KR102655952B1 - Positive photosensitive resin composition - Google Patents

Positive photosensitive resin composition Download PDF

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KR102655952B1
KR102655952B1 KR1020180131442A KR20180131442A KR102655952B1 KR 102655952 B1 KR102655952 B1 KR 102655952B1 KR 1020180131442 A KR1020180131442 A KR 1020180131442A KR 20180131442 A KR20180131442 A KR 20180131442A KR 102655952 B1 KR102655952 B1 KR 102655952B1
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ether
weight
resin composition
photosensitive resin
methacrylate
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KR20200048865A (en
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이상훈
윤혁민
여태훈
박종혁
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주식회사 동진쎄미켐
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Priority to KR1020180131442A priority Critical patent/KR102655952B1/en
Priority to CN201911054758.2A priority patent/CN111123644A/en
Priority to JP2019198679A priority patent/JP7469024B2/en
Priority to TW108139529A priority patent/TWI831859B/en
Publication of KR20200048865A publication Critical patent/KR20200048865A/en
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Abstract

포지티브형 감광성 수지 조성물이 제공된다. 포지티브형 감광성 조성물은
a) ⅰ) 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물;
ⅱ) 에폭시기 함유 불포화 화합물; 및
ⅲ) 올레핀계 불포화 화합물을 공중합시켜 얻어진 아크릴계 공중합체
b) 하기 화학식 1로 표시되는 공중합체
c) 1,2-퀴논디아지드 화합물
d) 용매를 포함하는 것을 특징으로 하는 감광성 수지 조성물:
[화학식 1]

화학식 1에서, a, b, c는 각 모노머 간의 몰비(mole ratio)를 나타내는 것으로, a는 1 내지 10이고, b, c는 각각 0 내지 9이며, a+b+c=10 이다. n은 1 내지 10이며, R은 H 또는 CH3 이다.A positive type photosensitive resin composition is provided. The positive photosensitive composition is
a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;
ii) an epoxy group-containing unsaturated compound; and
iii) Acrylic copolymer obtained by copolymerizing olefinic unsaturated compounds
b) Copolymer represented by the following formula (1)
c) 1,2-quinonediazide compounds
d) Photosensitive resin composition comprising a solvent:
[Formula 1]

In Formula 1, a, b, and c represent the mole ratio between each monomer, with a being 1 to 10, b and c being 0 to 9, respectively, and a+b+c=10. n is 1 to 10, and R is H or CH 3 .

Description

포지티브형 감광성 수지 조성물{POSITIVE PHOTOSENSITIVE RESIN COMPOSITION}Positive photosensitive resin composition {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION}

본 기재는 포지티브형 감광성 수지 조성물에 관한 것으로서, 더욱 상세하게는 해상도, 포토공정마진, 내열성 등이 우수한 포지티브형 감광성 수지 조성물에 관한 것이다. 특히 감도와 투명성이 우수하며, 접착력을 현저히 향상시켜 LCD 및 OLED 제조 공정의 층간절연막 및 PDL(Pixel Define Layer) 컬럼 스페이서(Column Spacer) 등을 형성하기에 적합한 포지티브형 감광성 수지 조성물에 관한 것이다.This disclosure relates to a positive photosensitive resin composition, and more specifically, to a positive photosensitive resin composition having excellent resolution, photo process margin, heat resistance, etc. In particular, it relates to a positive photosensitive resin composition that has excellent sensitivity and transparency and significantly improves adhesion, making it suitable for forming interlayer insulating films and PDL (Pixel Define Layer) column spacers in the LCD and OLED manufacturing process.

TFT형 액정 표시 장치(LCD)와 유기 발광 표시 장치(OLED) 제조공정시 층간에 배치되는 배선의 사이를 절연하기 위해서 층간절연막을 사용하고 있다. 그런데, 최근 고속응답, 고해상도 장치(Device)가 개발되면서 고개구율 및 저저항 배선기술이 요구됨에 따라 회로의 폭은 줄이고, 두께를 높게 형성하게 되어 TFT의 단차가 커지는 경향을 나타낸다. 이 경우, 평탄화도를 위해 적용되는 층간절연막의 두께가 상승되는데, 이는 감도, 투명성의 저하를 일으키는 원인이 되어 표시 장치 패널의 생산성 및 품질을 저하시키게 된다. 따라서, 감도, 투명성 등이 우수한 절연막 개발이 절실히 요구되고 있다. During the manufacturing process of a TFT-type liquid crystal display (LCD) and an organic light emitting display (OLED), an interlayer insulating film is used to insulate the wiring between layers. However, with the recent development of high-speed response and high-resolution devices, high aperture ratio and low-resistance wiring technology is required, and the width of the circuit is reduced and the thickness is increased, which tends to increase the step of the TFT. In this case, the thickness of the interlayer insulating film applied for flatness increases, which causes a decrease in sensitivity and transparency, thereby lowering the productivity and quality of the display device panel. Therefore, there is an urgent need to develop an insulating film with excellent sensitivity and transparency.

본 개시는 해상도, 포토공정마진, 내열성이 우수하고, 특히 감도, 투명성이 우수하며, 접착력을 현저히 향상시켜 LCD 및 OLED 제조공정의 층간절연막 및 PDL, 컬럼 스페이서 등을 형성하기에 적합한 감광성 수지 조성물을 제공한다. 또한 본 개시는 감광성 수지 조성물의 경화체를 포함하는 LCD와 OLED 기판을 제공한다. 또한 본 개시는 감광성 수지 조성물을 이용한 디스플레이 기판의 패턴형성방법을 제공한다. The present disclosure provides a photosensitive resin composition that has excellent resolution, photo process margin, heat resistance, especially sensitivity and transparency, and significantly improves adhesion, making it suitable for forming interlayer insulating films, PDL, column spacers, etc. in LCD and OLED manufacturing processes. to provide. Additionally, the present disclosure provides LCD and OLED substrates including a cured body of the photosensitive resin composition. Additionally, the present disclosure provides a method of forming a pattern of a display substrate using a photosensitive resin composition.

실시예들에 따른 감광성 수지 조성물은 The photosensitive resin composition according to the examples is

a) ⅰ) 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물,a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof,

ⅱ) 에폭시기 함유 불포화 화합물; 및ii) an epoxy group-containing unsaturated compound; and

ⅲ) 올레핀계 불포화 화합물을 공중합시켜 얻어진 아크릴계 공중합체ⅲ) Acrylic copolymer obtained by copolymerizing olefinic unsaturated compounds

b) 하기 화학식 1로 표시되는 공중합체b) Copolymer represented by the following formula (1)

c) 1,2-퀴논디아지드 화합물; 및c) 1,2-quinonediazide compounds; and

d) 용매를 포함한다. d) Contains a solvent.

[화학식 1][Formula 1]

화학식 1의 a, b, c는 각 모노머 간의 몰비(mole ratio)를 나타내는 것으로, a는 1 내지 10이고, b, C는 각각 0 내지 9이며, a+b+c=10 이다. n은 1 내지 10이며, R은 H 또는 CH3 이다.In Formula 1, a, b, and c represent the mole ratio between each monomer, where a is 1 to 10, b and C are 0 to 9, respectively, and a+b+c=10. n is 1 to 10, and R is H or CH 3 .

또한 실시예들에 따른 디스플레이 소자는 패턴 형성 방법에 의하여 형성된 포지티브형 감광성 수지 조성물 경화체를 포함한다. 또한, 실시예들에 따른 포지티브형 감광성 수지 조성물을 이용한 TFT-LCD, TSP (Touch Screen Panel), OLED, O-TFT, EPD, EWD 등의 디스플레이 소자의 패턴형성 방법을 제공한다.Additionally, display devices according to embodiments include a cured positive photosensitive resin composition formed by a pattern forming method. In addition, a method of forming patterns of display devices such as TFT-LCD, TSP (Touch Screen Panel), OLED, O-TFT, EPD, and EWD using the positive photosensitive resin composition according to the embodiments is provided.

기타 본 발명의 측면들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.Details of other aspects of the invention are included in the detailed description below.

실시예들에 따르면 포지티브형 감광성 수지 조성물은 해상도, 포토공정마진, 내열성이 우수하고, 특히 감도, 투과성이 우수하며, 접착력을 현저히 향상시켜 LCD 및 OLED 제조공정의 층간절연막 및 PDL, 컬럼 스페이서 등을 형성하기에 적합하다. 또한, 감광성 수지 조성물의 경화체를 포함하는 LCD와 OLED 기판 및 감광성 수지 조성물을 이용한 디스플레이 기판의 패턴형성방법을 제공한다. 패턴은 TFT-LCD, TSP (Touch Screen Panel), OLED, O-TFT, EPD, EWD 등의 패시베이션 절연막, 게이트 절연막, 평탄화막, 컬름 스페이서, 격벽 등의 재료로 사용될 수 있다.According to examples, the positive photosensitive resin composition has excellent resolution, photo process margin, and heat resistance, especially sensitivity and transmittance, and significantly improves adhesion, so that it can be used as an interlayer insulating film, PDL, and column spacer in the LCD and OLED manufacturing process. Suitable for forming. In addition, an LCD and OLED substrate including a cured photosensitive resin composition and a method of forming a pattern of a display substrate using the photosensitive resin composition are provided. Patterns can be used as materials such as passivation insulating films, gate insulating films, planarization films, column spacers, and partitions for TFT-LCD, TSP (Touch Screen Panel), OLED, O-TFT, EPD, and EWD.

이하 본 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 실시예들에 대하여 상세히 설명한다. 실시예는 여러가지 상이한 형태로 구현될 수 있으며, 여기에서 설명하는 구체적인 실시예로만 한정되지 않는다. 본 발명은 액정 표시 장치(LCD)와 유기 발광 표시 장치(OLED) 등의 층간에 배치되는 층간절연막, 패시베이션 절연막, 게이트 절연막, 오버코트, 컬럼 스페이서, PDL 격벽 등의 다양한 분야에 사용할 수 있는 포지티브형 감광성 수지 조성물에 관한 것이다.Hereinafter, embodiments will be described in detail so that those skilled in the art can easily implement them. Embodiments may be implemented in various different forms and are not limited to the specific embodiments described herein. The present invention is a positive photosensitive film that can be used in various fields such as interlayer insulating films, passivation insulating films, gate insulating films, overcoats, column spacers, and PDL partitions disposed between layers of liquid crystal display devices (LCDs) and organic light emitting display devices (OLEDs). It relates to a resin composition.

포지티브형 감광성 수지 조성물은,The positive photosensitive resin composition is,

a)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물,a)i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof,

ⅱ) 에폭시기 함유 불포화 화합물; 및ii) an epoxy group-containing unsaturated compound; and

ⅲ) 올레핀계 불포화 화합물을 공중합시켜 얻어진 아크릴계 공중합체iii) Acrylic copolymer obtained by copolymerizing olefinic unsaturated compounds

b) 하기 화학식 1로 표시되는 공중합체b) Copolymer represented by the following formula (1)

c) 1,2-퀴논디아지드 화합물; 및c) 1,2-quinonediazide compounds; and

d) 용매를 포함한다. d) Contains a solvent.

