KR20090061878A - Alkali developable resins and photosensitive composition comprising the same - Google Patents
Alkali developable resins and photosensitive composition comprising the same Download PDFInfo
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Abstract
Description
본 발명은 알칼리 가용성 수지 및 이를 포함하는 감광성 수지 조성물에 대한 것이다.The present invention relates to an alkali-soluble resin and a photosensitive resin composition comprising the same.
감광성 수지 조성물은 컬러필터용 감광재나 블랙 매트릭스용 감광재 뿐 아니라 오버코트 및 컬럼 스페이서 등에도 다양하게 사용될 수 있다.The photosensitive resin composition may be variously used for overcoats and column spacers as well as photoresists for color filters and photoresists for black matrices.
이러한 감광성 수지조성물은 빛에 의해 가교반응을 개시할 수 있는 광개시제와, 가교반응에 직접적으로 참여하는 에틸렌성 불포화 결합을 갖는 중합성 화합물 및 현상액에 의해 용해될 수 있는 알칼리 가용성 수지 등을 포함하고 있다.Such a photosensitive resin composition includes a photoinitiator capable of initiating a crosslinking reaction by light, a polymerizable compound having an ethylenically unsaturated bond directly participating in the crosslinking reaction, an alkali-soluble resin that can be dissolved by a developer, and the like. .
이때 사용되는 알칼리 가용성 수지는 현상 공정 단계에서 비노광 부위가 현상액에 의해 녹아 나갈 수 있도록 하는 역할 이외에도, 조성물 내에 포함되어 있는 여러가지 화합물 간의 상용성이나, 기판 위에 도포 시의 코팅성, 기판과 수지 조성물과의 접착성 등을 결정하는 역할도 동시에 한다.Alkali-soluble resin used at this time is in addition to the role that the non-exposed site can be dissolved by the developer in the development process step, the compatibility between the various compounds contained in the composition, the coating property when coating on the substrate, the substrate and the resin composition It also plays a role in determining adhesiveness and the like.
최근에는 컬러필터용 감광재에 보다 높은 선명도와 고색재현율을 요구하고 있는데, 블랙 매트릭스용 감광재 역시 보다 높은 차광성이 요구됨에 따라 감광성 조성물 내에 컬러 안료 또는 카본 블랙의 함량이 점점 높아지고 있는 실정이다.Recently, the sharpness and high color reproducibility are required for the color filter photoresist, and the black matrix photoresist is also required to have a higher content of color pigments or carbon black in the photosensitive composition as higher light shielding properties are required.
감광성 수지 조성물 내의 안료의 함량이 높아질수록 상대적으로 안료 외의 성분인 광개시제나 중합성 화합물, 바인더 등의 함량이 줄어들 수 밖에 없게 되는데, 그 결과 기판과 수지 조성물과의 접착성이 떨어지는 문제가 생긴다.As the content of the pigment in the photosensitive resin composition increases, the content of a photoinitiator, a polymerizable compound, a binder, and the like, which are components other than the pigment, is inevitably decreased. As a result, the adhesion between the substrate and the resin composition is inferior.
따라서, 현상성, 상용성, 코팅성을 유지하면서도 우수한 접착성까지 동시에 가지는 알칼리 가용성 수지 및 이를 포함하는 감광성 수지 조성물이 절실히 필요하다.Therefore, there is an urgent need for an alkali-soluble resin having a good adhesiveness while maintaining developability, compatibility, and coating property, and a photosensitive resin composition including the same.
본 발명이 해결하고자 하는 과제는 현상성, 상용성, 코팅성을 유지하면서도 접착성이 우수한 알칼리 가용성 수지 및 이를 포함하는 감광성 수지 조성물을 제공하는 것이다.The problem to be solved by the present invention is to provide an alkali-soluble resin and a photosensitive resin composition comprising the same while maintaining developability, compatibility, coating properties.
본 발명에 의한 알칼리 가용성 수지는,다음의 화학식 1 내지 화학식 3으로 표시되는 반복단위를 포함한다.Alkali-soluble resin by this invention contains the repeating unit represented by following formula (1)-(3).
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 1 내지 화학식 3에서,In
A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기, 이소보닐 옥시 카보닐기 중에서 선택되고,A is selected from phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbonyl group, cyclohexyl oxy carbonyl group, isobornyl oxy carbonyl group,
X1, X2는 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택되고, X 1 , X 2 are selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group,
Y는 탄소수 1~3의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이며,Y is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide having 1 to 3 carbon atoms,
Z는 탄소수 1~3의 알킬렌, 사이클로 헥센, 사이클로 헥산 및 벤젠기에서 선택된다.Z is selected from alkylene, cyclohexene, cyclohexane and benzene groups having 1 to 3 carbon atoms.
R1 및 R2는 수소 또는 하이드록시기이다.R 1 and R 2 are hydrogen or a hydroxyl group.
또한, 상기 알칼리 가용성 수지는, 다음의 화학식 4로 표시되고, a, b, c는 몰혼합비로서 각각 10~40일 수 잇다.In addition, the alkali-soluble resin is represented by the following formula (4), a, b, c may be 10 to 40, respectively, as a molar mixing ratio.
