a structure represented by Formula 4 below.

[화학식 4][Formula 4]

Figure pat00126
Figure pat00126

상기 화학식 4에서, Q1, Q2 및 Ra 각각은 상기 화학식 1a 및 1b에서 설명한 것과 실질적으로 동일하다. 상기 화학식 2에서는, x+y=1이되, 0.1 ≤ x ≤ 0.4이고 0.6 ≤ y ≤ 0.9일 수 있다.In Formula 4, Q 1 , Q 2 and Ra are each substantially the same as those described in Formulas 1a and 1b. In Chemical Formula 2, x+y=1, but may be 0.1≦x≦0.4 and 0.6≦y≦0.9.

일 실시예에서, 상기 화학식 1로 나타내는 구조를 갖는 화합물은 하기 화학식 5로 나타내는 구조를 포함할 수 있다.In one embodiment, the compound having a structure represented by Formula 1 may include a structure represented by Formula 5 below.

[화학식 5][Formula 5]

Figure pat00127
Figure pat00127

상기 화학식 5에서, Q2, Q3, Ra, 및 Rb 각각은 상기 화학식 1a 및 1c에서 설명한 것과 실질적으로 동일하다. 상기 화학식 5에서는, y+z=1이되, 0.1 ≤ z ≤ 0.4이고 0.6 ≤ y ≤ 0.9일 수 있다.In Formula 5, each of Q 2 , Q 3 , Ra, and Rb is substantially the same as described in Formulas 1a and 1c. In Chemical Formula 5, y+z=1, but may be 0.1≦z≦0.4 and 0.6≦y≦0.9.

상기 화학식 1로 나타내는 구조를 포함하는 폴리이미드계 화합물은 중량평균분자량은 1,000 내지 100,000인 것이 바람직하다. 또한, 유리전이온도는 200 내지 400℃인 것이 바람직하다. 중량평균분자량이 1,000 미만으로 너무 낮을 경우 충분한 기계적, 열적 안정성을 발휘하지 못할 수 있고, 100,000을 초과하여 너무 높을 경우 박막코팅 및 고해상도, 고감도의 구현이 어려워질 수 있다. 또한, 유리전이온도가 200℃미만으로 너무 낮을 경우 열적 안정성이 떨어져 후속고열고압 처리공정에서의 신뢰성 확보가 어려워질 수 있고, 400℃를 초과하여 너무 높을 경우 현상성이 떨어질 수 있다.The polyimide-based compound containing the structure represented by Chemical Formula 1 preferably has a weight average molecular weight of 1,000 to 100,000. In addition, the glass transition temperature is preferably 200 to 400°C. If the weight-average molecular weight is too low (below 1,000), sufficient mechanical and thermal stability may not be exhibited, and if it is too high (above 100,000), thin film coating, high resolution, and high sensitivity may be difficult to implement. In addition, if the glass transition temperature is too low, less than 200°C, thermal stability may drop and reliability in a subsequent high-temperature high-pressure treatment process may be difficult, and developability may be deteriorated when the temperature exceeds 400°C.

상기 화학식 1로 나타내는 구조를 포함하는 폴리이미드계 화합물은, i선 파장에서의 투과율이 70%이상일 수 있다.The polyimide-based compound including the structure represented by Chemical Formula 1 may have a transmittance of 70% or more at an i-ray wavelength.

감광성 조성물Photosensitive composition

본 발명의 감광성 조성물은 상기 화학식 1로 나타내는 구조를 포함하는 폴리이미드계 화합물과, 폴리아믹산을 포함한다.The photosensitive composition of the present invention includes a polyimide-based compound having a structure represented by Formula 1 and a polyamic acid.

상기 화학식 1로 나타내는 구조를 포함하는 폴리이미드계 화합물은, 감광성 조성물의 고형분 성분(용매 제외 부분) 100 중량% 중에서 1 내지 99 중량%일 수 있다.The polyimide-based compound comprising the structure represented by Chemical Formula 1 may be 1 to 99% by weight in 100% by weight of the solid component (excluding the solvent) of the photosensitive composition.

상기 폴리아믹산은 통상적으로 감광성 조성물을 제조하는데 이용되는 폴리아믹산은 특별히 제한 없이 이용할 수 있다.The polyamic acid is a polyamic acid that is usually used to prepare a photosensitive composition can be used without particular limitation.

상기 감광성 조성물은, 폴리아믹산 외에 이미드화 촉매 및 탈수제 중에서 선택된 1종 이상을 더 포함할 수 있는데, 상기 이미드화 촉매의 예로서는, 피리딘(pyridine), 이소퀴놀린(isoquinoline), β퀴놀린(β, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, N-비닐피롤리돈, N-메틸카프로락탐, 디메틸술폭시드, 테트라메틸요소, 피리딘, 디메틸술폰, 헥사메틸술폭시드, m-크레졸, γ-부티로락톤, 에틸셀로솔브, 부틸셀로솔브, 에틸카르비톨, 부틸카르비톨, 에틸카르비톨 아세테이트, 부틸카르비톨 아세테이트, 에틸렌글리콜, 프로필렌글리콜 모노메틸 에테르 아세테이트(PGMEA), 젖산에틸, 젖산부틸, 시클로헥사논, 시클로펜타논 등을 들 수 있다.The photosensitive composition may further include at least one selected from an imidization catalyst and a dehydrating agent in addition to the polyamic acid. Examples of the imidization catalyst include pyridine, isoquinoline, and β quinoline (β, N, N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide Seed, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, propylene glycol monomethyl ether acetate ( PGMEA), ethyl lactate, butyl lactate, cyclohexanone, cyclopentanone, and the like.

상기 탈수제는 아세트산무수물(acetic anhydride), 프탈산무수물(phthalic anhydride), 및 말레산무수물(maleic anhydride) 중에서 선택된 1종 이상을 포함할 수 있다.The dehydrating agent may include at least one selected from acetic anhydride, phthalic anhydride, and maleic anhydride.

상기 감광성 조성물은 반응촉매를 더 포함할 수 있다. 상기 반응촉매의 예로서는, 1,8-다이아자바이사이클로[5,4,0]운덱-7-엔(1,8-Diazabicyclo[5,4,0]undec-7-ene), 1,5-다이아자바이사이클로(4,3,0)-논-5-엔(1,5-Diazabicyclo(4,3,0)-non-5-ene), 트리에틸아민(trimethylamine), N-메틸이미다졸(Nmethylimidazole), 다이아이소프로필에틸렌아민(diisopropylethylamine) 등을 들 수 있다.The photosensitive composition may further include a reaction catalyst. Examples of the reaction catalyst are 1,8-diazabicyclo[5,4,0]undec-7-ene (1,8-Diazabicyclo[5,4,0]undec-7-ene), 1,5-dia Java dicyclo(4,3,0)-non-5-ene (1,5-Diazabicyclo(4,3,0)-non-5-ene), triethylamine, N-methylimidazole ( Nmethylimidazole), diisopropylethylamine, and the like.

또한, 상기 감광성 조성물은, 다양한 형태의 첨가제를 더 포함할 수 있으며, 구체적으로는 난연제, 접착력 향상제, 무기입자, 항산화제, 가소제 및 대전방지제 중에서 선택된 1종 이상의 첨가제를 더 포함할 수 있다. 또한, 본 발명은 상기 첨가제 외에도 용도 또는 환경에 따라서 산화방지제, 자외선 흡수제, 대전방지제 및 안료 등의 첨가제를 추가적으로 포함할 수 있다.In addition, the photosensitive composition may further include various types of additives, and may further include one or more additives selected from flame retardants, adhesion promoters, inorganic particles, antioxidants, plasticizers, and antistatic agents. In addition, the present invention may additionally include additives such as an antioxidant, an ultraviolet absorbent, an antistatic agent, and a pigment depending on the use or environment.