[화학식 1][Formula 1]

화학식 1의 a, b, c는 각 모노머 간의 몰비(mole ratio)를 나타내는 것으로, a는 1 내지 10이고, b, c는 각각 0 내지 9이며, a+b+c=10 이다. n은 1 내지 10이며, R은 H 또는 CH3 이다. In Formula 1, a, b, and c represent the mole ratio between each monomer, where a is 1 to 10, b and c are each 0 to 9, and a+b+c=10. n is 1 to 10, and R is H or CH 3 .

a)의 아크릴계 공중합체는 ⅰ) 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물, ⅱ에폭시기 함유 불포화 화합물; 및 ⅲ) 올레핀계 불포화 화합물을 단량체로 하여 용매 및 중합개시제의 존재하에서 라디칼 반응하여 합성한다. The acrylic copolymer of a) is ⅰ) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, ⅱunsaturated compound containing an epoxy group; and iii) synthesized by radical reaction using an olefinically unsaturated compound as a monomer in the presence of a solvent and a polymerization initiator.

a) ⅰ의 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물은 아크릴산(acrylic acid), 메타크릴산(methacrylic acid) 등의 불포화 모노카르본 산; 말레인산(maleic acid), 푸마르산(fumaric acid), 시트라콘산(citraconic acid), 메타콘산(methaconic acid), 이타콘산(itaconic acid) 등의 불포화 디카르본산; 또는 이들의 불포화 디카르본산의 무수물 등을 단독 또는 2 종 이상 혼합하여 사용할 수 있다. 특히 아크릴산, 메타크릴산, 또는 무수말레인산을 사용하는 것이 공중합 반응성과 현상액인 알칼리 수용액에 대한 용해성을 높일 수 있다. 불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물은 전체 총 단량체에 대하여 5 내지 40 중량부, 나아가 10 내지 30 중량부로 혼합될 수 있다. 그 함량이 5 중량부 미만일 경우에는 알칼리 수용액에 용해하기 어려울 수 있으며, 40 중량부를 초과할 경우에는 알칼리 수용액에 대한 용해성이 지나치게 커질 수 있다.
a) ⅱ의 에폭시기 함유 불포화 화합물은 아크릴산 글리시딜(glycidyl acrylate), 메타크릴산 글리시딜, α-에틸아크릴산 글리시딜, α-n-프로필아크릴산 글리시딜, α-n-부틸아크릴산 글리시딜, 아크릴산-β메틸글리시딜(acrylate-βglycidyl), 메타크릴산-β메틸글리시딜, 아크릴산-β에틸글리시딜, 메타크릴산-β에틸글리시딜, 아크릴산-3,4-에폭시부틸(3,4-epoxybutyl acrylate), 메타크릴산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸, α-에틸아크릴산-6,7-에폭시헵틸, o-비닐벤질글리시딜에테르(o-vinyl benzyl glycidyl ether), m-비닐벤질글리시딜에테르, 또는 p-비닐벤질글리시딜에테르, 메타크릴산 3,4-에폭시 사이클로헥실(3,4-epoxy cyclohexyl methacrylate), 메타크릴산 3,4-에폭시 사이클로헥실메틸, 아크릴산 3,4-에폭시 사이클로헥실, 아크릴산 3,4-에폭시 사이클로헥실메틸 등을 단독 또는 2 종 이상 혼합하여 사용할 수 있다. 메타크릴산 글리시딜, 메타크릴산-β메틸글리시딜, 메타크릴산-6,7-에폭시헵틸, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르, 또는 p-비닐벤질글리시딜에테르, 메타크릴산 3,4-에폭시 사이클로헥실등이 공중합 반응성 및 얻어지는 패턴의 내열성을 향상시킬 수 있다. 에폭시기 함유 불포화 화합물은 전체 총 단량체에 대하여 10 내지 70 중량부, 나아가 20 내지 50 중량부로 포함될 수 있다. 그 함량이 언급한 범위 내인 경우 유기절연막의 내열성 및 감광성 수지 조성물의 보존안정성을 동시에 만족시킬 수 있다. a) ⅰ unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, methaconic acid, and itaconic acid; Alternatively, these unsaturated dicarboxylic acid anhydrides can be used alone or in combination of two or more. In particular, using acrylic acid, methacrylic acid, or maleic anhydride can increase copolymerization reactivity and solubility in an aqueous alkaline developer solution. Unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof may be mixed in an amount of 5 to 40 parts by weight, and even 10 to 30 parts by weight, based on the total monomers. If the content is less than 5 parts by weight, it may be difficult to dissolve in an aqueous alkaline solution, and if it exceeds 40 parts by weight, the solubility in an aqueous alkaline solution may be excessively high.
a) ⅱ unsaturated compounds containing epoxy groups include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, and glycidyl α-n-butylacrylate. Cydyl, acrylate-βglycidyl, methacrylic acid-βmethylglycidyl, acrylic acid-βethylglycidyl, methacrylic acid-βethylglycidyl, acrylic acid-3,4- Epoxybutyl (3,4-epoxybutyl acrylate), methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7 -Epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p-vinylbenzyl glycidyl ether, 3,4-epoxy cyclohexyl methacrylic acid (3,4-epoxy cyclohexyl methacrylate), 3,4-epoxy cyclohexylmethyl methacrylate, 3,4-epoxy cyclohexyl acrylate, 3,4-epoxy cyclohexylmethyl acrylate, etc. can be used alone or in combination of two or more types. You can. Glycidyl methacrylate, β-methyl glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p-vinyl Benzyl glycidyl ether, 3,4-epoxy cyclohexyl methacrylate, etc. can improve copolymerization reactivity and heat resistance of the resulting pattern. The epoxy group-containing unsaturated compound may be included in an amount of 10 to 70 parts by weight, and even 20 to 50 parts by weight, based on the total monomers. If the content is within the mentioned range, the heat resistance of the organic insulating film and the storage stability of the photosensitive resin composition can be simultaneously satisfied.

a) ⅲ의 올레핀계 불포화 화합물은 메틸메타크릴레이트(methylmethacrylate), 에틸메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, tert-부틸 메타크릴레이트, 메틸아크릴레이트(methyl acrylate), 이소프로필 아크릴레이트(isopropyl acrylate), 시클로헥실 메타크릴레이트(cyclohexyl methacrylate), 2-메틸시클로 헥실메타크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐메타크릴레이트, 디시클로펜타닐메타크릴레이트, 1-아다만틸 아크릴레이트(1-adamantyl acrylate), 1-아다만틸 메타크릴레이트, 3-하이드록시 1-아다만틸 메타크릴레이트, 3-하이드록시 1-아다만틸 아크릴레이트, 5-하이드록시 1-아다만틸 메타크릴레이트, 5-하이드록시 1-아다만틸 아크릴레이트, 3,5-하이드록시 1-아다만틸메타크릴레이트, 3,5-하이드록시 1-아다만틸 아크릴레이트, 디시클로펜타닐옥시에틸메타크릴레이트(dicyclopentanyl oxyethyl methacrylate), 이소보로닐메타크릴레이트(isoboronyl methacrylate), 시클로헥실아크릴레이트, 2-메틸시클로헥실아크릴레이트, 디시클로펜타닐옥시에틸아크릴레이트, 이소보로닐아크릴레이트, 페닐메타크릴레이트(phenyl methacrylate), 페닐아크릴레이트, 벤질아크릴레이트(benzyl acrylate), 2-하이드록시에틸메타크릴레이트(2-hydroxy ethyl methacrylate), 스티렌(styrene), σ-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐톨루엔(vinyl toluene), p-메톡시 스티렌, 1,3-부타디엔, 이소프렌(isoprene), 또는 2,3-디메틸 1,3-부타디엔(2,3-dimethyl-1,3-butadiene), 2-[메타아크릴로일옥시]에틸 6-하이드록시헥사네이트, 4-비닐페놀, 4-비닐시클로헥사놀, 4-하이드록시벤질메타아크릴레이트, [[4-하이드록시메틸]시클로헥실]메틸메타아크릴레이트, 3-하이드록시-1-메타아크릴로일옥시아다만탄, 2-옥소테트라하이드로퓨란-3-일 메타아크릴레이트(2-oxotetrahydrofuran-3-yl methacrylate), 4-하이드록시클로헥실 메타아크릴레이트 등일 수 있다. 언급된 화합물을 단독 또는 2 종 이상 혼합하여 사용할 수 있다. 올레핀계 불포화 화합물은 전체 총 단량체에 대하여 10 내지 70 중량부, 나아가 20 내지 50 중량부로 포함될 수 있다. 그 함량이 범위 내인 경우 현상 후 팽윤(Swelling)이 생기지 않게 하며, 현상액인 알칼리 수용액에 용해성을 이상적으로 유지할 수 있다.a) ⅲ olefinic unsaturated compounds include methylmethacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, and methyl acrylate. , isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, Dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, 3-hydroxy 1-adamantyl methacrylate, 3-hydroxy 1-ah Damantyl acrylate, 5-hydroxy 1-adamantyl methacrylate, 5-hydroxy 1-adamantyl acrylate, 3,5-hydroxy 1-adamantyl methacrylate, 3,5-hydroxy Roxy 1-adamantyl acrylate, dicyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclo Fentanyloxyethyl acrylate, isoboronyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxy ethyl methacrylate, Styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1,3-butadiene, isoprene, or 2,3-dimethyl. 1,3-butadiene (2,3-dimethyl-1,3-butadiene), 2-[methacryloyloxy]ethyl 6-hydroxyhexanate, 4-vinylphenol, 4-vinylcyclohexanol, 4- Hydroxybenzyl methacrylate, [[4-hydroxymethyl]cyclohexyl]methyl methacrylate, 3-hydroxy-1-methacryloyloxyadamantane, 2-oxotetrahydrofuran-3-yl methacrylate It may be 2-oxotetrahydrofuran-3-yl methacrylate), 4-hydroxychlorhexyl methacrylate, etc. The mentioned compounds can be used alone or in combination of two or more. The olefinic unsaturated compound may be included in an amount of 10 to 70 parts by weight, and even 20 to 50 parts by weight, based on the total monomers. If the content is within the range, swelling will not occur after development, and solubility in the aqueous alkaline developer solution can be ideally maintained.

단량체들을 용액(Solution) 중합하기 위한 용매는 메탄올, 테트라히드록시퓨란, 톨루엔, 다이옥산 등을 사용할 수 있다. 용액 중합하기 위해 사용되는 중합개시제는 라디칼 중합개시제를 사용할 수 있으며, 구체적으로 2,2-아조비스이소부티로니트릴(2,2-azobisisobutyronitrile), 2,2-아조비스(2,4-디메틸발레로니트릴), 2,2-아조비스(4-메톡시 2,4-디메틸발레로니트릴), 1,1-아조비스(시클로헥산-1-카르보니트릴), 또는 디메틸 2,2'-아조비스이소부틸레이트(2,2'-azobisisobutylate) 등을 사용할 수 있다. Solvents for solution polymerization of monomers can be methanol, tetrahydroxyfuran, toluene, dioxane, etc. The polymerization initiator used for solution polymerization can be a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvalene) ronitrile), 2,2-azobis(4-methoxy 2,4-dimethylvaleronitrile), 1,1-azobis(cyclohexane-1-carbonitrile), or dimethyl 2,2'-azobis Isobutylate (2,2'-azobisisobutylate), etc. can be used.

