KR101315511B1 - Alkary developable resin and photosensitive resin composition comprising the same - Google Patents
Alkary developable resin and photosensitive resin composition comprising the same Download PDFInfo
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- KR101315511B1 KR101315511B1 KR1020080006906A KR20080006906A KR101315511B1 KR 101315511 B1 KR101315511 B1 KR 101315511B1 KR 1020080006906 A KR1020080006906 A KR 1020080006906A KR 20080006906 A KR20080006906 A KR 20080006906A KR 101315511 B1 KR101315511 B1 KR 101315511B1
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Abstract
본 발명은 화학식 1의 구조를 가지는 모노머를 포함하는 알칼리 가용성 수지에 대한 것이다.The present invention relates to an alkali-soluble resin comprising a monomer having the structure of formula (1).
본 발명에 의하면 현상시간을 감축시킬 수 있으며, 현상액과의 친화성이 향상되고, 분산성이 향상되어 현상성이 향상하였다. According to the present invention, the development time can be reduced, the affinity with the developing solution is improved, the dispersibility is improved, and the developability is improved.
또한, 높은 점도를 가지므로 적은 양의 고형분만으로도 원하는 점도의 조성물을 제공할 수 있으므로 원가절감에 기여할 수 있다.In addition, since it has a high viscosity can provide a composition of the desired viscosity with only a small amount of solid content it can contribute to cost reduction.
현상성, 알칼리 가용성 수지, 분산성, 점도 Developability, alkali-soluble resin, dispersibility, viscosity
Description
본 발명은 알칼리 가용성 수지와 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 액정표시소자(Liquid Crystal Display)나 유기발광다이오드(Organic light-Emitting Diode)의 컬러 필터, 수지 블랙 매트릭스, 컬럼 스페이서 등에 사용될 수 있다.The photosensitive resin composition may be used in a color filter, a resin black matrix, a column spacer, or the like of a liquid crystal display or an organic light-emitting diode.
감광성 수지 조성물은 기판상에 감광성 수지 조성물을 도포하여, 액체 상태의 박막을 형성하고 진공과 열을 가해 박막을 고형화시키는 코팅공정, 이 도막의 특정부분에 포토 마스크 등을 이용하여 방사선 조사에 의한 노광을 실시하는 노광공정, 감광되지 않은 부분을 알칼리 수용액을 이용하여 제거하고 순수로 세정하는 현상공정, 그리고 감광된 부분을 강화하기 위한 소성 공정을 거쳐 원하는 형태를 지닌 박막층을 제조하는데 사용될 수 있다.The photosensitive resin composition is a coating process of applying a photosensitive resin composition on a substrate to form a liquid thin film and applying vacuum and heat to solidify the thin film, and exposure by irradiation with a photomask or the like to a specific portion of the coating film. It can be used to produce a thin film layer having a desired shape through an exposure process for carrying out, a developing process for removing the unsensed portion using an aqueous alkali solution and washing with pure water, and a firing process for strengthening the photosensitive portion.
코팅 공정시 박막의 두께는 도포되는 조성물의 점도에 영향을 받는데, 감광성 포토레지스트의 제조시 고형분의 함량을 늘리면 원하는 점도를 맞출 수 있으나, 고형분의 함량이 늘어날수록 제조 원가가 상승하는 문제가 있다.The thickness of the thin film during the coating process is affected by the viscosity of the composition to be applied, while increasing the content of the solid content in the manufacture of the photosensitive photoresist can meet the desired viscosity, there is a problem that the manufacturing cost increases as the content of the solid content increases.
또한, 생산 단가의 절감을 위해 최소한의 공정 시간에 원하는 형상의 패턴을 형성하기 위해서는 현상 시간의 감소가 매우 중요하다.In addition, the reduction of development time is very important in order to form a desired shape pattern in a minimum process time to reduce the production cost.
또한, 감광성 수지 조성물을 이용하여 박막을 형성할 때 노광 공정은 필수적인 단계인데, 광감도가 우수한 경우 짧은 노광만으로도 박막의 형성이 가능하다.In addition, an exposure process is an essential step when forming a thin film using the photosensitive resin composition. However, when the light sensitivity is excellent, the thin film may be formed only by short exposure.
따라서, 점도가 높으면서도, 현상 시간을 단축시킬 수 있고 광감도도 우수한 알칼리 가용성 수지의 제공이 절실히 요구된다.Therefore, there is an urgent need to provide an alkali-soluble resin that can shorten the development time and have excellent light sensitivity while having a high viscosity.
본 발명은 분산성 및 현상성이 우수하고, 높은 점도를 가져서 낮은 고형분 함량으로도 원하는 점도를 가질 수 있어 원가 절감에 기여할 수 있는 알칼리 가용성 수지와 이를 포함하는 감광성 수지조성물과 이에 의해 제조된 컬럼스페이서를 제공하고자 하는 것이다.The present invention is excellent in dispersibility and developability, having a high viscosity to have a desired viscosity even at a low solids content, which can contribute to cost reduction, an alkali-soluble resin and a photosensitive resin composition comprising the same and a column spacer prepared thereby Is to provide.
본 발명에 의한 알칼리 가용성 수지는 다음의 화학식 1로 표시되는 모노머와, 산기를 포함하는 모노머와, 상기 산기를 포함하는 모노머와 공중합이 가능한 모노머와의 공중합체이다.Alkali-soluble resin which concerns on this invention is a copolymer of the monomer represented by following formula (1), the monomer containing an acidic radical, and the monomer copolymerizable with the monomer containing the said acidic radical.
