KR102542920B1 - Hexaarylbisimidazole-based mixed photoinitiator and applications - Google Patents
Hexaarylbisimidazole-based mixed photoinitiator and applications Download PDFInfo
- Publication number
- KR102542920B1 KR102542920B1 KR1020217020531A KR20217020531A KR102542920B1 KR 102542920 B1 KR102542920 B1 KR 102542920B1 KR 1020217020531 A KR1020217020531 A KR 1020217020531A KR 20217020531 A KR20217020531 A KR 20217020531A KR 102542920 B1 KR102542920 B1 KR 102542920B1
- Authority
- KR
- South Korea
- Prior art keywords
- bis
- chlorophenyl
- diimidazole
- dimethoxyphenyl
- meth
- Prior art date
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- 238000002834 transmittance Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
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Abstract
헥사아릴비스이미다졸계 혼합 광개시제는, 일반식 (I)과 같이 표시되는 구조를 가지며, 여기서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 비스이미다졸 화합물을 포함하고, 상기 4개의 연결위치의 비스이미다졸 화합물의 혼합 광개시제 내 총 질량 백분율 함량은 92% 이상이며, 일반식 (I)에서, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6는 각각 독립적으로 치환 또는 비치환된 아릴기를 나타낸다. 상기 헥사아릴비스이미다졸계 혼합 광개시제를 포함하는 감광성 수지 조성물은 상용성이 좋고, 감광도가 우수하며, 현상 슬러지량이 적어 건식필름(dry Film) 및 습식필름(wet film)의 방식으로 광범위하게 응용될 수 있다.
(I)The hexaarylbisimidazole-based mixed photoinitiator has a structure represented by general formula (I), wherein the bis of the four linking positions 1'-2, 2-3', 1-2', 2'-3 Including an imidazole compound, the total mass percentage content in the mixed photoinitiator of the four linking biimidazole compounds is 92% or more, and in the general formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 each independently represent a substituted or unsubstituted aryl group. The photosensitive resin composition containing the hexaarylbisimidazole-based mixed photoinitiator has good compatibility, excellent photosensitivity, and a small amount of developing sludge, so it can be widely applied in the form of dry film and wet film. can
(I)
Description
본 발명은 광경화 기술 분야에 속하는 것으로 상세하게는 헥사아릴비스이미다졸계 혼합 광개시제, 상기 광개시제를 포함하는 감광성 수지 조성물 및 감광성 수지 조성물의 응용에 관한 것이다.The present invention belongs to the field of photocuring technology, and more particularly, to a hexaarylbisimidazole-based mixed photoinitiator, a photosensitive resin composition including the photoinitiator, and applications of the photosensitive resin composition.
인쇄 회로 기판, 집적 회로, 박막 트랜지스터, 반도체 패키징 등의 마이크로 전자 회로의 제조에는 일반적으로 포토 리소그래피 공정(Photolithography)을 이용해 레지스트 패턴을 형성하는 방법이 포함된다. 포토 리소그래피 공정에서는, 기판에 코팅된 감광성 수지 조성물층 또는 적층체에 소정의 패턴을 갖는 마스크를 조합하여 노광을 수행하고, 그 다음 노광부와 비노광부에 대한 용해도가 다른 현상액으로 현상하여 레지스트 패턴을 형성하고, 이어서, 레지스트 패턴을 마스크로 하여 기판에 도금 및/또는 에칭 공정 등을 수행함으로써 원하는 도체 패턴을 기판에 형성한다. Manufacturing of microelectronic circuits such as printed circuit boards, integrated circuits, thin film transistors, and semiconductor packaging generally includes a method of forming a resist pattern using a photolithography process. In the photolithography process, exposure is performed by combining a mask having a predetermined pattern on a photosensitive resin composition layer or laminate coated on a substrate, and then developing with a developing solution having different solubility for the exposed and unexposed areas to form a resist pattern. Then, a desired conductor pattern is formed on the substrate by performing a plating and/or etching process on the substrate using the resist pattern as a mask.
정밀 전자 기기의 인쇄 회로 기판의 미세화와 함께 고감광도, 고분해능 및 해상도를 갖는 감광성 수지 조성물이 연구의 이슈가 되었다. 그중, 감광성 수지 조성물의 핵심 성분 중 하나인 광개시제는 높은 개시 효율, 우수한 시스템 상용성 및 우수한 용해도 등이 요구된다. 헥사아릴비스이미다졸계 화합물 (HABI)은 매우 중요한 자유 라디칼 광개시제로서 자외선의 작용하에서 광분해로 대분자 자유 라디칼을 생성할 수 있으나, HABI 및 그 유도체는 일반적인 상태에서 고체이기에 시스템에서의 용해도가 좋지 않다. 일면 광개시제의 완전한 용해 및 분산은 수지 시스템에서의 개시 효율에 직접 관계된다.Along with miniaturization of printed circuit boards of precision electronic devices, photosensitive resin compositions having high photosensitivity, high resolution and resolution have become issues of research. Among them, the photoinitiator, which is one of the core components of the photosensitive resin composition, requires high initiation efficiency, excellent system compatibility, and excellent solubility. Hexaarylbisimidazole-based compound (HABI) is a very important free radical photoinitiator and can generate large molecular free radicals through photolysis under the action of ultraviolet light. . The complete dissolution and dispersion of the one-sided photoinitiator is directly related to the initiation efficiency in the resin system.
용해도 및 감광도에 대한 필요 외에도, 현재 연구에서는 또한 감광성 조성물이 수상(aqueous phase)에서 현상되거나 처리될 수 있기를 많이 강조한다. 감광성 수지 조성물의 조성성분이 현상액 내 용해도가 낮다면, 현상 공정이 반복될 경우, 현상액에 분산성을 떨어뜨리는 불용성 성분이 크게 증가하여 응집물(슬러지)이 생성되고, 현상 공정이 계속되는 경우, 응집물이 기판에 다시 부착되어 단락이 발생할 수 있고, 현상 탱크의 배관이 막힐 수도 있다. Besides the need for solubility and photosensitivity, current research also places great emphasis on the ability of photosensitive compositions to be developed or processed in an aqueous phase. If the components of the photosensitive resin composition have low solubility in the developing solution, when the developing process is repeated, insoluble components that decrease dispersibility in the developing solution greatly increase to form agglomerates (sludge), and when the developing process continues, the agglomerates It may re-attach to the substrate and cause a short circuit, and the piping of the developing tank may be clogged.
HABI 및 그 유도체를 광개시제로 사용하는 종래의 감광성 수지 조성물은, 레지스트 패턴 형성 시, 고감광도, 고용해도, 적은 현상 슬러지(sludge) 등의 장점을 함께 갖지 못한다는 단점에 대해서, 본 발명의 목적은, 우선 HABI계 혼합 광개시제를 제공하는 것이다. The conventional photosensitive resin composition using HABI and its derivatives as a photoinitiator does not have the advantages of high photosensitivity, solubility in solubility, and low development sludge when forming a resist pattern, and the object of the present invention is to , First of all, to provide a HABI-based mixed photoinitiator.
본 발명의 헥사아릴비스이미다졸계 혼합 광개시제는, 일반식 (I)과 같이 표시되는 구조를 가지며, 여기서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 비스이미다졸 화합물을 포함하고, 상기 4개의 연결위치의 비스이미다졸 화합물의 혼합 광개시제 내 총 질량 백분율 함량은 92% 이상이다.The hexaarylbisimidazole-based mixed photoinitiator of the present invention has a structure represented by general formula (I), wherein the four linking positions 1'-2, 2-3', 1-2', 2'- Including the biimidazole compound of 3, the total mass percentage content in the mixed photoinitiator of the biimidazole compound at the 4 linking positions is 92% or more.
(I) (I)
일반식 (I)에서, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6는 서로 동일하거나 상이할 수 있고, 각각 독립적으로 치환 또는 비치환된 아릴기를 나타낸다. 상기 아릴기는 단순 방향족 고리에서 유도되는 임의의 관능기 또는 치환기를 의미하며, 예컨대, 페닐, o-톨릴(o-tolyl), 1-나프틸(또는 α-나프틸), 2-나프틸 등을 예로 들 수 있다. In Formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group. The aryl group refers to any functional group or substituent derived from a simple aromatic ring, and examples thereof include phenyl, o-tolyl, 1-naphthyl (or α-naphthyl), and 2-naphthyl. can be heard
본 발명의 목적은 또한 상기 혼합 광개시제를 포함하는 감광성 수지 조성물 및 상기 조성물의 인쇄 회로 기판, 보호 패턴, 도체 패턴, 리드 프레임(lead frame), 반도체 패키징 등의 제조 영역에서의 응용을 제공하는 것이다. Another object of the present invention is to provide a photosensitive resin composition containing the mixed photoinitiator and application of the composition in manufacturing areas such as printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packaging.
상기 헥사아릴비스이미다졸계 혼합 광개시제를 포함하는 감광성 수지 조성물은 상용성이 좋고, 감광도가 우수하며, 현상 슬러지량이 적어 건식필름(dry Film) 및 습식필름(wet film)의 방식으로 광범위하게 응용될 수 있다.The photosensitive resin composition containing the hexaarylbisimidazole-based mixed photoinitiator has good compatibility, excellent photosensitivity, and a small amount of developing sludge, so it can be widely applied in the form of dry film and wet film. can
본 발명의 목적에 기초해, 하기에서는 각 영역에 대해 보다 자세히 설명한다.Based on the object of the present invention, each area is described in more detail below.
본원의 용어 중 "슬러지(sludge)" 및 "현상 슬러지"는 현상액에 축적되는 물질을 의미하는 것으로, 현상액에 용해되지 않고 기 현상된 기판에 재증착되어 현상액의 효율을 감소시킨다.Among the terms herein, "sludge" and "developing sludge" refer to substances that accumulate in a developer solution, and are redeposited on a pre-developed substrate without being dissolved in the developer solution, thereby reducing the efficiency of the developer solution.
<헥사아릴비스이미다졸계 혼합 광개시제><Hexaarylbisimidazole-based mixed photoinitiator>
본 발명의 헥사아릴비스이미다졸계 혼합 광개시제는, 일반식 (I)과 같이 표시되는 구조를 가지며, 여기서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 비스이미다졸 화합물을 포함하고, 상기 4개의 연결위치의 비스이미다졸 화합물의 혼합 광개시제 내 총 질량 백분율 함량은 92% 이상이다.The hexaarylbisimidazole-based mixed photoinitiator of the present invention has a structure represented by general formula (I), wherein the four linking positions 1'-2, 2-3', 1-2', 2'- Including the biimidazole compound of 3, the total mass percentage content in the mixed photoinitiator of the biimidazole compound at the 4 linking positions is 92% or more.
(I) (I)
일반식 (I)에서, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6는 서로 동일하거나 상이할 수 있고, 각각 독립적으로 치환 또는 비치환된 아릴기를 나타낸다.In Formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group.
상세하게는, 일반식 (I)로 표시되는 구조의 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3를 만족하는 비스이미다졸 화합물은, 하기에 열거되는 구조를 갖는다: Specifically, the biimidazole compounds satisfying the four linking positions 1'-2, 2-3', 1-2', and 2'-3 of the structure represented by the general formula (I) are listed below has the structure:
. .
상기 치환된 아릴기는, 일치환 또는 다치환 될 수 있다. The substituted aryl group may be monosubstituted or polysubstituted.
바람직하게는, 아릴기의 치환기는 할로겐, 니트로기, 시아노기, 아미노기, 히드록시기, C1-C20의 알킬기 또는 알케닐기, C1-C8의 알콕시기 일 수 있으며, 여기서, 각각의 독립 변수(즉, 각 치환기) 중 메틸렌기는 산소, 황, 이미노기로 선택적으로 치환될 수 있다.Preferably, the substituent of the aryl group may be a halogen, a nitro group, a cyano group, an amino group, a hydroxy group, a C 1 -C 20 alkyl or alkenyl group, or a C 1 -C 8 alkoxy group, wherein each independent variable (ie, each substituent), the methylene group may be optionally substituted with an oxygen, sulfur, or imino group.
보다 바람직하게는, 아릴기의 치환기는 불소, 염소, 브롬, 니트로기, 시아노기, 아미노기, 히드록시기, C1-C10의 알킬기 또는 알케닐기, C1-C5의 알콕시기 일 수 있으며, 여기서, 각각의 독립 변수 중 메틸렌기는 산소, 황, 이미노기로 선택적으로 치환될 수 있다. More preferably, the substituent of the aryl group may be fluorine, chlorine, bromine, nitro group, cyano group, amino group, hydroxy group, C 1 -C 10 alkyl or alkenyl group, C 1 -C 5 alkoxy group, wherein , The methylene group of each independent variable may be optionally substituted with an oxygen, sulfur, or imino group.
보다 더 바람직하게는, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6 중 적어도 하나 이상은 할로겐 치환기를 포함하는 아릴기이다. 할로겐 치환기는 경화 과정중의 변색 효과를 향상시켜 현상 시 전자 눈(electronic eye)의 인식 능력(비고: 감광성 수지층은 노광을 거친 후 색 변화가 발생해 비노광 영역과의 색 차이가 형성됨으로써 전자 눈에 의해 인식되는데, 본 발명은 색 차이를 더 명확하게 할 수 있다)을 향상시킴으로써 응용 제품의 품질을 향상시킨다. 특히 바람직하게는, 할로겐 치환기는 염소이다. Even more preferably, at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 is an aryl group containing a halogen substituent. The halogen substituent enhances the discoloration effect during the curing process, and the recognition ability of the electronic eye during development (Note: The photosensitive resin layer undergoes exposure and then changes color, forming a color difference from the unexposed area, thereby perceived by the eye, the present invention can make color differences more distinct), thereby improving the quality of the applied product. Particularly preferably, the halogen substituent is chlorine.
본원에 기술되는 HABI는, 두 트리아릴이미다졸(아릴기의 치환기에 따라 동일하거나 상이할 수 있다)의 커플링에 의해 형성되는 헥사아릴비스이미다졸을 의미한다. 방향족 고리의 치환기의 유도 효과는 방향족 고리의 π전자 구름(electron cloud) 밀도를 감소시키기 때문에, 유도 효과는 방향족 고리의 왜곡을 촉진하고, 이미다졸 고리의 공액 중심의 편이를 유발해, 치환된 아릴을 이미다졸과 상이한 평면에 위치시켜(트리아릴이미다졸이 곡면상태를 형성한다) 최종적으로 두 이미다졸이 커플링하는 경우, N과 C의 연결로 상이한 공간 배열(configuration)이 발현되어 HABI의 성능에 큰 영향을 미치게 된다. HABI as described herein refers to a hexaarylbisimidazole formed by coupling of two triarylimidazoles (which may be the same or different depending on the substituents on the aryl groups). Since the inductive effect of the substituent on the aromatic ring reduces the π electron cloud density of the aromatic ring, the inductive effect promotes the distortion of the aromatic ring and causes the shift of the conjugate center of the imidazole ring, resulting in a substituted aryl When the two imidazoles are finally coupled by placing on a different plane from the imidazole (triarylimidazole forms a curved state), a different spatial configuration is expressed by the connection of N and C, resulting in HABI's It will have a big impact on performance.
HABI계 광개시제는, 상술한 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3를 제외한, 연결위치 1-4', 1-5', 3-4', 3-5', 1-1', 1-3', 3-1', 3-3', 4-1', 4-3', 5-1', 5-3' 등이 더 존재한다. 그러나, 출원인은 연구에서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3가 존재하고,그 총 함량이 HABI 총량의 92% 이상을 차지하는 경우에만, HABI가 가장 우수한 용해도 및 감광도를 보이는 것을 발견하였다. 임의의 어느 한 연결위치의 단일 물질의 용해도는 본 발명의 혼합물의 용해도 보다 모두 현저히 낮고, 이들 4개의 연결위치의 총 함량이 92% 미만일 경우, 감광도는 현저히 낮아지는 경향이 있다. HABI-based photoinitiators, excluding the above-mentioned four linking positions 1'-2, 2-3', 1-2', 2'-3, linking positions 1-4', 1-5', 3-4', 3-5', 1-1', 1-3', 3-1', 3-3', 4-1', 4-3', 5-1', 5-3' and the like are further present. However, in the study, the applicant found that only when there are four linking positions 1'-2, 2-3', 1-2', 2'-3, and their total content accounts for 92% or more of the total amount of HABI, HABI It was found that showed the best solubility and photosensitivity. The solubility of a single substance at any one linking position is significantly lower than that of the mixture of the present invention, and when the total content of these four linking positions is less than 92%, the photosensitivity tends to be significantly lowered.
본 발명의 HABI계 혼합 광개시제로는, 바람직하게는, 일반식 (I)로 표시되는 구조의 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3를 만족하는 비스이미다졸 화합물의 혼합 광개시제 내 총 질량 백분율 함량은 95% 이상이고, 특히 바람직하게는, 일반식 (I)로 표시되는 구조의 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3를 만족하는 비스이미다졸 화합물로 이루어진다. The HABI-based mixed photoinitiator of the present invention preferably satisfies the four linking positions 1'-2, 2-3', 1-2', 2'-3 of the structure represented by Formula (I) The total mass percentage content of the biimidazole compound in the mixed photoinitiator is 95% or more, and particularly preferably, the four linking positions 1'-2, 2-3', 1-2 of the structure represented by the general formula (I) ', 2'-3 is composed of a biimidazole compound that satisfies.
대표적으로, 선행기술 중 CN1292892A에는 포토 레지스트 광중합 시스템에 사용되는 HABI계 광개시제, 즉 통상적으로 "TCDM-HABI"라 불리우는 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1,2'-디이미다졸이 제시되어 있고, 상기 문헌에는, 적어도 하나 이상의 친수성 치환기(예를 들어, 메톡시)를 포함하는 HABI를 사용하면 재활용 현상액의 슬러지량을 크게 줄일 수 있다고 제시되어 있다. 그러나, 출원인은 연구에서, 단일 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1,2'-디이미다졸 또는 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1',2-디이미다졸은 부탄온 또는 PGMEA에서 용해도가 낮고, 예를 들면, PGMEA에서 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1,2'-디이미다졸의 용해도는 3%에 미치지 못하며; 상기 2종의 단일 HABI를 사용하여 제조된 감광성 수지 조성물은 현상 시, 현상액 내 슬러지량이 예상 효과보다 많이 떨어짐을 발견하였다. 예상치 못하게도, 4종의 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1,2'-디이미다졸, 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-2',3-디이미다졸, 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-2,3'-디이미다졸, 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1',2-디이미다졸을 서로 혼합하는 경우, 상기 혼합물의 용매 내 용해도가 크게 향상되고; 또한, 상기 혼합물을 감광성 수지 조성물에 적용하면 재활용 현상액의 슬러지량을 크게 줄일 수 있어 현상액을 반복해서 여러번 효과적으로 사용할 수 있다. Representatively, in the prior art, CN1292892A has a HABI-based photoinitiator used in a photoresist photopolymerization system, that is, 2,2',5-tris (o-chlorophenyl) -4- (3,4, commonly called "TCDM-HABI") -dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole is presented, in which HABI containing at least one or more hydrophilic substituents (eg methoxy) It is suggested that the sludge amount of the recycled developer can be greatly reduced. However, in the study, Applicants found that a single 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-di Imidazole or 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole is butanone or low solubility in PGMEA, for example 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1 in PGMEA The solubility of 2'-diimidazole is less than 3%; It was found that the photosensitive resin composition prepared using the two single HABIs had a much lower than expected effect in the amount of sludge in the developing solution during development. Unexpectedly, four types of 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimine dazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole, 2,2 ',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole, 2,2',5-tris When (o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole is mixed with each other, the solubility of the mixture in the solvent is high. improved; In addition, when the mixture is applied to the photosensitive resin composition, the sludge amount of the recycled developer can be greatly reduced, so that the developer can be used repeatedly and effectively several times.
HABI계 광개시제는 포토 레지스트 분야의 공지된 광개시제의 일종으로, 트리페닐이미다졸(triphenylimidazole)계 또는 치환된 트리페닐이미다졸계 화합물의 산화 커플링에 의해 제조될 수 있고, 구체적인 제조 공정은 예를 들어, US3784557, US4622286, US4311783 등과 같은 선행 기술의 기재(본원에 그 전문을 참고로 인용함)를 참조할 수 있다. 종래 공정에 기초해, 재결정 공정을 추가하면, 본 발명의 상기 조성 요건을 충족하는 HABI계 혼합 광개시제를 바로 용이하게 얻을 수 있다. 상기 용매는 톨루엔, 메탄올, 에틸아세테이트, 디클로로메탄, 물 중 하나이거나 또는 2종 이상의 조합물일 수 있다.HABI-based photoinitiator is a kind of photoinitiator known in the field of photoresist, and can be prepared by oxidative coupling of a triphenylimidazole-based or substituted triphenylimidazole-based compound, and a specific manufacturing process is, for example, For example, reference may be made to prior art descriptions such as US3784557, US4622286, US4311783, etc., which are incorporated herein by reference in their entirety. Based on the conventional process, by adding a recrystallization process, the HABI-based mixed photoinitiator satisfying the above compositional requirements of the present invention can be readily obtained. The solvent may be one of toluene, methanol, ethyl acetate, dichloromethane, water, or a combination of two or more.
<감광성 수지 조성물><Photosensitive resin composition>
본 발명의 감광성 수지 조성물은, 통상적으로 상기 HABI계 혼합 광개시제를 제외하고, 알칼리 가용성 중합체; 에틸렌성 불포화 이중 결합을 갖는 화합물; 기타 광개시제 및/또는 증감제; 및 선택적으로 함유되는 보조제를 더 포함한다. The photosensitive resin composition of the present invention, except for the HABI-based mixed photoinitiator, is usually an alkali-soluble polymer; compounds having ethylenically unsaturated double bonds; other photoinitiators and/or sensitizers; and an adjuvant optionally contained.
알칼리 가용성 중합체alkali soluble polymer
알칼리 가용성 중합체는 감광성 수지 조성물에 성막 성능을 부여할 수 있다. 알칼리 가용성 중합체로서는, 이러한 특성을 갖는 중합체라면 특별한 제한없이 적용될 수 있다.The alkali-soluble polymer can impart film-forming performance to the photosensitive resin composition. As the alkali-soluble polymer, any polymer having these characteristics can be applied without particular limitation.
예시적으로, 적용되는 알칼리 가용성 중합체는, (메타)아크릴계 중합체, 스티렌계 중합체, 에폭시계 중합체, 지방족 폴리우레탄(메타)아크릴레이트 중합체, 방향족 폴리우레탄(메타)아크릴레이트 중합체, 아미드계 수지, 아미드 에폭시계 수지, 알키드계 수지, 페놀계 수지(phenolic resins) 등일 수 있다.Illustratively, the alkali-soluble polymers applied include (meth)acrylic polymers, styrene-based polymers, epoxy-based polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic polyurethane (meth)acrylate polymers, amide-based resins, and amides. Epoxy-based resins, alkyd-based resins, phenolic resins, and the like may be used.