단량체를 용매와 중합개시제 존재하에서 라디칼 반응시키고, 침전 및 여과, 진공 건조(Vacuum Drying)공정을 통하여 미반응 단량체를 제거하여 얻어진 아크릴계 공중합체는 폴리스티렌 환산중량평균분자량(Mw)이 3,000 내지 20,000 일 수 있다. 폴리스티렌 환산중량평균분자량이 3,000 미만인 층간 절연막(유기 절연막)의 경우 현상성, 잔막율 등이 저하되거나, 패턴 현상, 내열성 등이 뒤떨어질 수 있으며, 20,000을 초과하는 층간절연막의 경우에는 패턴 현상이 뒤떨어질 수 있다. An acrylic copolymer obtained by radically reacting monomers in the presence of a solvent and a polymerization initiator and removing unreacted monomers through precipitation, filtration, and vacuum drying processes may have a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 20,000. there is. In the case of an interlayer insulating film (organic insulating film) with a polystyrene-equivalent weight average molecular weight of less than 3,000, developability, residual film rate, etc. may be reduced, or pattern development and heat resistance may be inferior, and in the case of an interlayer insulating film with a polystyrene conversion weight average molecular weight exceeding 20,000, pattern development may be delayed. It may fall.

b) 공중합체는 하기 화학식 1로 표현되며 a, b, c는 각 모노머 간의 몰비(mole ratio)를 나타내는 것으로 a는 1 내지 10이고, b, c는 각각 0 내지 9이며, a + b + c = 10 이다. n은 1 내지 10이며, R은 H 또는 CH3 이고, 공중합체의 분자량은 1,000 내지 50,000일 수 있다.b) The copolymer is represented by the following formula 1, where a, b, and c represent the mole ratio between each monomer, where a is 1 to 10, b and c are each 0 to 9, and a + b + c = 10. n is 1 to 10, R is H or CH 3 , and the molecular weight of the copolymer may be 1,000 to 50,000.

..

[화학식 1][Formula 1]

상기 b)의 공중합체는, a)아크릴계 공중합체 100 중량부에 대하여 5 내지 100 중량부로 포함될 수 있다. 그 함량이 5 중량부 미만일 경우에는 감도가 느린 문제점이 있다. 100 중량부를 초과할 경우에는 내열변색성 마진이 떨어지는 문제가 있다.The copolymer of b) may be included in an amount of 5 to 100 parts by weight based on 100 parts by weight of a) acrylic copolymer. If the content is less than 5 parts by weight, there is a problem of slow sensitivity. If it exceeds 100 parts by weight, there is a problem that the heat discoloration resistance margin decreases.

상기 b) 공중합체 중, 각 모노머 간의 몰비(mole ratio)를 나타내는 a, b, 및 c에 있어서, a는 1 내지 10이고, b, c는 각각 0 내지 9이며, a + b + c = 10이다. 만약, 화학식 1의 몰비가 상기 범위를 만족하지 못할 경우에는 감도가 저하, 백탁 발생 등의 문제가 발생할 수 있다.In a, b, and c representing the mole ratio between each monomer in the copolymer b), a is 1 to 10, b and c are each 0 to 9, and a + b + c = 10 am. If the molar ratio of Formula 1 does not satisfy the above range, problems such as decreased sensitivity and occurrence of white turbidity may occur.

c) 1,2-퀴논디아지드 화합물은 1,2-퀴논디아지드 4-술폰산 에스테르, 1,2-퀴논디아지드 5-술폰산 에스테르, 및 1,2-퀴논디아지드 6-술폰산 에스테르로 이루어지는 군으로부터 1종 이상 선택된 물질이 사용될 수 있다. 1,2-퀴논디아지드 화합물(Photo Active Compound: PAC)은 1,2-퀴논디아지드 술폰산 할로겐 화합물과 페놀 화합물을 약염기 하에서 반응시켜 제조할 수 있다. c) 1,2-quinonediazide compounds are a group consisting of 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide 6-sulfonic acid ester. One or more substances selected from may be used. 1,2-quinonediazide compound (Photo Active Compound: PAC) can be produced by reacting a 1,2-quinonediazide sulfonic acid halogen compound and a phenol compound under a weak base.

1,2-퀴논디아지드 화합물은 a)아크릴계 공중합체 100 중량부에 대하여 5 내지 50 중량부, 나아가 10 내지 40 중량부로 포함될 수 있다. 그 함량이 5 중량부 미만일 경우에는 노광부와 비노광부의 용해도 차가 작아져 패턴 형성이 어려울 수 있다. 50 중량부를 초과할 경우에는 단시간 동안 빛을 조사할 때 미반응 1,2-퀴논디아지드 화합물이 다량 잔존하여 현상액인 알칼리 수용액에 대한 용해도가 지나치게 낮아져 현상이 어려울 수 있다. The 1,2-quinonediazide compound may be included in an amount of 5 to 50 parts by weight , or even 10 to 40 parts by weight, based on 100 parts by weight of a) a) acrylic copolymer. If the content is less than 5 parts by weight, the difference in solubility between the exposed and non-exposed areas becomes small, making pattern formation difficult. If the amount exceeds 50 parts by weight, a large amount of unreacted 1,2-quinonediazide compound will remain when irradiated with light for a short period of time, and the solubility in the alkaline aqueous solution as a developer may be too low, making development difficult.

d)의 용매는 감광성 수지 조성물을 기판 등에 코팅하기 위해서 사용하며, 구체적인 예로는, 디에틸렌글리콜디메틸에테르(Diethylene glycol dimethyl ether), 디에틸렌글리콜메틸에틸에테르, 프로필렌글리콜메틸에테르아세테이트(propylene glycol methyl ether acetate), 프로필렌글리콜에틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜메틸에테르프로피오네이트(Propylene glycol methyl ether propionate), 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르프로피오네이트, 프로필렌글리콜메틸에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르, 디프로필렌글리콜디메틸에테르, 디포로필렌글리콜디에틸에테르, 부틸렌글리콜모노메틸에테르(butylene glycol monomethyl ether), 부틸렌글리콜모노에틸에테르, 디부틸렌글리콜디메틸에테르, 및 디부틸렌글리콜디에틸에테르, 디에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜부틸에틸에테르, 트리에틸렌글리콜디메틸에테르, 트리에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜터셔리부틸에테르, 테트라에틸렌글리콜디메틸에테르, 디에틸렌글리콜에틸헥실에테르, 디에틸렌글리콜메틸헥실에테르, 디프로필렌글리콜부틸메틸에테르, 디프로필렌글리콜에틸헥실에테르 및 디프로필렌글리콜메틸헥실에테르 등을 사용할 수 있으며, 단독 또는 2 종 이상 혼합하여 사용할 수 있다.The solvent of d) is used to coat the photosensitive resin composition on a substrate, etc. Specific examples include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and propylene glycol methyl ether. acetate), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether , propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, Dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether. , tetraethylene glycol dimethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, and dipropylene glycol methylhexyl ether, etc. can be used alone or in 2 More than one species can be mixed and used.

d)의 용매는 포지티브형 감광성 수지 조성물의 고형분 함량이 10 내지 50 중량%가 되도록 포함될 수 있다. 고형분 함량이 10 중량% 미만일 경우에는 코팅두께가 얇게 되고, 코팅 균일성(Uniformity)이 저하될 수 있으며, 50 중량%를 초과할 경우에는 코팅두께가 두꺼워지고, 코팅시 코팅장비에 무리를 줄 수 있다. 전체 조성물의 고형분 함량이 10 내지 25중량% 일 경우, 슬릿 코터(Slit Coater)에서 사용하는 것이 용이하며, 25내지 50중량%일 경우 스핀 코터(Spin Coater)나 슬릿앤스핀코터(Slit & Spin Coater)에서 사용하는 것이 용이하다. The solvent in d) may be included so that the solid content of the positive photosensitive resin composition is 10 to 50% by weight. If the solid content is less than 10% by weight, the coating thickness may become thin and coating uniformity may deteriorate, and if it exceeds 50% by weight, the coating thickness may become thick and cause strain on the coating equipment during coating. there is. If the solid content of the total composition is 10 to 25% by weight, it is easy to use in a slit coater, and if it is 25 to 50% by weight, it can be used in a spin coater or slit & spin coater. ) is easy to use.

또, 포지티브형 감광성 수지 조성물은 필요에 따라, a)의 아크릴계 공중합체 100 중량부에 대하여, e) 실란커플링제 0.1 내지 50 중량부를 더 포함할 수 있다.
상기 e) 실란커플링제는 (3-글리시드옥시프로필)트리메톡시실란, (3-글리시드옥시프로필)트리에톡시실란, (3-글리시드옥시프로필)메틸디메톡시실란, (3-글리시드옥시프로필)메틸디에톡시실란, (3-글리시드옥시프로필)디메틸에톡시실란, 3,4-에폭시부틸트리메톡시실레인, 3,4-에폭시부틸트리에톡시실란, 2-(3,4-에폭시시크로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시크로헥실)에틸트리에톡시실란, 아미노프로필트리메톡시실란, 아미노프로필트리에톡시실란, 3-트리에톡시실리-N-(1,3 디메틸-부틸리덴)프로필아민, N-2(아미노에틸)3-아미노프로필트리메톡시실란, N-2(아미노에틸)3-아미노프로필트리에톡시실란, N-2(아미노에틸)3-아미노프로필메틸디메톡시실란, N-페닐-3-아미노프로필트리메톡시실레인, 및 (3-이소시아네이트프로필)트리에톡시실란으로 이루어지는 군으로부터 1종 이상 선택되는 것을 사용할 수 있다.Additionally, the positive photosensitive resin composition may further include 0.1 to 50 parts by weight of e) a silane coupling agent, if necessary, based on 100 parts by weight of the acrylic copolymer of a).
The above e) silane coupling agent is (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl) Seedoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3, 4-Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-triethoxy Sicily-N-(1,3 dimethyl-butylidene)propylamine, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, N -One or more selected from the group consisting of 2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and (3-isocyanatepropyl)triethoxysilane. You can use it.

포지티브형 감광성 수지 조성물은 고형분 농도를 10 내지 50 중량%로 하여, 0.1 ~ 0.2 ㎛의 밀리포아필터(Millipore Filter) 등으로 여과한 뒤 사용하는 것이 좋다.It is recommended that the positive photosensitive resin composition be used after setting the solids concentration to 10 to 50% by weight and filtering it through a 0.1 to 0.2 ㎛ Millipore Filter.

실시예들에 따른 포지티브형 감광성 수지 조성물은 디스플레이(Display) 공정에서 절연막을 패턴을 형성할 때 사용될 수 있다.The positive photosensitive resin composition according to the embodiments can be used when forming an insulating film pattern in a display process.

먼저 포지티브형 감광성 수지 조성물을 스핀코팅, 슬릿앤스핀코팅, 슬릿코팅, 롤코팅 등으로 디스플레이 패널 기판 표면에 도포하고, 프리베이크에 의해 용매를 제거하여 도포막을 형성한다. 이때, 프리베이크는 100 ~ 120 ℃의 온도에서 1 ~ 3 분간 실시할 수 있다. 그 다음, 미리 준비된 패턴에 따라 가시광선, 자외선, 원자외선, 전자선, 엑스선 등을 형성된 도포막에 조사하고, 현상액으로 현상하여 불필요한 부분을 제거함으로써 소정의 패턴을 형성한다. First, the positive photosensitive resin composition is applied to the surface of the display panel substrate by spin coating, slit and spin coating, slit coating, roll coating, etc., and the solvent is removed by prebaking to form a coating film. At this time, prebake can be performed for 1 to 3 minutes at a temperature of 100 to 120°C. Next, visible light, ultraviolet light, deep ultraviolet light, electron beam,

현상액은 알칼리 수용액을 사용하는 것이 좋으며, 구체적으로 수산화나트륨, 수산화칼륨, 탄산나트륨 등의 무기 알칼리류; 에틸아민, n-프로필아민 등의 1급 아민류; 디에틸아민, n-프로필아민 등의 2급 아민류; 트리메틸아민, 메틸디에틸아민, 디메틸에틸아민, 트리에틸아민 등의 3급 아민류; 디메틸에탄올아민, 메틸디에탄올아민, 트리에탄올아민 등의 알콜아민류; 또는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드 등의 4급 암모늄염의 수용액 등을 사용할 수 있다. 이때, 현상액은 알칼리성 화합물을 0.1 내지 10 중량부의 농도로 용해시켜 사용되며, 메탄올, 에탄올 등과 같은 수용성 유기용매 및 계면활성제를 적정량 첨가할 수도 있다. It is recommended to use an aqueous alkaline solution as the developing solution, specifically inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate; Primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine; Alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; Alternatively, an aqueous solution of quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. At this time, the developer is used by dissolving an alkaline compound at a concentration of 0.1 to 10 parts by weight, and an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, etc. and a surfactant may be added.