상기 감광성 조성물로 다양한 형태의 성형체를 제조할 수 있는데, 예를 들면 필름, 보호막 또는 절연막을 포함하는 다층 프린트 배선판, 연성회로기판, 반도체용 적층체, OLED 디바이스용 감광성 유기 절연재 등으로 적용이 가능하다.Various types of molded products can be produced from the photosensitive composition, for example, a multilayer printed wiring board including a film, a protective film, or an insulating film, a flexible circuit board, a laminate for semiconductors, and a photosensitive organic insulating material for OLED devices. .

본 발명의 상기 화학식 1로 나타내는 구조를 포함하는 폴리이미드계 화합물을 감광성 조성물로 이용하여, 코팅한 후 노광시키면 노광된 영역의 감광성 조성물은 경화되고 비노광 영역의 감광성 조성물은 현상액에 의해 제거된다. 본 발명의 상기 화학식 1로 나타내는 구조를 포함하는 폴리이미드계 화합물을 이용함에 따라 적은 광량으로 노광하여도 높은 감도로 용이하게 광경화가 일어나고, 해상도를 향상시킬 수 있다.When the polyimide-based compound comprising the structure represented by Formula 1 of the present invention is used as a photosensitive composition, and exposed after coating, the photosensitive composition in the exposed area is cured and the photosensitive composition in the non-exposed area is removed by a developer. By using a polyimide-based compound comprising the structure represented by Formula 1 of the present invention, even when exposed to a small amount of light, photo-curing easily occurs with high sensitivity and resolution can be improved.

폴리이미드계 화합물의 제조 방법Method for producing polyimide-based compound

상기 화학식 1로 나타내는 구조를 포함하는 폴리이미드계 화합물은 이무수물 모노머와 디아미노벤조산을 반응시켜 1차 폴리이미드를 제조한 후(단계 1), 상기 1차 폴리이미드에 대하여 광반응기를 포함하는 화합물을 도입하여 제조(단계 2)한다.The polyimide-based compound comprising the structure represented by Chemical Formula 1 is prepared by reacting an dianhydride monomer with diaminobenzoic acid to prepare a primary polyimide (step 1), and then a compound containing a photoreactor for the primary polyimide Is introduced and manufactured (step 2).

광반응기가 도입된 폴리이미드에 대해서는 디카르복시산 화합물을 첨가하는 공정(단계 3)을 더 수행할 수 있다.For the polyimide into which the photoreactor is introduced, a process (step 3) of adding a dicarboxylic acid compound may be further performed.

상기 화학식 1에서, Q1 내지 Q3이 상기 이무수물 모노머로부터 유래된다.상기 단계 1에서 이용되는 상기 이무수물 모노머의 예로서는, 부탄-1,2,3,4-테트라카르복실산 이무수물, 무수 피로멜리트산, 3,3',4,4'-비페닐테트라카르복실산 이무수물, 3,3',4,4'-벤조페논테트라카르복실산 이무수물, 3,3',4,4'-디페닐에테르테트라카르복실산 이무수물, 3,3',4,4'-디페닐술폰테트라카르복실산 이무수물, 2,2-비스(3,4-디카르복시페닐)헥사플루오로이소프로필리덴 이무수물, 3,3',4,4'-비페닐테트라카르복실산 이무수물, 3,3',4,4'-벤조페논테트라카르복실산 이무수물, 4,4'-헥사플루오로이소프로필리덴디프탈산 무수물, 3,3',4,4'-디페닐술폰테트라카르복실산 이무수물, 1,2,3,4-시클로부탄테트라카르복실산 이무수물, 1,2-디메틸-1,2,3,4-시클로부탄테트라카르복실산 이무수물, 1,2,3,4-테트라메틸-1,2,3,4-시클로부탄테트라카르복실산 이무수물, 1,2,3,4-시클로펜탄테트라카르복실산 이무수물, 1,2,4,5-시클로헥산테트라카르복실산 이무수물, 3,4-디카르복시-1,2,3,4-테트라히드로-1-나프탈렌 숙신산 이무수물, 5-(2,5-디옥소테트라히드로푸릴)-3-메틸-3-시클로헥센-1,2-디카르복실산 이무수물, 2,3,5-트리카르복시-2-시클로펜탄 아세트산 이무수물, 비시클로[2.2.2]옥토-7-엔-2,3,5,6-테트라카르복실산 이무수물, 2,3,4,5-테트라히드로푸란테트라카르복실산 이무수물, 3,5,6-트리카르복시-2-노르보르난 아세트산 이무수물, 1,2,3,4-부탄테트라카르복실산 이무수물과 같은 지방족 테트라카르복실산 이무수물 또는 그 유도체 등을 들 수 있다.In the formula (1), Q 1 to Q 3 are derived from the dianhydride monomer. Examples of the dianhydride monomer used in step 1 include butane-1,2,3,4-tetracarboxylic dianhydride, anhydrous Pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4 '-Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoroiso Propylene dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoro Loisopropylidenediphthalic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- Naphthalene succinic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 2,3,5-tricarboxy-2- Cyclopentane acetic dianhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride And aliphatic tetracarboxylic dianhydrides or derivatives thereof such as water, 3,5,6-tricarboxy-2-norbornane acetic acid dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and the like. Can be.

상기 디아미노벤조산은 3,5-다이아미노벤조산일 수 있다.The diaminobenzoic acid may be 3,5-diaminobenzoic acid.

상기 단계 1에서, 상기 이무수물 모노머와 디아미노벤조산은 하기 반응식 1에 따라 반응하여 1차 폴리이미드를 제조할 수 있다.In step 1, the dianhydride monomer and diaminobenzoic acid may be reacted according to the following reaction formula 1 to prepare a primary polyimide.

[반응식 1][Scheme 1]

Figure pat00128
Figure pat00128

상기 반응식 1에서, Q는 Q2 또는 Q3을 의미하는 것이고, k는 1 이상의 정수를 나타낸다.In Reaction Scheme 1, Q is Q 2 or Q 3 , and k represents an integer of 1 or more.

상기 이무수물 모노머와 디아미노벤조산은 극성 용매 조건 하에서 반응될 수 있는데, 이때의 극성 용매의 예로서는, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, N-비닐피롤리돈, N-메틸카프로락탐, 디메틸술폭시드, 테트라메틸요소, 피리딘, 디메틸술폰, 헥사메틸술폭시드, m-크레졸, γ부티로락톤, 프로필렌 글리콜 모노메틸 에테르 아세테이트(PGMEA) 등을 이용할 수 있고, 이들은 각각 독립적으로 또는 2 이상을 혼합하여 사용할 수 있다.The dianhydride monomer and diaminobenzoic acid may be reacted under polar solvent conditions. Examples of the polar solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N- Vinylpyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ butyrolactone, propylene glycol monomethyl ether acetate (PGMEA), etc. can be used. These may be used either individually or in combination of two or more.

이때, 상기 디아미노벤조산과 함께 통상의 폴리이미드 중합체의 제조에 사용되는 유기 디아민이 함께 혼합되어 반응될 수 있다. At this time, the diaminobenzoic acid and the organic diamine used in the production of a conventional polyimide polymer can be mixed and reacted together.

상기 유기 디아민을 함께 혼합하는 경우, 상기 반응식 1과 동시에, 하기 반응식 2의 이무수물 모노머와 유기 디아민의 반응도 동시에 일어나고, 상기 1차 폴리이미드는 하기 반응식 2의 결과로 얻어지는 중합체 구조 또한 포함할 수 있다.When the organic diamine is mixed together, simultaneously with the reaction scheme 1, the reaction of the dianhydride monomer of the reaction scheme 2 with the organic diamine occurs simultaneously, and the primary polyimide may also include a polymer structure obtained as a result of the reaction scheme 2 below. .