또한, 알칼리 가용성 중합체는 중합성 단량체의 자유 라디칼 중합을 통해 얻을 수 있다. 중합성 단량체로서는, 예를 들어, 스티렌, 비닐톨루엔, α-메틸스티렌, p-메틸스티렌, p-에틸스티렌, p-클로로스티렌 등의 α-위치 또는 방향족 고리에서 치환된 중합 가능한 스티렌 유도체; 아크릴아미드, 디아세톤아크릴아미드 등의 아크릴아미드 유도체; 아크릴로니트릴, n-부틸비닐에테르 등의 비닐알코올의 에테르계 유도체; (메타)아크릴산, α-브로모(메타)아크릴산, α-클로로(메타)아크릴산, β-푸릴(메타)아크릴산, β-스티릴(메타)아크릴산 등의 (메타)아크릴산 유도체; 알킬(메타)아크릴레이트, 벤질(메타)아크릴레이트, 페녹시에틸메타크릴레이트, 테트라히드로푸르푸릴(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 디에틸아미노에틸(메타)아크릴레이트, 글리시딜(메타)아크릴레이트, 2,2,2-트리플루오로에틸(메타)아크릴레이트, 2,2,3,3-테트라플루오로프로필(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 테트라히드로푸르푸릴(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 디에틸아미노에틸(메타)아크릴레이트, 글리시딜(메타)아크릴레이트 등의 (메타)아크릴레이트계; 말레산, 말레산 무수물, 말레산 모노메틸 에스테르, 말레산 모노에틸 에스테르, 말레산 모노이소프로필 에스테르 등의 말레산 모노 에스테르; 푸마르산, 신남산, α-시아노신남산, 이타콘산, 크로톤산, 프로판올산(propanolic acid), N-비닐카프로락탐; N-비닐피롤리돈 등을 예로 들 수 있다. 이들 중합성 단량체는 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다.Alkali-soluble polymers can also be obtained through free radical polymerization of polymerizable monomers. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and p-chlorostyrene; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohol such as acrylonitrile and n-butyl vinyl ether; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; Alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, Glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate (meth)acrylate systems such as acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and glycidyl (meth)acrylate; maleic acid monoesters such as maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, and maleic acid monoisopropyl ester; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propanolic acid, N-vinyl caprolactam; N-vinylpyrrolidone and the like are exemplified. These polymerizable monomers may be used alone or in combination of two or more.
또한, 알칼리 현상성 및 밀착성 관점에서 고려하여 바람직하게는 카르복실기를 포함하는 알칼리 가용성 중합체를 사용한다. 카르복실기를 갖는 알칼리 가용성 중합체는, 단량체 단위로 (메타)아크릴산을 사용하여 카르복실기를 도입하는 단량체 단위로 (메타)아크릴산을 포함하는 아크릴 수지일 수 있고; (메타)아크릴산 제외하고 단량체 단위로 알킬(메타)아크릴레이트를 더 포함하는 공중합체일 수 있으며; 또한 (메타)아크릴산을 제외하고 단량체 성분으로 (메타)아크릴산 및 알킬(메타)아크릴레이트 이외의 중합성 단량체(예를 들어, 에틸렌성 불포화기를 갖는 단량체)를 더 포함하는 공중합체일 수 있다. Also, from the standpoint of alkali developability and adhesion, an alkali-soluble polymer containing a carboxyl group is preferably used. The alkali-soluble polymer having a carboxyl group may be an acrylic resin containing (meth)acrylic acid as a monomer unit introducing a carboxyl group using (meth)acrylic acid as a monomer unit; It may be a copolymer further including an alkyl (meth)acrylate as a monomer unit in addition to (meth)acrylic acid; In addition, it may be a copolymer that further includes a polymerizable monomer (eg, a monomer having an ethylenically unsaturated group) other than (meth)acrylic acid and alkyl (meth)acrylate as monomer components except for (meth)acrylic acid.
또한, 카르복실기를 포함하는 알칼리 가용성 중합체는, 카르복실기를 갖는 중합성 단량체와 기타 중합성 단량체의 자유 라디칼 중합을 통해 얻을 수 있고, 특히 (메타)아크릴레이트, 에틸렌성 불포화 카르복실산 및 기타 공중합 가능한 단량체의 공중합에 의해 형성되는 (메타)아크릴레이트계 중합체이다. 상기 (메타)아크릴레이트는, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 헵틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 운데실(메타)아크릴레이트, 도데실(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 벤질(메타)아크릴레이트, 디에틸아미노에틸(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 히드록시프로필(메타)아크릴레이트, 푸르푸릴(메타)아크릴레이트, 글리시딜(메타)아크릴레이트 등일 수 있다. 이들 (메타)아크릴레이트는 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다. 상기 에틸렌성 불포화 카르복실산은, 아크릴산, 메타크릴산, 부텐산(butenoic acid), 말레산, 푸마르산, 이타콘산 일 수 있고, 특히 바람직하게는, 아크릴산, 메타크릴산이다. 이들 에틸렌성 불포화 카르복실산은 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다. 상기 기타 공중합 가능한 단량체는, (메타)아크릴아미드, n-부틸(메타)아크릴레이트, 스티렌, 비닐나프탈렌, (메타)아크릴로니트릴, 비닐아세테이트, 비닐시클로헥산 등일 수 있다. 이들 기타 공중합 가능한 단량체는 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다.In addition, the alkali-soluble polymer containing a carboxyl group can be obtained through free radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers, particularly (meth)acrylates, ethylenically unsaturated carboxylic acids and other copolymerizable monomers. It is a (meth)acrylate-based polymer formed by copolymerization of The (meth)acrylate is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, Heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate )Acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, furfuryl (meth)acrylate, glycidyl (meth)acrylate, and the like. These (meth)acrylates may be used alone or in combination of two or more. The ethylenically unsaturated carboxylic acid may be acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, or itaconic acid, and particularly preferably, acrylic acid or methacrylic acid. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more. The other copolymerizable monomers may be (meth)acrylamide, n-butyl(meth)acrylate, styrene, vinylnaphthalene, (meth)acrylonitrile, vinylacetate, vinylcyclohexane, and the like. These other copolymerizable monomers can be used alone or in combination of two or more.
알칼리 가용성 중합체는 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다. 2종 이상을 조합하여 사용하는 알칼리 가용성 중합체로서는, 공중합 성분 구성이 상이한 2종 이상의 알칼리 가용성 중합체, 중량 평균 분자량이 상이한 2종 이상의 알칼리 가용성 중합체, 분산도가 상이한 2종 이상의 알칼리 가용성 중합체 등을 예로 들 수 있다. Alkali-soluble polymers can be used alone or in combination of two or more. Examples of the alkali-soluble polymers used in combination of two or more include two or more alkali-soluble polymers with different copolymerization component constitutions, two or more alkali-soluble polymers with different weight average molecular weights, two or more alkali-soluble polymers with different degrees of dispersion, and the like. can be heard
본 발명의 감광성 수지 조성물에 있어서, 알칼리 가용성 중합체의 중량 평균 분자량은 특별히 제한되지 않으나, 기계적 강도 및 알칼리 현상성 측면에서 종합적으로 고려하여, 중량 평균 분자량은 바람직하게는, 15000-200000, 보다 바람직하게는, 30000-150000, 특히 바람직하게는, 30000-120000이다. 중량 평균 분자량이 15000을 초과는 경우, 노광 후 내현상액성이 추가로 향상되는 경향이 있으며, 상기 중량 평균 분자량이 200000 미만일 경우, 현상 시간이 더 짧아지는 경향이 있고 광개시제 등의 기타 성분과의 상용성을 유지할 수 있다. 알칼리 가용성 중합체의 중량 평균 분자량은 겔투과크로마토그래피(GPC, Gel Permeation Chromatography)로 측정하고, 표준 폴리스티렌의 표준 곡선(standard curve)을 이용한 환산을 통해 얻는다. In the photosensitive resin composition of the present invention, the weight average molecular weight of the alkali-soluble polymer is not particularly limited, but comprehensively considered in terms of mechanical strength and alkali developability, the weight average molecular weight is preferably 15000-200000, more preferably is 30000-150000, particularly preferably 30000-120000. When the weight average molecular weight is more than 15000, the post-exposure solution resistance tends to be further improved, and when the weight average molecular weight is less than 200000, the developing time tends to be shorter and compatibility with other components such as photoinitiators can keep the castle. The weight average molecular weight of the alkali-soluble polymer is measured by gel permeation chromatography (GPC) and obtained through conversion using a standard polystyrene standard curve.
또한, 우수한 알칼리 현상성 관점에서 고려하여, 알칼리 가용성 중합체의 산가는 바람직하게는, 50-300mgKOH/g, 보다 바람직하게는, 50-250mgKOH/g, 보다 더 바람직하게는, 70-250mgKOH/g, 특히 바람직하게는, 100-250mgKOH/g이다. 알칼리 가용성 수지의 산가가 50mgKOH/g 미만일 경우, 충분한 현상 속도를 확보하기 어렵고, 300mgKOH/g을 초과할 경우, 밀착성이 감소하고 패턴 단락이 발생하기 쉬우며, 조성물의 보관 안정성이 저하되고, 점도가 올라가는 문제가 용이하게 발생한다. Also, from the standpoint of excellent alkali developability, the acid value of the alkali-soluble polymer is preferably 50-300 mgKOH/g, more preferably 50-250 mgKOH/g, still more preferably 70-250 mgKOH/g, Especially preferably, it is 100-250 mgKOH/g. When the acid value of the alkali-soluble resin is less than 50 mgKOH/g, it is difficult to secure a sufficient development rate, and when it exceeds 300 mgKOH/g, adhesion is reduced and pattern short circuits are likely to occur, storage stability of the composition is lowered, and viscosity is reduced. The problem of going up easily arises.
알칼리 가용성 수지의 분자량 분포[중량 평균 분자량(Mw) / 수 평균 분자량(Mn)]는 바람직하게는, 1.5-6.0, 특히 바람직하게는 1.8-3.7이다. 분자량 분포가 상기 범위일 경우, 현상성이 우수한다.The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.5 to 6.0, particularly preferably 1.8 to 3.7. When the molecular weight distribution is within the above range, developability is excellent.
감광성 수지 조성물의 전체 100 질량부에서, 조성물 중 알칼리 가용성 중합체의 함량은 바람직하게는 20-70 질량부, 보다 바람직하게는 30-60 질량부이다. 알칼리 가용성 중합체의 함량이 20 질량부 이상일 경우, 감광성 수지 조성물의 도금 처리, 에칭 처리 등에 대한 내구성 향상을 확보할 수 있으며, 함량이 70 질량부 이하일 경우, 감광성 수지 조성물의 감도를 높이는데 유리하다.In total 100 parts by mass of the photosensitive resin composition, the content of the alkali-soluble polymer in the composition is preferably 20-70 parts by mass, more preferably 30-60 parts by mass. When the content of the alkali-soluble polymer is 20 parts by mass or more, it is possible to secure improved durability of the photosensitive resin composition for plating and etching, and when the content is 70 parts by mass or less, it is advantageous to increase the sensitivity of the photosensitive resin composition.
에틸렌성 불포화 이중 결합을 갖는 화합물Compounds with ethylenically unsaturated double bonds
에틸렌성 불포화 이중 결합을 갖는 화합물은 감광성 수지 조성물의 성막을 촉진할 수 있다.A compound having an ethylenically unsaturated double bond can promote film formation of the photosensitive resin composition.
에틸렌성 불포화 이중 결합을 갖는 화합물은 특별히 제한되지 않고, 분자 내에 적어도 하나 이상의 에틸렌성 불포화 결합을 갖는 광중합성 화합물이면 사용할 수 있다. 예시적으로, α,β-불포화 카르복실산과 폴리올을 반응시켜 얻은 화합물, 비스페놀 A계 (메타)아크릴레이트 화합물, α,β-불포화 카르복실산과 글리시딜 함유 화합물을 반응시켜 얻은 화합물, 분자 내에 우레탄 결합을 갖는 (메타)아크릴레이트 화합물 등의 우레탄(urethane) 단량체, 노닐페녹시폴리에틸렌옥시아크릴레이트, γ-클로로-β-히드록시프로필-β'-(메타)아크릴로일옥시에틸-o-프탈레이트, β-히드록시에틸-β'-(메타)아크릴로일옥시에틸-o-프탈레이트, β-히드록시프로필-β'-(메타)아크릴로일옥시에틸-o-프탈레이트, 프탈산(phthalic acid)계 화합물, 알킬(메타)아크릴레이트 등을 예로 들 수 있다. 이들 화합물은 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다. The compound having an ethylenically unsaturated double bond is not particularly limited, and any photopolymerizable compound having at least one ethylenically unsaturated bond in a molecule may be used. Illustratively, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, a bisphenol A-based (meth)acrylate compound, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl-containing compound, in a molecule Urethane monomers such as (meth)acrylate compounds having urethane bonds, nonylphenoxypolyethyleneoxyacrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o- Phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, phthalic acid )-based compounds, alkyl (meth)acrylates, and the like. These compounds may be used alone or in combination of two or more.
상기 α,β-불포화 카르복실산과 폴리올을 반응시켜 얻은 화합물로서는, 예를 들어, 에틸렌옥사이드(ethylene oxide) 그룹수가 2-14인 폴리에틸렌글리콜디(메타)아크릴레이트, 프로필렌옥사이드 그룹수가 2-14인 폴리프로필렌글리콜디(메타)아크릴레이트, 에틸렌옥사이드그룹의 수가 2-14이고 프로필렌옥사이드그룹의 수가 2-14인 폴리에틸렌옥사이드·폴리프로필렌옥사이드 디올디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, EO 변성 트리메틸올프로판트리(메타)아크릴레이트, PO 변성 트리메틸올프로판트리(메타)아크릴레이트, EO, PO 변성 트리메틸올프로판트리(메타)아크릴레이트, 테트라메틸올메탄트리(메타)아크릴레이트, 테트라메틸올메탄테트라(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트, 폴리프로필렌글리콜모노(메타)아크릴레이트, 폴리에틸렌글리콜모노(메타)아크릴레이트, 트리프로필렌글리콜디(메타)아크릴레이트 등을 예로 들 수 있다. 이들 화합물은 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다. 여기서, "EO"는 에틸렌옥사이드(Ethylene oxide)를 나타내고, EO 변성 화합물은 에틸렌옥사이드기의 블록 구조를 갖는 화합물을 의미하고; "PO"는 프로필렌옥사이드(Propylene oxide)를 나타내고, PO 변성 화합물은 프로필렌옥사이드기의 블록 구조를 갖는 화합물을 의미한다.Examples of the compound obtained by reacting the α,β-unsaturated carboxylic acid with a polyol include polyethylene glycol di(meth)acrylate having 2-14 ethylene oxide groups and 2-14 propylene oxide groups. Polypropylene glycol di(meth)acrylate, polyethylene oxide/polypropylene oxide dioldi(meth)acrylate, trimethylolpropane di(meth)acrylate having 2-14 ethylene oxide groups and 2-14 propylene oxide groups Rate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, Tetramethylolmethanetri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polypropylene glycol mono(meth)acrylate ) acrylate, polyethylene glycol mono(meth)acrylate, tripropylene glycol di(meth)acrylate, and the like. These compounds may be used alone or in combination of two or more. Here, “EO” represents ethylene oxide, and the EO-modified compound means a compound having a block structure of an ethylene oxide group; "PO" represents propylene oxide, and the PO-modified compound means a compound having a block structure of a propylene oxide group.
상기 비스페놀 A계 (메타)아크릴레이트 화합물로서는, 예를 들어, 2,2-비스(4-((메타)아크릴로일옥시폴리에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시폴리프로폭시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시폴리부톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시폴리에톡시폴리프로폭시)페닐)프로판 등을 예로 들 수 있다. 상기 2,2-비스(4-((메타)아크릴로일옥시폴리에톡시)페닐)프로판으로서는, 예를 들어, 2,2-비스(4-((메타)아크릴로일옥시디에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시트리에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시테트라에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시펜타에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시헥사에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시헵타에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시옥타에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시노나에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시데카에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시운데카에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시도데카에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시트리데카에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시테트라데카에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시펜타데카에톡시)페닐)프로판, 2,2-비스(4-((메타)아크릴로일옥시헥사데카에톡시)페닐)프로판 등을 예로 들 수 있다. 상기 2,2-비스(4-((메타)아크릴로일옥시폴리에톡시)페닐)프로판의 1 분자내에 에틸렌옥사이드기의 수는 바람직하게는 4-20, 보다 바람직하게는 8-15이다. 이들 화합물은 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다.Examples of the bisphenol A-based (meth)acrylate compound include 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane and 2,2-bis(4-(( meth)acryloyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolybutoxy)phenyl)propane, 2,2-bis(4-((meth) acryloyloxypolyethoxypolypropoxy)phenyl)propane and the like are exemplified. As the 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, for example, 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl ) Propane, 2,2-bis(4-((meth)acryloyloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetraethoxy)phenyl)propane , 2,2-bis(4-((meth)acryloyloxypentaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyhexaethoxy)phenyl)propane, 2 ,2-bis(4-((meth)acryloyloxyheptaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyoctaethoxy)phenyl)propane, 2,2 -bis(4-((meth)acryloyloxynonaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydecaethoxy)phenyl)propane, 2,2-bis (4-((meth)acryloyloxyundecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydodecaethoxy)phenyl)propane, 2,2-bis(4 -((meth)acryloyloxytridecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetradecaethoxy)phenyl)propane, 2,2-bis(4 -((meth)acryloyloxypentadecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyhexadecaethoxy)phenyl)propane and the like. The number of ethylene oxide groups in one molecule of the 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane is preferably 4-20, more preferably 8-15. These compounds may be used alone or in combination of two or more.
상기 분자내에 우레탄 결합을 갖는 (메타)아크릴레이트 화합물로서는, 예를 들어, β 위치에 OH기를 갖는 (메타)아크릴레이트계 단량체와 디이소시아네이트 화합물(이소포론디이소시아네이트, 2,6-톨루엔디이소시아네이트, 2,4-톨루엔디이소시아네이트, 1,6-헥사메틸렌디이소시아네이트 등)의 부가 반응물, 트리스((메타)아크릴로일옥시테트라에틸렌디올이소시아네이트)헥사메틸렌이소시아누레이트, EO 변성 우레탄디(메타)아크릴레이트, PO 변성 우레탄디(메타)아크릴레이트, EO, PO 변성 우레탄디(메타)아크릴레이트 등을 예로 들 수 있다. 이들 화합물은 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다.As the (meth)acrylate compound having a urethane bond in the molecule, for example, a (meth)acrylate-based monomer having an OH group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.) addition reaction product, tris((meth)acryloyloxytetraethylenediol isocyanate) hexamethylene isocyanurate, EO modified urethane di(meth) Acrylates, PO-modified urethanedi(meth)acrylates, EO, PO-modified urethanedi(meth)acrylates and the like are exemplified. These compounds may be used alone or in combination of two or more.
상기 노닐페녹시폴리에틸렌옥시아크릴레이트로서는, 예를 들어, 노닐페녹시테트라에틸렌옥시아크릴레이트, 노닐페녹시펜타에틸렌옥시아크릴레이트, 노닐페녹시헥사에틸렌옥시아크릴레이트, 노닐페녹시헵타에틸렌옥시아크릴레이트, 노닐페녹시옥타에틸렌옥시아크릴레이트, 노닐페녹시노나에틸렌옥시아크릴레이트, 노닐페녹시데카에틸렌옥시아크릴레이트, 노닐페녹시운데카에틸렌옥시아크릴레이트 등을 예로 들 수 있다. 이들 화합물은 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다.Examples of the nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, Nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, nonylphenoxyundecaethyleneoxyacrylate and the like are exemplified. These compounds may be used alone or in combination of two or more.
상기 프탈산계 화합물로서는, 예를 들어, γ-클로로-β-히드록시프로필-β'-(메타)아크릴로일옥시에틸-o-프탈레이트, β-히드록시알킬-β'-(메타)아크릴로일옥시알킬-o-프탈레이트 등을 예로 들 수 있다. 이들 화합물은 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다.Examples of the phthalic acid compound include γ-chloro-β-hydroxypropyl-β′-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β′-(meth)acrylo yloxyalkyl-o-phthalate and the like are exemplified. These compounds may be used alone or in combination of two or more.
상기 알킬(메타)아크릴레이트로서는, 예를 들어, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, iso-프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, sec-부틸(메타)아크릴레이트, tert-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 페닐(메타)아크릴레이트, iso-보르닐(메타)아크릴레이트, 히드록시메틸(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 히드록시프로필(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 벤질(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 테트라히드로푸르푸릴 (메타)아크릴레이트, iso-옥틸(메타)아크릴레이트, 에톡시화 노닐페놀(메타)아크릴레이트, 프로필렌글리콜폴리프로필렌에테르디(메타)아크릴레이트(propylene glycol polypropylene ether di(meth)acrylate), 1,9-노난디올디(메타)아크릴레이트, 1,10-데칸디올디(메타)아크릴레이트, 에톡시화 폴리테트라히드로푸란디올디(메타)아크릴레이트, 에톡시화 폴리프로필렌글리콜디(메타)아크릴레이트 등을 예로 들 수 있다. 여기서, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 에톡시화 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 에톡시화 펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨헥사아크릴레이트가 바람직하다. 이들 화합물은 단독으로 사용할 수 있고, 2종 이상을 조합하여 사용할 수도 있다.As said alkyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, for example )acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, iso-bornyl (meth)acrylate, hydroxy hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl ( meth)acrylate, pentyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, iso-octyl (meth)acrylate, ethoxylated nonylphenol (meth)acrylate, propylene glycol polypropylene ether di(meth) Acrylate (propylene glycol polypropylene ether di(meth)acrylate), 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, ethoxylated polytetrahydrofurandioldi(meth)acrylate ) acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and the like. Here, methyl (meth) acrylate, ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexaacrylate are preferred. These compounds may be used alone or in combination of two or more.