또한, 와 같은 현상액으로 현상한 후 초순수로 30 ~ 90 초간 세정하여 불필요한 부분을 제거하고 건조하여 패턴을 형성하고, 형성된 패턴에 자외선 등의 빛을 조사한 후, 패턴을 오븐 등의 가열장치에 의해 150 ~ 400 ℃의 온도에서 30 ~ 90 분간 가열처리하여 최종 패턴을 얻을 수 있다.In addition, after developing with a developer such as The final pattern can be obtained by heat treatment at a temperature of ~ 400 ℃ for 30 ~ 90 minutes.

실시예들에 따른 포지티브형 감광성 수지 조성물은 평탄화도, 투과도, 아웃 가스(Outgas)가 우수하고, 특히 감도가 우수하며, 고온, 고습에서의 접착력, 명암비, 내화학성을 현저히 향상시켜 LCD 및 OLED 제조공정의 층간절연막 및 PDL 격벽 등을 형성하기에 적합하다.The positive photosensitive resin composition according to the examples has excellent flatness, transmittance, and outgassing, and especially has excellent sensitivity, and significantly improves adhesion, contrast ratio, and chemical resistance at high temperature and high humidity for LCD and OLED manufacturing. It is suitable for forming interlayer insulation films and PDL partitions in the process.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실험예들을 제시하나, 하기 실험예들은 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Below, preferred experimental examples are presented to aid understanding of the present invention. However, the following experimental examples are merely illustrative of the present invention and the scope of the present invention is not limited to the following examples.

[합성예 1] 아크릴계 공중합체(A) 제조 [Synthesis Example 1] Preparation of acrylic copolymer (A)

냉각기와 교반기가 구비된 플라스크에 프로필렌글리콜모노메틸에테르아세테이트 400 중량부, 하이드록시 에틸 메타아크릴레이트 30 중량부, 메타크릴산 20 중량부, 스티렌 20 중량부, 및 글리시딜메타크릴레이트 30 중량부의 혼합 용액을 투입하였다. 액상 조성물을 혼합 용기에서 600 rpm으로 충분히 혼합한 뒤, 2,2’-아조비스(2,4-디메틸발레로니트릴) 15 중량부를 첨가하였다. 중합 혼합용액을 55 ℃까지 천천히 상승시켜, 이 온도로 24시간 동안 유지 후 상온으로 냉각하고 중합 금지제로 하이드로 벤조페논을 500 ppm 첨가하여 고형분 농도가 25 중량%인 중합체 용액을 얻었다. 아크릴계 공중합체의 중량평균 분자량은 6,000이었다. 이때, 중량평균분자량은 GPC를 사용하여 측정한 폴리스티렌 환산 평균 분자량이다.In a flask equipped with a cooler and a stirrer, 400 parts by weight of propylene glycol monomethyl ether acetate, 30 parts by weight of hydroxy ethyl methacrylate, 20 parts by weight of methacrylic acid, 20 parts by weight of styrene, and 30 parts by weight of glycidyl methacrylate. The mixed solution was added. The liquid composition was thoroughly mixed at 600 rpm in a mixing container, and then 15 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55°C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone as a polymerization inhibitor was added to obtain a polymer solution with a solid content concentration of 25% by weight. The weight average molecular weight of the acrylic copolymer was 6,000. At this time, the weight average molecular weight is the polystyrene conversion average molecular weight measured using GPC.

[합성예 2] 아크릴계 공중합체(B) 제조 [Synthesis Example 2] Preparation of acrylic copolymer (B)

냉각기와 교반기가 구비된 플라스크에 테트라하이드로퓨란 400 중량부, 메타크릴산 30 중량부와 스티렌 30 중량부, 및 글리시딜메타크릴레이트 40 중량부의 혼합 용액을 투입하였다. 액상 조성물을 혼합 용기에서 600 rpm으로 충분히 혼합한 뒤, 2,2'-아조비스(2,4-디메틸발레로니트릴) 10 중량부를 첨가하였다. 중합혼합용액을 55 ℃까지 천천히 상승시켜, 이 온도로 24시간 동안 유지 후 상온으로 냉각하고 중합금지제로 하이드로벤조페논을 500 ppm 첨가하여 고형분 농도가 30 중량%인 중합체용액를 얻었다. A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. The liquid composition was thoroughly mixed at 600 rpm in a mixing container, and then 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55°C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone as a polymerization inhibitor was added to obtain a polymer solution with a solid content concentration of 30% by weight.

중합체용액의 미반응 단량체를 제거하기 위하여 n-헥산(n-Hexane)을 1000중량부에 대하여 중합체용액 100중량부를 침전시킨다. 침전 후, 메쉬(Mesh)를 이용한 여과(Filtering)공정을 통하여 미반응물이 용해된 빈 용매(Poor solvent)를 제거한다. 그 후, 여과공정 이후에도 남아있는 미반응 단량체가 함유된 용매들을 제거하기 위하여 30도 이하에서 진공 건조를 통해 완전히 제거하여 아크릴계 공중합체를 제조하였다.To remove unreacted monomers from the polymer solution, 100 parts by weight of n-hexane is precipitated per 1,000 parts by weight of the polymer solution. After precipitation, the poor solvent in which unreacted substances are dissolved is removed through a filtration process using a mesh. Afterwards, in order to remove the solvent containing unreacted monomers that remained even after the filtration process, they were completely removed through vacuum drying at 30 degrees or lower to prepare an acrylic copolymer.

아크릴계 공중합체의 중량평균분자량은 10,000이었다. 이때, 중량평균분자량은 GPC를 사용하여 측정한 폴리스티렌 환산평균분자량이다. The weight average molecular weight of the acrylic copolymer was 10,000. At this time, the weight average molecular weight is the polystyrene conversion average molecular weight measured using GPC.

[합성예 3] 아크릴계 공중합체(C) 제조 [Synthesis Example 3] Preparation of acrylic copolymer (C)

냉각기와 교반기가 구비된 플라스크에 테트라하이드로퓨란 400 중량부, 메타크릴산 30 중량부와 스티렌 30 중량부, 및 글리시딜메타크릴레이트 40 중량부의 혼합 용액을 투입하였다. 액상 조성물을 혼합 용기에서 600 rpm으로 충분히 혼합한 뒤, 2,2'-아조비스(2,4-디메틸발레로니트릴) 5 중량부를 첨가하였다. 중합혼합용액을 55 ℃까지 천천히 상승시켜, 이 온도로 24시간 동안 유지 후 상온으로 냉각하고 중합금지제로 하이드로벤조페논을 500 ppm 첨가하여 고형분 농도가 30 중량%인 중합체용액를 얻었다. A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. The liquid composition was thoroughly mixed at 600 rpm in a mixing container, and then 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55°C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone as a polymerization inhibitor was added to obtain a polymer solution with a solid content concentration of 30% by weight.

중합체용액의 미반응 단량체를 제거하기 위하여 n-헥산을 1000중량부에 대하여 중합체용액 100중량부를 침전시킨다. 침전후, 메쉬를 이용한 여과공정을 통하여 미반응물이 용해된 빈 용매를 제거한다. 그 후, 여과공정 이후에도 남아있는 미반응 단량체가 함유된 용매들을 제거하기 위하여 30도 이하에서 진공건조를 통해 완전히 제거하여 아크릴계 공중합체를 제조하였다.To remove unreacted monomers from the polymer solution, 100 parts by weight of the polymer solution are precipitated based on 1,000 parts by weight of n-hexane. After precipitation, empty solvent in which unreacted substances are dissolved is removed through a filtration process using a mesh. Afterwards, in order to remove the solvent containing unreacted monomers that remained even after the filtration process, they were completely removed through vacuum drying at 30 degrees or lower to prepare an acrylic copolymer.

아크릴계 공중합체의 중량평균분자량은 16,000이었다. 이때, 중량평균분자량은 GPC를 사용하여 측정한 폴리스티렌 환산평균분자량이다 The weight average molecular weight of the acrylic copolymer was 16,000. At this time, the weight average molecular weight is the average molecular weight converted to polystyrene measured using GPC.

[합성예 4] 1,2- 퀴논디아지드 화합물(A) 제조 [Synthesis Example 4] Preparation of 1,2- quinonediazide compound (A)

하기 화학식 2로 표시되는 4,4’-[1-[4-[1-[4-히드록시페닐]-1-메틸에틸]페닐]에틸리덴]비스페놀 1 몰과 1,2-나프토퀴논디아지드-5-술폰산[클로라이드] 2.0 몰을 축합반응시켜 4,4’-[1-[4-[1-[4-히드록시페닐]-1-메틸에틸]페닐]에틸리덴]비스페놀 1,2-나프토퀴논디아지드-5-술폰산 에스테르를 제조하였다.1 mole of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonedia represented by the following formula (2) 2.0 mol of zide-5-sulfonic acid [chloride] was condensed to obtain 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1,2 -Naphthoquinonediazide-5-sulfonic acid ester was prepared.

[화학식 2][Formula 2]

[합성예 5] 공중합체(A) 제조 [Synthesis Example 5] Preparation of copolymer (A)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌을 투입하고 자유 라디칼 중합반응시켜 15,000의 분자량을 갖는 4-아세톡시스티렌 중합체를 형성시킨다. 4-아세톡시스티렌 중합체를 가수분해시켜 14,000의 분자량을 갖는 4-히드록시스티렌 중합체를 제조하였다.4-acetoxystyrene is added to a flask equipped with a cooler and a stirrer and undergoes free radical polymerization to form 4-acetoxystyrene polymer with a molecular weight of 15,000. 4-Hydroxystyrene polymer with a molecular weight of 14,000 was prepared by hydrolyzing 4-acetoxystyrene polymer.

[합성예 6] 공중합체(B) 제조 [Synthesis Example 6] Preparation of copolymer (B)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌을 투입하고 자유 라디칼 중합반응시켜 11,000의 분자량을 갖는 4-아세톡시스티렌 중합체를 형성시킨다. 4-acetoxystyrene is added to a flask equipped with a cooler and a stirrer and undergoes free radical polymerization to form 4-acetoxystyrene polymer with a molecular weight of 11,000.

4-아세톡시스티렌 중합체를 가수분해시켜 10,000의 분자량을 갖는 4-히드록시스티렌 중합체를 제조하였다. 4-Hydroxystyrene polymer with a molecular weight of 10,000 was prepared by hydrolyzing 4-acetoxystyrene polymer.

[합성예 7] 공중합체(C) 제조 [Synthesis Example 7] Preparation of copolymer (C)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌을 투입하고 자유 라디칼 중합반응시켜 7,000의 분자량을 갖는 4-아세톡시스티렌 중합체를 형성시킨다. 4-acetoxystyrene is added to a flask equipped with a cooler and a stirrer and undergoes free radical polymerization to form 4-acetoxystyrene polymer with a molecular weight of 7,000.

4-아세톡시스티렌 중합체를 가수분해시켜 6,000의 분자량을 갖는 4-히드록시스티렌 중합체를 제조하였다. 4-Hydroxystyrene polymer with a molecular weight of 6,000 was prepared by hydrolyzing 4-acetoxystyrene polymer.