[화학식 4][Formula 4]
상기 화학식 4에서, A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기, 이소보닐 옥시 카보닐기 중에서 선택되고, X1, X2는 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택되고, Y는 탄소수 1~3의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이며, Z는 탄소수 1~3의 알킬렌, 사이클로 헥센, 사이클로 헥산 및 벤젠기에서 선택된다. R1 및 R2는 수소 또는 하이드록시기이다.In Formula 4, A is selected from phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbonyl group, cyclohexyl oxy carbonyl group, isobornyl oxy carbonyl group X 1 and X 2 are selected from hydrogen, an alkyl group having 1 to 3 carbon atoms and an alkoxy group, and Y is one selected from the group consisting of alkylene having 1 to 3 carbon atoms, ethylene oxide and propylene oxide, and Z is 1 carbon atom. ˜3 alkylene, cyclohexene, cyclohexane and benzene groups. R 1 and R 2 are hydrogen or a hydroxyl group.
또한, 상기 화학식 1로 표시되는 단위체는 스티렌, 벤질(메타)아크릴레이트, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, t-부틸 (메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트 중에서 1종 이상 선택될 수 있다.In addition, the unit represented by the formula (1) is styrene, benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, At least one selected from cyclohexyl (meth) acrylate and isobonyl (meth) acrylate can be selected.
또한, 상기 알칼리 가용성 수지의 산가는 30~200 KOH mg/g이고, 중량 평균 분자량은 1,000~200,000 g/mol의 범위를 가질 수 있다.In addition, the acid value of the alkali-soluble resin is 30 ~ 200 KOH mg / g, the weight average molecular weight may have a range of 1,000 ~ 200,000 g / mol.
본 발명에 의한 알칼리 가용성 수지의 제조방법은, a) 화학식 1로 표시되는 단위체와, 에폭시기를 포함하는 단위체를 중합하여 고분자를 제조하는 단계와, b) 상기 a)단계에서 제조된 고분자에 카복실산 화합물을 투입하여 고분자를 제조하는 단계와, c) 상기 b)단계에서 합성된 고분자에 고리형 무수물을 투입하여 산기를 형성하는 단계를 포함한다.The method for preparing an alkali-soluble resin according to the present invention comprises the steps of: a) polymerizing a unit represented by Chemical Formula 1 and a unit including an epoxy group to prepare a polymer, and b) a carboxylic acid compound in the polymer prepared in step a). Step of preparing a polymer, and c) adding a cyclic anhydride to the polymer synthesized in step b) to form an acid group.
또한, 상기 a)단계에서 상기 에폭시기를 포함하는 단위체는 화학식 5로 표시될 수 있다.In addition, the unit including the epoxy group in step a) may be represented by the formula (5).
[화학식 5][Formula 5]
X1은 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택되고, Y는 탄소수 1~3의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.X 1 is selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group, and Y is one selected from the group consisting of alkylene having 1 to 3 carbon atoms, ethylene oxide, and propylene oxide.
또한, 상기 b)단계에서 상기 카복실산 화합물은 다음의 화학식 6 및 화학식 7로 표시되는 화합물을 하나 이상 포함할 수 있다.In addition, the carboxylic acid compound in step b) may include one or more compounds represented by the following formula (6) and formula (7).
[화학식 6][Formula 6]
[화학식 7][Formula 7]
상기 화학식 6 및 화학식 7에서, X2는 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택되고, R1 및 R2는 수소 또는 하이드록시기이다.In
또한, 상기 c)단계에서 상기 고리형 무수물은, 숙신산 무수물, 테트라하이드로 프탈산 무수물, 말릭산 무수물, 프탈산 무수물 중에서 1종 이상 선택될 수 있다.In addition, the cyclic anhydride in step c) may be selected from one or more of succinic anhydride, tetrahydro phthalic anhydride, malic anhydride, phthalic anhydride.
또한 상기 알칼리 가용성 수지의 제조방법은 라디칼 중합 개시제를 이용하는 라디칼 중합에 의할 수 있다.Moreover, the manufacturing method of the said alkali-soluble resin can be based on radical polymerization using a radical polymerization initiator.
상기 라디칼 중합 개시제는 2,2'-아조비스이소부티로니트릴, s,s'-아조비스-(2,4-디메틸발레로니트릴), 벤조일퍼옥사이드 중에서 선택되는 1종 이상인 것일 수 있다.The radical polymerization initiator may be one or more selected from 2,2'-azobisisobutyronitrile, s, s'-azobis- (2,4-dimethylvaleronitrile), and benzoyl peroxide.
본 발명에 의한 감광성 수지 조성물은 상기 알칼리 가용성 수지와, 에틸렌성 불포화 결합을 갖는 중합성 화합물과, 광개시제를 포함한다.The photosensitive resin composition which concerns on this invention contains the said alkali-soluble resin, the polymeric compound which has an ethylenically unsaturated bond, and a photoinitiator.
상기 에틸렌성 불포화 결합을 갖는 중합성 화합물은, 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 에틸렌 글리콜 디(메타)아크릴레이트, 폴리에틸렌 글리콜 디(메타)아크릴레이트 중에서 선택될 수 있다.The polymerizable compound having an ethylenically unsaturated bond may be selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Can be.