상기 에틸렌성 불포화 이중 결합을 갖는 화합물은, 해상도, 내도금성, 밀착성 향상의 관점에서, 비스페놀 A계 (메타)아크릴레이트 화합물 및 분자 내에 우레탄 결합을 갖는 (메타)아크릴레이트 화합물이 바람직하고, 감도 및 해상도 향상의 관점에서, 비스페놀 A계 (메타)아크릴레이트 화합물이 바람직하다. 비스페놀 A계 (메타)아크릴레이트 화합물의 시판품으로는, 예시적으로, 2,2-비스(4-((메타)아크릴로일옥시폴리에톡시)페닐)프로판(예: Shin Nakamura Chemical Industry Co., Ltd., 제조의 BPE-200), 폴리에톡시비스페놀A메타크릴레이트(예: Shin Nakamura Chemical Industry Co., Ltd., 제조의 BPE-5000; Hitachi Chemical Co., Ltd., 제조의 FA-321M), 2,2-비스(4-((메타)아크릴로일옥시폴리부톡시)페닐)프로판(예: Shin Nakamura Chemical Industry Co., Ltd., 제조의 BPE-1300) 등을 들 수 있다.The compound having an ethylenically unsaturated double bond is preferably a bisphenol A-based (meth)acrylate compound and a (meth)acrylate compound having a urethane bond in the molecule, from the viewpoint of improving resolution, plating resistance, and adhesion, and sensitivity and From the viewpoint of resolution improvement, bisphenol A-based (meth)acrylate compounds are preferred. Commercially available products of the bisphenol A-based (meth)acrylate compound include, for example, 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane (e.g., Shin Nakamura Chemical Industry Co. , Ltd., BPE-200), polyethoxybisphenol A methacrylate (e.g., Shin Nakamura Chemical Industry Co., Ltd., BPE-5000; Hitachi Chemical Co., Ltd., FA- 321M), 2,2-bis(4-((meth)acryloyloxypolybutoxy)phenyl)propane (e.g. BPE-1300 manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and the like. .
감광성 수지 조성물 100 질량부에 있어서, 에틸렌성 불포화 이중 결합을 갖는 화합물의 함량은, 바람직하게는 20-50 질량부, 보다 바람직하게는 25-45 질량부이다. 상기 에틸렌성 불포화 이중 결합을 갖는 화합물의 함량이 20 질량부 이상일 경우, 감광성 수지 조성물의 감도 및 해상도는 추가로 향상될 수 있고; 그 함량이 50 질량부 이하일 경우, 감광성 수지 조성물은 더 용이하게 박막화되며, 에칭 처리에 대한 내구성이 추가로 향상된다. In 100 parts by mass of the photosensitive resin composition, the content of the compound having an ethylenically unsaturated double bond is preferably 20 to 50 parts by mass, more preferably 25 to 45 parts by mass. When the content of the compound having an ethylenically unsaturated double bond is 20 parts by mass or more, the sensitivity and resolution of the photosensitive resin composition can be further improved; When the content is 50 parts by mass or less, the photosensitive resin composition is more easily thinned, and durability to etching treatment is further improved.
HABI계 혼합 광개시제 HABI-based mixed photoinitiator
상술한 바와 같이, 본 발명의 HABI계 혼합 광개시제는, 일반식 (I)과 같이 표시되는 구조를 가지며, 여기서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 비스이미다졸 화합물을 포함하고, 상기 4개의 연결위치의 비스이미다졸 화합물의 혼합 광개시제 내 총 질량 백분율 함량은 92% 이상, 바람직하게는, 95% 이상, 특히 바람직하게는, 100%이다. As described above, the HABI-based mixed photoinitiator of the present invention has a structure represented by general formula (I), wherein the four linking positions 1'-2, 2-3', 1-2', 2' -3 including the biimidazole compound, and the total mass percentage content in the mixed photoinitiator of the bisimidazole compound at the four linking positions is 92% or more, preferably 95% or more, particularly preferably 100% .
(I) (I)
일반식 (I)에서, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6는 서로 동일하거나 상이할 수 있고, 각각 독립적으로 치환 또는 비치환된 아릴기를 나타낸다.In Formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group.
본 발명의 HAB계 혼합 광개시제는, 상기 특정된 제한 범위 내에서 예시적으로, 다음에서 선택되거나 또는 다음을 포함할 수 있다:The HAB-based mixed photoinitiator of the present invention may, illustratively within the limits specified above, be selected from or include:
화합물 A1:Compound A1:
화합물 A2:Compound A2:
화합물 A3:Compound A3:
화합물 A4:Compound A4:
화합물 A5:Compound A5:
화합물 A6:Compound A6:
화합물 A7:Compound A7:
화합물 A8:Compound A8:
화합물 A9:Compound A9:
본 발명의 헥사아릴비스이미다졸계 혼합 광개시제에는, 예하면 화합물 A1, 화합물 A2등은 단독으로 존재할 수도 있고, 2종 이상을 혼합하여 사용할 수도 있다.In the hexaarylbisimidazole-based mixed photoinitiator of the present invention, for example, Compound A1 and Compound A2 may be present alone or may be used in combination of two or more kinds.
감광성 수지 조성물 100 질량부에 있어서, 본 발명의 헥사아릴비스이미다졸계 혼합 광개시제는 1-10 질량부가 바람직하다. 상기 함량 범위 내에서, 조성물은 우수한 시스템 상용성 및 우수한 경화 성능을 나타낼 수 있다.In 100 parts by mass of the photosensitive resin composition, 1-10 parts by mass of the hexaarylbisimidazole-based mixed photoinitiator of the present invention is preferable. Within the above content range, the composition can exhibit excellent system compatibility and excellent curing performance.
기타 광개시제 및/또는 증감제Other photoinitiators and/or sensitizers
본 발명의 감광성 수지 조성물은, 상호/시너지 효과를 통해 감광성 수지 시스템의 상용성, 감광도 및 해상도를 증가시키기 위해, 기타 광개시제 및/또는 증감제를 더 포함할 수 있다. The photosensitive resin composition of the present invention may further include other photoinitiators and/or sensitizers in order to increase compatibility, photosensitivity, and resolution of the photosensitive resin system through a mutual/synergistic effect.
상기 기타 광개시제 및/또는 증감제는, 비스이미다졸계, 피라졸린계, 방향족 케톤계, 안트라퀴논계, 벤조인 및 벤조인알킬에테르계, 옥심에스테르계, 트리아진계, 트리페닐아민계, 쿠마린계, 티오크산톤계, 아크리딘계 및 당업자들에게 공지된 기타 광개시제를 포함할 수 있다(단, 이에 한정되지 않는다). 이들 광개시제는 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다. The other photoinitiators and/or sensitizers are biimidazole-based, pyrazoline-based, aromatic ketone-based, anthraquinone-based, benzoin and benzoin alkyl ether-based, oxime ester-based, triazine-based, triphenylamine-based, and coumarin-based , thioxanthone-based, acridine-based, and other photoinitiators known to those skilled in the art (but are not limited thereto). These photoinitiators may be used alone or in combination of two or more.
예시적으로, 비스이미다졸계 화합물은, 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라페닐-디이미다졸, 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1,1'-디이미다졸, 2,2',5-트리스(2-플루오로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-디이미다졸, 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐-디이미다졸, 2,2'-비스(2-플루오로페닐)-4-(o-클로로페닐)-5-(3,4-디메톡시페닐)-4',5'-디페닐-디이미다졸, 2,2'-비스(2-플루오로페닐)-4,4',5,5'-테트라페닐-디이미다졸, 2,2'-비스(2-메톡시페닐)-4,4',5,5'-테트라페닐-디이미다졸, 2,2'-비스(2-클로로-5-니트로페닐)-4,4'-비스(3,4-디메톡시페닐)-5,5'-비스(o-클로로페닐)-디이미다졸, 2,2'-비스(2-클로로-5-니트로페닐)-4-(3,4-디메톡시페닐)-5-(o-클로로페닐)-4',5'-디페닐-디이미다졸, 2,2'-비스(2,4-디클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-5,5'-비스(o-클로로페닐)-디이미다졸, 2-(2,4-디클로로페닐)-4-(3,4-디메톡시페닐)-,2',5-비스(o-클로로페닐)-4',5'-디페닐-디이미다졸, 2-(2,4-디클로로페닐)-2'-o-클로로페닐)-4,4',5,5'-테트라페닐-디이미다졸, 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐-디이미다졸 및 그 유사체를 포함한다. 이들 비스이미다졸계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the biimidazole-based compound is 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-diimidazole, 2,2', 5-tris ( o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,2',5-tris(2-fluorophenyl) )-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5 '-Tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'- Diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-methoxyphenyl) )-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4,4'-bis(3,4-dimethoxyphenyl) )-5,5'-bis(o-chlorophenyl)-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4-(3,4-dimethoxyphenyl)-5- (o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl) -5,5'-bis(o-chlorophenyl)-diimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl)-,2',5-bis(o -Chlorophenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-o-chlorophenyl)-4,4',5,5'-tetraphenyl -diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole and its analogues. These biimidazole compounds may be used alone or in combination of two or more.
예시적으로, 피라졸린계 화합물은, 1-페닐-3-(4-tert-부틸스티릴)-5-(4-tert-부틸페닐)-피라졸린, 1-페닐-3-비페닐-5-(4-tert-부틸페닐)-피라졸린, 에톡시화 (9) 트리메틸올피라졸린에스테르, 에톡시화 (10) 비스페놀A피라졸린에스테르 및 그 유사체를 포함한다. 이들 피라졸린계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the pyrazoline-based compound is 1-phenyl-3-(4-tert-butylstyryl)-5-(4-tert-butylphenyl)-pyrazoline, 1-phenyl-3-biphenyl-5 -(4-tert-butylphenyl)-pyrazoline, ethoxylated (9) trimethylolpyrazoline esters, ethoxylated (10) bisphenol A pyrazoline esters and their analogues. These pyrazoline compounds may be used alone or in combination of two or more.
예시적으로, 방향족 케톤계 화합물은, 아세토페논, 2,2-디메톡시-2-페닐아세토페논, 2,2-디에톡시-2-페닐아세토페논, 1,1-디클로로아세토페논, 벤조페논, 4-벤조일디페닐설파이드, 4-벤조일-4'-메틸디페닐설파이드, 4-벤조일-4'-에틸디페닐설파이드, 4-벤조일-4'-프로필디페닐설파이드, 4,4'-비스(디에틸아미노)벤조페논, 4-p-톨루엔메르캅토벤조페논, 2,4,6-트리메틸벤조페논, 4-메틸벤조페논, 4,4'-비스(디메틸아미노)벤조페논, 4,4'-비스(메틸,에틸아미노)벤조페논, 아세토페논디메틸케탈, 벤질(benzil)디메틸케탈, α,α'-디메틸벤질(benzil)케탈, α,α-디에톡시아세토페논, 2-히드록시-2-메틸-1-페닐프로판온, 1-히드록시시클로헥실페닐케톤, 2-히드록시-2-메틸-1-p-히드록시에틸에테르페닐프로판온, 2-메틸-1-(4-메틸메르캅토페닐)-2-모르폴린1-프로판온, 2-벤질-2-디메틸아미노-1-(4-모르폴린페닐)-1-부탄온, 페닐비스(2,4,6-트리메틸벤조일)포스핀옥사이드, 2,4,6-트리메틸벤조일-디페닐포스핀옥사이드, 2-히드록시-1-{3-[4-(2-히드록시-2-메틸-프로피오닐)-페닐]-1,1,3-트리메틸-인덴-5-일}-2-메틸프로판온; 및 2-히드록시-1-{1-[4-(2-히드록시-2-메틸-프로피오닐)-페닐]-1,3,3-트리메틸-인덴-5-일}-2-메틸프로판온, 1-(4-이소프로필페닐)-2-히드록시-2-메틸프로판-1-온, 4-(2-히드록시에톡시)-페닐-(2-히드록시-2-프로필)케톤 및 그 유사체를 포함한다. 이들 방향족 케톤계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the aromatic ketone compound is acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl-4'-ethyldiphenylsulfide, 4-benzoyl-4'-propyldiphenylsulfide, 4,4'-bis( Diethylamino) benzophenone, 4-p-toluenemercaptobenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4' -bis(methyl,ethylamino)benzophenone, acetophenone dimethyl ketal, benzil dimethyl ketal, α,α'-dimethylbenzyl ketal, α,α-diethoxyacetophenone, 2-hydroxy-2 -Methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-p-hydroxyethyl etherphenylpropanone, 2-methyl-1-(4-methylmer) Captophenyl)-2-morpholine 1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)-1-butanone, phenylbis(2,4,6-trimethylbenzoyl)phos Pine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-1-{3-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1, 1,3-trimethyl-inden-5-yl}-2-methylpropanone; and 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-inden-5-yl}-2-methylpropane One, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone and analogs thereof. These aromatic ketone compounds may be used alone or in combination of two or more.
예시적으로, 안트라퀴논계 화합물은, 2-페닐안트라퀴논, 2,3-디페닐안트라퀴논, 1-클로로안트라퀴논, 2-메틸안트라퀴논, 2,3-디메틸안트라퀴논, 2-에틸안트라센-9,10-디에틸에스테르, 1,2,3-트리메틸안트라센-9,10-디옥틸에스테르, 2-에틸안트라센-9,10-디(메틸 4-클로로부티레이트), 2-(3-((3-에틸옥세탄-3-일)메톡시)-3-옥소프로필)안트라센-9,10-디에틸에스테르, 9,10-디부톡시안트라센, 9,10-디에톡시-2-에틸안트라센, 9,10-비스(3-클로로프로폭시)안트라센, 9,10-비스(2-히드록시에틸메르캅토)안트라센, 9,10-비스(3-히드록시-1-프로필메르캅토)안트라센 및 그 유사체를 포함할 수 있다. 이들 안트라퀴논계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the anthraquinone-based compound is 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene- 9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10-di(methyl 4-chlorobutyrate), 2-(3-(( 3-ethyloxetan-3-yl)methoxy)-3-oxopropyl)anthracene-9,10-diethyl ester, 9,10-dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9 ,10-bis(3-chloropropoxy)anthracene, 9,10-bis(2-hydroxyethylmercapto)anthracene, 9,10-bis(3-hydroxy-1-propylmercapto)anthracene and analogues thereof can include These anthraquinone compounds may be used alone or in combination of two or more.
예시적으로, 벤조인 및 벤조인알킬에테르계 화합물은, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인페닐에테르 및 그 유사체를 포함한다. 이들 벤조인 및 벤조인알킬에테르계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the benzoin and benzoin alkyl ether compounds include benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and analogues thereof. These benzoin and benzoin alkyl ether compounds may be used alone or in combination of two or more.
예시적으로, 옥심에스테르계 화합물은, 1-(4-페닐티오페닐)-n-옥탄-1,2-디온-2-옥심벤조에이트, 1-(6-(2-메틸벤조일)-9-에틸카르바졸-3-일)-에탄-1-온-옥심아세테이트, 1-(6-(2-메틸벤조일)-9-에틸카르바졸-3-일)-부탄-1-온-옥심아세테이트, 1-(6-(2-메틸벤조일)-9-에틸카르바졸-3-일)-프로판-1-온-옥심아세테이트, 1-(6-(2-메틸벤조일)-9-에틸카르바졸-3-일)-1-시클로헥실-메탄-1-온-옥심아세테이트, 1-(6-(2-메틸벤조일)-9-에틸카르바졸-3-일)-3-시클로펜틸-프로판-1-온-옥심아세테이트, 1-(4-페닐티오페닐)-(3-시클로펜틸)-프로판-1,2-디온-2-옥심벤조에이트, 1-(4-페닐티오페닐)-(3-시클로헥실)-프로판-1,2-디온-2-옥심시클로헥실카르복실레이트(1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-cyclohexylformic acid oxime ester), 1-(6-(2-메틸벤조일)-9-에틸카르바졸-3-일)-(3-시클로펜틸)-프로판-1,2-디온-2-옥심아세테이트, 1-(6-o-메틸벤조일-9-에틸카르바졸-3-일)-(3-시클로펜틸)-프로판-1,2-디온-2-옥심벤조에이트, 1-(4-벤조일디페닐설파이드)-(3-시클로펜틸프로판온)-1-옥심아세테이트, 1-(6-o-메틸벤조일-9-에틸카르바졸-3-일)-(3-시클로펜틸프로판온)-1-옥심시클로헥실카르복실레이트, 1-(4-벤조일디페닐설파이드)-(3-시클로펜틸프로판온)-1-옥심시클로헥실카르복실레이트, 1-(6-o-메틸벤조일-9-에틸카르바졸-3-일)-(3-시클로펜틸)-프로판-1,2-디온-2-o-메틸옥심벤조에이트, 1-(4-페닐티오페닐)-(3-시클로펜틸)-프로판-1,2-디온-2-옥심시클로헥실카르복실레이트, 1-(4-테노일(Thenoyl)-디페닐설파이드-4'-일)-3-시클로펜틸-프로판-1-온-옥심아세테이트, 1-(4-벤조일디페닐설파이드)-(3-시클로펜틸)-프로판-1,2-디온-2-옥심아세테이트, 1-(6-니트로-9-에틸카르바졸-3-일)-3-시클로헥실-프로판-1-온-옥심아세테이트, 1-(6-o-메틸벤조일-9-에틸카르바졸-3-일)-3-시클로헥실-프로판-1-온-옥심아세테이트, 1-(6-테노일-9-에틸카르바졸-3-일)-(3-시클로헥실프로판온)-1-옥심아세테이트, 1-(6-푸란푸로일(Furanfuroyl)-9-에틸카르바졸-3-일)-(3-시클로펜틸프로판온)-1-옥심아세테이트, 1,4-디페닐프로판-1,3-디온-2-옥심아세테이트, 1-(6-푸로일-9-에틸카르바졸-3-일)-(3-시클로헥실)-프로판-1,2-디온-2-옥심아세테이트, 1-(4-페닐티오페닐)-(3-시클로헥실)-프로판-1,2-디온-2-옥심아세테이트, 1-(6-푸란푸로일-9-에틸카르바졸-3-일)-(3-시클로헥실프로판온)-1-옥심아세테이트, 1-(4-페닐티오페닐)-(3-시클로헥실)-프로판-1,2-디온-3-옥심벤조에이트, 1-(6-테노일-9-에틸카르바졸-3-일)-(3-시클로헥실)-프로판-1,2-디온-2-옥심아세테이트, 2-((벤조일옥시) 이미노)-1-페닐프로판-1-온, 1-페닐-1,2-프로판디온-2-(옥소아세틸)옥심, 1-(4-페닐티오페닐)-2-(2-메틸페닐)-에탄-1,2-디온-2-옥심아세테이트, 1-(9,9-디부틸-7-니트로플루오렌-2-일)-3-시클로헥실-프로판-1-온-옥심아세테이트, 1-(4-(4-(티오펜-2-포르밀)페닐티오)페닐)-3-시클로펜틸프로판-1,2-디온-2-옥심아세테이트, 1-(9,9-디부틸-2-일)-3-시클로헥실프로필프로판-1,2-디온-2-옥심아세테이트, 1-(6-(2-(벤조일옥시이미노)-3-시클로헥실프로필-9-에틸카르바졸-3-일)옥탄-1,2-디온-2-옥심벤조에이트, 1-(7-니트로-9,9-디알릴플루오렌-2-일)-1-(2-메틸페닐)메탄온-옥심아세테이트, 1-(6-(2-메틸벤조일)-9-에틸카르바졸-3-일)-3-시클로펜틸-프로판-1-온-옥심벤조에이트, 1-(7-(2-메틸벤조일)-9,9-디부틸플루오렌-2-일)-3-시클로헥실프로판-1,2-디온-2-옥심아세테이트, 1-(6-(푸란-2-포르밀)-9-에틸카르바졸-3-일)-3-시클로헥실프로판-1,2-디온-2-에톡시포르밀옥심에스테르(1-(6-(furan-2-formyl)-9-ethylcarbazol-3-yl)-3-cyclohexylpropane-1,2-dione-2-ethoxyformyl oxime ester) 및 그 유사체를 포함한다. 이들 옥심에스테르계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the oxime ester compound is 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-oxime benzoate, 1-(6-(2-methylbenzoyl)-9- Ethylcarbazol-3-yl)-ethan-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-butan-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-propan-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazole- 3-yl)-1-cyclohexyl-methan-1-one-oximeacetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopentyl-propan-1 -One-oximeacetate, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-oximebenzoate, 1-(4-phenylthiophenyl)-(3- Cyclohexyl)-propane-1,2-dione-2-oximecyclohexylcarboxylate (1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-cyclohexylformic acid oxime ester) , 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-oximeacetate, 1-(6-o -Methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-oximebenzoate, 1-(4-benzoyldiphenylsulfide)-(3- Cyclopentylpropanone)-1-oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentylpropanone)-1-oximecyclohexylcarboxylate, 1-(4-benzoyldiphenylsulfide)-(3-cyclopentylpropanone)-1-oximecyclohexylcarboxylate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)- (3-cyclopentyl)-propane-1,2-dione-2-o-methyloximebenzoate, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2 -Oximecyclohexylcarboxylate, 1-(4-thenoyl-diphenylsulfide-4'-yl)-3-cyclopentyl-propan-1-one-oximeacetate, 1-(4-benzoyldi Phenylsulfide)-(3-cyclopentyl)-propane-1,2-dione-2-oximeacetate, 1-(6-nitro-9-ethylcarbazol-3-yl)-3-cyclohexyl-propan-1 -one-oximeacetate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-3-cyclohexyl-propan-1-one-oximeacetate, 1-(6-thenoyl-9 -Ethylcarbazol-3-yl)-(3-cyclohexylpropanone)-1-oxime acetate, 1-(6-furanfuroyl-9-ethylcarbazol-3-yl)-(3- Cyclopentylpropanone)-1-oxime acetate, 1,4-diphenylpropane-1,3-dione-2-oxime acetate, 1-(6-furoyl-9-ethylcarbazol-3-yl)-( 3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 1 -(6-furanfuroyl-9-ethylcarbazol-3-yl)-(3-cyclohexylpropanone)-1-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)- Propane-1,2-dione-3-oximebenzoate, 1-(6-thenoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2- Oxime acetate, 2-((benzoyloxy)imino)-1-phenylpropan-1-one, 1-phenyl-1,2-propanedione-2-(oxoacetyl)oxime, 1-(4-phenylthiophenyl )-2-(2-methylphenyl)-ethane-1,2-dione-2-oximeacetate, 1-(9,9-dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propane -1-one-oxime acetate, 1-(4-(4-(thiophene-2-formyl)phenylthio)phenyl)-3-cyclopentylpropane-1,2-dione-2-oximeacetate, 1- (9,9-dibutyl-2-yl)-3-cyclohexylpropylpropane-1,2-dione-2-oximeacetate, 1-(6-(2-(benzoyloxyimino)-3-cyclohexylpropyl -9-ethylcarbazol-3-yl)octane-1,2-dione-2-oximebenzoate, 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2 -methylphenyl)methanone-oximeacetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopentyl-propan-1-one-oximebenzoate, 1-( 7-(2-methylbenzoyl)-9,9-dibutylfluoren-2-yl)-3-cyclohexylpropane-1,2-dione-2-oximeacetate, 1-(6-(furan-2- Formyl)-9-ethylcarbazol-3-yl)-3-cyclohexylpropane-1,2-dione-2-ethoxyformyloxime ester (1-(6-(furan-2-formyl)-9 -ethylcarbazol-3-yl)-3-cyclohexylpropane-1,2-dione-2-ethoxyformyl oxime ester) and its analogues. These oxime ester compounds may be used alone or in combination of two or more.