[합성예 8] 공중합체(D) 제조 [Synthesis Example 8] Preparation of copolymer (D)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 50 중량부와 스티렌50 중량부을 투입하고 자유 라디칼 중합반응시켜 15,000의 분자량을 갖는 4-아세톡시스티렌, 스티렌 공중합체를 형성시킨다. 50 parts by weight of 4-acetoxystyrene and 50 parts by weight of styrene are added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to form 4-acetoxystyrene and styrene copolymer with a molecular weight of 15,000.

4-아세톡시스티렌, 스티렌 공중합체를 가수분해시켜 14,000의 분자량을 갖는 4-히드록시스티렌, 스티렌 공중합체를 제조하였다. 4-Hydroxystyrene and styrene copolymers having a molecular weight of 14,000 were prepared by hydrolyzing 4-acetoxystyrene and styrene copolymers.

[합성예 9] 공중합체(E) 제조 [Synthesis Example 9] Preparation of copolymer (E)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 50 중량부와 스티렌50 중량부을 투입하고 자유 라디칼 중합반응시켜 11,000의 분자량을 갖는 4-아세톡시스티렌, 스티렌 공중합체를 형성시킨다. 50 parts by weight of 4-acetoxystyrene and 50 parts by weight of styrene are added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to form 4-acetoxystyrene and styrene copolymer with a molecular weight of 11,000.

4-아세톡시스티렌, 스티렌 공중합체를 가수분해시켜 10,000의 분자량을 갖는 4-히드록시스티렌, 스티렌 공중합체를 제조하였다. 4-Hydroxystyrene and styrene copolymers having a molecular weight of 10,000 were prepared by hydrolyzing 4-acetoxystyrene and styrene copolymers.

[합성예 10] 공중합체(F) 제조 [Synthesis Example 10] Preparation of copolymer (F)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 50 중량부와 스티렌50 중량부을 투입하고 자유 라디칼 중합반응시켜 7,000의 분자량을 갖는 4-아세톡시스티렌, 스티렌 공중합체를 형성시킨다. 50 parts by weight of 4-acetoxystyrene and 50 parts by weight of styrene are added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to form 4-acetoxystyrene and styrene copolymer with a molecular weight of 7,000.

4-아세톡시스티렌, 스티렌 공중합체를 가수분해시켜 6,000의 분자량을 갖는 4-히드록시스티렌, 스티렌 공중합체를 제조하였다. 4-Hydroxystyrene and styrene copolymers having a molecular weight of 6,000 were prepared by hydrolyzing 4-acetoxystyrene and styrene copolymers.

[합성예 11] 공중합체(G) 제조 [Synthesis Example 11] Preparation of copolymer (G)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 80 중량부와 하이드록시에틸메타크릴레이트 20 중량부을 투입하고 자유 라디칼 중합반응시켜 15,000의 분자량을 갖는 4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 형성시킨다. 80 parts by weight of 4-acetoxystyrene and 20 parts by weight of hydroxyethyl methacrylate were added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to produce 4-acetoxystyrene and hydroxyethyl methacrylate with a molecular weight of 15,000. Forms a copolymer.

4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 가수분해시켜 14,000의 분자량을 갖는 4-히드록시스티렌, 하이드록시에틸메타크릴레이트공중합체를 제조하였다. 4-Hydroxystyrene and hydroxyethyl methacrylate copolymers having a molecular weight of 14,000 were prepared by hydrolyzing the 4-acetoxystyrene and hydroxyethyl methacrylate copolymers.

[합성예 12] 공중합체(H) 제조 [Synthesis Example 12] Preparation of copolymer (H)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 80 중량부와 하이드록시에틸메타크릴레이트 20 중량부을 투입하고 자유 라디칼 중합반응시켜 11,000의 분자량을 갖는 4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 형성시킨다. 80 parts by weight of 4-acetoxystyrene and 20 parts by weight of hydroxyethyl methacrylate were added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to produce 4-acetoxystyrene and hydroxyethyl methacrylate with a molecular weight of 11,000. Forms a copolymer.

4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 가수분해시켜 10,000의 분자량을 갖는 4-히드록시스티렌, 하이드록시에틸메타크릴레이트공중합체를 제조하였다. 4-Hydroxystyrene and hydroxyethyl methacrylate copolymers having a molecular weight of 10,000 were prepared by hydrolyzing the 4-acetoxystyrene and hydroxyethyl methacrylate copolymers.

[합성예 13] 공중합체(I) 제조 [Synthesis Example 13] Preparation of copolymer (I)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 80 중량부와 하이드록시에틸메타크릴레이트 20 중량부을 투입하고 자유 라디칼 중합반응시켜 7,000의 분자량을 갖는 4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 형성시킨다. 80 parts by weight of 4-acetoxystyrene and 20 parts by weight of hydroxyethyl methacrylate were added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to produce 4-acetoxystyrene and hydroxyethyl methacrylate with a molecular weight of 7,000. Forms a copolymer.

4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 가수분해시켜 6,000의 분자량을 갖는 4-히드록시스티렌, 하이드록시에틸메타크릴레이트공중합체를 제조하였다. 4-Hydroxystyrene and hydroxyethyl methacrylate copolymers having a molecular weight of 6,000 were prepared by hydrolyzing the 4-acetoxystyrene and hydroxyethyl methacrylate copolymers.

[합성예 14] 공중합체(J) 제조 [Synthesis Example 14] Preparation of copolymer (J)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 70 중량부와 하이드록시에틸메타크릴레이트 30 중량부을 투입하고 자유 라디칼 중합반응시켜 15,000의 분자량을 갖는 4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 형성시킨다. 70 parts by weight of 4-acetoxystyrene and 30 parts by weight of hydroxyethyl methacrylate were added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to produce 4-acetoxystyrene and hydroxyethyl methacrylate with a molecular weight of 15,000. Forms a copolymer.

4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 가수분해시켜 14,000의 분자량을 갖는 4-히드록시스티렌, 하이드록시에틸메타크릴레이트공중합체를 제조하였다. 4-Hydroxystyrene and hydroxyethyl methacrylate copolymers having a molecular weight of 14,000 were prepared by hydrolyzing the 4-acetoxystyrene and hydroxyethyl methacrylate copolymers.

[합성예 15] 공중합체(K) 제조 [Synthesis Example 15] Preparation of copolymer (K)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 70 중량부와 하이드록시에틸메타크릴레이트 30 중량부을 투입하고 자유 라디칼 중합반응시켜 11,000의 분자량을 갖는 4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 형성시킨다. 70 parts by weight of 4-acetoxystyrene and 30 parts by weight of hydroxyethyl methacrylate were added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to produce 4-acetoxystyrene and hydroxyethyl methacrylate with a molecular weight of 11,000. Forms a copolymer.

4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 가수분해시켜 10,000의 분자량을 갖는 4-히드록시스티렌, 하이드록시에틸메타크릴레이트공중합체를 제조하였다. 4-Hydroxystyrene and hydroxyethyl methacrylate copolymers having a molecular weight of 10,000 were prepared by hydrolyzing the 4-acetoxystyrene and hydroxyethyl methacrylate copolymers.

[합성예 16] 공중합체(L) 제조 [Synthesis Example 16] Preparation of copolymer (L)

냉각기와 교반기가 구비된 플라스크에 4-아세톡시스티렌 70 중량부와 하이드록시에틸메타크릴레이트 30 중량부을 투입하고 자유 라디칼 중합반응시켜 7,000의 분자량을 갖는 4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 형성시킨다. 70 parts by weight of 4-acetoxystyrene and 30 parts by weight of hydroxyethyl methacrylate were added to a flask equipped with a cooler and a stirrer and subjected to free radical polymerization to produce 4-acetoxystyrene and hydroxyethyl methacrylate with a molecular weight of 7,000. Forms a copolymer.

4-아세톡시스티렌, 하이드록시에틸메타크릴레이트 공중합체를 가수분해시켜 6,000의 분자량을 갖는 4-히드록시스티렌, 하이드록시에틸메타크릴레이트공중합체를 제조하였다. 4-Hydroxystyrene and hydroxyethyl methacrylate copolymers having a molecular weight of 6,000 were prepared by hydrolyzing the 4-acetoxystyrene and hydroxyethyl methacrylate copolymers.

[비교합성예 1] 아크릴계 공중합체(D) 제조 [Comparative Synthesis Example 1] Preparation of acrylic copolymer (D)

냉각기와 교반기가 구비된 플라스크에 테트라하이드로퓨란 400 중량부, 메타크릴산 30 중량부와 스티렌 30 중량부, 및 글리시딜메타크릴레이트 40 중량부의 혼합 용액을 투입하였다. 액상 조성물을 혼합 용기에서 600 rpm으로 충분히 혼합한 뒤, 2,2'-아조비스(2,4-디메틸발레로니트릴) 18 중량부를 첨가하였다. 중합혼합용액을 55 ℃까지 천천히 상승시켜, 이 온도로 24시간 동안 유지 후 상온으로 냉각하고 중합금지제로 하이드로벤조페논을 500 ppm 첨가하여 고형분 농도가 30 중량%인 중합체용액를 얻었다. A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. The liquid composition was thoroughly mixed at 600 rpm in a mixing container, and then 18 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55°C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone as a polymerization inhibitor was added to obtain a polymer solution with a solid content concentration of 30% by weight.

중합체용액의 미반응 단량체를 제거하기 위하여 n-헥산을 1000중량부에 대하여 중합체용액 100중량부를 침전시킨다. 침전 후, 메쉬를 이용한 여과공정을 통하여 미반응물이 용해된 빈 용매를 제거한다. 그 후, 여과공정 이후에도 남아있는 미반응 단량체가 함유된 용매들을 제거하기 위하여 30도 이하에서 진공 건조를 통해 완전히 제거하여 아크릴계 공중합체를 제조하였다.To remove unreacted monomers from the polymer solution, 100 parts by weight of the polymer solution are precipitated based on 1,000 parts by weight of n-hexane. After precipitation, empty solvent in which unreacted substances are dissolved is removed through a filtration process using a mesh. Afterwards, in order to remove the solvent containing unreacted monomers that remained even after the filtration process, they were completely removed through vacuum drying at 30 degrees or lower to prepare an acrylic copolymer.

아크릴계 공중합체의 중량평균분자량은 2,500이었다. 이때, 중량평균분자량은 GPC를 사용하여 측정한 폴리스티렌 환산평균분자량이다 The weight average molecular weight of the acrylic copolymer was 2,500. At this time, the weight average molecular weight is the average molecular weight converted to polystyrene measured using GPC.

[비교합성예 2] 아크릴계 공중합체(E) 제조 [Comparative Synthesis Example 2] Preparation of acrylic copolymer (E)

냉각기와 교반기가 구비된 플라스크에 테트라하이드로퓨란 400 중량부, 메타크릴산 30 중량부와 스티렌 30 중량부, 및 글리시딜메타크릴레이트 40 중량부의 혼합 용액을 투입하였다. 액상 조성물을 혼합 용기에서 600 rpm으로 충분히 혼합한 뒤, 2,2'-아조비스(2,4-디메틸발레로니트릴) 1.5 중량부를 첨가하였다. 중합혼합용액을 55 ℃까지 천천히 상승시켜, 이 온도로 24시간 동안 유지 후 상온으로 냉각하고 중합금지제로 하이드로벤조페논을 500 ppm 첨가하여 고형분 농도가 30 중량%인 중합체용액를 얻었다. A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. The liquid composition was thoroughly mixed at 600 rpm in a mixing container, and then 1.5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55°C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone as a polymerization inhibitor was added to obtain a polymer solution with a solid content concentration of 30% by weight.