또한, 상기 광개시제는, 2,4-트리클로로메틸-(4’-메톡시페닐)-6-트리아진, 2,4-트리클로로메틸-(4’-메톡시스티릴)-6-트리아진, 2,4-트리클로로메틸-(피플로닐)-6-트리아진 등의 트리아진 화합물과, 1-히드록시시클로헥실 페닐 케톤, 4-(2-히드록시에톡시)-페닐 (2-히드록시)프로필 케톤으로 이루어진 아세토페논계 화합물 및 벤조페논, 2,4,6-트리메틸아미노벤조페논으로 이루어진 벤조페논계 화합물 중에서 선택되는 1종 이상의 화합물일 수 있다.In addition, the photoinitiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine And triazine compounds such as 2,4-trichloromethyl- (pipelonyl) -6-triazine, 1-hydroxycyclohexyl phenyl ketone, and 4- (2-hydroxyethoxy) -phenyl (2- It may be at least one compound selected from acetophenone-based compound consisting of hydroxy) propyl ketone and a benzophenone-based compound consisting of benzophenone and 2,4,6-trimethylaminobenzophenone.
또한, 상기 용매는, 메틸 에틸 케톤, 프로필렌 글리콜 디에틸 에테르, 프로필렌 글리콜 메틸 에테르 아세테이트, 3-메톡시부틸 아세테이트, 디프로플렌 글리콜 모노메틸 에테르 중에서 선택되는 1종 이상인 것일 수 있다.In addition, the solvent may be one or more selected from methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, dipropene glycol monomethyl ether.
또한, 전체 감광성 수지 조성물 중 상기 알칼리 가용성 수지는 1~20중량%, 상기 에틸렌성 불포화 결합을 갖는 중합성 화합물은 0.5~10중량%, 상기 광개시제는 0.1~5 중량%,상기 용매는 10~95 중량% 일 수 있다.In addition, the alkali-soluble resin is 1 to 20% by weight of the total photosensitive resin composition, 0.5 to 10% by weight of the polymerizable compound having the ethylenically unsaturated bond, 0.1 to 5% by weight of the photoinitiator, the solvent is 10 to 95 Weight percent.
또한, 착색제를 더 포함할 수 있는데, 상기 착색제는 전체 감광성 수지 조성물 중 0.5~20 중량% 일 수 있다.In addition, the colorant may further include, the colorant may be 0.5 to 20% by weight of the total photosensitive resin composition.
본 발명에 의하면 알칼리 가용성 수지의 기판과의 접착성을 향상시켜, 현상성, 상용성, 코팅성 및 접착성이 우수한 감광성 수지 조성물을 제조할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness of alkali-soluble resin with the board | substrate can be improved and the photosensitive resin composition excellent in developability, compatibility, coating property, and adhesiveness can be manufactured.
본 발명에 의한 알칼리 가용성 수지는, 다음의 화학식 1 내지 화학식 3으로 표시되는 단위체를 포함한다. Alkali-soluble resin by this invention contains the unit represented by following formula (1)-(3).
화학식 1
화학식 2
화학식 3
상기 화학식 1 내지 화학식 3에서,In
A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기, 이 소보닐 옥시 카보닐기 중에서 선택되고,A is selected from a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbonyl group, cyclohexyl oxy carbonyl group, isobornyl oxy carbonyl group,
X1, X2는 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택되고, X 1 , X 2 are selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group,
Y는 탄소수 1~3의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이며,Y is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide having 1 to 3 carbon atoms,
Z는 탄소수 1~3의 알킬렌, 사이클로 헥센, 사이클로 헥산 및 벤젠기에서 선택된다.Z is selected from alkylene, cyclohexene, cyclohexane and benzene groups having 1 to 3 carbon atoms.
R1 및 R2는 수소 또는 하이드록시기이다.R 1 and R 2 are hydrogen or a hydroxyl group.
이러한, 알칼리 가용성 수지는 다음의 화학식 4의 반복단위를 가질 수 있는데, 여기서 a, b, c는 몰혼합비로서 각각 10~40이다.Such an alkali-soluble resin may have a repeating unit represented by the following Formula 4, wherein a, b, and c are each 10 to 40 as a molar mixing ratio.
화학식 4Formula 4
A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기, 이 소보닐 옥시 카보닐기 중에서 선택되고, X1, X2는 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택되고, Y는 탄소수 1~3의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이며, Z는 탄소수 1~3의 알킬렌, 사이클로 헥센, 사이클로 헥산 및 벤젠기에서 선택된다. R1 및 R2는 수소 또는 하이드록시기이다.A is selected from phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbonyl group, cyclohexyl oxy carbonyl group, isobornyl oxy carbonyl group, X 1 , X 2 is selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, Y is one selected from the group consisting of alkylene having 1 to 3 carbon atoms, ethylene oxide and propylene oxide, Z is alkyl having 1 to 3 carbon atoms Ethylene, cyclohexene, cyclohexane and benzene groups. R 1 and R 2 are hydrogen or a hydroxyl group.
A가 벤질 옥시 카보닐기이고, X1은 메틸기이고, X2가 수소, Y가 메틸렌기, Z가 사이클로 헥센인 동시에, R1 및 R2가 모두 하이드록시기인 경우, 다음과 같은 반복단위를 가지는 알칼리 가용성 수지로 표시할 수 있다.When A is a benzyl oxycarbonyl group,
상기 화학식 1로 표시되는 단위체는 치환기 A의 종류에 따라 본 발명의 알칼리 가용성 수지의 전체적인 특성에 영향을 주게 되는데, 스티렌, 벤질(메타)아크릴레이트, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 이소부틸(메타)아크릴 레이트, t-부틸(메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트 중에서 1종 이상 선택될 수 있다.The monomer represented by
알칼리 가용성 수지가 감광성 수지 조성물에 사용될 때의 함께 섞이게 되는 광개시제나 에틸렌성 불포화 결합을 갖는 중합성 화합물 등과의 상용성, 코팅성 및 현상성 등을 고려해 볼 때, 이 중 벤질 옥시 카르보닐기를 치환기 A로 선택하는 경우가 바람직하다.When the alkali-soluble resin is used in the photosensitive resin composition, considering the compatibility, coating property and developability with the photoinitiator or polymerizable compound having an ethylenically unsaturated bond, the benzyl oxycarbonyl group is substituted with substituent A. It is preferable to select.