[반응식 2][Scheme 2]

Figure pat00129
Figure pat00129

상기 반응식 2에서, Q1은 상기 화학식 1의 Q1과 실질적으로 동일하고, Y 및 x 또한 상기 화학식 1의 Y 및 x와 실질적으로 동일하다. 따라서, 중복되는 상세한 설명은 생략한다. 즉, 상기 유기 디아민의 종류에 따라, 상기 화학식 1b로 나타내는 단위구조가 결정될 수 있다.In Reaction Scheme 2, Q 1 is substantially the same as Q 1 in Formula 1, and Y and x are also substantially the same as Y and x in Formula 1. Therefore, detailed description of overlapping is omitted. That is, the unit structure represented by Formula 1b may be determined according to the type of the organic diamine.

상기 반응식 2에 이용되는 상기 유기 디아민의 예로서는, p-페닐렌디아민, m-페닐렌디아민, 2,4,6-트리메틸-1,3-페닐렌디아민, 2,3,5,6-테트라메틸-1,4-페닐렌디아민, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 3,3'-디아미노디페닐에테르, 4,4'-디아미노디페닐설피드, 4,4'-디아미노디페닐메탄, 3,4'-디아미노디페닐메탄, 3,3'-디아미노디페닐메탄, 4,4'-메틸렌-비스(2-메틸아닐린), 4,4'-메틸렌-비스(2,6-디메틸아닐린), 4,4'-메틸렌-비스(2,6-디에틸아닐린), 4,4'-메틸렌-비스(2-이소프로필-6-메틸아닐린), 4,4'-메틸렌-비스(2,6-디이소프로필아닐린), 4,4'-디아미노디페닐술폰, 3,3'-디아미노디페닐술폰, 벤지딘, o-톨리딘, m-톨리딘, 3,3',5,5'-테트라메틸벤지딘, 2,2'-비스(트리플루오로메틸)벤지딘, 1,4-비스(4-아미노페녹시)벤젠, 1,3-비스(4-아미노페녹시)벤젠, 1,3-비스(3-아미노페녹시)벤젠, 비스[4-(4-아미노페녹시)페닐]술폰, 비스[4-(3-아미노페녹시)페닐]술폰, 2,2-비스[4-(4-아미노페녹시)페닐]프로판, 및 2,2-비스[4-(3-아미노페녹시)페닐]프로판으로 이루어진 그룹에서 선택되는 1종 이상의 방향족 디아민; 1,6-헥산디아민, 1,4-시클로헥산디아민, 1,3-시클로헥산디아민, 1,4-비스(아미노메틸)시클로헥산, 1,3-비스(아미노메틸)시클로헥산, 4,4'-디아미노디시클로헥실메탄, 4,4'-디아미노-3,3'-디메틸디시클로헥실메탄 등을 들 수 있으며, 상기 방향족 및 지방족 디아민을 혼합하여 사용할 수 있다. 그러나, 이에 한정되는 것은 아니다.Examples of the organic diamine used in Reaction Scheme 2 include p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl -1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodi Phenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-methylene-bis(2-methylaniline ), 4,4'-methylene-bis(2,6-dimethylaniline), 4,4'-methylene-bis(2,6-diethylaniline), 4,4'-methylene-bis(2-isopropyl) -6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-Tolidine, m-Tolidine, 3,3',5,5'-tetramethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 1,4-bis(4-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-( 3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 2,2-bis[4-(3-aminophenoxy)phenyl]propane At least one aromatic diamine selected from the group; 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4 And'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, and the like can be used by mixing the aromatic and aliphatic diamines. However, it is not limited thereto.

상기와 같이 얻어진 1차 폴리이미드는 하기 화학식 6a로 나타내는 구조 및/또는 하기 화학식 6b로 나타내는 구조를 포함할 수 있다.The primary polyimide obtained as described above may include a structure represented by the following formula 6a and/or a structure represented by the following formula 6b.

[화학식 6a][Formula 6a]

Figure pat00130
Figure pat00130

[화학식 6b] [Formula 6b]

Figure pat00131
Figure pat00131

상기 화학식 6a 및 6b에서 Q는 Q2 또는 Q3일 수 있다.In Chemical Formulas 6a and 6b, Q may be Q 2 or Q 3 .

상기 단계 2에서, 상기 화학식 6a 또는 6b로 나타내는 구조를 포함하는 1차 폴리이미드를, 다시 광반응기를 포함하는 화합물을 반응시켜 화학식 7a 또는 화학식 7b로 나타내는 구조를 포함하는 폴리이미드계 화합물을 유도할 수 있다. 이때, 상기 화학식 6a와 6b로 나타내는 구조를 포함하는 화합물에서 카르복시산 작용기의 일부에는 광반응기를 포함하는 화합물과 반응하여 하기 화학식 7a와 7b와 같은 말단 작용기가 유도되고, 일부는 카르복시산 작용기가 그대로 잔류할 수 있다. 상기 1차 폴리이미드에 대한 광반응기를 포함하는 화합물의 첨가량을 조절하여 하기 화학식 7a나 화학식 7b와 같은 구조가 유도될 수 있다.In step 2, the primary polyimide containing the structure represented by the formula 6a or 6b is reacted with a compound containing a photoreactor to induce a polyimide-based compound comprising the structure represented by the formula 7a or formula 7b. Can be. At this time, in the compound containing the structures represented by the formulas 6a and 6b, a part of the carboxylic acid functional group is reacted with a compound containing a photoreactive group to induce terminal functional groups such as the following formulas 7a and 7b, and a part of the carboxylic acid functional group remains. Can be. A structure such as the following Chemical Formula 7a or Chemical Formula 7b may be derived by adjusting the amount of the compound containing the photoreactor to the primary polyimide.

[화학식 7a][Formula 7a]

Figure pat00132
Figure pat00132

[화학식 7b][Formula 7b]

Figure pat00133
Figure pat00133

상기 화학식 7a 및 7b에서, Q는 상기 화학식 1의 Q2 또는 Q3와 실질적으로 동일하고, f 및 g는 각각 독립적으로 1 내지 5의 정수를 나타내며, W는 상기에서 설명한 W1 또는 W2와 동일하고, R은 상기에서 설명한 R1 또는 R2와 동일하다.In Formulas 7a and 7b, Q is substantially the same as Q 2 or Q 3 in Formula 1, f and g each independently represent an integer of 1 to 5, W is W 1 or W 2 described above The same, R is the same as R 1 or R 2 described above.

상기 화학식 7a 및/또는 7b로 나타내는 구조를 포함하는 폴리이미드계 화합물에 대하여 디카르복시산 화합물을 첨가하여, 하기 화학식 8a 및/또는 8b로 나타내는 구조를 포함하는 폴리이미드계 화합물을 유도할 수 있다.A dicarboxylic acid compound may be added to a polyimide-based compound including a structure represented by Chemical Formulas 7a and/or 7b to derive a polyimide-based compound comprising a structure represented by Chemical Formulas 8a and/or 8b.

[화학식 8a][Formula 8a]

Figure pat00134
Figure pat00134

[화학식 8b][Formula 8b]

Figure pat00135
Figure pat00135

상기 화학식 8a 및 8b에서 L은 화학식 1a에서 설명한 것과 실질적으로 동일하다.In Formulas 8a and 8b, L is substantially the same as described in Formula 1a.

이에 따라, 본 발명에 따른 폴리이미드계 화합물은 상기 화학식 1a로 나타내는 단위구조와 함께, 상기 화학식 1b 및 1c 중 적어도 어느 하나의 단위구조를 더 포함하는 구조로서 상기 화학식 1로 나타내는 구조를 포함할 수 있다.Accordingly, the polyimide-based compound according to the present invention may include a structure represented by Formula 1 as a structure further comprising at least one unit structure of Formula 1b and 1c together with the unit structure represented by Formula 1a. have.