중합체용액의 미반응 단량체를 제거하기 위하여 n-헥산을 1000중량부에 대하여 중합체용액 100중량부를 침전시킨다. 침전후, 메쉬를 이용한 여과공정을 통하여 미반응물이 용해된 빈 용매를 제거한다. 그 후, 여과공정 이후에도 남아있는 미반응 단량체가 함유된 용매들을 제거하기 위하여 30도 이하에서 진공 건조를 통해 완전히 제거하여 아크릴계 공중합체를 제조하였다.To remove unreacted monomers from the polymer solution, 100 parts by weight of the polymer solution are precipitated based on 1,000 parts by weight of n-hexane. After precipitation, empty solvent in which unreacted substances are dissolved is removed through a filtration process using a mesh. Afterwards, in order to remove the solvent containing unreacted monomers that remained even after the filtration process, they were completely removed through vacuum drying at 30 degrees or lower to prepare an acrylic copolymer.

아크릴계 공중합체의 중량평균분자량은 22,000이었다. 이때, 중량평균분자량은 GPC를 사용하여 측정한 폴리스티렌 환산평균분자량이다. The weight average molecular weight of the acrylic copolymer was 22,000. At this time, the weight average molecular weight is the polystyrene conversion average molecular weight measured using GPC.

[실험예 1] 포지티브 감광성 수지 조성물 제조 [Experimental Example 1] Preparation of positive photosensitive resin composition

합성예 1에서 제조한 아크릴계 공중합체(A) 100 중량부에 대하여,합성예 5에서 제조한 공중합체(A) 15 중량부, 합성예 4에서 제조한 4,4’-[1-[4-[1-[4-히드록시페닐]-1-메틸에틸]페닐]에틸리덴]비스페놀 1,2-나프토퀴논디아지드-5-술폰산 에스테르 30 중량부 및 실란커플링제로 (3-글리시드옥시프로필)트리메톡시실란 3 중량부를 혼합물의 고형분 함량이 20 중량%가 되도록 프로필렌글리골모노메틸에테르아세테이트로 용해시킨 후, 0.1 ㎛의 밀리포아필터로 여과하여 감광성 수지 조성물을 제조하였다.Based on 100 parts by weight of the acrylic copolymer (A) prepared in Synthesis Example 1, 15 parts by weight of the copolymer (A) prepared in Synthesis Example 5, 4,4'-[1-[4- prepared in Synthesis Example 4 [1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight and silane coupling agent (3-glycidoxy 3 parts by weight of propyl)trimethoxysilane was dissolved in propylene glycol monomethyl ether acetate so that the solid content of the mixture was 20% by weight, and then filtered through a 0.1 ㎛ Millipore filter to prepare a photosensitive resin composition.

[실험예 2] 포지티브 감광성 수지 조성물 제조 [Experimental Example 2] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 6의 공중합체(B)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (B) of Synthesis Example 6 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실험예 3] 포지티브 감광성 수지 조성물 제조 [Experimental Example 3] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 7의 공중합체(C)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (C) of Synthesis Example 7 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실험예 4] 포지티브 감광성 수지 조성물 제조 [Experimental Example 4] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 8의 공중합체(D)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (D) of Synthesis Example 8 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실험예 5] 포지티브 감광성 수지 조성물 제조 [Experimental Example 5] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 9의 공중합체(E)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (E) of Synthesis Example 9 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실시예 6] 포지티브 감광성 수지 조성물 제조 [Example 6] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 10의 공중합체(F)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (F) of Synthesis Example 10 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실시예 7] 포지티브 감광성 수지 조성물 제조 [Example 7] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 11의 공중합체(G)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (G) of Synthesis Example 11 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실시예 8] 포지티브 감광성 수지 조성물 제조 [Example 8] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 12의 공중합체(H)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (H) of Synthesis Example 12 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실시예 9] 포지티브 감광성 수지 조성물 제조 [Example 9] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 13의 공중합체(I)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (I) of Synthesis Example 13 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실험예 10] 포지티브 감광성 수지 조성물 제조 [Experimental Example 10] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 14의 공중합체(J)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (J) of Synthesis Example 14 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실험예 11] 포지티브 감광성 수지 조성물 제조 [Experimental Example 11] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 5의 공중합체(A)를 대신하여 합성예 15의 공중합체(K)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (K) of Synthesis Example 15 was used instead of the copolymer (A) of Synthesis Example 5 in Experimental Example 1.

[실험예 12] 포지티브 감광성 수지 조성물 제조 [Experimental Example 12] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 1의 공중합체(A)를 대신하여 합성예 16의 공중합체(L)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the copolymer (L) of Synthesis Example 16 was used instead of the copolymer (A) of Synthesis Example 1.

[실험예 13] 포지티브 감광성 수지 조성물 제조 [Experimental Example 13] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 1의 아크릴계 공중합체(A)를 대신하여 합성예 2의 아크릴계 공중합체(B)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the acrylic copolymer (B) of Synthesis Example 2 was used instead of the acrylic copolymer (A) of Synthesis Example 1.

[실험예 14] 포지티브 감광성 수지 조성물 제조 [Experimental Example 14] Preparation of positive photosensitive resin composition

실험예 1에서 합성예 1의 아크릴계 공중합체(A)를 대신하여 합성예 3의 아크릴계 공중합체(C)를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as in Experimental Example 1, except that the acrylic copolymer (C) of Synthesis Example 3 was used instead of the acrylic copolymer (A) of Synthesis Example 1.

[비교예 1] 포지티브 감광성 수지 조성물 제조 [Comparative Example 1] Preparation of positive photosensitive resin composition

합성예 1에서 제조한 아크릴계 공중합체(A) 100 중량부에 대하여, 합성예 4에서 제조한 4,4’-[1-[4-[1-[4-히드록시페닐]-1-메틸에틸]페닐]에틸리덴]비스페놀 1,2-나프토퀴논디아지드-5-술폰산 에스테르 30 중량부 및 실란커플링제로 (3-글리시드옥시프로필)트리메톡시실란 3 중량부를 혼합물의 고형분 함량이 20 중량%가 되도록 프로필렌글리골모노메틸에테르아세테이트로 용해시킨 후, 0.1 ㎛의 밀리포아필터로 여과하여 감광성 수지 조성물을 제조하였다.For 100 parts by weight of the acrylic copolymer (A) prepared in Synthesis Example 1, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl prepared in Synthesis Example 4 ]phenyl]ethylidene]bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight and (3-glycidoxypropyl)trimethoxysilane as a silane coupling agent 3 parts by weight so that the solid content of the mixture is 20 After dissolving the solution in propylene glycol monomethyl ether acetate to a weight percent, it was filtered through a 0.1 ㎛ Millipore filter to prepare a photosensitive resin composition.

[비교예 2] 포지티브 감광성 수지 조성물 제조 [Comparative Example 2] Preparation of positive photosensitive resin composition

비교예 1에서 합성예 1의 아크릴계 공중합체(A)를 대신하여 합성예 2의 아크릴계 공중합체(B)를 사용한 것을 제외하고는 비교예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as Comparative Example 1, except that the acrylic copolymer (B) of Synthesis Example 2 was used instead of the acrylic copolymer (A) of Synthesis Example 1.

[비교예 3] 포지티브 감광성 수지 조성물 제조 [Comparative Example 3] Preparation of positive photosensitive resin composition

비교예 1에서 합성예 1의 아크릴계 공중합체(A)를 대신하여 합성예 3의 아크릴계 공중합체(C)를 사용한 것을 제외하고는 비교예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as Comparative Example 1, except that the acrylic copolymer (C) of Synthesis Example 3 was used instead of the acrylic copolymer (A) of Synthesis Example 1.

[비교예 4] 포지티브 감광성 수지 조성물 제조 [Comparative Example 4] Preparation of positive photosensitive resin composition

비교예 1에서 합성예 1의 아크릴계 공중합체(A)를 대신하여 비교합성예 1의 아크릴계 공중합체(D)를 사용한 것을 제외하고는 비교예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as Comparative Example 1, except that the acrylic copolymer (D) of Comparative Synthesis Example 1 was used instead of the acrylic copolymer (A) of Synthesis Example 1.

[비교예 5] 포지티브 감광성 수지 조성물 제조 [Comparative Example 5] Preparation of positive photosensitive resin composition

비교예 1에서 합성예 1의 아크릴계 공중합체(A)를 대신하여 비교합성예 2의 아크릴계 공중합체(E)를 사용한 것을 제외하고는 비교예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.A photosensitive resin composition was prepared in the same manner as Comparative Example 1, except that the acrylic copolymer (E) of Comparative Synthesis Example 2 was used instead of the acrylic copolymer (A) of Synthesis Example 1.

[비교예 6] 포지티브 감광성 수지 조성물 제조 [Comparative Example 6] Preparation of positive photosensitive resin composition

합성예 1에서 제조한 아크릴계 공중합체(A) 100 중량부에 대하여, 합성예 5에서 제조한 공중합체(A) 3 중량부, 합성예 4에서 제조한 4,4’-[1-[4-[1-[4-히드록시페닐]-1-메틸에틸]페닐]에틸리덴]비스페놀 1,2-나프토퀴논디아지드-5-술폰산 에스테르 30 중량부 및 실란커플링제로 (3-글리시드옥시프로필)트리메톡시실란 3 중량부를 혼합물의 고형분 함량이 20 중량%가 되도록 프로필렌글리골모노메틸에테르아세테이트로 용해시킨 후, 0.1 ㎛의 밀리포아필터로 여과하여 감광성 수지 조성물을 제조하였다.Based on 100 parts by weight of the acrylic copolymer (A) prepared in Synthesis Example 1, 3 parts by weight of the copolymer (A) prepared in Synthesis Example 5, 4,4'-[1-[4- prepared in Synthesis Example 4 [1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight and silane coupling agent (3-glycidoxy 3 parts by weight of propyl)trimethoxysilane was dissolved in propylene glycol monomethyl ether acetate so that the solid content of the mixture was 20% by weight, and then filtered through a 0.1 ㎛ Millipore filter to prepare a photosensitive resin composition.

[비교예 7] 포지티브 감광성 수지 조성물 제조 [Comparative Example 7] Preparation of positive photosensitive resin composition

합성예 1에서 제조한 아크릴계 공중합체(A) 100 중량부에 대하여, 합성예 5에서 제조한 공중합체(A) 105 중량부, 합성예 4에서 제조한 4,4’-[1-[4-[1-[4-히드록시페닐]-1-메틸에틸]페닐]에틸리덴]비스페놀 1,2-나프토퀴논디아지드-5-술폰산 에스테르 30 중량부 및 실란커플링제로 (3-글리시드옥시프로필)트리메톡시실란 3 중량부를 혼합물의 고형분 함량이 20 중량%가 되도록 프로필렌글리골모노메틸에테르아세테이트로 용해시킨 후, 0.1 ㎛의 밀리포아필터로 여과하여 감광성 수지 조성물을 제조하였다.Based on 100 parts by weight of the acrylic copolymer (A) prepared in Synthesis Example 1, 105 parts by weight of the copolymer (A) prepared in Synthesis Example 5, 4,4'-[1-[4- prepared in Synthesis Example 4 [1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight and silane coupling agent (3-glycidoxy 3 parts by weight of propyl)trimethoxysilane was dissolved in propylene glycol monomethyl ether acetate so that the solid content of the mixture was 20% by weight, and then filtered through a 0.1 ㎛ Millipore filter to prepare a photosensitive resin composition.