예시적으로, 트리아진계 화합물은, 2-(4-에틸비페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(3,4-메틸렌옥시페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 3-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}프로피온산, 1,1,1,3,3,3-헥사플루오로이소프로필-3-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}프로피오네이트, 에틸-2-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}아세테이트, 2-에톡시에틸-2-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}아세테이트, 시클로헥실-2-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}아세테이트, 벤질-2-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}아세테이트, 3-{클로로-4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}프로피온산, 3-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}프로피온아미드, 2,4-비스(트리클로로메틸)-6-p-메톡시스티릴-s-트리아진, 2,4-비스(트리클로로메틸)-6-(1-p-디메틸아미노페닐)-1,3,-부타디에닐-s-트리아진, 2-트리클로로메틸-4-아미노-6-p-메톡시스티릴-s-트리아진 및 그 유사체를 포함한다. 이들 트리아진계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the triazine-based compound is 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methyleneoxyphenyl) -4,6-bis(trichloromethyl)-1,3,5-triazine, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} Propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}pro Cionate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 2-ethoxyethyl-2-{4-[2, 4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6- yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2, 4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenyl Thio} Propionamide, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylamino phenyl)-1,3,-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like. These triazine-based compounds may be used alone or in combination of two or more.
예시적으로, 트리페닐아민계 화합물은, N,N-비스-[4-(2-스티릴-1-일)-페닐]-N,N-비스(2-에틸-6메틸페닐)-1,1-비스페닐-4,4-디아민, N,N-비스-[4-(2-스티릴-1-일)-4'-메틸페닐]-N,N-비스(2-에틸-6메틸페닐)-1,1-비스페닐-4,4-디아민 및 그 유사체를 포함한다. 이들 트리페닐아민계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the triphenylamine-based compound is N,N-bis-[4-(2-styryl-1-yl)-phenyl]-N,N-bis(2-ethyl-6methylphenyl)-1, 1-bisphenyl-4,4-diamine, N,N-bis-[4-(2-styryl-1-yl)-4'-methylphenyl]-N,N-bis(2-ethyl-6methylphenyl) -1,1-bisphenyl-4,4-diamine and its analogues. These triphenylamine compounds may be used alone or in combination of two or more.
예시적으로, 쿠마린계 화합물은, 3,3'-카르보닐비스(7-디에틸아미노쿠마린), 3-벤조일-7-디에틸아미노쿠마린, 3,3'-카르보닐비스(7-메톡시쿠마린), 7-(디에틸아미노)-4-메틸쿠마린, 3-(2-벤조티아졸)-7-(디에틸아미노)쿠마린, 7-(디에틸아미노)-4-메틸-2H-1-벤조피란-2-온(7-(디에틸아미노)-4-메틸쿠마린), 3-벤조일-7-메톡시쿠마린 및 그 유사체를 포함한다. 이들 쿠마린계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the coumarin-based compound is 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3,3'-carbonylbis (7-methoxy Coumarin), 7-(diethylamino)-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin, 7-(diethylamino)-4-methyl-2H-1 -benzopyran-2-one (7-(diethylamino)-4-methylcoumarin), 3-benzoyl-7-methoxycoumarin and its analogues. These coumarin-type compounds may be used alone or in combination of two or more.
예시적으로, 티오크산톤계 화합물은, 티오크산톤, 2,4-디메틸티오크산톤, 2,4-디에틸티오크산톤, 2,4-디이소프로필티오크산톤, 2-클로로티오크산톤, 1-클로로-4-프로폭시티오크산톤, 이소프로필티오크산톤, 디이소프로필티오크산톤 및 유사체를 포함한다. 이들 티오크산톤계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the thioxanthone-based compound is thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone xanthones, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone and the like. These thioxanthone-based compounds may be used alone or in combination of two or more.
예시적으로, 아크리딘계 화합물은, 9-페닐아크리딘, 9-p-메틸페닐아크리딘, 9-m-메틸페닐아크리딘, 9-o-클로로페닐아크리딘, 9-o-플루오로페닐아크리딘, 2-에틸-2-(히드록시메틸)-1,3-프로판디올에테르시클로에탄에테르의 [4-(9-아크리디닐)페녹시]아세테이트(즉, PAD107, Changzhou Tronly New Electronic Materials Co.,Ltd. 제조), 1,7-비스(9-아크리디닐)헵탄, 9-에틸아크리딘, 9-(4-브로모페닐)아크리딘, 9-(3-클로로페닐)아크리딘, 1,7-비스(9-아크리딘)헵탄, 1,5-비스(9-아크리딘펜탄), 1,3-비스(9-아크리딘)프로판 및 그 유사체를 포함한다. 이들 아크리딘계 화합물은 단독으로 사용하거나 2종 이상을 조합하여 사용할 수도 있다.Illustratively, the acridine-based compound is 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluoro [4-(9-acridinyl)phenoxy]acetate of lophenylacridine, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether cycloethaneether (i.e. PAD107, Changzhou Tronly Manufactured by New Electronic Materials Co., Ltd.), 1,7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3- Chlorophenyl) acridine, 1,7-bis (9-acridine) heptane, 1,5-bis (9-acridine pentane), 1,3-bis (9-acridine) propane and their contain analogues. These acridine-based compounds may be used alone or in combination of two or more.
바람직하게는, 감광성 수지 조성물 100 질량부에 있어서, 상기 기타 광개시제 및/또는 증감제의 함량은 8 질량부 이하이다.Preferably, in 100 parts by mass of the photosensitive resin composition, the content of the other photoinitiator and/or sensitizer is 8 parts by mass or less.
보조제supplements
본 발명의 감광성 수지 조성물은, 상술한 각 성분 외에도, 선택적으로 필요에 따라 적당량의 기타 보조제를 더 포함할 수 있다. 예시적으로, 보조제는, 말라카이트 그린 등의 염료, 트리브로모페닐술폰, 류코 크리스탈 바이올렛 등의 광발색제, 안료, 충전제, 가소제, 안정제, 코팅 보조제, 박리 촉진제 등일 수 있다.The photosensitive resin composition of the present invention, in addition to the components described above, may optionally further contain an appropriate amount of other adjuvants as needed. Illustratively, the adjuvant may be a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leuco crystal violet, a pigment, a filler, a plasticizer, a stabilizer, a coating adjuvant, or an exfoliation accelerator.
상기 염료, 안료 및 광발색제로서는, 예시적으로, 트리스(4-디메틸아미노페닐)메탄, 트리스(4-디메틸아미노-2메틸페닐)메탄, 플루오란 염료, 톨루엔설폰산일수화물(toluenesulfonic acid monohydrate), 베이직 푸크신(basic fuchsin), 프탈로시아닌 그린 및 프탈로시아닌 블루 등의 프탈로시아닌계, 오라민 염기(auramine base), 파라로사닐린(pararosaniline), 크리스탈 바이올렛, 메틸 오렌지, 나일 블루 2B, 빅토리아 블루, 말라카이트 그린, 다이아몬드 그린, 베이직 블루 20(basic blue 20), 브릴리언트 그린(brilliant Green), 에오신(eosin), 에틸 바이올렛(ethyl violet), 에리트로신 나트륨염 B(erythrosin sodium salt B), 메틸 그린(methyl Green), 페놀프탈레인, 알리자린 레드 S, 티몰 프탈레인, 메틸 바이올렛 2B, 퀴날딘 레드, 로즈벵갈(rose bengal), 메타닐 옐로, 티몰술폰프탈레인, 자일레놀 블루(xylenol blue), 메틸 오렌지, 오렌지 IV, 디페닐티오카르바존, 2,7-디클로로플루오레세인, 메틸 레드, 콩고 레드, 벤조퍼푸린 4B(benzopurpurine 4B), α-나프틸 레드, 페나세틴, 메틸 바이올렛, 빅토리아 퓨어블루 BOH, 로다민 6G, 디페닐아민, 디벤질아닐린, 트리페닐아민, 디에틸아닐린, 디페닐-p-페닐렌디아민(diphenyl-p-phenylenediamine), P-톨루이딘, 벤조트리아졸, 메틸벤조트리아졸, 4,4'-비페닐디아민, o-클로로아닐린, 류코 크리스탈 바이올렛, 류코 말라카이트 그린, 류코 아닐린, 류코 메틸 바이올렛, 아조계 등의 유기 안료, 이산화티타늄 등의 무기 안료일 수 있다. 우수한 콘트라스트를 고려하여 바람직하게는 트리스(4-디메틸아미노페닐)메탄(즉, 류코 크리스탈 바이올렛, LCV)을 사용한다. 이들 염료, 안료 및 광발색제는 단독으로 사용할 수 있고, 2종 이상을 혼합하여 사용할 수도 있다. Examples of the dye, pigment, and photochromic agent include tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, fluoran dye, toluenesulfonic acid monohydrate, basic Phthalocyanines such as basic fuchsin, phthalocyanine green and phthalocyanine blue, auramine base, pararosaniline, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green , basic blue 20, brilliant green, eosin, ethyl violet, erythrosin sodium salt B, methyl green, phenolphthalein, Alizarin Red S, Thymol Phthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymolsulfonphthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenylthio Carbazone, 2,7-dichlorofluorescein, methyl red, congo red, benzopurpurine 4B, α-naphthyl red, phenacetin, methyl violet, victoria pure blue BOH, rhodamine 6G, diphenyl Amine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, benzotriazole, methylbenzotriazole, 4,4'-biphenyl organic pigments such as diamine, o-chloroaniline, leuco crystal violet, leuco malachite green, leuco aniline, leuco methyl violet, azo-based pigments, and inorganic pigments such as titanium dioxide. Considering the excellent contrast, tris(4-dimethylaminophenyl)methane (ie, Leuco Crystal Violet, LCV) is preferably used. These dyes, pigments, and photochromes may be used alone or in combination of two or more.
상기 충전제로서는, 예시적으로, 실리카, 산화알루미늄, 탈크, 탄산칼슘, 황산바륨 등의 충전제일 수 있다(상기 무기 안료는 포함하지 않는다). 충전제는 단독으로 사용할 수 있고, 2종 이상을 혼합하여 사용할 수도 있다. Examples of the filler may include fillers such as silica, aluminum oxide, talc, calcium carbonate, and barium sulfate (the inorganic pigments are not included). The fillers may be used alone or in combination of two or more.
상기 가소제로서는, 예시적으로, 디부틸프탈레이트, 디헵틸프탈레이트, 디옥틸프탈레이트, 디알릴프탈레이트 등의 프탈산에스테르, 트리에틸렌글리콜디아세테이트, 테트라에틸렌글리콜디아세테이트 등의 에틸렌글리콜에스테르, P-톨루엔술폰아미드, 벤젠술폰아미드, n-부틸벤젠술폰아미드 등의 술폰아미드계, 트리페닐 인산에스테르, 트리메틸포스페이트, 트리에틸포스페이트, 트리페닐포스페이트, 트리톨릴포스페이트,트리자일레닐포스페이트(trixylyl phosphate), 톨릴디페닐포스페이트, 트리자일레닐포스페이트, 2-나프틸디페닐포스페이트, 톨릴-비스2,6-자일레닐포스페이트, 방향족 축합 인산에스테르, 트리스(클로로프로필)포스페이트, 트리스(트리브로모네오펜틸)포스페이트, 할로겐 함유 축합 인산에스테르, 트리에틸렌글리콜디카프릴레이트(triethylene glycol dicaprylate), 트리에틸렌글리콜디(2-에틸헥사노에이트), 테트라에틸렌글리콜디헵타노에이트, 디에틸세바케이트(Diethyl sebacate), 디부틸수베레이트(Dibutyl suberate), 트리스(2-에틸에틸포스페이트), Brij 30〔C12H25(OCH2CH2)4OH〕, Brij 35〔C12H25(OCH2CH2)20OH〕등일 수 있다. 가소제는 단독으로 사용할 수 있고, 2종 이상을 혼합하여 사용할 수도 있다. Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate, ethylene glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate, and p-toluenesulfonamide. , sulfonamides such as benzenesulfonamide and n-butylbenzenesulfonamide, triphenyl phosphate esters, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tritolyl phosphate, trixylyl phosphate, tolyl diphenyl Phosphate, trixylenyl phosphate, 2-naphthyldiphenyl phosphate, tolyl-bis 2,6-xylenyl phosphate, aromatic condensed phosphate ester, tris(chloropropyl)phosphate, tris(tribromoneopentyl)phosphate, halogen Condensed phosphoric acid ester, triethylene glycol dicaprylate, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate (Dibutyl suberate), tris (2-ethylethyl phosphate), Brij 30 [C 12 H 25 (OCH 2 CH 2 ) 4 OH], Brij 35 [C 12 H 25 (OCH 2 CH 2 ) 20 OH] and the like. . A plasticizer can be used independently and can also be used in mixture of 2 or more types.
상기 안정제로서는, 예시적으로, 히드로퀴논, 1,4,4-트리메틸-디아조비시클로(3.2.2)-논-2-엔-2,3-디옥사이드(1,4,4-Trimethyl-diazobicyclo(3.2.2)-non-2-ene-2,3-dioxide), 1-페닐-3-피라졸리디논, p-메톡시페놀, 알킬 및 아릴 치환된 히드로퀴논 및 퀴논, tert-부틸카테콜, 피로갈롤(pyrogallol), 커퍼레지네이트(copper resinate), 나프틸아민, β-나프톨, 염화제일구리(cuprous chloride), 2,6-디-tert-부틸-p-크레졸, 페노티아진, 피리딘, 니트로벤젠, 디니트로벤젠, p-톨루퀴논(p-toluquinone) 및 클로라닐(chloranil) 등일 수 있다. 안정제는 단독으로 사용할 수 있고, 2종 이상을 혼합하여 사용할 수도 있다. Examples of the stabilizer include hydroquinone, 1,4,4-trimethyl-diazobicyclo (3.2.2) -non-2-ene-2,3-dioxide (1,4,4-Trimethyl-diazobicyclo (3.2 .2)-non-2-ene-2,3-dioxide), 1-phenyl-3-pyrazolidinone, p-methoxyphenol, alkyl and aryl substituted hydroquinones and quinones, tert-butylcatechol, pyrogallol (pyrogallol), copper resinate, naphthylamine, β-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitro benzene, dinitrobenzene, p-toluquinone, and chloranil. The stabilizer may be used alone or in combination of two or more.
상기 코팅 보조제로서는, 안전성과 범용성 측면에서 고려하여, 아세톤, 메탄올, 메틸알코올, 에틸알코올, 이소프로필알코올, 메틸에틸케톤, 프로필렌 글리콜 모노메틸 에테르 아세테이트(propylene glycol monomethyl ether acetate), 에틸락테이트(ethyl lactate), 시클로헥사논, γ-부티로락톤, 디클로로메탄 등일 수 있다. 코팅 보조제는 단독으로 사용할 수 있고, 2종 이상을 혼합하여 사용할 수도 있다. As the coating aid, in consideration of safety and versatility, acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate lactate), cyclohexanone, γ-butyrolactone, dichloromethane, and the like. The coating aid may be used alone or in combination of two or more.
상기 박리 촉진제로서는, 예시적으로, 벤젠술폰산, 톨루엔술폰산, 자일렌술폰산, 페놀술폰산, 메틸, 프로필, 헵틸, 옥틸, 데실, 도데실 등의 알킬벤젠술폰산 등일 수 있다. 박리 촉진제는 단독으로 사용할 수 있고, 2종 이상을 혼합하여 사용할 수도 있다. Examples of the exfoliation accelerator include benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, methyl, propyl, heptyl, octyl, decyl, dodecyl, and the like. The peeling accelerator may be used alone or in combination of two or more.
바람직하게는, 감광성 수지 조성물 100 질량부에 있어서, 보조제의 함량은 10 질량부 이하이다. Preferably, in 100 parts by mass of the photosensitive resin composition, the content of the adjuvant is 10 parts by mass or less.
<응용><application>
본 발명의 감광성 수지 조성물은 건식필름(dry film), 즉 감광성 수지 적층체로 제조될 수 있고, 인쇄 회로 기판, 보호 패턴, 도체 패턴, 리드 프레임, 반도체 패키징의 제조에 적용되어 서로 다른 공정을 통해 서로 다른 기판(substrate)에 필요한 패턴을 형성한다. The photosensitive resin composition of the present invention can be made into a dry film, that is, a photosensitive resin laminate, and is applied to the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packaging through different processes. Form the pattern needed for another substrate.
본 발명의 감광성 수지 조성물은 또한 습식필름 코터를 통해 각각 대응되는 제조 단계에서 상응하는 기판에 도포될 수 있고, 즉, 습식필름(wet film)으로서 인쇄 회로 기판, 보호 패턴, 도체 패턴, 리드 프레임, 반도체 패키징의 제조에 적용되어 서로 다른 공정을 통해 서로 다른 기판에 필요한 패턴을 형성한다. The photosensitive resin composition of the present invention can also be applied to a corresponding substrate in each corresponding manufacturing step through a wet film coater, that is, as a wet film, printed circuit boards, protective patterns, conductor patterns, lead frames, It is applied to the manufacture of semiconductor packaging to form patterns required for different substrates through different processes.
건식필름의 응용Application of dry film
본 발명의 건식필름, 즉 감광성 수지 적층체는 감광성 수지 조성물로 형성되는 감광성 수지층 및 상기 감광성 수지층을 지지하는 지지체를 포함한다.The dry film of the present invention, that is, the photosensitive resin laminate includes a photosensitive resin layer formed of a photosensitive resin composition and a support for supporting the photosensitive resin layer.
통상적으로, 건식필름의 제조에는, 지지체에 감광성 수지 조성물을 도포하고 건조하여 감광성 수지층을 형성하는 단계; 선택적으로, 필요에 따라 커버필름(보호층)을 접착하는 단계가 포함된다. 바람직하게는, 건조 조건은 60-100℃에서 0.5-15min 건조한다. 감광성 수지층의 두께는, 바람직하게는 5-95μm, 보다 바람직하게는 10-50μm, 보다 더 바람직하게는 15-30μm이다. 감광성 수지층의 두께가 5μm 미만이면 절연성이 좋지 않고, 감광성 수지층의 두께가 95μm를 초과하면 해상도가 열위할 수 있다.Typically, the production of a dry film includes the steps of applying a photosensitive resin composition to a support and drying it to form a photosensitive resin layer; Optionally, a step of adhering a cover film (protective layer) is included as needed. Preferably, drying conditions are 0.5-15 min at 60-100 ° C. The thickness of the photosensitive resin layer is preferably 5 to 95 μm, more preferably 10 to 50 μm, and still more preferably 15 to 30 μm. If the thickness of the photosensitive resin layer is less than 5 μm, insulation properties are poor, and if the thickness of the photosensitive resin layer exceeds 95 μm, resolution may be inferior.
지지체로서는, 구체적인 예로 다양한 유형의 플라스틱 필름, 예를 들면, 폴리에틸렌테레프탈레이트(polyethylene terephthalate), 폴리에틸렌나프탈레이트(polyethylene naphthalate), 폴리프로필렌, 폴리에틸렌, 셀룰로오스아세테이트, 폴리알킬메타크릴레이트, 메타크릴레이트 공중합체(methacrylate copolymer), 폴리비닐클로라이드, 폴리비닐알코올, 폴리카보네이트, 폴리스티렌, 셀로판, 비닐클로라이드 공중합체, 폴리아미드, 폴리이미드, 비닐클로라이드-비닐아세테이트 공중합체, 폴리테트라플루오로에틸렌, 폴리트리플루오로에틸렌 및 그 유사체를 예로 들 수 있다. 또한, 2종 이상의 재료로 조성된 복합 재료도 사용할 수 있다. 바람직하게는, 우수한 광 투과성을 갖는 폴리에틸렌테레프탈레이트를 사용한다. 지지체의 두께는 바람직하게는 5-150μm, 보다 바람직하게는 10-50μm이다.As the support, specific examples include various types of plastic films, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polyalkyl methacrylate, and methacrylate copolymers. (methacrylate copolymer), polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene and analogs thereof. In addition, a composite material composed of two or more types of materials can also be used. Preferably, polyethylene terephthalate having excellent light transmittance is used. The thickness of the support is preferably 5-150 μm, more preferably 10-50 μm.
감광성 수지 조성물의 코팅은 특별히 제한되지 않으며, 예를 들어 스프레이 코팅법(spray coating), 드럼 코팅법(drum coating), 스핀 코팅법 (spin coating), 슬릿 코팅법(slit coating), 압출 코팅법, 커튼 코팅법, 다이 코팅법(dye coating), 와이어 바 코팅법(wire bar coating), 나이프 코팅법(knife coating), 롤러 코팅법, 닥터 블레이드 코팅법(doctorblade coating), 스프레이 코팅법, 딥 코팅법(dip coating) 등의 통상적인 방법을 사용할 수 있다. Coating of the photosensitive resin composition is not particularly limited, and examples include spray coating, drum coating, spin coating, slit coating, extrusion coating, Curtain coating method, dye coating method, wire bar coating method, knife coating method, roller coating method, doctor blade coating method, spray coating method, dip coating method A conventional method such as (dip coating) may be used.
또한, 본 발명은 인쇄 회로 기판의 제조에 있어서의 상기 건식필름의 응용에 대하여 제공하며, 이는 다음을 포함한다: The present invention also provides for the application of the dry film in the manufacture of printed circuit boards, including:
(1) 라미네이션 공정 : 감광성 수지 적층체를 동박 적층판(Copper Clad Laminate) 또는 가요성 기판에 라미네이팅한다;(1) Lamination process: the photosensitive resin laminate is laminated to a copper clad laminate or a flexible substrate;
(2) 노광 공정 : 감광성 수지 적층체의 감광성 수지층을 노광하고 패턴모양으로 활성광선을 조사하여 노광 부분을 광경화시킨다;(2) Exposure step: the photosensitive resin layer of the photosensitive resin laminate is exposed to light, and actinic rays are irradiated in a pattern to photocur the exposed portion;
(3) 현상 공정 : 감광성 수지층의 비노광 부분을 현상액으로 제거하여 보호 패턴을 형성한다;(3) Developing process: the unexposed portion of the photosensitive resin layer is removed with a developing solution to form a protective pattern;
(4) 도체 패턴 형성 공정 : 동박 적층판 또는 가요성 기판 표면 중 보호 패턴으로 커버되지 않은 부분을 에칭 또는 도금한다. (4) Conductor pattern formation process: A portion of the surface of the copper clad laminate or flexible substrate not covered with the protective pattern is etched or plated.