본 발명에 따르면, 광에 대한 고해상도 및 고감도를 가질 뿐만 아니라, 기계적, 화학적으로 우수한 제반 물성을 가지며, 특히 광학적으로 투명성이 우수하면서도 저온 경화성이 우수하다. 또한, 본 발명에 따른 폴리이미드계 화합물은 알칼리 용매에 대한 불용성을 갖는 바, 별도의 용해억제제(또는 가교제), 광염기/산 발생제 및 가교제를 사용하지 않으므로 제조상의 비용절감, 제조공정 단순화가 가능하여 경제성이 우수하다.According to the present invention, it not only has high resolution and high sensitivity to light, but also has excellent mechanical and chemical properties, particularly excellent optical transparency and low temperature curing. In addition, since the polyimide-based compound according to the present invention has insolubility in an alkali solvent, it does not use a separate dissolution inhibitor (or crosslinking agent), photobase/acid generator, and crosslinking agent, thereby reducing manufacturing cost and simplifying the manufacturing process. It is possible and has excellent economic efficiency.

이하에서는, 구체적인 제조예를 통해서 본 발명에 따른 폴리이미드계 화합물에 대해서 보다 구체적으로 설명하기로 한다. 하기의 제조예 및 그를 통해서 얻어진 폴리이미드계 화합물은 본 발명을 설명하기 위한 것일 뿐, 이 제조예 및 폴리이미드계 화합물에 본 발명이 제한되는 것은 아니다.Hereinafter, the polyimide-based compound according to the present invention will be described in more detail through specific production examples. The following preparation examples and the polyimide-based compounds obtained therefrom are only for explaining the present invention, and the present invention is not limited to these preparation examples and the polyimide-based compounds.

하기 중합예 1 내지 5 각각에서 제조된 결과물은 하기 화학식 9로 나타내는 구조를 포함하는 폴리이미드계 화합물이고, 하기 중합예 1 내지 5 각각에서 a, b, c 및 d는 각각 하기 화학식 9에서의 a, b, c 및 d를 의미하는 것이다. 화학식 9에서 폴리이미드계 화합물은 2개의 부분으로 나타내었으나 화학식 9의 “

Figure pat00136
” 부분으로 2개의 부분은 서로 연결되는 것을 나타낸다. The results prepared in each of the following polymerization examples 1 to 5 are polyimide-based compounds comprising a structure represented by the following formula 9, and in each of the following polymerization examples 1 to 5, a, b, c and d are respectively a in formula 9 , b, c and d. In the formula (9), the polyimide-based compound is represented by two parts, “
Figure pat00136
The two parts indicate that they are connected to each other.

[화학식 9][Formula 9]

Figure pat00137
Figure pat00137

[중합예 1] 감광성 폴리이미드 제조[Polymerization Example 1] Preparation of photosensitive polyimide

[반응식 4][Reaction Scheme 4]

Figure pat00138
Figure pat00138

상기 반응식 4에 따라, 100ml 3구 플라스크에 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 27ml와 3,5-다이아미노벤조산(3,5-Diaminobenzoic acid) (7 mmol) 그리고 2,2'-비스(트리플루오로메틸)벤지딘(2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol)를 혼합하였다.According to Reaction Scheme 4, 27 ml of N-Methyl-2-pyrrolidone (NMP) and 3,5-diaminobenzoic acid (7, 3,5-Diaminobenzoic acid) (7 mmol) and 2,2'-bis(trifluoromethyl)benzidine (2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol) were mixed.

위 반응기에 4,4'-(헥사플루오로이소프로필리엔)디프탈릭언하드라드(6FDA) (10 mmol)을 첨가하고, 상온에서 5시간 교반하였다. 이후, 165℃로 승온하여 4시간 동안 환류시킨 후 상온으로 식혀 반응을 종료하여 반응 용액을 제조하였다. To the above reactor, 4,4'-(hexafluoroisopropylene) diphthalic unhardrad (6FDA) (10 mmol) was added and stirred at room temperature for 5 hours. Thereafter, the temperature was raised to 165°C, refluxed for 4 hours, and then cooled to room temperature to complete the reaction to prepare a reaction solution.

다음으로 반응 용액을 메탄올과 증류수 혼합액에 서서히 투입하여 침전시킨 뒤, 고형분을 여과한 다음 건조시켜 폴리이미드를 얻었다. (a=0.7, d=0.3)Next, the reaction solution was slowly introduced into a mixture of methanol and distilled water to precipitate, and then the solid was filtered and dried to obtain a polyimide. (a=0.7, d=0.3)

제조한 폴리이미드 2g을 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 20 mL에 용해시켰다. 이후, 카복실산 몰수 기준 70 mol%에 해당하는 글리시딜 메타크릴레이트(Glycidyl methacrylate, GMA) 및 트리에틸아민(Triethylamine, TEA) 0.23 g을 주입한 뒤 110℃에서 16시간 동안 반응시켜 반응 용액을 제조하였다. (a=0.21, b=0.49 d=0.3)2 g of the prepared polyimide was dissolved in 20 mL of N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP). Thereafter, 0.23 g of glycidyl methacrylate (GMA) and triethylamine (TEA) corresponding to 70 mol% based on the number of moles of carboxylic acids were injected, and then reacted at 110° C. for 16 hours to prepare a reaction solution. Did. (a=0.21, b=0.49 d=0.3)

[반응식 5][Scheme 5]

Figure pat00139
Figure pat00139

상기 반응식 5에 따라, 이 용액에 카복실산 몰수 기준 70 mol%에 해당하는 테트라하이드로프탈릭 무수물(Tetrahydrophthalic anhydride, THPA) 0.53g 및 트리에틸아민(Triethylamine, TEA) 0.1 g을 주입한 뒤 95℃에서 6시간 동안 반응시켜 반응 용액을 제조하여 감광성 폴리이미드를 얻었다. (a=0.21, b=0.147, c=0.343 d=0.3)According to Reaction Scheme 5, 0.53 g of tetrahydrophthalic anhydride (THPA) and 0.1 g of triethylamine (TEA) corresponding to 70 mol% based on the number of moles of carboxylic acids were injected into the solution, followed by 6 at 95°C. The reaction solution was reacted for a time to obtain a photosensitive polyimide. (a=0.21, b=0.147, c=0.343 d=0.3)

[중합예 2] 감광성 폴리이미드 제조[Polymerization Example 2] Preparation of photosensitive polyimide

100ml 3구 플라스크에 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 27ml와 3,5-다이아미노벤조산(3,5-Diaminobenzoic acid) (7 mmol)과 2,2'-비스(트리플루오로메틸)벤지딘(2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol)를 혼합하였다.27 ml of N-Methyl-2-pyrrolidone (NMP) and 3,5-Diaminobenzoic acid (7 mmol) and 2,2 in a 100 ml 3-neck flask '-Bis(trifluoromethyl)benzidine (2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol) was mixed.

위 반응기에 3,4,3',4'-비페닐 테트라카르복실산 이무수물(3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA) (10 mmol)을 첨가하고, 상온에서 5시간 교반하였다. 이후, 165℃로 승온하여 4시간 동안 환류시킨 후 상온으로 식혀 반응을 종료하여 반응 용액을 제조하였다.3,4,3',4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA) (10 mmol) was added to the above reactor and stirred at room temperature for 5 hours. Did. Thereafter, the temperature was raised to 165°C, refluxed for 4 hours, and then cooled to room temperature to complete the reaction to prepare a reaction solution.