상기 알칼리 가용성 수지의 산가는 30~200 KOH mg/g이고, 중량 평균 분자량은 1,000~200,000 g/mol의 범위를 갖는 것이 바람직하다. 산가가 30 KOH mg/g 미만이면 알칼리 현상액에 대한 용해도가 낮아 현상시간이 길어지고 기판에 잔사가 남을 우려가 있으며, 산가가 200 KOH mg/g을 초과하면 패턴의 탈착이 일어나고, 패턴의 직직성을 확보할 수 없으며 패턴의 테이퍼각이 90도가 넘어가는 역테이퍼를 보이게 된다. It is preferable that the acid value of the said alkali-soluble resin is 30-200 KOH mg / g, and the weight average molecular weight has a range of 1,000-200,000 g / mol. If the acid value is less than 30 KOH mg / g, the solubility in the alkaline developer is low, there is a fear that the development time is long, and residues remain on the substrate, if the acid value exceeds 200 KOH mg / g, the pattern is desorption, the pattern is straight The taper angle of the pattern can not be secured, and the inverse taper will be over 90 degrees.
또한, 상기 알칼리 가용성 수지의 분자량이 1,000 미만일 경우에는 바인더 폴리머로서 요구되는 구성 성분간의 바인등 능력이 약하고 현상시 물리적 외력에 견딜 수 없어 패턴이 소실되며 기본적인 내열성 및 내화학성 등의 물성을 만족할 수 없다. 중량 평균 분자량이 200,000 초과일 경우에는 알칼리 현상액에 대한 현상성이 과도하게 적어 현상 공정 특성이 저하되고 현상이 불가능해진다. 또한, 흐름성도 나빠져서 코팅 두께의 제어나 두께의 균일성 확보가 어려워진다.In addition, when the molecular weight of the alkali-soluble resin is less than 1,000, the ability to bind between the constituents required as the binder polymer is weak, it cannot endure physical external forces during development, the pattern is lost, and the physical properties such as basic heat resistance and chemical resistance cannot be satisfied. . When the weight average molecular weight is more than 200,000, the developability with respect to the alkaline developing solution is excessively low, so that the developing process characteristics are lowered and development is impossible. In addition, the flowability also worsens, making it difficult to control the coating thickness and ensure uniformity of the thickness.
본 발명에 의한 알칼리 가용성 수지는, Alkali-soluble resin according to the present invention,
a) 화학식 1로 표시되는 단위체와, 에폭시기를 포함하는 단위체를 중합하여 고분자를 제조하는 단계와, a) preparing a polymer by polymerizing a unit represented by
b) 상기 a)단계에서 제조된 고분자에 카복실산 화합물을 투입하여 고분자를 제조하는 단계와,b) preparing a polymer by adding a carboxylic acid compound to the polymer prepared in step a);
c) 상기 b)단계에서 합성된 고분자에 고리형 무수물을 투입하여 산기를 형성하는 단계를 포함한다.c) adding an cyclic anhydride to the polymer synthesized in step b) to form an acid group.
상기 a)단계에서 상기 에폭시기를 포함하는 단위체는 화학식 5로 표시될 수 있다.The unit including the epoxy group in step a) may be represented by the formula (5).
화학식 5
상기 화학식 5에서, X1은 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택되고, Y는 탄소수 1~3의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.In
화학식 5로 표시되는 단위체의 경우, b)단계에서 투입되는 카복실산 화합물과 반응할 수 있는 에폭시기를 포함하는 단위체이면 무엇이든 무방하나, 가장 바람직하게는 글리시딜(메타)아크릴레이트가 사용될 수 있다.In the case of the unit represented by
상기 b)단계에서 상기 카복실산 화합물은 다음의 화학식 6 및 화학식 7로 표시되는 화합물을 하나 이상 포함할 수 있다.In step b), the carboxylic acid compound may include one or more compounds represented by the following
화학식 6Formula 6
X2는 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택된다.X 2 is selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group.
화학식 7
R1 및 R2는 수소 또는 하이드록시기이다.R 1 and R 2 are hydrogen or a hydroxyl group.
화학식 6에 해당하는 단위체로는 아크릴산 또는 메타크릴산이 가장 바람직하다.As the unit corresponding to Formula 6, acrylic acid or methacrylic acid is most preferred.
이 화합물은 화학식 5의 에폭시기와 반응하여 다음의 화학식 8 같은 단위체가 되며, 이는 알칼리 가용성 수지의 측쇄에 광중합성 관능기로써 감광성 수지 조성물의 감광도를 높이는데 기여한다.The compound reacts with the epoxy group of the formula (5) to form a unit such as the following formula (8), which contributes to enhancing the photosensitivity of the photosensitive resin composition as a photopolymerizable functional group in the side chain of the alkali-soluble resin.