(5) 박리 공정 : 상기 동박 적층판 또는 가요성 기판으로부터 보호 패턴을 박리한다.(5) Peeling step: The protective pattern is peeled off from the copper clad laminate or flexible board.
또한, 본 발명은 상술한 바와 같은 라미네이션 공정, 노광 공정, 현상 공정을 포함하는 보호 패턴 제조에 있어서의 상기 건식필름의 응용에 대하여 제공한다. 다만 차이점이라면, 라미네이션 공정에서 감광성 수지 적층체가 다양한 서로 다른 소재의 기판에 라미네이팅 될 수 있는 점이 다르다. In addition, the present invention provides for the application of the dry film in manufacturing a protective pattern including the lamination process, exposure process, and development process as described above. The only difference is that the photosensitive resin laminate can be laminated to substrates of various different materials in the lamination process.
또한, 본 발명은 상술한 바와 같은 라미네이션 공정, 노광 공정, 현상 공정 및 도체 패턴 형성 공정을 포함하는 도체 패턴 제조에 있어서의 상기 건식필름의 응용에 대하여 제공한다. 다만 차이점이라면, 라미네이션 공정에서 감광성 수지 적층체가 금속판 또는 금속 코팅 절연판에 라미네이팅 되는 점이 다르다. In addition, the present invention provides for the application of the dry film in the manufacture of a conductor pattern including the lamination process, exposure process, development process and conductor pattern formation process as described above. The only difference is that the photosensitive resin laminate is laminated to a metal plate or a metal-coated insulating plate in the lamination process.
또한, 본 발명은 상술한 바와 같은 라미네이션 공정, 노광 공정, 현상 공정 및 도체 패턴 형성 공정을 포함하는 리드 프레임 제조에 있어서의 상기 건식필름의 응용에 대하여 제공한다. 다만 차이점이라면, 라미네이션 공정에서 감광성 수지 적층체가 금속판에 라미네이팅 되고, 도체 패턴 형성 공정에서 보호 패턴으로 커버되지 않은 부분에 에칭이 수행되는 점이 다르다.In addition, the present invention provides for the application of the dry film in lead frame manufacturing including the lamination process, exposure process, development process and conductor pattern formation process as described above. The only difference is that the photosensitive resin laminate is laminated to the metal plate in the lamination process, and etching is performed on the portion not covered by the protective pattern in the conductor pattern formation process.
또한, 본 발명은 상술한 바와 같은 라미네이션 공정, 노광 공정, 현상 공정 및 도체 패턴 형성 공정을 포함하는 반도체 패키징 제조에 있어서의 상기 건식필름의 응용에 대하여 제공한다. 다만 차이점이라면, 라미네이션 공정에서 감광성 수지 적층체가 대규모 집적 회로가 구비되는 웨이퍼에 라미네이팅 되고, 도체 패턴 형성 공정에서 보호 패턴으로 커버되지 않은 부분에 도금이 수행되는 점이다. In addition, the present invention provides for the application of the dry film in semiconductor packaging manufacturing including the lamination process, exposure process, development process and conductor pattern formation process as described above. The only difference is that in the lamination process, the photosensitive resin laminate is laminated to a wafer having large-scale integrated circuits, and in the conductor pattern formation process, plating is performed on a portion not covered with a protective pattern.
습식필름의 응용Application of wet film
본 발명의 감광성 수지 조성물은 인쇄 회로 기판, 보호 패턴, 도체 패턴, 리드 프레임, 반도체 패키징 등의 제조에 사용하기 위해 습식필름 방식으로 기판에 직접 도포하여 사용할 수 있다.The photosensitive resin composition of the present invention may be directly applied to a substrate in a wet film method for use in manufacturing printed circuit boards, protective patterns, conductor patterns, lead frames, semiconductor packaging, and the like.
제한없이, 롤러 코팅, 닥터 블레이드 코팅, 스프레이 코팅, 딥 코팅 등의 통상적인 방법을 이용해 감광성 수지 조성물을 기판에 도포할 수 있고, 건조 후 감광성 수지층을 형성한다.Without limitation, the photosensitive resin composition may be applied to a substrate using conventional methods such as roller coating, doctor blade coating, spray coating, and dip coating, and after drying, a photosensitive resin layer is formed.
기판에 감광성 수지층을 형성한 후, 건식필름의 응용 방식을 참조하여 노광 공정, 현상 공정, 도체 패턴 형성 공정 및 박리 공정과 같은 후속 공정을 모두 수행할 수 있다. After forming the photosensitive resin layer on the substrate, subsequent processes such as an exposure process, a developing process, a conductor pattern formation process, and a peeling process may all be performed with reference to the dry film application method.
공정단계process step
노광 공정에서 노광은 마스크 노광법(배선 패턴의 네거티브 또는 포지티브 마스크 패턴으로 활성광선을 패턴모양으로 조사하는 방법), 투영식 노광법(projection exposure)을 예로 들 수 있고, 레이저 다이렉트 이미징(Laser Direct Imaging) 노광법, 디지털 라이트 프로세싱(digital light processing) 노광법 등의 다이렉트 드로잉 노광법을 통해 활성광선을 패턴모양으로 조사하는 방법도 사용할 수 있다. 활성광선의 광원으로서는, 공지의 광원으로, 예를 들면 카본 아크 램프, 수은 증기 아크 램프, 초고압 인디케이터 램프, 고압 인디케이터 램프, 크세논 램프, 아르곤 레이저 등의 가스 레이저, YAG 레이저 등의 고체 레이저, 반도체 레이저 및 질화 갈륨계 블루-바이올렛(Blue-violet) 레이저 등 자외선을 효과적으로 방출하는 광원을 사용할 수 있다. 이밖에도, 사진용 플러드(floodlight) 램프, 형광 램프 등 가시광선을 효과적으로 방출하는 광원을 사용할 수도 있다. Exposure in the exposure process includes, for example, a mask exposure method (a method of irradiating active rays in a pattern with a negative or positive mask pattern of a wiring pattern), a projection exposure method, and laser direct imaging (Laser Direct Imaging). ) exposure method, a method of irradiating actinic rays in a pattern through a direct drawing exposure method such as a digital light processing exposure method can also be used. As the light source of the actinic light, it is a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure indicator lamp, a high pressure indicator lamp, a xenon lamp, a gas laser such as an argon laser, a solid-state laser such as a YAG laser, and a semiconductor laser. and a light source that effectively emits ultraviolet light, such as a gallium nitride-based blue-violet laser. In addition, a light source that effectively emits visible light, such as a floodlight lamp for photography or a fluorescent lamp, may be used.
본 발명의 감광성 수지 조성물은 활성광선의 광원 종류에 대해 특별히 제한되지 않으며, 노광량은 10-1000 mJ/cm2이 바람직하다.The photosensitive resin composition of the present invention is not particularly limited to the kind of light source of actinic light, and the exposure amount is preferably 10-1000 mJ/cm 2 .
현상 공정에서는 감광성 수지층의 비노광 부분을 현상액을 이용해 제거한다. 감광성 수지층에 지지체가 존재하는 경우, 자동 박리기 등을 이용하여 지지체를 먼저 제거할 수 있고, 그 다음 이어서 알칼리 수용액, 수성 현상액, 유기 용제 등의 현상액을 이용해 비노광 부분을 제거한다. 알칼리성 수용액의 예로는 0.1-5 질량%의 탄산나트륨 용액, 0.1-5 질량%의 탄산칼륨 용액, 0.1-5 질량%의 수산화나트륨 용액 등을 예로 들 수 있고, pH 값은 9-11이 바람직하다. 알칼리성 수용액에는 계면 활성제, 소포제, 유기 용제 등을 더 추가할 수 있다. 현상 방법은 디핑(dipping), 스프레이, 브러싱 등의 통상적인 방법일 수 있다.In the developing step, the unexposed portion of the photosensitive resin layer is removed using a developing solution. When a support is present in the photosensitive resin layer, the support may be first removed using an automatic peeler or the like, and then the unexposed portion is removed using a developing solution such as aqueous alkali solution, aqueous developer, or organic solvent. Examples of the alkaline aqueous solution include 0.1-5 mass% sodium carbonate solution, 0.1-5 mass% potassium carbonate solution, 0.1-5 mass% sodium hydroxide solution and the like, and the pH value is preferably 9-11. A surfactant, an antifoaming agent, an organic solvent and the like can be further added to the alkaline aqueous solution. The developing method may be a conventional method such as dipping, spraying, or brushing.
에칭 처리에서는 기판에 형성된 레지스트 패턴(즉, 보호 패턴)을 마스크로 사용하여 커버되지 않은 회로 형성용 기판의 도체층을 에칭으로 제거하여 도체 패턴을 형성한다. 에칭 처리 방법은 제거할 도체층에 따라 선택할 수 있다. 예를 들어, 에칭액으로는, 산화 구리 용액, 산화철 용액, 알칼리 에칭 용액, 과산화수소계 에칭액 등을 예로 들 수 있다.In the etching treatment, a conductor pattern is formed by removing the uncovered conductor layer of the substrate for circuit formation by etching using a resist pattern (i.e., a protective pattern) formed on the substrate as a mask. The etching treatment method can be selected according to the conductor layer to be removed. For example, examples of the etching solution include a copper oxide solution, an iron oxide solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.
도금 처리에서는 기판에 형성된 레지스트 패턴을 마스크로 사용하여 커버되지 않은 회로 형성용 기판의 절연판에 구리 도금 및 솔더(solder) 등을 수행한다. 도금 처리 후, 레지스트 패턴을 제거하여 도체 패턴을 형성한다. 도금 처리 방법으로는, 전기 도금 처리 또는 무전해 도금 처리일 수 있고, 바람직하게는 무전해 도금 처리이다. 무전해 도금 처리로서는, 황산구리 도금 및 피로인산구리(copper pyrophosphate) 도금 등의 구리 도금, high-throw solder 도금 등의 솔더 도금, 와트욕(watts bath, 황산니켈-염화니켈) 도금 및 술파믹산(Sulfamic Acid) 니켈 도금 등의 니켈 도금, 경질 금 도금 및 연질 금 도금 등의 금 도금을 예로 들 수 있다. In the plating process, copper plating and soldering are performed on an insulating plate of an uncovered circuit formation board using a resist pattern formed on the board as a mask. After the plating process, the resist pattern is removed to form a conductor pattern. The plating treatment method may be an electroplating treatment or an electroless plating treatment, and preferably an electroless plating treatment. As the electroless plating treatment, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watts bath (nickel sulfate-nickel chloride) plating, and sulfamic acid (sulfamic acid) Acid) nickel plating such as nickel plating, gold plating such as hard gold plating and soft gold plating.
레지스트 패턴의 제거는, 현상 단계에서 사용하는 알칼리성 수용액보다 염기성이 더 강한 수용액으로 박리할 수 있다. 강알칼리성 수용액의 예로는, 예컨대 1-10 질량%의 수산화 나트륨 수용액을 사용할 수 있다. The resist pattern can be removed with an aqueous solution having a stronger basicity than the alkaline aqueous solution used in the developing step. As an example of the strong alkaline aqueous solution, for example, 1-10% by mass sodium hydroxide aqueous solution can be used.
도 1은 화합물 a1의 고성능 액체 크로마토그래피(HPLC) 그래프이다.
도 2는 단결정 회절로 얻은 T1의 구조 스펙트럼입니다.
도 3은 화합물 a1, a2, a3, a8, a9, a10의 감광도 테스트 결과를 비교한 것이다.1 is a high-performance liquid chromatography (HPLC) graph of compound a1.
Figure 2 is the structural spectrum of T1 obtained by single crystal diffraction.
3 compares photosensitivity test results of compounds a1, a2, a3, a8, a9, and a10.
하기에서는 구체적인 실시예와 함께 본 발명에 대해 더 상세히 설명하나 이는 본 발명의 보호 범위를 한정하는 것으로 간주되어서는 안된다.In the following, the present invention is described in more detail with specific examples, but this should not be considered as limiting the protection scope of the present invention.
1. 헥사아릴비스이미다졸계 혼합 광개시제1. Hexaarylbisimidazole-based mixed photoinitiator
1.1 헥사아릴비스이미다졸계 혼합 광개시제 a1의 제조1.1 Preparation of hexaarylbisimidazole-based mixed photoinitiator a1
질소 분위기하에, 1L의 4구 플라스크에 2-(o-클로로페닐)-4,5-디페닐-이미다졸(M1, 2-(o-Chlorophenyl)-4,5-diphenyl-imidazole) 31.8g, 2,5-비스(o-클로로페닐)-4-(4,5-디메톡시페닐)-이미다졸(M2, 2,5-Bis(o-chlorophenyl)-4-(4,5-dimethoxyphenyl)-imidazole) 51.3g, 30% 액화 가성소다 4.2g, 테트라부틸암모늄 브로마이드(Tetrabutylammonium bromide) 4.0g, 톨루엔 300g을 투입하고, 가열 교반하여 60-65℃일 때 차아염소산나트륨(Sodium hypochlorite, 11%수용액) 85g을 적하하였다. 적하완료 후 보온 반응시키고, 샘플링을 M1과 M2가 모두 1% 미만으로 반응이 완료될 때까지 HPLC을 통해 제어하고, 보온을 종료하였다. Under a nitrogen atmosphere, 31.8 g of 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (M1, 2-(o-Chlorophenyl)-4,5-diphenyl-imidazole) in a 1 L four-necked flask, 2,5-bis (o-chlorophenyl) -4- (4,5-dimethoxyphenyl) -imidazole (M2, 2,5-Bis (o-chlorophenyl) -4- (4,5-dimethoxyphenyl) - imidazole) 51.3g, 30% liquefied caustic soda 4.2g, tetrabutylammonium bromide 4.0g, and toluene 300g were added, heated and stirred to obtain sodium hypochlorite (11% aqueous solution) at 60-65°C. 85 g was added dropwise. After completion of the dropping, the warming reaction was performed, and sampling was controlled through HPLC until the reaction was completed with both M1 and M2 less than 1%, and the warming was terminated.
보온 반응 종료 후, 순수 100g으로 4회 세척하고, 이어서 톨루엔 20g으로 수층을 1회 추출한 다음, 유기층을 감압 증류하였다. 증류로 얻은 물질에 메탄올 70g을 첨가하여 용해액이 맑게 될 때까지 가열 교반하고, 이어서, 용해액을 메탄올 30g과 순수 50g으로 배합된 재결정 용액에 적하하고, 적하완료 후 여과, 린싱, 베이킹 건조하여 생성물 a1 79.1g을 수득하였다.After completion of the warming reaction, the mixture was washed 4 times with 100 g of pure water, then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. 70 g of methanol was added to the material obtained by distillation, and the solution was heated and stirred until the solution became clear, and then the solution was added dropwise to the recrystallized solution mixed with 30 g of methanol and 50 g of pure water. 79.1 g of product a1 was obtained.
생성물은 고성능 액체 크로마토그래피(HPLC)을 이용해 분석하였다.The product was analyzed using high performance liquid chromatography (HPLC).
도 1은 생성물 a1의 고성능 액체 크로마토그래피 그래프이다. 분석 결과는 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 생성물의 피크 총 함량이 92.5%임을 보여준다. 1 is a high-performance liquid chromatography graph of product a1. The analysis results show that the total peak content of the products of the four linking positions 1'-2, 2-3', 1-2', and 2'-3 is 92.5%.
생성물 a1은 서로 다른 두 모노-이미다졸(즉, M1 및 M2)의 동종의 호모(homo) 커플링 및 크로스(cross) 커플링으로 얻어지는 혼합물로 T1, T2, T3를 포함한다. 생성물의 구조 조성을 정확히 검증하기 위해, 성분 a1-1, a1-2, a1-3에 대해 각각 검증분석을 수행하였다. Product a1 is a mixture obtained by homogeneous homo-coupling and cross-coupling of two different mono-imidazoles (ie, M1 and M2), and includes T1, T2 and T3. In order to accurately verify the structural composition of the product, verification analysis was performed on components a1-1, a1-2, and a1-3, respectively.
모노-이미다졸의 호모 커플링, 컬럼크로마토크래피, 크로마토그래피 분리 등의 방법을 통해 순수한 T1, T2, T3를 각각 수득하고, 구조 확인을 각각 수행하였다. Pure T1, T2, and T3 were respectively obtained through homo-coupling of mono-imidazole, column chromatography, chromatographic separation, and the like, and structural confirmation was performed, respectively.
T1은 도 2를 참조하면 액상 중 피크가 하나만 존재하나, 단결정 회절에 의하면 2개의 피크 형상이 획득된다. 구조적 특성을 결합하면, 두 모노-이미다졸의 커플링에 의한 주요 생성물은, 그 중 한 이미다졸의 수소를 포함하는 N이 또 다른 이미다졸의 2위치의 C와 연결되어 형성되는 혼합물임을 확인할 수 있고, 이에 의해, T1의 구조는 본 발명에 기재된 2개의 연결위치 1-2' 및 2'-3 임을 알 수 있다. Referring to FIG. 2, T1 has only one peak in the liquid phase, but two peak shapes are obtained according to single crystal diffraction. Combining the structural properties, it can be confirmed that the main product of the coupling of two mono-imidazoles is a mixture formed by the N containing hydrogen of one of the imidazoles being linked to the C of the 2-position of the other imidazole. Thereby, it can be seen that the structure of T1 is the two linking positions 1-2' and 2'-3 described in the present invention.
T1을 합성하는 이미다졸인 M1은 대칭형 이미다졸에 속한다. 때문에 커플링으로 얻은 1-2', 2'-3의 극성은 유사하고 액상 분리가 어렵다. M1의 구조 대칭성으로 인해 호모 커플링으로 얻은 생성물의 구조 중 1-2'와 1'-2의 구조는 동일하고, 2'-3, 3-2'의 구조도 동일하다. 때문에 T1의 주요 구조는 두개의 연결위치 1-2'와 3-2'의 생성물로 구조식은 하기와 같이 표시되며, 각각 T1-1: 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라페닐-1,2'-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazol) 및 T1-2: 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라페닐-2'-3-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2'-3-diimidazol)이다. M1, the imidazole that synthesizes T1, belongs to the symmetric imidazole class. Therefore, the polarities of 1-2' and 2'-3 obtained by coupling are similar and liquid phase separation is difficult. Due to the structural symmetry of M1, the structures of 1-2' and 1'-2 of the products obtained by homo-coupling are the same, and the structures of 2'-3 and 3-2' are also the same. Therefore, the main structure of T1 is a product of two linking positions 1-2' and 3-2', and the structural formula is represented as follows, respectively, T1-1: 2,2'-bis (o-chlorophenyl) -4, 4',5,5'-tetraphenyl-1,2'-diimidazol ) And T1-2: 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-2'-3-diimidazole (2,2'-Bis (o- chlorophenyl) -4,4',5,5'-tetraphenyl-2'-3-diimidazol).
동일하게, 분리하여 얻은 순수한 T2를 분석하였다. 주요 구조는 4개의 연결위치의 생성물로 LCMS를 수행해 구조를 확인하였다. 849 및 850의 분자 조각 피크(fragment peak)는 질량 분석 보조기에 구비된 소프트웨어를 통해 얻었으며, 생성물의 분자량은 848로 T+1 및 T+2에 부합되었다. 이는 4개의 생성물이 구조가 유사하고, 분자량이 동일함을 증명한다. T2를 합성하는 모노-이미다졸인 M2는 비대칭 모노-이미다졸에 속하며, M2-1 및 M2-2의 두개의 구조가 존재하고, 아래와 같이 표시된다: Similarly, pure T2 obtained by separation was analyzed. The main structure was confirmed by performing LCMS as a product of four linkages. Molecular fragment peaks of 849 and 850 were obtained through the software provided in the mass spectrometer, and the molecular weight of the product was 848, which corresponded to T+1 and T+2. This proves that the four products are similar in structure and identical in molecular weight. M2, the mono-imidazole synthesizing T2, belongs to an asymmetric mono-imidazole, and has two structures, M2-1 and M2-2, and is represented as follows:
T2는 비대칭 모노-이미다졸의 커플링에 의해 합성되고, 이론적으로는 1-2 및 2-3의 연결위치에 연결되는 8개의 주요 구조가 존재하나, 호모 커플링된 모노-이미다졸의 경우는, 구조 중 1-2'와 1'-2의 구조가 동일하고, 2'-3과 3-2'의 구조도 동일하기 때문에 T2는 실제로 1-2 및 2-3의 연결위치에 연결되는 4개의 주요 구조가 존재하고, 그 조성은 각각 다음과 같다: T2 is synthesized by asymmetric mono-imidazole coupling, and theoretically, there are 8 main structures connected to the linking positions of 1-2 and 2-3, but in the case of homo-coupled mono-imidazole , Since the structures of 1-2' and 1'-2 are the same, and the structures of 2'-3 and 3-2' are also the same, T2 is actually connected to the connection position of 1-2 and 2-3. There are two main structures, the composition of which is respectively:
T2-1: 2,2',5,5'-테트라(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-2'-3-디이미다졸(2,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole), T2-2: 2,2',4,5'-테트라(o-클로로페닐)-4',5-비스(3,4-디메톡시페닐)-1-2'-디이미다졸(2,2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole), T2-3: 2,2',5,5'-테트라(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-1-2'-디이미다졸(2,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole), T2-4: 2,2',4,5'-테트라(o-클로로페닐)-4',5-비스(3,4-디메톡시페닐)-2'-3-디이미다졸(2,2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2',3-diimidazole), 구조는 아래와 같이 표시된다: T2-1: 2,2',5,5'-tetra (o-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) -2'-3-diimidazole (2,2 ',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole), T2-2: 2,2',4,5'- Tetra (o-chlorophenyl) -4 ', 5-bis (3,4-dimethoxyphenyl) -1-2'-diimidazole (2,2', 4,5'-Tetra (o-chlorophenyl) - 4',5-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole), T2-3: 2,2',5,5'-tetra(o-chlorophenyl)-4,4'-bis (3,4-dimethoxyphenyl)-1-2'-diimidazole (2,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)- 1-2'-diimidazole), T2-4: 2,2',4,5'-tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2'-3 -Diimidazole (2,2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2',3-diimidazole), the structure is shown below :
T3는 M1과 M2의 커플링에 의해 형성되고, 분리하여 얻은 순수한 T3의 액상 내 주요 구조는 4개의 연결위치의 생성물로 LCMS를 수행해 4개의 연결위치의 생성물 구조를 확인하였다. 755 및 756의 분자 조각 피크(fragment peak)는 질량 분석 보조기에 구비된 소프트웨어를 통해 얻었으며, 생성물의 분자량은 754로 T+1 및 T+2에 부합되었다. 이는 4개의 생성물이 구조가 유사하고, 분자량이 동일함을 증명한다. T3는 대칭 이미다졸 M1과 비대칭 이미다졸 M2의 커플링에 의해 형성되고, 1-2 및 2-3의 연결위치에 연결되는 4개의 주요 구조가 존재하며, 그 조성은 각각 다음과 같다: T3 was formed by the coupling of M1 and M2, and the main structure in the liquid phase of pure T3 obtained by separation was a product of four linkages, and LCMS was performed to confirm the structure of the product of four linkages. Molecular fragment peaks of 755 and 756 were obtained through the software provided in the mass spectrometer, and the molecular weight of the product was 754, which corresponded to T+1 and T+2. This proves that the four products are similar in structure and identical in molecular weight. T3 is formed by the coupling of symmetric imidazole M1 and asymmetric imidazole M2, and there are four main structures connected to the linking positions of 1-2 and 2-3, the composition of which is as follows, respectively:
T3-1: 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1,2'-디이미다졸(2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole), T3-2: 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-2',3-디이미다졸(2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole), T3-3: 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-2,3'-디이미다졸(2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole), T3-4: 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1',2-디이미다졸(2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole), 구조식은 다음과 같다:T3-1: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole (2 ,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole), T3-2: 2,2',5- Tris (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4', 5'-diphenyl-2', 3-diimidazole (2,2', 5-Tris (o-chlorophenyl )-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole), T3-3: 2,2',5-tris(o-chlorophenyl)-4-( 3,4-dimethoxyphenyl) -4',5'-diphenyl-2,3'-diimidazole (2,2',5-Tris (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4',5'-diphenyl-2,3'-diimidazole), T3-4: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4' ,5'-diphenyl-1',2-diimidazole (2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1' ,2-diimidazole), the structural formula is:
상기 실험 분석을 종합하면, 생성물 a1은 T1(T1-1, T1-2), T2(T2-1, T2-2, T2-3, T2-4), T3(T3-1, T3-2, T3-3, T3-4)을 포함하는 것을 확인할 수 있고, 여기서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3로 구성되는 비스이미다졸 화합물의 a1 내 함량은 92.5%이다.Summarizing the above experimental analysis, product a1 is T1 (T1-1, T1-2), T2 (T2-1, T2-2, T2-3, T2-4), T3 (T3-1, T3-2, T3-3, T3-4), wherein a1 of the biimidazole compound consisting of four linking positions 1'-2, 2-3', 1-2', 2'-3 My content is 92.5%.