실험예 1 내지 14 및 비교예 1 내지 5에 대하여 감도, 해상도, 경화공정마진, 투과도, 내열변색성, 접착력, 내열성 등의 물성을 측정하여 하기 표 1에 나타내었다. 글래스(glass) 기판 상에 스핀코터를 사용하여 실험예 1 내지 15 및 비교예 1내지 17에서 감광성 수지 조성물을 도포한 뒤, 100 ℃로 2분간 핫 플레이트상에서 프리베이크하여 두께가 3.0 ㎛인 막을 형성하였다.For Experimental Examples 1 to 14 and Comparative Examples 1 to 5, physical properties such as sensitivity, resolution, curing process margin, transmittance, heat discoloration resistance, adhesion, and heat resistance were measured and are shown in Table 1 below. The photosensitive resin compositions of Experimental Examples 1 to 15 and Comparative Examples 1 to 17 were applied on a glass substrate using a spin coater, and then prebaked on a hot plate at 100°C for 2 minutes to form a film with a thickness of 3.0 ㎛. did.

가) 감도 - 위와 같이 형성된 막에 소정 패턴 마스크(pattern mask)를 사용하여 Broadband에서의 강도가 20 ㎽/㎠인 자외선을 감도가 10 ㎛ Contact Hole CD기준 Dose량을 조사한 후, 테트라메틸 암모늄히드록시드 2.38 중량%의 수용액으로 23 ℃에서 1분간 현상한 후, 초순수로 1분간 세정하였다. a) Sensitivity - After irradiating the film formed as above with ultraviolet rays with an intensity of 20 mW/㎠ in Broadband using a predetermined pattern mask and the dose based on a contact hole CD with a sensitivity of 10 ㎛, tetramethyl ammonium hydroxide It was developed for 1 minute at 23°C with an aqueous solution containing 2.38% by weight of seeds, and then washed with ultrapure water for 1 minute.

그 다음, 에서 현상 된 패턴에 365 ㎚에서의 강도가 20 ㎽/㎠인 자외선을 400 mJ/㎠ 조사하고, 오븐속에서 230 ℃로 30분간 경화시켜 두께가 3.0 ㎛인 패턴 막을 얻었다.Next, the developed pattern was irradiated with 400 mJ/cm2 of ultraviolet rays with an intensity of 20 mW/cm2 at 365 nm, and cured in an oven at 230°C for 30 minutes to obtain a patterned film with a thickness of 3.0 ㎛.

나) 해상도 - 가)의 감도 측정시 형성된 10 ㎛ Contact Hole 패턴(Pattern)의 최소 크기로 측정하였다.B) Resolution - Measured as the minimum size of the 10 ㎛ Contact Hole Pattern formed during the sensitivity measurement in A).

다) 경화공정 마진 - 가)의 감도 측정시와 동일한 방법으로 패턴(Pattern)막을 형성하되 10 ㎛ Contact Hole CD기준으로 경화 전,후의 CD변화율을 측정하였다. 이때, 변화율이 0 ~ 10%인 경우를 ○10 ~ 20%인 경우를 △20%를 넘는 경우를 × 로 표시하였다.c) Curing process margin - A pattern film was formed in the same way as when measuring sensitivity in a), but the CD change rate before and after curing was measured based on a 10 ㎛ Contact Hole CD. At this time, cases where the rate of change was 0 to 10% were marked as ○10 to 20%, and cases where it exceeded △20% were marked as ×.

라) 투과도 - 투과도 평가는 가)의 감도 측정시 형성된 패턴(Pattern)막을 분광광도계를 이용하여 패턴 막의 400 ㎚의 투과율을 측정하였다. 이때의 투과율가 90% 이상인 경우를 ○85 ~ 90%인 경우를 △80% 미만은 경우를 × 로 표시하였다.d) Transmittance - For transmittance evaluation, the transmittance at 400 nm of the pattern film formed during the sensitivity measurement in a) was measured using a spectrophotometer. At this time, the case where the transmittance was 90% or more was marked as ○85 to 90%, and the case where it was less than △80% was marked as ×.

마) 내열변색성 - 라)의 투명성 평가시의 측정 기판에 추가로 230℃의 오븐에서 30분씩 2회 경화하여 경화 전후에 있어서의 패턴(Pattern)막의 400 nm투과율변화에 의해 내열변색성을 평가하였다. 이때의 변화율이 3% 미만인 경우를 ○3 ~ 5%인 경우를 △5%를 넘는 경우를 × 로 표시하였다.e) Heat discoloration resistance - In addition to the measurement substrate used in the transparency evaluation in d), the heat discoloration resistance is evaluated by curing twice in an oven at 230°C for 30 minutes each and measuring the change in transmittance of the pattern film at 400 nm before and after curing. did. At this time, cases where the change rate was less than 3% were marked as ○3 to 5%, and cases where it exceeded △5% were marked as ×.

바) 접착력 - 가)의 감도 측정시 형성된 패턴(Pattern)막을 Scope를 통하여 패턴 유실여부를 통해 접착력을 평가하였다.b) Adhesion - When measuring the sensitivity of a), the adhesion was evaluated through a scope on the pattern film formed to determine whether the pattern was lost.

프리베이크 온도가 95℃이상에서 접착력이 확보되는 경우를 ○, 100-105℃에서 접착력이 확보되는 경우를 △105℃를 초과하여 접착력이 확보되거나, 패턴이 유실되는 경우를 × 로 나타내었다.Cases where adhesion was secured at a prebake temperature of 95°C or higher were denoted as ○, cases where adhesion was secured at 100-105°C were denoted as ×, cases where adhesion was secured beyond △105°C or the pattern was lost were denoted as ×.

사) 내열성 - 내열성은 TGA를 이용하여 측정하였다. 가)의 감도 측정시 형성된 패턴(Pattern)막을 샘플링 한 후, TGA를 이용하여 상온에서 900℃까지 분당 10℃씩 승온하였다. 5 중량% Loss 온도가 300℃초과인 경우를 ○5 중량% Loss 온도가 280-300℃인 경우를 △5 중량% Loss 온도가 280℃미만인 경우를 × 로 나타내었다. G) Heat resistance - Heat resistance was measured using TGA. After sampling the pattern film formed during the sensitivity measurement in a), the temperature was raised at a rate of 10°C per minute from room temperature to 900°C using TGA. The case where the 5% by weight loss temperature is greater than 300℃ is indicated by ○, the case where the 5% by weight loss temperature is 280-300℃ is indicated by Δ, and the case where the 5% by weight loss temperature is less than 280℃ is indicated by ×.

구분division a)Acryl Resina)Acryl Resin b) 공중합체b) copolymer 감도
(mJ/cm2)Sensitivity
(mJ/ cm2 ) 해상도
(um)resolution
(um) 경화공정
마진Hardening process
margin 투과도Transmittance 내열
변색성heat resistance
discoloration 접착력adhesion 내열성heat resistance 분자량Molecular Weight TypeType 분자량Molecular Weight 실험예 1Experimental Example 1 6,0006,000 AA 14,00014,000 8585 33 ○○ ○○ ○○ ○○ ○○ 실험예 2Experimental Example 2 6,0006,000 BB 10,00010,000 7575 33 ○○ ○○ ○○ ○○ ○○ 실험예 3Experimental Example 3 6,0006,000 CC 6,0006,000 6565 33 ○○ ○○ ○○ ○○ ○○ 실험예 4Experimental Example 4 6,0006,000 DD 14,00014,000 9595 33 ○○ ○○ ○○ ○○ ○○ 실험예 5Experimental Example 5 6,0006,000 EE 10,00010,000 9090 33 ○○ ○○ ○○ ○○ ○○ 실험예 6Experimental Example 6 6,0006,000 FF 6,0006,000 8080 33 ○○ ○○ ○○ ○○ ○○ 실험예 7Experimental Example 7 6,0006,000 GG 14,00014,000 7575 33 ○○ ○○ ○○ ○○ ○○ 실험예 8Experimental Example 8 6,0006,000 HH 10,00010,000 6565 33 ○○ ○○ ○○ ○○ ○○ 실험예 9Experimental Example 9 6,0006,000 II 6,0006,000 5555 33 ○○ ○○ ○○ ○○ ○○ 실험예 10Experimental Example 10 6,0006,000 JJ 14,00014,000 7070 33 ○○ ○○ ○○ ○○ ○○ 실험예 11Experimental Example 11 6,0006,000 KK 10,00010,000 6060 33 ○○ ○○ ○○ ○○ ○○ 실험예 12Experimental Example 12 6,0006,000 LL 6,0006,000 5050 33 ○○ ○○ ○○ ○○ ○○ 실험예 13Experimental Example 13 10,00010,000 AA 14,00014,000 8585 33 ○○ ○○ ○○ ○○ ○○ 실험예 14Experimental Example 14 16,00016,000 AA 14,00014,000 9090 33 ○○ ○○ ○○ ○○ ○○ 비교예 1Comparative Example 1 6,0006,000 -- -- 140140 33 ○○ ○○ ○○ ○○ ○○ 비교예 2Comparative Example 2 10,00010,000 -- -- 132132 33 ○○ ○○ ○○ ○○ ○○ 비교예 3Comparative Example 3 16,00016,000 -- -- 130130 33 ○○ ○○ ○○ ○○ ○○ 비교예 4Comparative Example 4 2,5002,500 -- -- 140140 55 ×× ○○ ○○ ×× ×× 비교예 5Comparative Example 5 22,00022,000 -- -- 155155 33 ○○ ○○ ○○ ×× ○○ 비교예 6Comparative Example 6 6,0006,000 AA 14,00014,000 135135 33 ○○ ○○ ○○ ○○ ○○ 비교예 7Comparative Example 7 6,0006,000 AA 14,00014,000 5050 33 ○○ △△ ×× ○○ ○○

표 1을 통하여, 본 발명에 따라 실험예 1 내지 14에서 제조한 포지티브형 감광성 절연막 조성물은 감도, 해상도, 경화공정마진, 투과도, 내열변색성, 접착력, 내열성 등의 성능이 모두 우수하였다. 또한, 비교예 1 내지 7은실험예 1 내지 14와 비교하였을 때 감도가 떨어졌고, 비교예 4는 경화공정마진과 접착력, 내열성이 떨어졌으며 비교예 5는 접착력이 떨어졌다. 비교예 6은 b) 공중합체 함량이 5% 미만이라 감도가 떨어지는 결과를 보였고 비교예 7은 b) 공중합체 함량이 100%를 초과하여 내열변색성 마진이 떨어지는 결과를 보였다. As shown in Table 1, the positive photosensitive insulating film compositions prepared in Experimental Examples 1 to 14 according to the present invention were all excellent in sensitivity, resolution, curing process margin, transmittance, heat discoloration resistance, adhesion, and heat resistance. In addition, Comparative Examples 1 to 7 had lower sensitivity compared to Experimental Examples 1 to 14, Comparative Example 4 had lower curing process margin, adhesion, and heat resistance, and Comparative Example 5 had lower adhesion. Comparative Example 6 showed a result of poor sensitivity because b) copolymer content was less than 5%, and Comparative Example 7 showed a result of poor heat discoloration resistance margin because b) copolymer content exceeded 100%.

실험예 1 내지 14는 감도가 비교예 1 내지 7와 비교하여 우수함으로써, 공정 시간(tact)를 단축할 수 있으며, 해상도, 접착력, 내열성이 양호하여 우수한 공정(Process) 마진을 확보할 수 있었다. 이를 통해 다양한 디스플레이 공정에서 감광성 수지조성물이 적용 가능함을 알 수 있었다.Experimental Examples 1 to 14 had superior sensitivity compared to Comparative Examples 1 to 7, allowing the process time (tact) to be shortened, and excellent process margins to be secured due to good resolution, adhesion, and heat resistance. Through this, it was found that the photosensitive resin composition can be applied in various display processes.