다음으로 반응 용액을 메탄올과 증류수 혼합액에 서서히 투입하여 침전시킨 뒤, 고형분을 여과한 다음 건조시켜 폴리이미드를 얻었다. (a=0.7, d=0.3)Next, the reaction solution was slowly introduced into a mixture of methanol and distilled water to precipitate, and then the solid was filtered and dried to obtain a polyimide. (a=0.7, d=0.3)

제조한 폴리이미드 2g을 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 20 mL에 용해시켰다. 이후, 카복실산 몰수 기준 70 mol%에 해당하는 글리시딜 메타크릴레이트(Glycidyl methacrylate, GMA) 및 트리에틸아민(Triethylamine, TEA) 0.23 g을 주입한 뒤 110℃에서 16시간 동안 반응시켜 반응 용액을 제조하였다. (a=0.21, b=0.49 d=0.3)2 g of the prepared polyimide was dissolved in 20 mL of N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP). Thereafter, 0.23 g of glycidyl methacrylate (GMA) and triethylamine (TEA) corresponding to 70 mol% based on the number of moles of carboxylic acids were injected, and then reacted at 110° C. for 16 hours to prepare a reaction solution. Did. (a=0.21, b=0.49 d=0.3)

이 용액에 카복식산 몰수 기준 70 mol%에 해당하는 테트라하이드로프탈릭 무수물(Tetrahydrophthalic anhydride, THPA) 0.53g 및 트리에틸아민(Triethylamine, TEA) 0.1 g을 주입한 뒤 95℃에서 6시간 동안 반응시켜 반응 용액을 제조하여 감광성 폴리이미드를 얻었다. (a=0.21, b=0.147, c=0.343 d=0.3)0.53 g of tetrahydrophthalic anhydride (THPA) and 0.1 g of triethylamine (TEA) corresponding to 70 mol% based on the number of moles of carboxylic acid were injected into the solution, followed by reaction at 95°C for 6 hours. The reaction solution was prepared to obtain a photosensitive polyimide. (a=0.21, b=0.147, c=0.343 d=0.3)

[중합예 3] 감광성 폴리이미드 제조[Polymerization Example 3] Preparation of photosensitive polyimide

100ml 3구 플라스크에 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 27ml와 3,5-다이아미노벤조산(3,5-Diaminobenzoic acid) (7 mmol) 그리고 2,2'-비스(트리플루오로메틸)벤지딘(2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol)를 혼합하였다. 27 ml of N-Methyl-2-pyrrolidone (NMP) and 3,5-Diaminobenzoic acid (7 mmol) and 2,2 in a 100 ml 3-neck flask '-Bis(trifluoromethyl)benzidine (2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol) was mixed.

위 반응기에 4,4'-(헥사플루오로이소프로필리엔)디프탈릭언하드라드(6FDA) (10 mmol)을 첨가하고, 상온에서 5시간 교반하였다. 이후, 165℃로 승온하여 4시간 동안 환류시킨 후 상온으로 식혀 반응을 종료하여 반응 용액을 제조하였다. To the above reactor, 4,4'-(hexafluoroisopropylene) diphthalic unhardrad (6FDA) (10 mmol) was added and stirred at room temperature for 5 hours. Thereafter, the temperature was raised to 165°C, refluxed for 4 hours, and then cooled to room temperature to complete the reaction to prepare a reaction solution.

다음으로 반응 용액을 메탄올과 증류수 혼합액에 서서히 투입하여 침전 시킨 뒤, 고형분을 여과한 다음 건조시켜 폴리이미드를 얻었다. (a=0.7, d=0.3)Next, the reaction solution was slowly added to a mixture of methanol and distilled water to precipitate, and then the solid was filtered and dried to obtain a polyimide. (a=0.7, d=0.3)

제조한 폴리이미드 2g을 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 20 mL에 용해시켰다. 이후, 카복실산 몰수 기준 70 mol%에 해당하는 글리시딜 메타크릴레이트(Glycidyl methacrylate, GMA) 및 트리에틸아민(Triethylamine, TEA) 0.23 g을 주입한 뒤 110℃에서 16시간 동안 반응시켜 반응 용액을 제조하였다. (a=0.21, b=0.49 d=0.3)2 g of the prepared polyimide was dissolved in 20 mL of N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP). Thereafter, 0.23 g of glycidyl methacrylate (GMA) and triethylamine (TEA) corresponding to 70 mol% based on the number of moles of carboxylic acids were injected, and then reacted at 110° C. for 16 hours to prepare a reaction solution. Did. (a=0.21, b=0.49 d=0.3)

이 용액에 카복식산 몰수 기준 70 mol%에 해당하는 석신산무수물(Succinic anhydride, SA) 및 트리에틸아민(Triethylamine, TEA) 0.1 g을 주입한 뒤 95℃에서 6시간 동안 반응시켜 반응 용액을 제조하여 감광성 폴리이미드를 얻었다. (a=0.21, b=0.147, c=0.343 d=0.3)0.1 g of succinic anhydride (SA) and triethylamine (TEA) corresponding to 70 mol% based on moles of carboxylic acid were injected into this solution, and then reacted at 95°C for 6 hours to prepare a reaction solution. To obtain a photosensitive polyimide. (a=0.21, b=0.147, c=0.343 d=0.3)

[중합예 4] 감광성 폴리이미드 제조[Polymerization Example 4] Preparation of photosensitive polyimide

100ml 3구 플라스크에 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 27ml와 3,5-다이아미노벤조산(3,5-Diaminobenzoic acid) (7 mmol)과 2,2'-비스(트리플루오로메틸)벤지딘(2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol)를 혼합하였다.27 ml of N-Methyl-2-pyrrolidone (NMP) and 3,5-Diaminobenzoic acid (7 mmol) and 2,2 in a 100 ml 3-neck flask '-Bis(trifluoromethyl)benzidine (2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol) was mixed.

위 반응기에 3,4,3',4'-비페닐 테트라카르복실산 이무수물(3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA) (10 mmol)을 첨가하고, 상온에서 5시간 교반하였다. 이후, 165℃로 승온하여 4시간 동안 환류시킨 후 상온으로 식혀 반응을 종료하여 반응 용액을 제조하였다.3,4,3',4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA) (10 mmol) was added to the above reactor and stirred at room temperature for 5 hours. Did. Thereafter, the temperature was raised to 165°C, refluxed for 4 hours, and then cooled to room temperature to complete the reaction to prepare a reaction solution.

다음으로 반응 용액을 메탄올과 증류수 혼합액에 서서히 투입하여 침전시킨 뒤, 고형분을 여과한 다음 건조시켜 폴리이미드를 얻었다. (a=0.7, d=0.3)Next, the reaction solution was slowly introduced into a mixture of methanol and distilled water to precipitate, and then the solid was filtered and dried to obtain a polyimide. (a=0.7, d=0.3)

제조한 폴리이미드 2g을 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 20 mL에 용해시켰다. 이후, 카복실산 몰수 기준 70 mol%에 해당하는 글리시딜 메타크릴레이트(Glycidyl methacrylate, GMA) 및 트리에틸아민(Triethylamine, TEA) 0.23 g을 주입한 뒤 110℃에서 16시간 동안 반응시켜 반응 용액을 제조하였다. (a=0.21, b=0.49 d=0.3)2 g of the prepared polyimide was dissolved in 20 mL of N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP). Thereafter, 0.23 g of glycidyl methacrylate (GMA) and triethylamine (TEA) corresponding to 70 mol% based on the number of moles of carboxylic acids were injected, and then reacted at 110° C. for 16 hours to prepare a reaction solution. Did. (a=0.21, b=0.49 d=0.3)

이 용액에 카복식산 몰수 기준 70 mol% 석신산무수물(Succinic anhydride, SA) 0.38g 및 트리에틸아민(Triethylamine, TEA) 0.1 g을 주입한 뒤 95℃에서 6시간 동안 반응시켜 반응 용액을 제조하여 감광성 폴리이미드를 얻었다. (a=0.21, b=0.147, c=0.343 d=0.3)0.38 g of 70 mol% succinic anhydride (SA) and 0.1 g of triethylamine (TEA) were injected into the solution, and reacted at 95°C for 6 hours to prepare a reaction solution. A photosensitive polyimide was obtained. (a=0.21, b=0.147, c=0.343 d=0.3)

[비교중합예 1] 폴리이미드 제조[Comparative polymerization example 1] polyimide production

100ml 3구 플라스크에 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 27ml와 3,5-다이아미노벤조산(3,5-Diaminobenzoic acid) (7 mmol)과 2,2'-비스(트리플루오로메틸)벤지딘(2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol)를 혼합하였다.27 ml of N-Methyl-2-pyrrolidone (NMP) and 3,5-Diaminobenzoic acid (7 mmol) and 2,2 in a 100 ml 3-neck flask '-Bis(trifluoromethyl)benzidine (2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol) was mixed.