1.2 a2-a10의 제조1.2 Preparation of a2-a10
a2-a10을 각각 제조하였으며, 각 생성물의 상황은 하기 표 1에 제시된 바와 같다.A2-a10 were prepared, respectively, and the status of each product is shown in Table 1 below.
용해도 in butanone
solubility
상기 표의 용해도 데이터를 통해 볼 수 있듯이, 단일 구조의 순수한 HABI(a6 및 a7)는 용해도가 매우 열위하여 기타 HABI와 혼합(a4 및 a5)하더라도 용해도를 향상시킬 수 없고, 본 발명의 상기 HABI계 혼합 광개시제는 반드시 동일한 치환기의 구조로 동시에 4개의 연결위치가 존재해야 본 발명이 제시하는 최적의 용해도에 도달할 수 있다. As can be seen from the solubility data in the table above, pure HABIs (a6 and a7) of a single structure have very poor solubility, so even if mixed with other HABIs (a4 and a5), the solubility cannot be improved, and the HABI-based mixture of the present invention The photoinitiator must have the same substituent structure and have four linking positions at the same time to reach the optimum solubility suggested by the present invention.
1.3 감광도 테스트1.3 Light sensitivity test
순수한 T2-3 또는 T3-4을 사용하는 경우, 용해도가 열위해 감광도 테스트가 어렵기 때문에 a1, a2, a3, a8, a9, a10의 감광도 데이터만 테스트하였다.In the case of using pure T2-3 or T3-4, only the photosensitivity data of a1, a2, a3, a8, a9, and a10 were tested because the photosensitivity test was difficult due to poor solubility.
표 2에 제시된 조성에 따라, 비교예 1-6의 감광성 수지 조성물을 제조하여 감광도를 테스트하였다. 표에서 각 물질의 용량 단위는 g이다.According to the composition shown in Table 2, photosensitive resin compositions of Comparative Examples 1-6 were prepared and photosensitivity was tested. The unit of dosage for each substance in the table is g.
표 1에서, TMPTA는 Tianjin Beilian Fine Chemicals Development Co., Ltd. 에서 구매하였고, NPG는 Shenzhen Pengshunxing Technology Co., Ltd. 에서 구매하였으며, PGMEA는 Jinan Huifengda Chemical Co., Ltd.에서 구매하였다.In Table 1, TMPTA is Tianjin Beilian Fine Chemicals Development Co., Ltd. and NPG was purchased from Shenzhen Pengshunxing Technology Co., Ltd. , and PGMEA was purchased from Jinan Huifengda Chemical Co., Ltd.
상술한 조성에 따라 시료를 제조하고, 균일하게 혼합한 후 시료 1.0mg을 취하여 도가니의 바닥부에 평탄하게 도포한 다음, 시차주사열량계(모델명: DSC8000, 제조사: PerkinElmer)의 스토브에 투입하여 테스트를 수행하였다. Samples were prepared according to the above-described composition, and after uniform mixing, 1.0 mg of the sample was taken and spread evenly on the bottom of the crucible, and then put into the stove of a differential scanning calorimeter (model name: DSC8000, manufacturer: PerkinElmer) to conduct a test. performed.
피크값은 최대 열 방출량 mw/mg을 나타내고, 열 방출이 클수록 감광도가 높다. 기울기는 경화 속도를 나타내고, 기울기가 작을수록 감광도가 높다.The peak value represents the maximum heat release mw/mg, and the higher the heat release, the higher the photosensitivity. The slope represents the curing speed, and the smaller the slope, the higher the photosensitivity.
결과는 도 3에 도시된 바와 같으며, 감광도 테스트 결과는 다음과 같다: a10(76.1%)<a9(83.0%)a8(88.5%)<a1(92.5%)a2(95.6%)a3(98.3). 이는 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3로 구성되는 비스이미다졸 화합물의 혼합 광개시제 내 총 질량이 감광도에 일정한 영향을 미치며, 함량이 92%를 초과하는 경우 감광도가 향상되었다는 것을 추가로 증명하였다.The results are as shown in Fig. 3, and the photosensitivity test results are as follows: a10 (76.1%) < a9 (83.0%) a8(88.5%)<a1(92.5%) a2(95.6%) a3 (98.3). This is because the total mass in the mixed photoinitiator of the biimidazole compound composed of four linking positions 1'-2, 2-3', 1-2', and 2'-3 has a certain effect on the photosensitivity, and the content is 92% It was further demonstrated that photosensitivity was improved when exceeding.
1.4 a11의 제조1.4 Preparation of a11
질소 분위기하에, 1L의 4구 플라스크에 2-(4-클로로페닐)-5-(6-클로로페닐)-4-(3,4-디메톡시페닐)-이미다졸(M3, 2-(4-Chlorophenyl)-5-(6-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole) 50g, 2,5-비스(o-클로로페닐)-4-(3,4-디메톡시페닐)-이미다졸(M2, 2,5-Bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole) 51g, 30%액화 가성소다5.6g, 테트라부틸암모늄 브로마이드 4.0g, 톨루엔 300g을 투입하고, 가열 교반하여 60-65℃일 때 차아염소산나트륨(11%수용액) 90g을 적하하였다. 적하완료 후 보온 반응시키고, 샘플링을 M2와 M3가 모두 1% 미만으로 반응이 완료될 때까지 HPLC을 통해 제어하고, 보온을 종료하였다.2-(4-chlorophenyl)-5-(6-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole (M3, 2-(4- Chlorophenyl)-5-(6-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole) 50g, 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole 51 g of dazole (M2, 2,5-Bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole), 5.6 g of 30% liquefied caustic soda, 4.0 g of tetrabutylammonium bromide, and 300 g of toluene were added, After stirring with heating, 90 g of sodium hypochlorite (11% aqueous solution) was added dropwise at 60-65°C. After completion of the dropping, the warming reaction was performed, and sampling was controlled through HPLC until the reaction was completed with both M2 and M3 less than 1%, and the warming was terminated.
보온 반응 종료 후, 순수 100g으로 4회 세척하고, 이어서 톨루엔 20g으로 수층을 1회 추출한 다음, 유기층을 감압 증류하였다. 증류로 얻은 물질에 메탄올 70g을 첨가하여 용해액에 맑게 될 때까지 가열 교반하고, 이어서, 용해액을 메탄올 30g과 순수 50g으로 배합된 재결정 용액에 적하하고, 적하완료 후. 린싱, 건조, 베이킹하여 생성물 a11 98g을 수득하였다.After completion of the warming reaction, the mixture was washed 4 times with 100 g of pure water, then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. 70 g of methanol was added to the substance obtained by distillation, the solution was heated and stirred until it became clear, and then the solution was added dropwise to a recrystallized solution blended with 30 g of methanol and 50 g of pure water, and the addition was completed. Rinsing, drying and baking gave 98 g of product a11.
분석 결과는 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 생성물의 피크 총 함량이 92.5%임을 보여준다.The analysis results show that the total peak content of the products of the four linking positions 1'-2, 2-3', 1-2', and 2'-3 is 92.5%.
생성물 a11은 서로 다른 두 모노-이미다졸(즉, M2 및 M3)의 동종의 호모(homo) 커플링 및 크로스(cross) 커플링으로 얻어지는 혼합물로 T2, T4, T5를 포함한다. 생성물의 구조 조성을 정확히 검증하기 위해, 성분 T2, T4, T5에 대해 각각 검증분석을 수행하였다.Product a11 is a mixture obtained by homogeneous homo-coupling and cross-coupling of two different mono-imidazoles (ie, M2 and M3), and includes T2, T4 and T5. In order to accurately verify the structural composition of the product, verification analysis was performed on components T2, T4, and T5, respectively.
모노-이미다졸의 호모 커플링, 컬럼크로마토크래피, 크로마토그래피 분리 등의 방법을 통해 T2, T4, T5를 각각 수득하고, 각각 구조 확인을 수행하였다.T2, T4, and T5 were obtained through homo-coupling of mono-imidazole, column chromatography, chromatographic separation, etc., respectively, and their structures were confirmed.
T2는 화합물 a1과 구조가 일치한다. T2 has the same structure as compound a1.
T4는 비대칭 모노-이미다졸 M3의 호모 커플링에 의해 형성되고, 1-2 및 2-3의 연결위치에 연결되는 4개의 주요 구조가 존재하며, 그 조성은 각각 다음과 같다: T4 is formed by homo-coupling of asymmetric mono-imidazole M3, and there are four main structures connected to the linking positions of 1-2 and 2-3, and their compositions are as follows, respectively:
T4-1: 2,2'-비스(4-클로로페닐)-5,5'-비스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-2,3'-디이미다졸(2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole), T4-2: 2,2'-비스(4-클로로페닐)-4,5'-비스(o-클로로페닐)-4',5-비스(3,4-디메톡시페닐)-1,2'-디이미다졸(2,2'-Bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), T4-3: 2,2'-비스(4-클로로페닐)-5,5'-비스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-1,2'-디이미다졸(2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), T4-4: 2,2'-비스(4-클로로페닐)-4',5-비스(o-클로로페닐)-4,5'-비스(3,4-디메톡시페닐)-2,3'-디이미다졸(2,2'-Bis(4-chlorophenyl)-4',5-bis(o-chlorophenyl)-4,5'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole), 구조식은 아래와 같이 표시된다:T4-1: 2,2'-bis (4-chlorophenyl) -5,5'-bis (o-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) -2,3' -Diimidazole (2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole) , T4-2: 2,2'-bis (4-chlorophenyl) -4,5'-bis (o-chlorophenyl) -4', 5-bis (3,4-dimethoxyphenyl) -1,2 '-Diimidazole (2,2'-Bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole ), T4-3: 2,2'-bis (4-chlorophenyl) -5,5'-bis (o-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) -1, 2'-diimidazole (2,2'-Bis (4-chlorophenyl) -5,5'-bis (o-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) -1,2'- diimidazole), T4-4: 2,2'-bis(4-chlorophenyl)-4',5-bis(o-chlorophenyl)-4,5'-bis(3,4-dimethoxyphenyl)-2 ,3'-diimidazole (2,2'-Bis(4-chlorophenyl)-4',5-bis(o-chlorophenyl)-4,5'-bis(3,4-dimethoxyphenyl)-2,3' -diimidazole), the structural formula of which is shown below:
LCMS를 수행해 구조를 확인하였으며, 4개 구조의 스펙트럼이 일치했다. 849 및 850의 분자 조각 피크(fragment peak)는 질량 분석 보조기에 구비된 소프트웨어를 통해 얻었으며, 생성물의 분자량은 848로 T+1 및 T+2에 부합되었다. 이는 4개의 생성물이 구조가 유사하고, 분자량이 동일함을 증명한다.LCMS was performed to confirm the structure, and the spectra of the four structures were consistent. Molecular fragment peaks of 849 and 850 were obtained through the software provided in the mass spectrometer, and the molecular weight of the product was 848, which corresponded to T+1 and T+2. This proves that the four products are similar in structure and identical in molecular weight.
T5는 비대칭 M2와 비대칭 M3의 커플링에 의해 형성되고, 1-2 및 2-3의 연결위치에 연결되는 4개의 주요 구조가 존재하며, 그 조성은 각각 다음과 같다:T5 is formed by the coupling of asymmetric M2 and asymmetric M3, and there are four main structures connected to the linking positions of 1-2 and 2-3, and their compositions are as follows, respectively:
T5-1: 2-(4-클로로페닐)-2',5,5'-트리스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-2,3'-디이미다졸(2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole), T5-2: 2'-(4-클로로페닐)-2,5,5'-트리스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-1,2'-디이미다졸(2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), T5-3: 2-(4-클로로페닐)-2',5,5'-트리스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-2',3-디이미다졸(2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole), T5-4: 2'-(4-클로로페닐)-2,5,5'-트리스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-1',2-디이미다졸(2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1',2-diimidazole), 구조식은 아래와 같이 표시된다:T5-1: 2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'- Diimidazole (2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole), T5 -2: 2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-di Imidazole (2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), T5- 3: 2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimine Dazole (2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole), T5-4 : 2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1',2-diimidazole (2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1',2-diimidazole), the structural formula is as follows displayed:
LCMS를 수행해 구조를 확인하였으며, 4개 구조의 스펙트럼이 일치했다. 849 및 850의 분자 조각 피크(fragment peak)는 질량 분석 보조기에 구비된 소프트웨어를 통해 얻었으며, 생성물의 분자량은 848로 T+1 및 T+2에 부합되었다. 이는 4개의 생성물이 구조가 유사하고, 분자량이 동일함을 증명한다.LCMS was performed to confirm the structure, and the spectra of the four structures were consistent. Molecular fragment peaks of 849 and 850 were obtained through the software provided in the mass spectrometer, and the molecular weight of the product was 848, which corresponded to T+1 and T+2. This proves that the four products are similar in structure and identical in molecular weight.
상기 실험 분석을 종합하면, 생성물 a11은 T2(T2-1, T2-2, T2-3, T2-4), T4(T4-1, T4-2, T4-3, T4-4), T5(T5-1, T5-2, T5-3, T5-4)로 이루어지는 것을 확인할 수 있고, 여기서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3로 구성되는 비스이미다졸 화합물의 a11 내 함량은 92.5%이다.Summarizing the above experimental analysis, products a11 are T2 (T2-1, T2-2, T2-3, T2-4), T4 (T4-1, T4-2, T4-3, T4-4), T5 ( T5-1, T5-2, T5-3, T5-4), which consists of four connection positions 1'-2, 2-3', 1-2', 2'-3 The content of the biimidazole compound in a11 is 92.5%.
a12-a20을 각각 제조하였으며, 각 생성물의 상황은 하기 표 3에 제시된 바와 같다.a12-a20 were prepared, respectively, and the status of each product is shown in Table 3 below.
광개시제HABI system
photoinitiator
상기 표의 용해도 데이터는, 단일 구조의 순수한 HABI(a16 및 a17)는 용해도가 매우 열위하여 기타 HABI와 혼합(a14 및 a15)하더라도 용해도를 향상시킬 수 없고, 본 발명의 상기 HABI계 혼합 광개시제는 반드시 동일한 치환기의 구조로 동시에 4개의 연결위치가 존재해야 본 발명이 제시하는 최적의 용해도에 도달할 수 있음을 추가로 보여준다.The solubility data in the table above shows that single-structured pure HABIs (a16 and a17) have very poor solubility, so that the solubility cannot be improved even when mixed with other HABIs (a14 and a15), and the HABI-based mixed photoinitiator of the present invention is necessarily the same. It is further shown that the optimal solubility proposed by the present invention can be reached only when four linking positions are present at the same time in the structure of the substituent.
1.5 a21의 제조1.5 Manufacture of a21
질소 분위기하에, 1L의 4구 플라스크에 2-(o-클로로페닐)-4,5-디페닐-이미다졸(M1, 2-(o-Chlorophenyl)-4,5-diphenyl-imidazole) 35g, 2-(2,4-디클로로페닐)-4.5-디페닐-이미다졸(M4, 2-(2,4-dichlorophenyl)-4,5-diphenyl-imidazole) 39g, 30% 액화 가성소다 5.6g, 테트라부틸암모늄 브로마이드 4.0g, 톨루엔 250g을 투입하고, 가열 교반하여 60-65℃일 때 차아염소산나트륨 87g을 적하하였다. 적하완료 후 보온 반응시키고, 샘플링을 M1과 M4가 모두 1% 미만으로 반응이 완료될 때까지 HPLC을 통해 제어하고, 보온을 종료하였다.Under a nitrogen atmosphere, 35 g of 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (M1, 2-(o-Chlorophenyl)-4,5-diphenyl-imidazole) was placed in a 1 L four-necked flask, 2 -(2,4-dichlorophenyl)-4.5-diphenyl-imidazole (M4, 2-(2,4-dichlorophenyl)-4,5-diphenyl-imidazole) 39g, 30% liquefied caustic soda 5.6g, tetrabutyl 4.0 g of ammonium bromide and 250 g of toluene were added, heated and stirred, and 87 g of sodium hypochlorite was added dropwise at 60-65°C. After completion of the dropping, the warming reaction was performed, and sampling was controlled through HPLC until the reaction was completed with both M1 and M4 less than 1%, and the warming was terminated.
보온 반응 종료 후, 순수 100g으로 4회 세척하고, 이어서 톨루엔 20g으로 수층을 1회 추출한 다음, 유기층을 감압 증류하였다. 증류로 얻은 물질에 메탄올 60g을 첨가하여 용해액이 맑게 될 때까지 가열 교반하고, 이어서, 용해액을 메탄올 30g과 순수 50g으로 배합된 재결정 용액에 적하하고, 적하완료 후. 린싱, 건조, 베이킹하여 생성물 a21 66g을 수득하였다.After completion of the warming reaction, the mixture was washed 4 times with 100 g of pure water, then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. 60 g of methanol was added to the material obtained by distillation, the solution was heated and stirred until the solution became clear, and then the solution was added dropwise to a recrystallized solution blended with 30 g of methanol and 50 g of pure water, and the addition was completed. Rinsing, drying and baking gave 66 g of product a21.
분석 결과는 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 생성물의 피크 총 함량이 92.1%임을 보여준다.The analysis results show that the total peak content of the products at the four linking positions 1'-2, 2-3', 1-2', and 2'-3 is 92.1%.
생성물 a21은 서로 다른 두 대칭형 모노-이미다졸(즉, M1 및 M4)의 동종의 호모(homo) 커플링 및 크로스(cross) 커플링으로 얻어지는 혼합물로 T1, T6, T7을 포함한다. 생성물의 구조 조성을 정확히 검증하기 위해, 성분 T1, T6, T7에 대해 각각 검증분석을 수행하였다.Product a21 is a mixture obtained by homogeneous homo-coupling and cross-coupling of two different symmetrical mono-imidazoles (i.e., M1 and M4), and includes T1, T6, and T7. In order to accurately verify the structural composition of the product, verification analysis was performed on components T1, T6, and T7, respectively.
모노-이미다졸의 호모 커플링, 컬럼크로마토크래피, 크로마토그래피 분리 등의 방법을 통해 T1, T6, T7을 각각 수득하고, 각각 구조 확인을 수행하였다.T1, T6, and T7 were respectively obtained through homo-coupling of mono-imidazole, column chromatography, chromatographic separation, and the like, and structural confirmation was performed.
T1는 화합물 a1과 구조가 일치한다.T1 has the same structure as compound a1.
T6은 2개의 구조를 갖지만 액상 중 피크는 하나만 존재하고, 구조의 조성은 T1과 유사하다. T6은 대칭형 이미다졸의 호모 커플링으로 얻어지기 때문에 커플링으로 얻은 1-2', 2'-3의 극성은 유사하고 액상 분리가 어렵다. 구조식은 하기와 같이 표시되며, 각각 다음과 같다: T6-1: 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐-1,2'-디이미다졸(2,2'-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole), T6-2: 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐-2',3-디이미다졸(2,2'-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole);T6 has two structures, but only one peak exists in the liquid phase, and the composition of the structure is similar to that of T1. Since T6 is obtained by homo-coupling of symmetrical imidazole, polarities of 1-2' and 2'-3 obtained by coupling are similar and liquid phase separation is difficult. The structural formula is shown as follows, respectively: T6-1: 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Diimidazole (2,2'-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole), T6-2: 2,2'-bis(2 ,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole (2,2'-Bis(2,4-dichlorophenyl)-4,4',5, 5'-tetraphenyl-2',3-diimidazole);
분리하여 얻은 순수한 T6를 분석하고, LCMS를 수행해 구조를 확인하였다. 729 및 730의 분자 조각 피크(fragment peak)는 질량 분석 보조기에 구비된 소프트웨어를 통해 얻었으며, 생성물의 분자량은 728로 T+1 및 T+2에 부합되었다. 이는 두 생성물이 피크 구조가 유사하고, 분자량이 동일함을 증명한다.The isolated pure T6 was analyzed and the structure was confirmed by LCMS. Molecular fragment peaks of 729 and 730 were obtained through the software provided in the mass spectrometer, and the molecular weight of the product was 728, which corresponded to T+1 and T+2. This proves that the two products have similar peak structures and the same molecular weight.