화학식 8Formula 8
상기 화학식 8에서, X1, X2는 수소, 탄소수 1~3의 알킬기, 알콕시기 중에서 선택되고, Y는 탄소수 1~3의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.In Formula 8, X 1 , X 2 is selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, Y is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide having 1 to 3 carbon atoms.
화학식 2로 표시되는 단위체는 상기 화학식 8로 표시되는 단위체에 숙신산 무수물 또는 테트라 하이드로 프탈산 무수물을 투입하는 c)단계를 거쳐 알코올기와 무수물간의 반응으로 산기를 형성한 것이다.The unit represented by
상기 c)단계에서 상기 고리형 무수물은, 숙신산 무수물, 테트라 하이드로 프탈산 무수물, 말릭산 무수물, 프탈산 무수물 중에서 1종 이상 선택될 수 있다.In the step c), the cyclic anhydride may be selected from at least one of succinic anhydride, tetrahydro phthalic anhydride, malic anhydride and phthalic anhydride.
한편, 상기 화학식 3으로 표시되는 단위체는, 상기 화학식 5로 표시되는 단위체의 에폭시기와 상기 화학식 7로 표시되는 콜릭산 유도체의 카복실산 그룹을 서로 반응시킴으로서 얻어진다.On the other hand, the unit represented by the formula (3) is obtained by reacting the epoxy group of the unit represented by the formula (5) with the carboxylic acid group of the collic acid derivative represented by the formula (7).
화학식 1로 표시되는 단위체와, 화학식 2 및 화학식 3으로 표시되는 단위체로 알칼리 가용성 수지를 제조하면 콜릭산 유도체의 여러 개의 하이드록시기의 영향으로 알칼리 가용성 수지와 기판과의 접착성이 향상되는 효과가 있다. 또한, 고리형 무수물에 의해 산기가 형성됨으로써 현상이 가능하게 되고, 불포화 이중결합도 함께 갖고 있기 때문에 네가티브형 감광재에서 노광에 의해 가교가 일어날 때 바인더의 불포화 이중결합도 함께 가교반응에 참여할 수 있으므로 감도가 향상된다. When the alkali-soluble resin is prepared from the unit represented by the formula (1) and the unit represented by the formula (2) and the formula (3), the effect of improving the adhesion between the alkali-soluble resin and the substrate is affected by the influence of several hydroxyl groups of the cholic acid derivative. have. In addition, since the acid groups are formed by the cyclic anhydride, development is possible, and since unsaturated double bonds are also present, when the negative photosensitive material crosslinks by exposure, the unsaturated double bonds of the binder may also participate in the crosslinking reaction. Sensitivity is improved.
본 발명에 의한 알칼리 가용성 수지는 라디칼 중합, 양이온 중합, 음이온 중합, 축합 중합 중의 어느 하나에 의해 제조될 수 있으며, 제조의 용이성이나 경제성을 고려했을 때는 라디칼 중합을 이용하는 것이 바람직하다.The alkali-soluble resin according to the present invention can be produced by any one of radical polymerization, cationic polymerization, anionic polymerization and condensation polymerization, and in consideration of ease of production and economical efficiency, it is preferable to use radical polymerization.
라디칼 중합을 이용하는 경우, 라디칼 중합 개시제를 이용할 수 있는데, When using radical polymerization, a radical polymerization initiator can be used,
상기 라디칼 중합 개시제는 2,2'-아조비스이소부티로니트릴, s,s'-아조비스-(2,4-디메틸발레로니트릴), 벤조일퍼옥사이드 중에서 선택되는 1종 이상을 사용할 수 있다.The radical polymerization initiator may be used at least one selected from 2,2'-azobisisobutyronitrile, s, s'-azobis- (2,4-dimethylvaleronitrile), and benzoyl peroxide.
또한, 중합온도는 50~150℃, 중합시간은 1시간~48시간으로 하는 것이 바람직하다.Moreover, it is preferable to make polymerization temperature 50-150 degreeC, and polymerization time into 1 hour-48 hours.
또한, 본 발명에 의한 알칼리 가용성 수지와, 에틸렌성 불포화 결합을 갖는 중합성 화합물과, 광개시제 및 용매 포함하는 감광성 수지 조성물을 제공할 수 있다.Moreover, the photosensitive resin composition containing alkali-soluble resin, the polymeric compound which has an ethylenically unsaturated bond, photoinitiator, and a solvent by this invention can be provided.
상기 에틸렌성 불포화 결합을 갖는 중합성 화합물은, 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 에틸렌 글리콜 디(메타)아크릴레이트, 폴리에틸렌 글리콜 디(메타)아크릴레이트 중에서 선택될 수 있다.The polymerizable compound having an ethylenically unsaturated bond may be selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Can be.
또한, 상기 용매는 메틸 에틸 케톤, 프로필렌 글리콜 디에틸 에테르, 프로필렌 글리콜 메틸 에테르 아세테이트, 3-메톡시부틸 아세테이트, 디프로플렌 글리콜 모노메틸 에테르 중에서 선택되는 1종 이상일 수 있다.In addition, the solvent may be at least one selected from methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, dipropene glycol monomethyl ether.