Claims (12)

감광성 수지 조성물에 있어서,
a)ⅰ) 불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물;
ⅱ) 에폭시기 함유 불포화 화합물; 및
ⅲ) 올레핀계 불포화 화합물을 공중합시켜 얻어진 아크릴계 공중합체;
b) 하기 화학식 1로 표시되는 공중합체 ;
c) 1,2-퀴논디아지드 화합물; 및
d) 용매를 포함하며,
상기 b)의 공중합체는, 상기 a)아크릴계 공중합체 100 중량부에 대하여 5 내지 100 중량부로 포함되는 감광성 수지 조성물:
[화학식 1]

(상기 화학식 1에서, a, b, c는 각 모노머 간의 몰비(mole ratio)를 나타내는 것으로, a는 1 내지 10이고, b, c는 각각 0 내지 9이며, a+b+c=10 이다. n은 1 내지 10이며, R은 H 또는 CH3 이다.).
In the photosensitive resin composition,
a)i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;
ii) an unsaturated compound containing an epoxy group; and
iii) an acrylic copolymer obtained by copolymerizing an olefinically unsaturated compound ;
b) a copolymer represented by the following formula (1) ;
c) 1,2-quinonediazide compounds; and
d) contains a solvent,
The photosensitive resin composition wherein the copolymer of b) is included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the a) acrylic copolymer:
[Formula 1]

(In Formula 1, a, b, and c represent the mole ratio between each monomer, where a is 1 to 10, b and c are each 0 to 9, and a+b+c=10. n is 1 to 10, and R is H or CH 3. ).
 제 1항에 있어서,
a)ⅰ불포화 카르본산, 불포화 카르본산 무수물, 또는 이들의 혼합물 5 내지 40 중량부;
ⅱ) 에폭시기 함유 불포화 화합물 10 내지 70 중량부; 및
ⅲ) 올레핀계 불포화 화합물 5 내지 70 중량부를 공중합시켜 얻어진 아크릴계 공중합체 100 중량부;
b) 상기 화학식 1로 표시되는 공중합체 5 내지 100 중량부;
c) 1,2-퀴논디아지드 화합물 5 내지 100 중량부; 및
d) 용매를 감광성 수지 조성물 내의 고형분의 함량이 10 내지 50 중량%가 되도록 포함하는 감광성 수지 조성물.
According to clause 1,
a) 5 to 40 parts by weight of i unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof;
ii) 10 to 70 parts by weight of an epoxy group-containing unsaturated compound; and
iii) 100 parts by weight of an acrylic copolymer obtained by copolymerizing 5 to 70 parts by weight of an olefinic unsaturated compound;
b) 5 to 100 parts by weight of a copolymer represented by Formula 1;
c) 5 to 100 parts by weight of a 1,2-quinonediazide compound; and
d) A photosensitive resin composition containing a solvent such that the solid content in the photosensitive resin composition is 10 to 50% by weight.
 제 1항에 있어서,
상기 a)ⅰ불포화 카르본산, 불포화 카르본산 무수물 또는 이들의 혼합물이 아크릴산, 메타크릴산, 말레인산, 푸마르산, 시트라콘산, 메타콘산, 이타콘산, 및 이들의 불포화 디카르본산의 무수물로 이루어지는 군으로부터 1 종 이상 선택되는 것인, 감광성 수지 조성물.
According to clause 1,
a) ⅰunsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof are selected from the group consisting of anhydrides of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, and unsaturated dicarboxylic acids thereof. A photosensitive resin composition selected from one or more types.
 제 1항에 있어서, 상기 a)ⅱ의 에폭시기 함유 불포화 화합물이 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸아크릴산 글리시딜, α-n-프로필아크릴산 글리시딜, α-n-부틸아크릴산 글리시딜, 아크릴산-β메틸글리시딜, 메타크릴산-β메틸글리시딜, 아크릴산-β에틸글리시딜, 메타크릴산-β에틸글리시딜, 아크릴산-3,4-에폭시부틸, 메타크릴산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸, α-에틸아크릴산-6,7-에폭시헵틸, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르, 및 p-비닐벤질글리시딜에테르, 메타크릴산 3,4-에폭시 사이클로헥실, 메타크릴산 3,4-에폭시 사이클로헥실메틸, 아크릴산 3,4-에폭시 사이클로헥실, 아크릴산 3,4-에폭시 사이클로헥실메틸로 이루어지는 군으로부터 1 종 이상 선택되는 것인, 감광성 수지 조성물.
The method of claim 1, wherein the epoxy group-containing unsaturated compound of a) ii is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, and α-n- Glycidyl butylacrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate. , methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycylate Dyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether, 3,4-epoxy cyclohexyl methacrylic acid, 3,4-epoxy cyclohexylmethyl methacrylic acid, 3,4-acrylic acid. A photosensitive resin composition selected from the group consisting of epoxy cyclohexyl and 3,4-epoxy cyclohexylmethyl acrylic acid.
 제 1항에 있어서,
상기 a)ⅲ의 올레핀계 불포화 화합물이 메틸메타크릴레이트, 에틸메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, tert-부틸 메타크릴레이트, 메틸아크릴레이트, 이소프로필 아크릴레이트, 시클로헥실 메타크릴레이트, 2-메틸시클로 헥실메타크릴레이트, 디시클로펜테닐아크릴레이트, 디시클로펜타닐아크릴레이트, 디시클로펜테닐메타크릴레이트, 디시클로펜타닐메타크릴레이트, 1-아다만틸 아크릴레이트, 1-아다만틸 메타크릴레이트, 3-하이드록시 1-아다만틸 메타크릴레이트, 3-하이드록시 1-아다만틸 아크릴레이트, 5-하이드록시 1-아다만틸 메타크릴레이트, 5-하이드록시 1-아다만틸 아크릴레이트, 3,5-하이드록시 1-아다만틸메타크릴레이트, 3,5-하이드록시 1-아다만틸 아크릴레이트, 디시클로펜타닐옥시에틸메타크릴레이트, 이소보로닐메타크릴레이트, 시클로헥실아크릴레이트, 2-메틸시클로헥실아크릴레이트, 디시클로펜타닐옥시에틸아크릴레이트, 이소보로닐아크릴레이트, 페닐메타크릴레이트, 페닐아크릴레이트, 벤질아크릴레이트, 2-하이드록시에틸메타크릴레이트, 스티렌, σ-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐톨루엔, p-메톡시 스티렌, 1,3-부타디엔, 이소프렌, 및 2,3-디메틸 1,3-부타디엔으로 이루어지는 군으로부터 1 종 이상 선택되는 것인, 감광성 수지 조성물.
According to clause 1,
The olefinically unsaturated compounds of a) iii include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate , 1-adamantyl methacrylate, 3-hydroxy 1-adamantyl methacrylate, 3-hydroxy 1-adamantyl acrylate, 5-hydroxy 1-adamantyl methacrylate, 5- Hydroxy 1-adamantyl acrylate, 3,5-hydroxy 1-adamantyl methacrylate, 3,5-hydroxy 1-adamantyl acrylate, dicyclopentanyloxyethyl methacrylate, isobor Ronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isoboronyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hyde Roxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, and 2,3-dimethyl 1,3- A photosensitive resin composition selected from the group consisting of butadiene.
 제 1항에 있어서,
상기 a)의 아크릴계 공중합체의 폴리스티렌 환산중량평균분자량(Mw)이 3,000 내지 20,000인 감광성 수지 조성물.
According to clause 1,
A photosensitive resin composition wherein the acrylic copolymer of a) has a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 20,000.
 제 1항에 있어서,
상기 c)의 1,2-퀴논디아지드 화합물이 1,2-퀴논디아지드 4-술폰산 에스테르, 1,2-퀴논디아지드 5-술폰산 에스테르, 및 1,2-퀴논디아지드 6-술폰산 에스테르로 이루어지는 군으로부터 1종 이상 선택되는 것인, 감광성 수지 조성물.
According to clause 1,
The 1,2-quinonediazide compound of c) is composed of 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide 6-sulfonic acid ester. A photosensitive resin composition selected from the group consisting of at least one member.
 제 1항에 있어서,
상기 d)의 용매가 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르프로피오네이트, 프로필렌글리콜메틸에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르, 디프로필렌글리콜디메틸에테르, 디포로필렌글리콜디에틸에테르, 부틸렌글리콜모노메틸에테르, 부틸렌글리콜모노에틸에테르, 디부틸렌글리콜디메틸에테르, 및 디부틸렌글리콜디에틸에테르, 디에틸렌글리콜부틸 메틸에테르, 디에틸렌글리콜부틸에틸에테르, 트리에틸렌글리콜디메틸에테르, 트리에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜터셔리부틸에테르, 테트라에틸렌글리콜디메틸에테르, 디에틸렌글리콜에틸헥실에테르, 디에틸렌글리콜메틸헥실에테르, 디프로필렌글리콜부틸메틸에테르 디프로필렌글리콜에틸헥실에테르 , 및 디프로필렌 글리콜메틸헥실에테르로 이루어지는 군으로부터 1 종 이상 선택되는 것인, 감광성 수지 조성물.
According to clause 1,
The solvent in d) is diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propylene. Cypionate, propylene glycol propyl etherpropionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol monomethyl. Ether, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl. Ether, diethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butylmethyl ether, dipropylene glycol ethylhexyl ether, and dipropylene glycol methylhexyl ether. A photosensitive resin composition selected from the group consisting of at least one member.
 제 1항에 있어서,
e) 실란커플링제를 0.1 내지 50 중량부를 더 포함하는 감광성 수지 조성물.
According to clause 1,
e) A photosensitive resin composition further comprising 0.1 to 50 parts by weight of a silane coupling agent.
 제 9항에 있어서,
상기 e) 실란커플링제가 (3-글리시드옥시프로필)트리메톡시실란, (3-글리시드옥시프로필)트리에톡시실란, (3-글리시드옥시프로필)메틸디메톡시실란, (3-글리시드옥시프로필)메틸디에톡시실란, (3-글리시드옥시프로필)디메틸에톡시실란, 3,4-에폭시부틸트리메톡시실레인, 3,4-에폭시부틸트리에톡시실란, 2-(3,4-에폭시시크로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시크로헥실)에틸트리에톡시실란, 아미노프로필트리메톡시실란, 아미노프로필트리에톡시실란, 3-트리에톡시실리-N-(1,3 디메틸-부틸리덴)프로필아민, N-2(아미노에틸)3-아미노프로필트리메톡시실란, N-2(아미노에틸)3-아미노프로필트리에톡시실란, N-2(아미노에틸)3-아미노프로필메틸디메톡시실란, N-페닐-3-아미노프로필트리메톡시실레인, (3-이소시아네이트프로필)트리에톡시실란으로 이루어지는 군으로부터 1종 이상 선택되는 것인, 감광성 수지 조성물.
According to clause 9,
The above e) silane coupling agent is (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl) Seedoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3, 4-Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-triethoxy Sicily-N-(1,3 dimethyl-butylidene)propylamine, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, N -2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and (3-isocyanate propyl)triethoxysilane. , photosensitive resin composition.
 제 1항 내지 제 10항 중 어느 한 항의 감광성 수지 조성물의 경화체를 포함하는 것을 특징으로 하는 디스플레이(display).
A display comprising a cured body of the photosensitive resin composition of any one of claims 1 to 10.
 제 1항 내지 제 10항 중 어느 한 항의 감광성 수지 조성물을 이용한 디스플레이(display)의 패턴형성방법.A method of forming a pattern for a display using the photosensitive resin composition of any one of claims 1 to 10.
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