T7는 대칭 M1와 대칭 M4의 커플링에 의해 형성되고, 1-2 및 2-3의 연결위치에 연결되는 4개의 주요 구조가 존재하며, 그 조성은 각각 다음과 같다:T7 is formed by the coupling of symmetric M1 and symmetric M4, and there are four main structures connected to the connecting positions of 1-2 and 2-3, the composition of which is as follows, respectively:
T7-1: 2-(2,4-디클로로페닐)-2'-(o-클로로페닐)-4,4',5,5'-테트라페닐-2,3'-디이미다졸(2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,3'-diimidazole), T7-2: 2-(2,4-디클로로페닐)-2'-(o-클로로페닐)-4,4',5,5'-테트라페닐-1',2-디이미다졸(2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1',2-diimidazole), T7-3: 2-(2,4-디클로로페닐)-2'-(o-클로로페닐)-4,4',5,5'-테트라페닐-1,2'-디이미다졸(2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole), T7-4: 2-(2,4-디클로로페닐)-2'-(o-클로로페닐)-4,4',5,5'-테트라페닐-2',3-디이미다졸(2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole), 구조식은 아래와 같이 표시된다:T7-1: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,3'-diimidazole (2-( 2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,3'-diimidazole), T7-2: 2-(2,4-dichlorophenyl) -2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1',2-diimidazole (2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl )-4,4',5,5'-tetraphenyl-1',2-diimidazole), T7-3: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-diimidazole (2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl- 1,2'-diimidazole), T7-4: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3 -Diimidazole (2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole), the structural formula is shown below :
분리하여 얻은 순수한 T7를 분석하고, LCMS를 수행해 구조를 확인하였다. 695 및 696의 분자 조각 피크(fragment peak)는 질량 분석 보조기에 구비된 소프트웨어를 통해 얻었으며, 생성물의 분자량은 694로 T+1 및 T+2에 부합되었다. 이는 4개의 생성물이 피크 구조가 유사하고, 분자량이 동일함을 증명한다.The isolated pure T7 was analyzed and the structure was confirmed by LCMS. Molecular fragment peaks of 695 and 696 were obtained through the software provided in the mass spectrometer, and the molecular weight of the product was 694, which corresponded to T+1 and T+2. This proves that the four products have similar peak structures and identical molecular weights.
상기 실험 분석을 종합하면, 생성물 a21은 T1(T1-1, T1-2), T6(T6-1, T6-2), T7(T7-1, T7-2, T7-3, T7-4)로 이루어지는 것을 확인할 수 있고, 여기서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3로 구성되는 비스이미다졸 화합물의 a21 내 함량은 92.1%이다.Summarizing the above experimental analysis, product a21 is T1 (T1-1, T1-2), T6 (T6-1, T6-2), T7 (T7-1, T7-2, T7-3, T7-4) It can be confirmed that it consists of, where the content of the biimidazole compound consisting of four linking positions 1'-2, 2-3', 1-2', 2'-3 in a21 is 92.1%.
a22-a30을 각각 제조하였으며, 각 생성물의 상황은 하기 표 4에 제시된 바와 같다.a22-a30 were prepared, respectively, and the status of each product is shown in Table 4 below.
광개시제HABI system
photoinitiator
상기 표의 용해도 데이터는, 단일 구조의 순수한 HABI(a26 및 a27)는 용해도가 매우 열위하여 기타 HABI와 혼합(a24 및 a25)하더라도 용해도를 향상시킬 수 없고, 본 발명의 상기 HABI계 혼합 광개시제는 반드시 동일한 치환기의 구조로 동시에 4개의 연결위치가 존재해야 본 발명이 제시하는 최적의 용해도에 도달할 수 있음을 추가로 보여준다.The solubility data in the table above shows that pure HABIs (a26 and a27) of a single structure have very poor solubility and cannot be improved even when mixed with other HABIs (a24 and a25), and the HABI-based mixed photoinitiator of the present invention is necessarily the same. It is further shown that the optimal solubility proposed by the present invention can be reached only when four linking positions are present at the same time in the structure of the substituent.
1.5 a31의 제조1.5 Manufacture of a31
질소 분위기하에, 1L의 4구 플라스크에 2-(o-클로로페닐)-4,5-디페닐-이미다졸(M1, 2-(o-Chlorophenyl)-4,5-diphenyl-imidazole) 35g, 2-(o-클로로 페닐)-4,5-비스(2-나프틸)-이미다졸(M5, 2-(o-chlorophenyl)-4,5-bis(2-naphthyl)-imidazole) 44g, 30%액화 가성소다5.6g, 테트라부틸암모늄 브로마이드 4.0g, 톨루엔 300g을 투입하고, 가열 교반하여 60-65℃일 때 차아염소산나트륨 97g을 적하하였다. 적하완료 후 보온 반응시키고, 샘플링을 M1과 M5가 모두 1% 미만으로 반응이 완료될 때까지 HPLC을 통해 제어하고, 보온을 종료하였다.Under a nitrogen atmosphere, 35 g of 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (M1, 2-(o-Chlorophenyl)-4,5-diphenyl-imidazole) was placed in a 1 L four-necked flask, 2 -(o-chlorophenyl)-4,5-bis(2-naphthyl)-imidazole (M5, 2-(o-chlorophenyl)-4,5-bis(2-naphthyl)-imidazole) 44g, 30% 5.6 g of liquefied caustic soda, 4.0 g of tetrabutylammonium bromide, and 300 g of toluene were added, heated and stirred, and 97 g of sodium hypochlorite was added dropwise at 60-65°C. After completion of the dropping, the warming reaction was performed, and sampling was controlled through HPLC until the reaction was completed with both M1 and M5 less than 1%, and the warming was terminated.
보온 반응 종료 후, 순수 100g으로 4회 세척하고, 이어서 톨루엔 20g으로 수층을 1회 추출한 다음, 유기층을 감압 증류하였다. 증류로 얻은 물질에 메탄올 60g을 첨가하여 용해액이 맑게 될 때까지 가열 교반하고, 이어서, 용해액을 메탄올 30g과 순수 50g으로 배합된 재결정 용액에 적하하고, 적하완료 후. 린싱, 건조, 베이킹하여 생성물 a31 76g을 수득하였다.After completion of the warming reaction, the mixture was washed 4 times with 100 g of pure water, then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. 60 g of methanol was added to the material obtained by distillation, the solution was heated and stirred until the solution became clear, and then the solution was added dropwise to a recrystallized solution blended with 30 g of methanol and 50 g of pure water, and the addition was completed. Rinsing, drying and baking gave 76 g of product a31.
분석 결과는 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 생성물의 피크 총 함량이 92.7%임을 보여준다.The analysis results show that the total peak content of the products at the four linking positions 1'-2, 2-3', 1-2', and 2'-3 is 92.7%.
생성물 a31은 서로 다른 두 대칭형 모노-이미다졸(즉, M1 및 M5)의 동종의 호모(homo) 커플링 및 크로스(cross) 커플링으로 얻어지는 혼합물로 T1, T8, T9를 포함한다. 생성물의 구조 조성을 정확히 검증하기 위해, 성분 T1, T8, T9에 대해 각각 검증분석을 수행하였다.Product a31 is a mixture obtained by homogeneous homo-coupling and cross-coupling of two different symmetrical mono-imidazoles (i.e., M1 and M5), and includes T1, T8, and T9. In order to accurately verify the structural composition of the product, verification analysis was performed on components T1, T8, and T9, respectively.
모노-이미다졸의 호모 커플링, 컬럼크로마토크래피, 크로마토그래피 분리 등의 방법을 통해 T1, T8, T9를 각각 수득하고, 각각 구조 확인을 수행하였다.T1, T8, and T9 were respectively obtained through homo-coupling of mono-imidazole, column chromatography, chromatographic separation, and the like, and structural confirmation was performed.
T1는 화합물 a1과 구조가 일치한다. T1 has the same structure as compound a1.
T8은 2개의 구조를 갖지만 액상 중 피크는 하나만 존재하고, 구조의 조성은 T1과 유사하다. T8은 대칭형 이미다졸(M5)의 호모 커플링으로 얻어지기 때문에 커플링으로 얻은 1-2', 2'-3의 극성은 유사하고 액상 분리가 어렵다. 구조식은 하기와 같이 표시되고, 각각 다음과 같다: T8-1: 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라(2-나프틸)-1,2'-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetra(2-naphthyl)-1,2'-diimidazole), T8-2: 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라(2-나프틸)-2',3- 디이미다졸(2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetra(2-naphthyl)-2',3-diimidazole);T8 has two structures, but only one peak exists in the liquid phase, and the composition of the structure is similar to that of T1. Since T8 is obtained by homo-coupling of symmetrical imidazole (M5), polarities of 1-2' and 2'-3 obtained by coupling are similar and liquid phase separation is difficult. The structural formula is shown as follows, respectively: T8-1: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(2-naphthyl)-1, 2'-diimidazole (2,2'-Bis (o-chlorophenyl) -4,4', 5,5'-tetra (2-naphthyl) -1,2'-diimidazole), T8-2: 2, 2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (2-naphthyl) -2', 3-diimidazole (2,2'-Bis (o-chlorophenyl) - 4,4',5,5'-tetra(2-naphthyl)-2',3-diimidazole);
분리하여 얻은 순수한 T8를 분석하고, LCMS를 수행해 구조를 확인하였다. 860 및 861의 분자 조각 피크(fragment peak)는 질량 분석 보조기에 구비된 소프트웨어를 통해 얻었으며, 생성물의 분자량은 859로 T+1 및 T+2에 부합되었다. 이는 두 생성물이 피크 구조가 유사하고, 분자량이 동일함을 증명한다.The isolated pure T8 was analyzed and the structure was confirmed by LCMS. Molecular fragment peaks of 860 and 861 were obtained through the software provided in the mass spectrometer, and the molecular weight of the product was 859, which corresponded to T+1 and T+2. This proves that the two products have similar peak structures and the same molecular weight.
T9는 대칭 M1와 대칭 M5의 커플링에 의해 형성되고, 1-2 및 2-3의 연결위치에 연결되는 4개의 주요 구조가 존재하며, 그 조성은 각각 다음과 같다:T9 is formed by the coupling of symmetrical M1 and symmetrical M5, and there are four main structures connected to the connecting positions of 1-2 and 2-3, the composition of which is as follows, respectively:
T9-1: 2,2'-비스(o-클로로페닐)-4,5-비스(2-나프틸)-4',5'-디페닐-1,2'-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1,2'-diimidazole), T9-2: 2,2'-비스(o-클로로페닐)-4,5-비스(2-나프틸)-4',5'-디페닐-2',3-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2',3-diimidazole), T9-3: 2,2'-비스(o-클로로페닐)-4,5-비스(2-나프틸)-4',5'-디페닐-1',2-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1',2-diimidazole), T9-4: 2,2'-비스(o-클로로페닐)-4,5-비스(2-나프틸)-4',5'-디페닐-2,3'-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2.3'-diimidazole), 구조식은 다음과 같다:T9-1: 2,2'-bis (o-chlorophenyl) -4,5-bis (2-naphthyl) -4', 5'-diphenyl-1,2'-diimidazole (2,2 '-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1,2'-diimidazole), T9-2: 2,2'-bis(o-chlorophenyl) ) -4,5-bis (2-naphthyl) -4 ', 5'-diphenyl-2', 3-diimidazole (2,2'-Bis (o-chlorophenyl) -4,5-bis ( 2-naphthyl)-4'5'-diphenyl-2',3-diimidazole), T9-3: 2,2'-bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4 ',5'-diphenyl-1',2-diimidazole (2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1', 2-diimidazole), T9-4: 2,2'-bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4',5'-diphenyl-2,3'-diimine Dazole (2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2.3'-diimidazole), the structural formula is:
분리하여 얻은 순수한 T9를 분석하고, LCMS를 수행해 구조를 확인하였다. 760 및 761의 분자 조각 피크(fragment peak)는 질량 분석 보조기에 구비된 소프트웨어를 통해 얻었으며, 생성물의 분자량은 759로 T+1 및 T+2에 부합되었다. 이는 4개의 생성물이 피크 구조가 유사하고, 분자량이 동일함을 증명한다.The isolated pure T9 was analyzed and the structure was confirmed by LCMS. Molecular fragment peaks of 760 and 761 were obtained through the software provided in the mass spectrometer, and the molecular weight of the product was 759, which corresponded to T+1 and T+2. This proves that the four products have similar peak structures and identical molecular weights.
상기 실험 분석을 종합하면, 생성물 a31은 T1(T1-1, T1-2), T8(T8-1, T8-2), T9(T9-1, T7-2, T9-3, T9-4)로 이루어지는 것을 확인할 수 있고, 여기서, 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3로 구성되는 비스이미다졸 화합물의 a21 내 함량은 92.7%이다.Summarizing the above experimental analysis, product a31 is T1 (T1-1, T1-2), T8 (T8-1, T8-2), T9 (T9-1, T7-2, T9-3, T9-4) It can be confirmed that it consists of, where the content of the biimidazole compound consisting of four linking positions 1'-2, 2-3', 1-2', 2'-3 in a21 is 92.7%.
a32-a40을 각각 제조하였으며, 각 생성물의 상황은 하기 표 5에 제시된 바와 같다.a32-a40 were prepared, respectively, and the status of each product is shown in Table 5 below.
광개시제HABI system
photoinitiator
상기 표의 용해도 데이터는, 단일 구조의 순수 HABI(a36 및 a37)는 용해도가 매우 열위하여 기타 HABI와 혼합(a34 및 a35)하더라도 용해도를 향상시킬 수 없고, 본 발명의 상기 HABI계 혼합 광개시제는 반드시 동일한 치환기의 구조로 동시에 4개의 연결위치가 존재해야 본 발명이 제시하는 최적의 용해도에 도달할 수 있음을 추가로 보여준다.The solubility data in the table above shows that pure HABIs (a36 and a37) of a single structure have very poor solubility, so that the solubility cannot be improved even when mixed with other HABIs (a34 and a35), and the HABI-based mixed photoinitiator of the present invention is necessarily the same It is further shown that the optimal solubility proposed by the present invention can be reached only when four linking positions are present at the same time in the structure of the substituent.
2. 감광성 수지 조성물의 제조2. Preparation of photosensitive resin composition
표 5-7에 제시된 조성에 따라, 각 성분들을 균일하게 혼합하여 감광성 수지 조성물을 제조하였다. 특별히 명시되지 않는 한, 표에 표시된 숫자는 모두 질량부이다.According to the composition shown in Tables 5-7, each component was uniformly mixed to prepare a photosensitive resin composition. Unless otherwise specified, all figures in the tables are parts by mass.
표 6-9에서 각각의 구성 코드가 대표하는 의미는 표 10에 표기된 바와 같다.The meaning represented by each component code in Tables 6-9 is as indicated in Table 10.
표 10에서 알칼리 가용성 고분자 C1의 제조는 다음과 같다: 질소 분위기하에 메틸셀로솔브(methyl cellosolve)와 톨루엔을 3 : 2의 질량비로 배합한 혼합 용매 500g을 교반기, 환류 냉각기, 온도계, 적하 깔대기가 장착된 플라스크에 투입하고, 80℃로 교반 가열하였다. 메타크릴산(methacrylic acid) 100g, 에틸메타크릴레이트(ethyl methacrylate) 200g, 에틸아크릴레이트(ethyl acrylate) 100g, 스티렌(Styrene) 100g, 아조비스이소부티로니트릴(Azobisisobutyronitrile) 0.8g을 혼합하여 용액을 제조한 다음, 적하시간 4시간에 걸쳐 천천히 플라스크에 적하하고, 적하 완료 후, 계속해서 2시간 동안 반응시켰다. 이어서, 플라스크에 아조비스이소부티로니트릴 1.2g이 용해되어 있는 혼합 용매(조성은 위와 같음) 100g을 적하시간 10분에 걸쳐 적하하고, 적하 완료 후, 80℃에서 3 시간 더 반응시키고, 다시 90℃로 승온시켜 2시간 동안 계속해서 반응시켰다. 반응 종료 후, 여과하여 중량 평균 분자량 약 80000인 알칼리 가용성 폴리머 C1을 수득하였다. In Table 10, the preparation of alkali-soluble polymer C1 is as follows: 500 g of a mixed solvent in which methyl cellosolve and toluene were mixed in a mass ratio of 3: 2 under a nitrogen atmosphere were mixed with a stirrer, a reflux condenser, a thermometer, and a dropping funnel. It was put into the attached flask and stirred and heated at 80°C. A solution was prepared by mixing 100 g of methacrylic acid, 200 g of ethyl methacrylate, 100 g of ethyl acrylate, 100 g of styrene, and 0.8 g of azobisisobutyronitrile. After preparation, it was slowly added dropwise to the flask over 4 hours of dropping time, and after completion of the dropping, reaction was continued for 2 hours. Subsequently, 100 g of a mixed solvent (composition as above) in which 1.2 g of azobisisobutyronitrile is dissolved was added dropwise to the flask over a dropping time of 10 minutes, and after completion of the dropping, the reaction was carried out at 80° C. for another 3 hours, and the The temperature was raised to °C and the reaction was continued for 2 hours. After completion of the reaction, it was filtered to obtain an alkali-soluble polymer C1 having a weight average molecular weight of about 80000.
3. 성능 평가3. Performance evaluation
3.1 평가 방식3.1 Evaluation method
건식필름의 응용 방법을 예시로, 상술한 실시예 및 비교예에 제시된 감광성 수지 조성물의 다양한 응용 성능을 평가하였다.Taking the dry film application method as an example, various application performances of the photosensitive resin composition presented in the above-described Examples and Comparative Examples were evaluated.
<건식필름의 제조><Manufacture of dry film>
감광성 수지 조성물을 충분히 교반하고, 이를 바 코터(bar coater)를 이용해 지지체인 두께 25μm의 폴리에틸렌테레프탈레이트 박막 표면에 균일하게 도포하고, 95℃ 건조기에서 5분간 건조시켜 두께 40μm의 감광성 수지층을 형성하였다. 그 다음, 폴리에틸렌테레프탈레이트 박막이 적층되지 않은 감광성 수지층의 표면에 보호층으로서 두께 15μm의 폴리에틸렌(polyethylene) 박막을 점착하여 건식필름을 얻었다.The photosensitive resin composition was sufficiently stirred, and uniformly applied on the surface of a polyethylene terephthalate thin film having a thickness of 25 μm, which is a support, using a bar coater, and dried in a dryer at 95° C. for 5 minutes to form a photosensitive resin layer having a thickness of 40 μm. . Then, a polyethylene thin film having a thickness of 15 μm was adhered as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate thin film was not laminated to obtain a dry film.
<기판 표면 평탄화><Substrate Surface Planarization>
기판으로서는 두께 35μm의 압연 동박이 적층되어 있는 두께 1.2mm의 동박 적층판을 사용하고, 표면에 습식 버프롤 연마(buff roller polishing, 3M 제조의 Scotch-Brite(등록 상표) HD#600, 2회 통과)를 수행하였다.As a substrate, a copper clad laminate having a thickness of 1.2 mm on which rolled copper foils having a thickness of 35 μm are laminated is used, and the surface is subjected to wet buff roller polishing (Scotch-Brite (registered trademark) HD#600 manufactured by 3M, passed through twice). was performed.
<라미네이션><Lamination>
폴리에틸렌 박막 보호층을 건식필름으로부터 박리한 다음, 핫 롤러 라미네이터(hot roller laminator, Asahi Kasei Co., Ltd. 제조의 AL-70)를 사용해 105℃의 롤러 온도로 60℃로 예열된 동박 적층판에 라미네이팅하였다. 가스 압력은 0.35MPa, 라미네이팅 속도는 1.5m/min로 하였다. The polyethylene thin film protective layer is peeled off from the dry film, and then laminated to a copper clad laminate preheated to 60°C with a roller temperature of 105°C using a hot roller laminator (AL-70 manufactured by Asahi Kasei Co., Ltd.) did The gas pressure was 0.35 MPa and the laminating speed was 1.5 m/min.
<노광><Exposure>
마스크를 지지체인 폴리에틸렌테레프탈레이트 박막에 배치하고, 초고압 수은 램프(ORCMANUFACTURINGCO., LTD. 제조의 HMW-201KB)로 노광하였다. A mask was placed on a polyethylene terephthalate thin film serving as a support, and exposed with an ultra-high pressure mercury lamp (HMW-201KB manufactured by ORCMANUFACTURING CO., LTD.).
<현상><Phenomena>
폴리에틸렌테레프탈레이트 박막을 박리하고, 알칼리 현상기(FujiKikoCo.,Ltd. 제조의 건식필름용 현상기)를 사용하여 30℃의 1질량% Na2CO3 수용액을 감광성 수지층에 스프레이하고, 최소 현상 시간의 2배의 시간을 사용하여 감광성 수지층의 비노광 부분을 용해하여 제거하였다. 비노광 부분의 감광성 수지층을 완전히 용해하는데 필요한 최소의 시간이 최소 현상 시간이다. The polyethylene terephthalate thin film was peeled off, and an aqueous solution of 1% by mass Na 2 CO 3 at 30 ° C was sprayed onto the photosensitive resin layer using an alkali developing machine (developer for dry film manufactured by FujiKiko Co., Ltd.), and the development time of 2 min. Using twice the time, the unexposed portion of the photosensitive resin layer was dissolved and removed. The minimum time required to completely dissolve the photosensitive resin layer in the non-exposed portion is the minimum development time.
3.2 평가 내용 3.2 Evaluation contents
(1) 상용성(1) compatibility
감광성 수지 조성물을 충분히 교반하고, 조성물을 바 코터를 이용해 지지체인 두께 25μm의 폴리에틸렌테레프탈레이트 박막 표면에 균일하게 도포하였다. 95℃ 건조기에서 5분간 건조시켜 감광성 수지층을 형성하였다. 그 다음, 감광성 수지층 표면을 눈으로 관찰하고, 하기 방식으로 등급을 나누었다. The photosensitive resin composition was sufficiently stirred, and the composition was uniformly applied on the surface of a polyethylene terephthalate thin film having a thickness of 25 μm as a support using a bar coater. A photosensitive resin layer was formed by drying in a dryer at 95° C. for 5 minutes. Then, the surface of the photosensitive resin layer was visually observed and graded in the following manner.
◇: 표면이 균일함; ◇: The surface is uniform;
◆: 표면에 불용성 물질이 석출됨. ◆: Insoluble substances are deposited on the surface.