전체 감광성 수지 조성물 중 상기 알칼리 가용성 수지는 1~20중량%, 상기 에틸렌성 불포화 결합을 갖는 중합성 화합물은 0.5~10중량%, 상기 광개시제는 0.1~5 중량%,상기 용매는 10~95 중량% 일 수 있는데, 1-20% by weight of the alkali-soluble resin, 0.5-10% by weight of the polymerizable compound having an ethylenically unsaturated bond, 0.1-5% by weight of the photoinitiator, and 10-95% by weight of the solvent. Can be
네가티브형 칼라필터용 감광재와 블랙 매트릭스용 감광재의 경우, 착색제를 더 포함할 수 있다. 이때 착색제로는 흑색안료, 레드안료, 옐로우 안료, 블루안료, 바이올렛안료 중에서 1종 이상을 사용할 수 있다. 흑색안료로는 카본 블랙, 티탄블랙 등이 있고, 컬러 안료로는 프탈로시아닌 그린, 프탈로시아닌 블루, 페릴렌 블루, 리놀옐로우, 빅토리아 퓨어 블루 등이 있다. 또한, 상기 착색제는 전체 수지조성물 중 0.5~20중량%로 포함할 수 있다.In the case of the photosensitive material for negative color filters and the photosensitive material for black matrices, a colorant may be further included. In this case, one or more of black pigments, red pigments, yellow pigments, blue pigments and violet pigments may be used as the colorant. Black pigments include carbon black and titanium black, and color pigments include phthalocyanine green, phthalocyanine blue, perylene blue, linol yellow, and Victoria pure blue. In addition, the colorant may be contained in 0.5 to 20% by weight of the total resin composition.
이하에서는, 본 발명의 실시예를 통하여 본 발명에 대해 상세히 설명하나. 하기의 실시예에 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail through embodiments of the present invention. The present invention is not limited to the following examples.
<합성예 1> Synthesis Example 1
벤질 메타아크릴레이트 70g, 글리시딜 메타아크릴레이트 130g, 도데칸티올 2g을 250g의 프로필렌 글리콜 모노메틸에테르 아세테이트에 혼합하고 질소로 버블링시켰다. 질소 분위기 하에서 반응기의 온도를 60도로 높이고 혼합물의 온도가 60도가 되었을 때 열중합 개시제인 AIBN 3g을 넣고 12시간 동안 교반하였다. 12시간 후, 중합 수율 97%, 분자량 10,000g/mol, 고형분 25%의 고분자 수지 바인더 용액을 얻었다.70 g of benzyl methacrylate, 130 g of glycidyl methacrylate, and 2 g of dodecanethiol were mixed in 250 g of propylene glycol monomethylether acetate and bubbled with nitrogen. When the temperature of the reactor was raised to 60 degrees under a nitrogen atmosphere and the mixture temperature reached 60 degrees, 3 g of AIBN, a thermal polymerization initiator, was added thereto and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 97%, a molecular weight of 10,000 g / mol and a solid content of 25% was obtained.
이 고분자 용액의 온도를 다시 80도로 높이고, 테트라부틸암모늄 브로마이드 1g과 열중합 금지제인 MEHQ 0.1g을 넣고 30분간 교반한 후, 아크릴산 15g, 콜릭산 30g 을 넣고 120도에서 24시간 동안 교반하였다. 24시간 후, 분자량 15,000g/mol, 고형분 28%의 고분자 수지 바인더 용액을 얻었다. The temperature of the polymer solution was again increased to 80 degrees, 1 g of tetrabutylammonium bromide and 0.1 g of MEHQ, a thermal polymerization inhibitor, were stirred for 30 minutes, and 15 g of acrylic acid and 30 g of colic acid were added and stirred at 120 degrees for 24 hours. After 24 hours, a polymer resin binder solution having a molecular weight of 15,000 g / mol and a solid content of 28% was obtained.
마지막 합성 단계로, 이 고분자 용액에 테트라하이드로 프탈산 무수물 15g을 넣고 90도에서 15시간동안 교반하여 분자량 18,000g/mol, 산가 100, 고형분 30%의 원하는 알칼리 가용성 수지 용액을 얻었다. 이 알칼리 가용성 수지의 NMR 그래프를 도1에 나타내었다. As a final synthesis step, 15 g of tetrahydro phthalic anhydride was added to the polymer solution and stirred at 90 ° for 15 hours to obtain a desired alkali-soluble resin solution having a molecular weight of 18,000 g / mol, an acid value of 100 and a solid content of 30%. The NMR graph of this alkali-soluble resin is shown in FIG.
<합성예 2> Synthesis Example 2
벤질 메타아크릴레이트 70g, 글리시딜 메타아크릴레이트 130g, 도데칸티올 2g을 250g의 프로필렌 글리콜 모노메틸에테르 아세테이트에 혼합하고 질소로 버블링시켰다. 질소 분위기 하에서 반응기의 온도를 60도로 높이고 혼합물의 온도가 60도가 되었을 때 열중합 개시제인 AIBN 3g을 넣고 12시간 동안 교반하였다. 12시간 후, 중합 수율 97%, 분자량 10,000g/mol, 고형분 25%의 고분자 수지 바인더 용액을 얻었다.70 g of benzyl methacrylate, 130 g of glycidyl methacrylate, and 2 g of dodecanethiol were mixed in 250 g of propylene glycol monomethylether acetate and bubbled with nitrogen. When the temperature of the reactor was raised to 60 degrees under a nitrogen atmosphere and the mixture temperature reached 60 degrees, 3 g of AIBN, a thermal polymerization initiator, was added thereto and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 97%, a molecular weight of 10,000 g / mol and a solid content of 25% was obtained.