위 반응기에 4,4'-(헥사플루오로이소프로필리엔)디프탈릭언하드라드(6FDA) (10 mmol)을 첨가하고, 상온에서 5시간 교반하였다. 이후, 165℃로 승온하여 4시간 동안 환류시킨 후 상온으로 식혀 반응을 종료하여 반응 용액을 제조하였다. (a=0.7, d=0.3)To the above reactor, 4,4'-(hexafluoroisopropylene) diphthalic unhardrad (6FDA) (10 mmol) was added and stirred at room temperature for 5 hours. Thereafter, the temperature was raised to 165°C, refluxed for 4 hours, and then cooled to room temperature to complete the reaction to prepare a reaction solution. (a=0.7, d=0.3)

[화학식 10][Formula 10]

Figure pat00140
Figure pat00140

다음으로 반응 용액을 메탄올과 증류수 혼합액에 서서히 투입하여 침전시킨 뒤, 고형분을 여과한 다음 건조시켜 폴리이미드를 얻었다.Next, the reaction solution was slowly introduced into a mixture of methanol and distilled water to precipitate, and then the solid was filtered and dried to obtain a polyimide.

[비교중합예 2][Comparative polymerization example 2]

100ml 3구 플라스크에 N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone, NMP) 27ml와 3,5-다이아미노벤조산(3,5-Diaminobenzoic acid) (7 mmol)과 2,2'-비스(트리플루오로메틸)벤지딘(2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol)를 혼합하였다. 27 ml of N-Methyl-2-pyrrolidone (NMP) and 3,5-Diaminobenzoic acid (7 mmol) and 2,2 in a 100 ml 3-neck flask '-Bis(trifluoromethyl)benzidine (2,2'-Bis(trifluoromethyl)benzidine, TFMB) (3 mmol) was mixed.

위 반응기에 3,4,3',4'-비페닐 테트라카르복실산 이무수물(3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA) (10 mmol)을 첨가하고, 상온에서 5시간 교반하였다. 이후, 165℃로 승온하여 4시간 동안 환류시킨 후 상온으로 식혀 반응을 종료하여 반응 용액을 제조하였다.3,4,3',4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA) (10 mmol) was added to the above reactor and stirred at room temperature for 5 hours. Did. Thereafter, the temperature was raised to 165°C, refluxed for 4 hours, and then cooled to room temperature to complete the reaction to prepare a reaction solution.

다음으로 반응 용액을 메탄올과 증류수 혼합액에 서서히 투입하여 침전시킨 뒤, 고형분을 여과한 다음 건조시켜 폴리이미드를 얻었다. (a=0.7, d=0.3)Next, the reaction solution was slowly introduced into a mixture of methanol and distilled water to precipitate, and then the solid was filtered and dried to obtain a polyimide. (a=0.7, d=0.3)

[화학식 10][Formula 10]

감광성 조성물의 준비Preparation of photosensitive composition

상기에서 중합예 1 내지 5와 비교중합예 1 및 2 각각으로 얻어진 폴리이미드를 이용하여 감광성 조성물을 제조하였다.In the above, using the polyimide obtained in each of the polymerization examples 1 to 5 and the comparative polymerization examples 1 and 2, photosensitive compositions were prepared.

특성평가Characteristic evaluation

(1) 해상력 평가(1) Resolution evaluation

얻어진 감광성 조성물 1 내지 5와 비교예 조성물 1 및 2 각각으로, 4인치 실리콘웨이퍼에 상기 실시예 및 비교예에서 제조된 감광성 수지 조성물을 스핀 코팅하고, 핫 플레이트 상에서 120℃에서 2분간 가열하여, 15㎛ 두께의 감광성 필름을 형성시켰다. 포토마스크에 상기 전열 처리 완료한 실리콘웨이퍼를 진공밀착시킨 후, G-line 스테퍼 Nikon NSR 1505 G4로 20mJ/㎠ 부터 5mJ/㎠ 간격으로 600mJ/㎠까지 순차적으로 노광시켰고 23℃에서 80초간 현상한 후 초순수로 60초간 세정 및 건조하여 노광부가 선명하게 남아있는 패턴을 얻었다. 이와 같이 패턴화된 실리콘웨이퍼를 질소기류하에, 핫 플레이트상에서 실온에서 시작하여 180℃가 될 때까지 약 30분간 서서히 가열하고, 이어 180℃에서 60분간 유지한 후, 300℃가 될 때까지 30분간 서서히 가열한 후, 300℃에서 60분간 유지하여 열처리하였다.With the obtained photosensitive compositions 1 to 5 and Comparative Example compositions 1 and 2, spin-coated the photosensitive resin compositions prepared in Examples and Comparative Examples on a 4 inch silicone wafer, and heated at 120° C. for 2 minutes on a hot plate, 15 A photosensitive film having a thickness of µm was formed. After vacuum-sealing the heat-treated silicon wafer on a photomask, G-line stepper Nikon NSR 1505 G4 was sequentially exposed from 20mJ/㎠ to 5mJ/㎠ at intervals of 600mJ/㎠ and developed at 23℃ for 80 seconds. After washing and drying for 60 seconds with ultrapure water, a pattern in which the exposed portion remained clearly was obtained. The silicon wafer patterned in this way was started at room temperature on a hot plate under nitrogen flow, and gradually heated for about 30 minutes until it reached 180°C, and then held at 180°C for 60 minutes, and then 30 minutes until it reached 300°C. After heating slowly, the mixture was maintained at 300°C for 60 minutes and heat-treated.

그 결과, 본 발명에 따른 폴리이미드계 화합물 1 내지 5를 이용하여 제조한 필름은 두께가 10㎛이고, 패턴의 최소 선폭이 3 ㎛로 우수한 해상도를 나타내었다. 반면, 비교예 1의 조성물로부터 완성된 필름은 최소 선폭이 20 ㎛로 본 발명의 조성물과 비교할 때 해상도가 떨어졌으며, 비교예 2의 경우에도 마찬가지로 실시예보다 해상도가 떨어짐을 확인할 수 있었다.As a result, the films produced using the polyimide-based compounds 1 to 5 according to the present invention had a thickness of 10 µm and a minimum line width of the pattern of 3 µm, which showed excellent resolution. On the other hand, the finished film from the composition of Comparative Example 1 has a minimum line width of 20 μm, and the resolution is inferior when compared to the composition of the present invention.

(2) 잔막율 평가(2) Residual rate evaluation

잔막율은 하기 수학식 1에 의해 측정하였으며, 막 두께 측정은 STM-602 기기(제조사: 일본 스쿠링사)를 이용하였다.The residual film rate was measured by the following equation (1), and the film thickness was measured using an STM-602 instrument (manufacturer: Skuring, Japan).

[수학식 1][Equation 1]

잔막율(%) = (현상 후의 막 두께 / 프리 베이크 후의 막 두께) x 100Residual film rate (%) = (film thickness after development / film thickness after pre-baking) x 100

그 결과, 본 발명의 실시예 1 내지 5에서는 낮은 광 조사량에서도 매우 높은 잔막율을 갖는 것을 확인할 수 있다. 그러나, 비교예 1 및 2의 경우, 동일한 광조사량에서 매우 낮은 잔막율로 측정되었다.As a result, it can be confirmed that Examples 1 to 5 of the present invention have a very high residual film rate even at a low light irradiation amount. However, in Comparative Examples 1 and 2, it was measured at a very low residual film rate at the same light irradiation amount.