(2) 감광도 (2) photosensitivity
투명부터 검정까지 21 등급의 명도 변화를 갖는 Stouffer 제조의 21 등급 단계식 노광계(exposure meter)를 사용하여 감광성 수지층을 15분간 노광하고 그 감광도를 평가하였다. 노광 후, 최소 현상 시간의 2배의 시간으로 현상을 수행하고, 레지스트 필름(resist film)이 완전히 잔류하는 단계식 노광계의 등급 8인 노광량에 따라 하기와 같이 등급을 나누었다.The photosensitive resin layer was exposed to light for 15 minutes using a 21 grade stepwise exposure meter manufactured by Stouffer having a brightness change of 21 grades from transparent to black, and its photosensitivity was evaluated. After exposure, development was carried out for a time twice the minimum development time, and the grades were divided as follows according to the exposure amount, which is a grade 8 of the stepwise exposure system in which the resist film completely remained.
○: 노광량은 20mJ/cm2 이하임.○: The exposure amount is 20 mJ/cm 2 or less.
◎: 노광량은 20mJ/cm2 - 50mJ/cm2, 엔드포인트 불포함.◎: Exposure amount is 20mJ/cm 2 - 50mJ/cm 2 , endpoint not included.
●: 노광량은 50mJ/cm2 이상임. ●: The exposure amount is 50 mJ/cm 2 or more.
(3) 해상도(3) Resolution
Line/Space = 10:10 - 150:150(단위:μm)의 배선 패턴을 갖는 포토 마스크를 이용해 노광 및 현상을 수행한 다음 건식필름의 해상도를 측정하였다. 해상도는 노광 후 현상하여 형성된 레지스트 패턴 중 비노광 부분을 깨끗히 제거한 후의 패턴의 최소값이다.After exposure and development were performed using a photomask having a wiring pattern of Line/Space = 10:10 - 150:150 (unit: μm), the resolution of the dry film was measured. The resolution is the minimum value of the pattern after the unexposed portion of the resist pattern formed by development after exposure is cleanly removed.
○: 해상도 값은 30μm 이하임.○: The resolution value is 30 μm or less.
◎: 해상도 값은 30μm - 50μm, 엔드포인트 불포함.◎: The resolution value is 30 μm - 50 μm, without endpoints.
●: 해상도 값은 50μm 이상임.●: The resolution value is 50μm or more.
(4) 친수성(4) hydrophilicity
친수성은 감광성 수지층의 용해 후 석출량으로 평가하였다.Hydrophilicity was evaluated by the precipitation amount after dissolution of the photosensitive resin layer.
감광성 수지 조성물을 충분히 교반하고, 바 코터를 이용해 지지체인 두께 25μm의 폴리에틸렌테레프탈레이트 박막 표면에 균일하게 도포하였다. 95℃ 건조기에서 4분간 건조시켜 층 두께 약 30.5μm, 층 무게 약 3.2g의 감광성 수지층을 형성하였다.The photosensitive resin composition was sufficiently stirred and uniformly applied to the surface of a polyethylene terephthalate thin film having a thickness of 25 μm as a support using a bar coater. It was dried for 4 minutes in a dryer at 95° C. to form a photosensitive resin layer having a layer thickness of about 30.5 μm and a layer weight of about 3.2 g.
탄산나트륨 20g을 물 2L에 용해하고, Pluronic RPG3110(BASF, Mt. Olive, NJ, 본 시제는 폴리옥시에틸렌(Polyoxyethylene)과 폴리옥시프로필렌(polyoxypropylene)의 공중합체 가소제임) 1.5ml를 첨가하여 현상액을 제조하였다. 상기 감광성 수지층이 점착된 박막을 현상액 100g에 투입하고, 수지층이 용해될 때까지 시편을 그대로 방치하였다. 침전량은 하기 등급에 따라 확정하였다: Prepare a developer by dissolving 20 g of sodium carbonate in 2 L of water and adding 1.5 ml of Pluronic RPG3110 (BASF, Mt. Olive, NJ, this sample is a copolymer plasticizer of polyoxyethylene and polyoxypropylene) did The thin film to which the photosensitive resin layer was adhered was put into 100 g of a developing solution, and the specimen was left as it was until the resin layer was dissolved. The amount of precipitation was determined according to the following scale:
0= 침전량은 0.005g 미만임.0 = Settling amount is less than 0.005 g.
1= 소량의 미세하게 분산된 담황색 물질, 침전량은 0.005 - 0.01g 사이.1 = A small amount of finely dispersed light yellow substance, with a precipitate between 0.005 and 0.01 g.
5= 중간량의 담황색 물질(통상 미세함), 침전량은 0.05 - 0.08g 사이.5 = Moderate pale yellow substance (usually fine), sediment amount between 0.05 and 0.08 g.
10= 다량의 고체층 담황색 물질(통상 박편 형상을 나타냄), 침전량은 0.1g 이상.10 = A large amount of solid layer pale yellow material (usually in the form of flakes), with a precipitate amount of 0.1 g or more.
(5) 현상성(5) developability
현상 후, 주사 전자 현미경(SEM)으로 포토 레지스트 패턴을 관찰하여 현상성을 평가하였다.After development, the photoresist pattern was observed with a scanning electron microscope (SEM) to evaluate developability.
현상성은 하기 기준에 따라 평가되었다:Developability was evaluated according to the following criteria:
□: 비노광 부분에서 잔류물이 관찰되지 않았음.□: No residue was observed in the unexposed part.
△: 비노광 부분에서 소량의 잔류물이 관찰되었으나 잔류량은 허용 가능함.△: A small amount of residue was observed in the unexposed part, but the amount of residue was acceptable.
×: 비노광 부분에서 잔류물이 명확히 관찰되었음.x: Residue was clearly observed in the unexposed part.
3.3 평가 결과 3.3 Evaluation results
평가 결과는 표 11에 표시된 바와 같다. The evaluation results are as shown in Table 11.
본 발명의 HABI계 혼합 광개시제는 감광성 수지 조성물에 응용되는 경우, 우수한 상용성, 조성물의 높은 감광도, 우수한 해상도, 현상성, 친수성을 갖고 있어 현상액을 반복 사용할 수 있고, 현상 슬러지로 인한 필터 스크린 막힘 현상이 발생하지 않는다. 본 발명의 종합 응용 성능은 비교예 1-28의 감광성 수지 조성물에 비해 월등히 우수하다. When the HABI-based mixed photoinitiator of the present invention is applied to a photosensitive resin composition, it has excellent compatibility, high photosensitivity of the composition, excellent resolution, developability, and hydrophilicity, so that the developer can be used repeatedly, and the filter screen is clogged due to developing sludge. this doesn't happen The overall application performance of the present invention is far superior to that of the photosensitive resin composition of Comparative Example 1-28.
상술한 실시예는 본 발명의 바람직한 실시예이나, 본 발명의 실시방식은 상술한 실시예에 제한되지 않는다. 본 발명의 사상 및 원칙 내에서 이루어지는 기타 모든 변경, 수정, 대체, 결합 및 단순화는 모두 균등 치환 방식으로 본 발명의 보호 범위 내에 포함된다. The above-described embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited to the above-described embodiment. All other changes, modifications, substitutions, combinations and simplifications made within the spirit and principle of the present invention shall fall within the protection scope of the present invention by equivalent substitution.
Claims (20)
4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 비스이미다졸 화합물을 포함하며, 상기 4개의 연결위치로 이루어지는 비스이미다졸 화합물의 헥사아릴비스이미다졸 혼합 광개시제 내 총 질량 백분율 함량은 92% 내지 100%인 것을 특징으로 하는 헥사아릴비스이미다졸계 혼합 광개시제.
(I)
일반식 (I)에서, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6는 서로 동일하거나 상이할 수 있고, 각각 독립적으로 치환 또는 비치환된 아릴기를 나타내고,
상기 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3의 비스이미다졸 화합물은 다음과 같이 구성된다:
(1) T1-1, T1-2, T2-1, T2-2, T2-3, T2-4, T3-1, T3-2, T3-3, 및 T3-4;
(2) T2-1, T2-2, T2-3, T2-4, T4-1, T4-2, T4-3, T4-4, T5-1, T5-2, T5-3, 및 T5-4;
(3) T1-1, T1-2, T6-1, T6-2, T7-1, T7-2, T7-3, 및 T7-4; 또는
(4) T1-1, T1-2, T8-1, T8-2, T9-1, T9-2, T9-3, 및 T9-4
[T1-1: 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라페닐-1,2'-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazol),
T1-2: 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라페닐-2'-3-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2'-3-diimidazol),
T2-1: 2,2',5,5'-테트라(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-2'-3-디이미다졸(2,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole),
T2-2: 2,2',4,5'-테트라(o-클로로페닐)-4',5-비스(3,4-디메톡시페닐)-1-2'-디이미다졸(2,2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole),
T2-3: 2,2',5,5'-테트라(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-1-2'-디이미다졸(2,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole),
T2-4: 2,2',4,5'-테트라(o-클로로페닐)-4',5-비스(3,4-디메톡시페닐)-2'-3-디이미다졸(2,2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2',3-diimidazole),
T3-1: 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1,2'-디이미다졸(2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole),
T3-2: 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-2',3-디이미다졸(2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole),
T3-3: 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-2,3'-디이미다졸(2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole),
T3-4: 2,2',5-트리스(o-클로로페닐)-4-(3,4-디메톡시페닐)-4',5'-디페닐-1',2-디이미다졸(2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole),
T4-1: 2,2'-비스(4-클로로페닐)-5,5'-비스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-2,3'-디이미다졸(2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole),
T4-2: 2,2'-비스(4-클로로페닐)-4,5'-비스(o-클로로페닐)-4',5-비스(3,4-디메톡시페닐)-1,2'-디이미다졸(2,2'-Bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole),
T4-3: 2,2'-비스(4-클로로페닐)-5,5'-비스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-1,2'-디이미다졸(2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole),
T4-4: 2,2'-비스(4-클로로페닐)-4',5-비스(o-클로로페닐)-4,5'-비스(3,4-디메톡시페닐)-2,3'-디이미다졸(2,2'-Bis(4-chlorophenyl)-4',5-bis(o-chlorophenyl)-4,5'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole),
T5-1: 2-(4-클로로페닐)-2',5,5'-트리스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-2,3'-디이미다졸(2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole),
T5-2: 2'-(4-클로로페닐)-2,5,5'-트리스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-1,2'-디이미다졸(2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole),
T5-3: 2-(4-클로로페닐)-2',5,5'-트리스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-2',3-디이미다졸(2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole),
T5-4: 2'-(4-클로로페닐)-2,5,5'-트리스(o-클로로페닐)-4,4'-비스(3,4-디메톡시페닐)-1',2-디이미다졸(2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1',2-diimidazole),
T6-1: 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐-1,2'-디이미다졸(2,2'-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole),
T6-2: 2,2'-비스(2,4-디클로로페닐)-4,4',5,5'-테트라페닐-2',3-디이미다졸(2,2'-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole);
T7-1: 2-(2,4-디클로로페닐)-2'-(o-클로로페닐)-4,4',5,5'-테트라페닐-2,3'-디이미다졸(2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,3'-diimidazole),
T7-2: 2-(2,4-디클로로페닐)-2'-(o-클로로페닐)-4,4',5,5'-테트라페닐-1',2-디이미다졸(2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1',2-diimidazole),
T7-3: 2-(2,4-디클로로페닐)-2'-(o-클로로페닐)-4,4',5,5'-테트라페닐-1,2'-디이미다졸(2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole),
T7-4: 2-(2,4-디클로로페닐)-2'-(o-클로로페닐)-4,4',5,5'-테트라페닐-2',3-디이미다졸(2-(2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole),
T8-1: 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라(2-나프틸)-1,2'-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetra(2-naphthyl)-1,2'-diimidazole),
T8-2: 2,2'-비스(o-클로로페닐)-4,4',5,5'-테트라(2-나프틸)-2',3- 디이미다졸(2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetra(2-naphthyl)-2',3-diimidazole),
T9-1: 2,2'-비스(o-클로로페닐)-4,5-비스(2-나프틸)-4',5'-디페닐-1,2'-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1,2'-diimidazole),
T9-2: 2,2'-비스(o-클로로페닐)-4,5-비스(2-나프틸)-4',5'-디페닐-2',3-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2',3-diimidazole),
T9-3: 2,2'-비스(o-클로로페닐)-4,5-비스(2-나프틸)-4',5'-디페닐-1',2-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1',2-diimidazole), 및
T9-4: 2,2'-비스(o-클로로페닐)-4,5-비스(2-나프틸)-4',5'-디페닐-2,3'-디이미다졸(2,2'-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2.3'-diimidazole)].
In the hexaarylbisimidazole-based mixed photoinitiator having a structure represented by Formula (I),
Hexaarylbisimidazole mixture of a biimidazole compound consisting of four linking positions 1'-2, 2-3', 1-2', 2'-3 containing a biimidazole compound, and consisting of the four linking positions A hexaarylbisimidazole-based mixed photoinitiator, characterized in that the total mass percentage content in the photoinitiator is 92% to 100%.
(I)
In Formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group,
The bimidazole compound at the four linking positions 1'-2, 2-3', 1-2', and 2'-3 is composed of the following:
(1) T1-1, T1-2, T2-1, T2-2, T2-3, T2-4, T3-1, T3-2, T3-3, and T3-4;
(2) T2-1, T2-2, T2-3, T2-4, T4-1, T4-2, T4-3, T4-4, T5-1, T5-2, T5-3, and T5- 4;
(3) T1-1, T1-2, T6-1, T6-2, T7-1, T7-2, T7-3, and T7-4; or
(4) T1-1, T1-2, T8-1, T8-2, T9-1, T9-2, T9-3, and T9-4
[T1-1: 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-diimidazole (2,2'-Bis (o-chlorophenyl )-4,4',5,5'-tetraphenyl-1,2'-diimidazol),
T1-2: 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-2'-3-diimidazole (2,2'-Bis (o-chlorophenyl) -4,4',5,5'-tetraphenyl-2'-3-diimidazol),
T2-1: 2,2',5,5'-tetra (o-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) -2'-3-diimidazole (2,2 ',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole),
T2-2: 2,2',4,5'-tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole (2,2 ',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole),
T2-3: 2,2',5,5'-tetra (o-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) -1-2'-diimidazole (2,2 ',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole),
T2-4: 2,2', 4,5'-tetra (o-chlorophenyl) -4', 5-bis (3,4-dimethoxyphenyl) -2'-3-diimidazole (2,2 ',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2',3-diimidazole),
T3-1: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole (2 ,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole),
T3-2: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole (2 ,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole),
T3-3: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole (2 ,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole),
T3-4: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole (2 ,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole),
T4-1: 2,2'-bis (4-chlorophenyl) -5,5'-bis (o-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) -2,3' -Diimidazole (2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole) ,
T4-2: 2,2'-bis (4-chlorophenyl) -4,5'-bis (o-chlorophenyl) -4', 5-bis (3,4-dimethoxyphenyl) -1,2' -Diimidazole (2,2'-Bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole) ,
T4-3: 2,2'-bis (4-chlorophenyl) -5,5'-bis (o-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) -1,2' -Diimidazole (2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole) ,
T4-4: 2,2'-bis (4-chlorophenyl) -4', 5-bis (o-chlorophenyl) -4,5'-bis (3,4-dimethoxyphenyl) -2,3' -Diimidazole (2,2'-Bis(4-chlorophenyl)-4',5-bis(o-chlorophenyl)-4,5'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole) ,
T5-1: 2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'- Diimidazole (2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole),
T5-2: 2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'- Diimidazole (2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole),
T5-3: 2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3- Diimidazole (2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole),
T5-4: 2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1',2- Diimidazole (2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1',2-diimidazole),
T6-1: 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-diimidazole (2,2'-Bis (2, 4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole),
T6-2: 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-2', 3-diimidazole (2,2'-Bis (2, 4-dichlorophenyl) -4,4',5,5'-tetraphenyl-2',3-diimidazole);
T7-1: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,3'-diimidazole (2-( 2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,3'-diimidazole),
T7-2: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1',2-diimidazole (2-( 2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1',2-diimidazole),
T7-3: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole (2-( 2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole),
T7-4: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole (2-( 2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole),
T8-1: 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (2-naphthyl) -1,2'-diimidazole (2,2'-Bis (o-chlorophenyl)-4,4',5,5'-tetra(2-naphthyl)-1,2'-diimidazole),
T8-2: 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (2-naphthyl) -2', 3-diimidazole (2,2'-Bis (o-chlorophenyl)-4,4',5,5'-tetra(2-naphthyl)-2',3-diimidazole),
T9-1: 2,2'-bis (o-chlorophenyl) -4,5-bis (2-naphthyl) -4', 5'-diphenyl-1,2'-diimidazole (2,2 '-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1,2'-diimidazole),
T9-2: 2,2'-bis (o-chlorophenyl) -4,5-bis (2-naphthyl) -4', 5'-diphenyl-2', 3-diimidazole (2,2 '-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2',3-diimidazole),
T9-3: 2,2'-bis (o-chlorophenyl) -4,5-bis (2-naphthyl) -4', 5'-diphenyl-1', 2-diimidazole (2,2 '-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1',2-diimidazole), and
T9-4: 2,2'-bis (o-chlorophenyl) -4,5-bis (2-naphthyl) -4', 5'-diphenyl-2,3'-diimidazole (2,2 '-Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2.3'-diimidazole)].
일반식 (I)로 표시되는 구조의 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3를 만족하는 비스이미다졸 화합물의 혼합 광개시제 내 총 질량 백분율 함량은 95% 내지 100%인 것을 특징으로 하는 헥사아릴비스이미다졸계 혼합 광개시제.
According to claim 1,
The total mass percentage content in the mixed photoinitiator of the biimidazole compound satisfying the four linking positions 1'-2, 2-3', 1-2', 2'-3 of the structure represented by Formula (I) is 95 Hexaarylbisimidazole-based mixed photoinitiator, characterized in that % to 100%.
일반식 (I)로 표시되는 구조의 4개의 연결위치 1'-2, 2-3', 1-2', 2'-3를 만족하는 비스이미다졸 화합물로 이루어지는 것을 특징으로 하는 헥사아릴비스이미다졸계 혼합 광개시제.
According to claim 1,
Hexaarylbisimi, characterized in that it consists of a biimidazole compound satisfying four linking positions 1'-2, 2-3', 1-2', 2'-3 of the structure represented by the general formula (I) Dazole-based mixed photoinitiator.
A photosensitive resin composition comprising the hexaarylbisimidazole-based mixed photoinitiator according to claim 1.
알칼리 가용성 중합체; 에틸렌성 불포화 이중 결합을 갖는 화합물; 기타 광개시제 및/또는 증감제를 더 포함하며, 선택적으로 보조제를 더 포함하는 감광성 수지 조성물.
According to claim 4,
alkali soluble polymers; compounds having ethylenically unsaturated double bonds; A photosensitive resin composition further comprising other photoinitiators and/or sensitizers, and optionally further comprising an auxiliary agent.
상기 알칼리 가용성 중합체는, (메타)아크릴계 중합체, 스티렌계 중합체, 에폭시계 중합체, 지방족 폴리우레탄(메타)아크릴레이트 중합체, 방향족 폴리우레탄(메타)아크릴레이트 중합체, 아미드계 수지, 아미드 에폭시계 수지, 알키드계 수지, 페놀계 수지로부터 선택되는 것을 특징으로 하는 감광성 수지 조성물.
According to claim 5,
The alkali-soluble polymer is a (meth)acrylic polymer, a styrenic polymer, an epoxy polymer, an aliphatic polyurethane (meth)acrylate polymer, an aromatic polyurethane (meth)acrylate polymer, an amide resin, an amide epoxy resin, an alkyd A photosensitive resin composition characterized in that it is selected from resin-based resins and phenol-based resins.
상기 알칼리 가용성 중합체는, 카르복실기를 포함하는 알칼리 가용성 중합체인 것을 특징으로 하는 감광성 수지 조성물.
According to claim 5,
The alkali-soluble polymer is a photosensitive resin composition, characterized in that the alkali-soluble polymer containing a carboxyl group.
상기 카르복실기를 포함하는 알칼리 가용성 중합체는, (메타)아크릴레이트, 에틸렌성 불포화 카르복실산 및 기타 공중합 가능한 단량체의 공중합에 의해 형성되는 (메타)아크릴레이트계 중합체인 것을 특징으로 하는 감광성 수지 조성물.
According to claim 7,
The photosensitive resin composition, characterized in that the alkali-soluble polymer containing a carboxyl group is a (meth) acrylate-based polymer formed by copolymerization of (meth) acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers.
상기 에틸렌성 불포화 이중 결합을 갖는 화합물은, 분자 내에 적어도 하나 이상의 에틸렌성 불포화 결합을 갖는 광중합성 화합물인 것을 특징으로 하는 감광성 수지 조성물.
According to claim 5,
The photosensitive resin composition, characterized in that the compound having an ethylenically unsaturated double bond is a photopolymerizable compound having at least one ethylenically unsaturated bond in a molecule.
상기 에틸렌성 불포화 이중 결합을 갖는 화합물은, 비스페놀 A계 (메타)아크릴레이트 화합물 및 분자 내에 우레탄 결합을 갖는 (메타)아크릴레이트 화합물로부터 선택되는 것을 특징으로 하는 감광성 수지 조성물.
According to claim 5,
The photosensitive resin composition, characterized in that the compound having an ethylenically unsaturated double bond is selected from bisphenol A-based (meth)acrylate compounds and (meth)acrylate compounds having a urethane bond in the molecule.
상기 기타 광개시제 및/또는 증감제는, 비스이미다졸계, 피라졸린계, 방향족 케톤계, 안트라퀴논계, 벤조인 및 벤조인알킬에테르계, 옥심에스테르계, 트리아진계, 트리페닐아민계, 쿠마린계, 티오크산톤계, 아크리딘계 광개시제 중에서 적어도 하나 이상이 선택되는 것을 특징으로 하는 감광성 수지 조성물.
According to claim 5,
The other photoinitiators and/or sensitizers are biimidazole-based, pyrazoline-based, aromatic ketone-based, anthraquinone-based, benzoin and benzoin alkyl ether-based, oxime ester-based, triazine-based, triphenylamine-based, and coumarin-based A photosensitive resin composition, characterized in that at least one or more selected from thioxanthone-based and acridine-based photoinitiators.
상기 보조제는, 염료, 광발색제, 안료, 충전제, 가소제, 안정제, 코팅 보조제, 박리 촉진제 중에서 적어도 하나 이상이 선택되는 것을 특징으로 하는 감광성 수지 조성물.
According to claim 5,
The adjuvant is a photosensitive resin composition, characterized in that at least one or more selected from dyes, photochromic agents, pigments, fillers, plasticizers, stabilizers, coating adjuvants, peeling accelerators.
A photosensitive resin laminate comprising a photosensitive resin layer formed from the photosensitive resin composition according to claim 4 and a support body supporting the photosensitive resin layer.
Application of the photosensitive resin laminate according to claim 13 in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packaging.
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