이 고분자 용액의 온도를 다시 80도로 높이고, 테트라부틸암모늄 브로마이드 1g과 열중합 금지제인 MEHQ 0.1g을 넣고 30분간 교반한 후, 아크릴산 8g, 콜릭산 50g 을 넣고 120도에서 24시간 동안 교반하였다. 24시간 후, 분자량 20,000g/mol, 고형분 30%의 고분자 수지 바인더 용액을 얻었다. The temperature of the polymer solution was again increased to 80 degrees, 1 g of tetrabutylammonium bromide and 0.1 g of MEHQ, a thermal polymerization inhibitor, were stirred for 30 minutes, and then 8 g of acrylic acid and 50 g of colic acid were added and stirred at 120 degrees for 24 hours. After 24 hours, a polymer resin binder solution having a molecular weight of 20,000 g / mol and a solid content of 30% was obtained.
마지막 합성 단계로, 이 고분자 용액에 테트라하이드로 프탈산 무수물 20g을 넣고 90도에서 15시간동안 교반하여 분자량 25,000g/mol, 산가 110, 고형분 33%의 원하는 알칼리 가용성 수지 용액을 얻었다. 이 알칼리 가용성 수지의 NMR 그래프를 도2에 나타내었다. As a final synthesis step, 20 g of tetrahydro phthalic anhydride was added to the polymer solution and stirred at 90 ° for 15 hours to obtain a desired alkali-soluble resin solution having a molecular weight of 25,000 g / mol, an acid value of 110 and a solid content of 33%. The NMR graph of this alkali-soluble resin is shown in FIG.
<비교 합성예 1>Comparative Synthesis Example 1
벤질 메타아크릴레이트 70g, 글리시딜 메타아크릴레이트 130g, 도데칸티올 2g을 250g의 프로필렌 글리콜 모노메틸에테르 아세테이트에 혼합하고 질소로 버블링시켰다. 질소 분위기 하에서 반응기의 온도를 60도로 높이고 혼합물의 온도가 60도가 되었을 때 열중합 개시제인 AIBN 3g을 넣고 12시간 동안 교반하였다. 12시간 후, 중합 수율 97%, 분자량 13,000g/mol, 고형분 25%의 고분자 수지 바인더 용액을 얻었다.70 g of benzyl methacrylate, 130 g of glycidyl methacrylate, and 2 g of dodecanethiol were mixed in 250 g of propylene glycol monomethylether acetate and bubbled with nitrogen. When the temperature of the reactor was raised to 60 degrees under a nitrogen atmosphere and the mixture temperature reached 60 degrees, 3 g of AIBN, a thermal polymerization initiator, was added thereto and stirred for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 97%, a molecular weight of 13,000 g / mol and a solid content of 25% was obtained.
이 고분자 용액의 온도를 다시 80도로 높이고, 테트라부틸암모늄 브로마이드 1g과 열중합 금지제인 MEHQ 0.1g을 넣고 30분간 교반한 후, 아크릴산 30g 을 넣고 120도에서 24시간 동안 교반하였다. 24시간 후, 분자량 16,000g/mol, 고형분 26%의 고분자 수지 바인더 용액을 얻었다. The temperature of the polymer solution was further increased to 80 degrees, 1 g of tetrabutylammonium bromide and 0.1 g of MEHQ, a thermal polymerization inhibitor, were stirred for 30 minutes, and 30 g of acrylic acid was added thereto and stirred at 120 degrees for 24 hours. After 24 hours, a polymer resin binder solution having a molecular weight of 16,000 g / mol and a solid content of 26% was obtained.
마지막 합성 단계로, 이 고분자 용액에 테트라하이드로 프탈산 무수물 12g을 넣고 90도에서 15시간 동안 교반하여 분자량 20,000g/mol, 산가 100, 고형분 28%의 알칼리 가용성 수지 용액을 얻었다. As a final synthesis step, 12 g of tetrahydro phthalic anhydride was added to the polymer solution and stirred at 90 ° for 15 hours to obtain an alkali soluble resin solution having a molecular weight of 20,000 g / mol, an acid value of 100 and a solid content of 28%.
<실시예 1> <Example 1>
상기 합성예 1에서 합성한 알칼리 가용성 수지 3g을 레드 안료 C.I. Pigment Red 254 분산액 30g, 광개시제 I-369 1.5g, 디펜타에리스리톨 헥사아크릴레이트 2g, 프로필렌글리콜 메틸 에테르 아세테이트 30g 및 계면활성제 0.1g 을 혼합하여 1시간 정도 교반하여 감광성 수지 조성물을 준비하였다. 3 g of alkali-soluble resin synthesized in Synthesis Example 1 was used as red pigment C.I. 30 g of Pigment Red 254 dispersion, 1.5 g of photoinitiator I-369, 2 g of dipentaerythritol hexaacrylate, 30 g of propylene glycol methyl ether acetate, and 0.1 g of a surfactant were mixed and stirred for about 1 hour to prepare a photosensitive resin composition.
<실시예 2><Example 2>
상기 합성예 2에서 합성한 알칼리 가용성 수지 3g을 상기 실시예 1에서 사용된 것과 동일한 조성으로 하여 혼합하고, 1시간 정도 교반하여 감광성 수지 조성물을 준비하였다. 3 g of the alkali-soluble resin synthesized in Synthesis Example 2 was mixed in the same composition as used in Example 1, and stirred for about 1 hour to prepare a photosensitive resin composition.