(3) 내화학성, 현상성 및 잔사유무 특성 평가(3) Evaluation of chemical resistance, developability, and residue characteristics

본 발명에 따른 감광성 조성물 1 내지 5와 비교예 조성물 1 및 2 각각으로 패턴을 제조하여 내화학성, 현상성 및 잔사유무를 평가하였다. 그 결과를 하기 표 1에 나타낸다.Patterns were prepared with each of the photosensitive compositions 1 to 5 and Comparative Example compositions 1 and 2 according to the present invention to evaluate chemical resistance, developability and presence or absence of residue. The results are shown in Table 1 below.

내화학성Chemical resistance 현상성Developability 잔사유무Residue 실시예 1Example 1 ◎◎ ◎◎ ◎◎ 실시예 2Example 2 ◎◎ ○○ ○○ 실시예 3Example 3 ◎◎ ◎◎ ◎◎ 실시예 4Example 4 ◎◎ ◎◎ ◎◎ 실시예 5Example 5 ◎◎ ○○ ○○ 비교예 1Comparative Example 1 ○○ △△ △△ 비교예 2Comparative Example 2 ○○ △△ △△

표 1에서, ◎는 매우 좋음, ○는 좋음, △는 보통, X는 나쁨을 나타낸다.In Table 1, ◎ is very good, ○ is good, △ is normal, and X is bad.

표 1을 참조하면, 본 발명에 따른 감광성 조성물 1 내지 5와 비교예 조성물 1 및 2 각각으로 패턴을 제조할 때, 본 발명의 실시예 1 내지 4 각각의 내화학성 및 현상성, 그리고 잔사유무에 있어 비교예 1 및 2에 비해 전체적으로 좋게 나타나는 것을 확인할 수 있다.Referring to Table 1, when preparing a pattern with each of the photosensitive compositions 1 to 5 and Comparative Examples compositions 1 and 2 according to the present invention, the chemical resistance and developability of each of Examples 1 to 4 of the present invention, and the presence or absence of residue Therefore, it can be confirmed that it appears as a whole better than Comparative Examples 1 and 2.

상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although described above with reference to the preferred embodiments of the present invention, those skilled in the art may variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that you can.

Claims (8)

하기 화학식 1로 나타내는 구조를 포함하는 폴리이미드계 화합물;
[화학식 1]
Figure pat00141

상기 화학식 1에서,
Ra 는 하기 화학식 2로 나타내고,
[화학식 2]
Figure pat00142

Rb는 -C(=O)OH 또는 하기 화학식 3으로 나타내고,
[화학식 3]
Figure pat00143

상기 화학식 2 및 3에서,
R1 및 R2 는 각각 독립적으로 수소 또는 C1-6 알킬기를 나타내고,
a, b, d 및 e는 각각 독립적으로 1 내지 5의 정수를 나타내고,
W1 및 W2는 각각 독립적으로 산소원자 또는 단결합을 나타내고,
상기 화학식 2의 L은 C5-10 아릴렌, C1-6 알킬렌, C3-6 알케닐렌, C3-6 알키닐렌, C3-7 헤테로아릴렌, C5-10사이클로알킬렌, C3-10 불포화탄화수소고리 또는 C3-7 불포화헤테로고리를 나타내고,
상기 화학식 1에서, Q1, Q2 및 Q3는 각각 독립적으로
Figure pat00144
,
Figure pat00145
,
Figure pat00146
,
Figure pat00147
,
Figure pat00148
,
Figure pat00149
,
Figure pat00150
,
Figure pat00151
,
Figure pat00152
,
Figure pat00153
,
Figure pat00154
또는
Figure pat00155
를 나타내며,
Y 는
Figure pat00156
,
Figure pat00157
,
Figure pat00158
,
Figure pat00159
,
Figure pat00160
,
Figure pat00161
,
Figure pat00162
,
Figure pat00163
,
Figure pat00164
,
Figure pat00165
,
Figure pat00166
,
Figure pat00167
,
Figure pat00168
,
Figure pat00169
,
Figure pat00170
또는
Figure pat00171
를 나타내며,
0 ≤ x ≤ 0.4이고 0.1 ≤ y ≤ 0.9이며 0 ≤ z ≤ 0.5이되, x와 z는 동시에 0이 될 수 없고, x+y+z=1 이다.
A polyimide-based compound comprising a structure represented by Formula 1 below;
[Formula 1]
Figure pat00141

In Chemical Formula 1,
Ra is represented by the following formula (2),
[Formula 2]
Figure pat00142

Rb is represented by -C(=O)OH or Formula 3 below,
[Formula 3]
Figure pat00143

In Chemical Formulas 2 and 3,
R 1 and R 2 each independently represent hydrogen or a C 1-6 alkyl group,
a, b, d and e each independently represent an integer of 1 to 5,
W 1 and W 2 each independently represent an oxygen atom or a single bond,
L of Formula 2 is C 5-10 arylene, C 1-6 alkylene, C 3-6 alkenylene, C 3-6 alkynylene, C 3-7 heteroarylene, C 5-10 cycloalkylene, Represents a C 3-10 unsaturated hydrocarbon ring or C 3-7 unsaturated heterocycle,
In Formula 1, Q 1 , Q 2 and Q 3 are each independently
Figure pat00144
,
Figure pat00145
,
Figure pat00146
,
Figure pat00147
,
Figure pat00148
,
Figure pat00149
,
Figure pat00150
,
Figure pat00151
,
Figure pat00152
,
Figure pat00153
,
Figure pat00154
or
Figure pat00155
Represents
Y is
Figure pat00156
,
Figure pat00157
,
Figure pat00158
,
Figure pat00159
,
Figure pat00160
,
Figure pat00161
,
Figure pat00162
,
Figure pat00163
,
Figure pat00164
,
Figure pat00165
,
Figure pat00166
,
Figure pat00167
,
Figure pat00168
,
Figure pat00169
,
Figure pat00170
or
Figure pat00171
Represents
0 ≤ x ≤ 0.4, 0.1 ≤ y ≤ 0.9, and 0 ≤ z ≤ 0.5, but x and z cannot be 0 at the same time, and x+y+z=1.
하기 화학식 1a로 나타내는 단위구조를 포함하는, 폴리이미드계 화합물;
[화학식 1a]
Figure pat00172

상기 화학식 1a에서, Ra 는 하기 화학식 2로 나타내고,
[화학식 2]
Figure pat00173

상기 화학식 2에서, R1은 수소 또는 C1-6 알킬기를 나타내고, a 및 b는 각각 독립적으로 1 내지 5의 정수를 나타내고, W1는 산소원자 또는 단결합을 나타내며, L은 C5-10 아릴렌, C1-6 알킬렌, C3-6 알케닐렌, C3-6 알키닐렌, C3-7 헤테로아릴렌, C5-10사이클로알킬렌, C3-10 불포화탄화수소고리 또는 C3-7 불포화헤테로고리를 나타내고,
Q2는
Figure pat00174
,
Figure pat00175
,
Figure pat00176
,
Figure pat00177
,
Figure pat00178
,
Figure pat00179
,
Figure pat00180
,
Figure pat00181
,
Figure pat00182
,
Figure pat00183
,
Figure pat00184
또는
Figure pat00185
를 나타내며,
y는 1 이상의 정수를 나타낸다.
A polyimide-based compound comprising a unit structure represented by Formula 1a below;
[Formula 1a]
Figure pat00172

In Chemical Formula 1a, Ra is represented by Chemical Formula 2 below,
[Formula 2]
Figure pat00173

In Formula 2, R 1 represents hydrogen or a C 1-6 alkyl group, a and b each independently represent an integer of 1 to 5, W 1 represents an oxygen atom or a single bond, and L is C 5-10 Arylene, C 1-6 alkylene, C 3-6 alkenylene, C 3-6 alkynylene, C 3-7 heteroarylene, C 5-10 cycloalkylene, C 3-10 unsaturated hydrocarbon ring or C 3 -7 represents an unsaturated heterocycle,
Q 2 is
Figure pat00174
,
Figure pat00175
,
Figure pat00176
,
Figure pat00177
,
Figure pat00178
,
Figure pat00179
,
Figure pat00180
,
Figure pat00181
,
Figure pat00182
,
Figure pat00183
,
Figure pat00184
or
Figure pat00185
Represents
y represents an integer of 1 or more.
제2항에 있어서,
하기 화학식 1b 및 하기 화학식 1c로 나타내는 단위구조 중 적어도 어느 하나를 더 포함하는, 폴리이미드계 화합물;
[화학식 1b]
Figure pat00186