<비교 실시예 1>Comparative Example 1
상기 비교예 1에서 합성한 알칼리 가용성 수지 3g을 상기 실시예 1에서 사용된 것과 동일한 조성으로 하여 혼합하고, 1시간 정도 교반하여 감광성 수지 조성물을 준비하였다. 3 g of the alkali-soluble resin synthesized in Comparative Example 1 was mixed in the same composition as used in Example 1, and stirred for about 1 hour to prepare a photosensitive resin composition.
<실험예 1>Experimental Example 1
실시예 1, 실시예 2 및 비교 실시예 1에서 제조한 각각의 감광성 수지 조성물 용액을 유리 위에 스핀 코팅하고, 110도에서 2분 동안 전열 처리하여 1.5 μm 두께의 도막을 만들었다. 이를 포토마스크를 이용하여 노광 갭 100 μm 로 고압수은 램프 하에서 60 mJ/cm2의 에너지로 노광 시킨 후, 노광된 기판을 25도의 온도에서 0.04% KOH수용액으로 60초간 현상하였다. 현상 단계 후, 세정 및 건조 과정을 거쳐 220도 컨벡션 오븐에서 30분간 포스트베이크를 한 후, 패턴의 상태를 관찰하 였다. Each of the photosensitive resin composition solutions prepared in Examples 1, 2 and Comparative Example 1 was spin coated onto glass and subjected to an electrothermal treatment at 110 degrees for 2 minutes to form a 1.5 μm thick coating film. This was exposed to an energy of 60 mJ / cm 2 under a high pressure mercury lamp with an exposure gap of 100 μm using a photomask, and then the exposed substrate was developed for 60 seconds with a 0.04% KOH aqueous solution at a temperature of 25 degrees. After the development step, after the post-baking for 30 minutes in a 220 degree convection oven through a cleaning and drying process, the state of the pattern was observed.
상기 실험예 1에서 얻어진 각각의 패턴 상태를 광학 현미경으로 관찰하여 최소 패턴의 크기를 하기 표 1과 같이 비교해 보았다. 또한, 각각의 실시예 및 비교 실시예에서 제조한 감광성 수지 조성물의 기판 위에서의 코팅성 및 현상성을 하기 표 1에 함께 표시하였다. Each pattern state obtained in Experimental Example 1 was observed with an optical microscope to compare the size of the minimum pattern as shown in Table 1 below. In addition, the coating property and developability on the board | substrate of the photosensitive resin composition produced by each Example and the comparative example were shown together in following Table 1.
[표 1]TABLE 1
상기 표 1에서와 같이 본 발명에 따른 알칼리 가용성 수지를 포함하는 실시예 1 및 2의 경우, 비교 실시예 1과 동등한 수준의 코팅성 및 현상성을 유지하는 것으로 나타났고, 동일 노광 조건과 동일한 현상시간에서 기판 위의 접착성이 우수한 것을 확인하였다In Examples 1 and 2 including the alkali-soluble resin according to the present invention as shown in Table 1, it was found to maintain the same level of coating and developability as Comparative Example 1, the same phenomenon as the same exposure conditions It was confirmed that the adhesion on the substrate was excellent in time.
도 1 및 도 2는 본 발명에 의한 알칼리 가용성 수지의 NMR 그래프이다.1 and 2 are NMR graphs of alkali-soluble resins according to the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013018986A1 (en) * | 2011-08-04 | 2013-02-07 | 주식회사 엘지화학 | Polymer compound comprising dye and curable resin composition comprising same |
| US8822110B2 (en) | 2011-12-02 | 2014-09-02 | Cheil Industries Inc. | Photosensitive resin composition for color filter and color filter including the same |
| US9334399B2 (en) | 2012-12-12 | 2016-05-10 | Cheil Industries Inc. | Photosensitive resin composition and black spacer using the same |
| KR20170113457A (en) * | 2016-03-31 | 2017-10-12 | 주식회사 엘지화학 | Alkally developable resin and photo-sensitive resin composition, photo spacer and display apparatus comprising the same |
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| KR100709891B1 (en) * | 2004-03-22 | 2007-04-20 | 주식회사 엘지화학 | Alkali-developable resins and photosensitive composition comprising the same |
| JP4691416B2 (en) | 2005-08-22 | 2011-06-01 | 三洋化成工業株式会社 | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013018986A1 (en) * | 2011-08-04 | 2013-02-07 | 주식회사 엘지화학 | Polymer compound comprising dye and curable resin composition comprising same |
| CN103249749A (en) * | 2011-08-04 | 2013-08-14 | 株式会社Lg化学 | Polymer compound comprising dye and curable resin composition comprising same |
| US8633260B2 (en) | 2011-08-04 | 2014-01-21 | Lg Chem, Ltd. | Polymer compound comprising dye and curable resin composition comprising same |
| CN103249749B (en) * | 2011-08-04 | 2015-05-27 | 株式会社Lg化学 | Polymer compound comprising dye and curable resin composition comprising same |
| US8822110B2 (en) | 2011-12-02 | 2014-09-02 | Cheil Industries Inc. | Photosensitive resin composition for color filter and color filter including the same |
| US9334399B2 (en) | 2012-12-12 | 2016-05-10 | Cheil Industries Inc. | Photosensitive resin composition and black spacer using the same |
| KR20170113457A (en) * | 2016-03-31 | 2017-10-12 | 주식회사 엘지화학 | Alkally developable resin and photo-sensitive resin composition, photo spacer and display apparatus comprising the same |
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