[화학식 1c]
Figure pat00187

상기 화학식 1b 및 1c에서, Q1 및 Q3은 각각 독립적으로
Figure pat00188
,
Figure pat00189
,
Figure pat00190
,
Figure pat00191
,
Figure pat00192
,
Figure pat00193
,
Figure pat00194
,
Figure pat00195
,
Figure pat00196
,
Figure pat00197
,
Figure pat00198
또는
Figure pat00199
를 나타내고,
상기 화학식 1b에서, Y 는
Figure pat00200
,
Figure pat00201
,
Figure pat00202
,
Figure pat00203
,
Figure pat00204
,
Figure pat00205
,
Figure pat00206
,
Figure pat00207
,
Figure pat00208
,
Figure pat00209
,
Figure pat00210
,
Figure pat00211
,
Figure pat00212
,
Figure pat00213
,
Figure pat00214
또는
Figure pat00215
를 나타내고,
상기 화학식 1c의 Rb는 -C(=O)OH 또는 하기 화학식 3으로 나타내고,
[화학식 3]
Figure pat00216

상기 화학식 3에서, W2는 산소원자 또는 단결합을 나타내고,
d 및 e는 각각 독립적으로 1 내지 5의 정수를 나타내고,
x 및 z는 각각 독립적으로 1 이상의 정수를 나타낸다.
According to claim 2,
A polyimide-based compound further comprising at least one of the unit structures represented by the following Chemical Formulas 1b and 1c;
[Formula 1b]
Figure pat00186

[Formula 1c]
Figure pat00187

In Formulas 1b and 1c, Q 1 and Q 3 are each independently
Figure pat00188
,
Figure pat00189
,
Figure pat00190
,
Figure pat00191
,
Figure pat00192
,
Figure pat00193
,
Figure pat00194
,
Figure pat00195
,
Figure pat00196
,
Figure pat00197
,
Figure pat00198
or
Figure pat00199
And
In the above formula 1b, Y is
Figure pat00200
,
Figure pat00201
,
Figure pat00202
,
Figure pat00203
,
Figure pat00204
,
Figure pat00205
,
Figure pat00206
,
Figure pat00207
,
Figure pat00208
,
Figure pat00209
,
Figure pat00210
,
Figure pat00211
,
Figure pat00212
,
Figure pat00213
,
Figure pat00214
or
Figure pat00215
And
Rb of Formula 1c is represented by -C(=O)OH or Formula 3 below,
[Formula 3]
Figure pat00216

In Chemical Formula 3, W 2 represents an oxygen atom or a single bond,
d and e each independently represent an integer of 1 to 5,
x and z each independently represent an integer of 1 or more.
제3항에 있어서,
x:y=1:9 내지 4:6이고, y:z=1:9 내지 5:5이며, x:z=4:6 내지 5:5인,
폴리이미드계 화합물.
According to claim 3,
x:y=1:9 to 4:6, y:z=1:9 to 5:5, and x:z=4:6 to 5:5,
Polyimide-based compound.
제3항에 있어서,
상기 화학식 1a로 나타내는 구조는 하기 화학식 A로 나타내고,
상기 화학식 1c로 나타내는 구조는 하기 화학식 B 및 하기 화학식 D 중 적어도 어느 하나를 나타내는,
폴리이미드계 화합물;
[화학식 A]
Figure pat00217

[화학식 B]
Figure pat00218

[화학식 D]
Figure pat00219

상기 화학식 A, B 및 D에서 n은 각각 독립적으로 1 이상의 정수를 나타낸다.
According to claim 3,
The structure represented by Formula 1a is represented by the following Formula A,
The structure represented by Chemical Formula 1c represents at least one of the following Chemical Formula B and the following Chemical Formula D,
Polyimide compounds;
[Formula A]
Figure pat00217

[Formula B]
Figure pat00218

[Formula D]
Figure pat00219

In Formulas A, B, and D, each independently represents an integer of 1 or more.
제1항 내지 제5항 중 어느 한 항에 따른 폴리이미드계 화합물, 폴리아믹산, 및 이미드화 촉매를 포함하는, 감광성 조성물.
A photosensitive composition comprising the polyimide-based compound according to any one of claims 1 to 5, a polyamic acid, and an imidation catalyst.
제6항에 있어서,
상기 이미드화 촉매는 피리딘(pyridine), 이소퀴놀린(isoquinoline), β퀴놀린(β, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, N-비닐피롤리돈, N-메틸카프로락탐, 디메틸술폭시드, 테트라메틸요소, 피리딘, 디메틸술폰, 헥사메틸술폭시드, m-크레졸, γ-부티로락톤, 에틸셀로솔브, 부틸셀로솔브, 에틸카르비톨, 부틸카르비톨, 에틸카르비톨 아세테이트, 부틸카르비톨 아세테이트, 에틸렌글리콜, 프로필렌글리콜 모노메틸 에테르 아세테이트(PGMEA), 젖산에틸, 젖산부틸, 시클로헥사논, 및 시클로펜타논 중에서 선택된 1종 이상을 포함하는,
감광성 조성물.
The method of claim 6,
The imidization catalyst is pyridine, isoquinoline, β-quinoline (β, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone , N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ-butyrolactone, ethylcellosolve, butylcellosolve, ethylcarbitol, butyl Comprising at least one selected from carbitol, ethylcarbitol acetate, butylcarbitol acetate, ethylene glycol, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone,
Photosensitive composition.
제6항에 있어서,
1,8-다이아자바이사이클로[5,4,0]운덱-7-엔(1,8-Diazabicyclo[5,4,0]undec-7-ene), 1,5-다이아자바이사이클로(4,3,0)-논-5-엔(1,5-Diazabicyclo(4,3,0)-non-5-ene), 트리에틸아민(trimethylamine), N-메틸이미다졸(Nmethylimidazole) 및 다이아이소프로필에틸렌아민(diisopropylethylamine)중에서 선택된 1종 이상의 반응촉매를 더 포함하는,
감광성 조성물.The method of claim 6,
1,8-Diazabicyclo[5,4,0]undec-7-ene, 1,5-diazabicyclo(4,3 ,0)-non-5-ene (1,5-Diazabicyclo(4,3,0)-non-5-ene), triethylamine, N-methylimidazole and diisopropyl Further comprising at least one reaction catalyst selected from ethyleneamine (diisopropylethylamine),
Photosensitive composition.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003167336A (en) * 2001-11-30 2003-06-13 Kanegafuchi Chem Ind Co Ltd Photosensitive cover lay film
KR20080059815A (en) * 2006-12-26 2008-07-01 주식회사 엘지화학 Black matrix high sensitive photoresist composition for liquid crystal display and black matrix prepared by using the same
KR20110007588A (en) * 2009-07-16 2011-01-24 주식회사 엘지화학 Polyimide and photoresist resin composition comprising therof
US20180263122A1 (en) * 2017-03-13 2018-09-13 Microcosm Technology Co. Ltd. Photosensitive and via-forming circuit board

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003167336A (en) * 2001-11-30 2003-06-13 Kanegafuchi Chem Ind Co Ltd Photosensitive cover lay film
KR20080059815A (en) * 2006-12-26 2008-07-01 주식회사 엘지화학 Black matrix high sensitive photoresist composition for liquid crystal display and black matrix prepared by using the same
KR20110007588A (en) * 2009-07-16 2011-01-24 주식회사 엘지화학 Polyimide and photoresist resin composition comprising therof
US20180263122A1 (en) * 2017-03-13 2018-09-13 Microcosm Technology Co. Ltd. Photosensitive and via-forming circuit board

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