화학식 1Formula 1
R은 수소, 메틸기, 에틸기 중에서 선택되고,R is selected from hydrogen, methyl group, ethyl group,
X는 탄소와 수소의 비가 1:2인 유기체인이고, X is an organism with a carbon to hydrogen ratio of 1: 2,
Y는 OH이다.Y is OH.
또한, 상기 X의 정의에서 상기 유기체인은 탄소수 1~3인 알킬렌기, -CH2-CHOH-CH2- 중에서 선택된다. Further, in the definition of X, the organism is selected from an alkylene group having 1 to 3 carbon atoms, -CH 2 -CHOH-CH 2- .
본 발명에 의한 알칼리 가용성수지는 다음의 화학식 1로 표시되는 모노머와, 산기를 포함하는 모노머와, 상기 산기를 포함하는 모노머와 공중합이 가능한 모노머와, 에폭시기를 함유한 에틸렌성 불포화 화합물과의 고분자 반응에 의해 제조된 것일 수 있다.The alkali-soluble resin according to the present invention is a polymer reaction between a monomer represented by the following formula (1), a monomer containing an acid group, a monomer copolymerizable with the monomer including the acid group, and an ethylenically unsaturated compound containing an epoxy group. It may be prepared by.
화학식 1Formula 1
R은 수소, 메틸기, 에틸기 중에서 선택되고,R is selected from hydrogen, methyl group, ethyl group,
X는 탄소와 수소의 비가 1:2인 유기체인이고, X is an organism with a carbon to hydrogen ratio of 1: 2,
Y는 OH이다.Y is OH.
또한, 상기 X의 정의에서 상기 유기체인은 탄소수 1~3인 알킬렌기, -CH2-CHOH-CH2- 중에서 선택되는 것일 수 있다.In addition, in the definition of X, the organism may be selected from an alkylene group having 1 to 3 carbon atoms, -CH 2 -CHOH-CH 2- .
또한, 상기 산기를 포함하는 모노머는, (메타)아크릴산, 크로톤산, 이타콘산, 말레인산, 이소플렌 술폰산, 스티렌 술폰산, 5-노보넨-2-카르복실산, 모노-2-((메타)아크릴로일옥시)에틸 프탈레이트, 모노-2-((메타)아크릴로옥시)에틸숙시네이트, ω-카르복시 폴리카프로락톤 모노(메타)아크릴레이트 중에서 1종 이상 선택되는 것일 수 있다.Moreover, the monomer containing the said acid group is (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid, mono-2-((meth) acrylic acid It may be one or more selected from royloxy) ethyl phthalate, mono-2-((meth) acrylooxy) ethyl succinate, and ω-carboxy polycaprolactone mono (meth) acrylate.
또한, 상기 산기를 포함하는 모노머와 공중합이 가능한 모노머는, 스티렌, 클로로 스티렌, α-메틸 스티렌, 비닐 톨루엔, 2-에틸헥실(메타)아크릴레이트, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 벤질(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 2-페녹시에틸(메타)아크릴레이트, 테트라히드로퍼프릴(메타)아크릴레이트, 2-히드록시-3-클로로프로필(메타)아크릴레이트, 디메틸아미노메틸(메타)아크릴레이트, 디에틸아미노(메타)아크릴레이트, 아실옥틸옥시-2-히드록시프로필(메타)아크릴레이트, 에틸헥실아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 3-메톡시부틸(메타)아크릴레이트, 부톡시에틸(메타)아크릴레이트, 에톡시디에틸렌글리콜(메타)아크릴레이트, 메톡시트리에틸렌글리콜(메타)아크릴레이트, 메톡시트리프로필렌글리콜(메타)아크릴레이트, 메톡시폴리에틸렌글리콜(메타)아크릴레이트, 페녹시디에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리프로필렌글리콜(메타)아크릴레이트, 테트라플루오로프로필(메타)아크릴레이트, 1,1,1,3,3,3,-헥사플루오로이소프로필(메타)아크릴레이트, 옥타플루오로펜틸(메타)아크릴레이트, 헵타데카플루오로데실(메타)아크릴레이트, 트리브로모페닐(메타)아크릴레이트, β-(메타)아실올옥시에틸히드로겐수시네이트, N-페닐말레이미드, N-(4-클로로페닐)말레이미드 중에서 1종 이상 선택되는 것일 수 있다.Moreover, the monomer copolymerizable with the monomer containing the said acid group is styrene, chloro styrene, (alpha) -methyl styrene, vinyl toluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acryl Rate, butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate , Cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobonyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, 2-hydride Hydroxy-3-chloropropyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylamino (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2- Methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, meth Oxytripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene Glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3, -hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate , Heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, β- (meth) acyloloxyethylhydrogensusinate, N-phenylmaleimide, N- (4-chlorophenyl) 1 type from maleimide The above may be selected.
또한, 상기 에폭시기를 함유한 에틸렌성 불포화 화합물은, 알릴글리시딜 에 테르, 글리시딜(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트, 글리시딜 5-노보덴-2-메틸-카복실레이트(엔도, 엑소 혼합물), 1,2-에폭시-헥센, 1,2-에폭시-9-데센 중에서 1종 이상 선택되는 것일 수 있다.Moreover, the ethylenically unsaturated compound containing the said epoxy group is allyl glycidyl ether, glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbodene. It may be one or more selected from -2-methyl-carboxylate (endo, exo mixture), 1,2-epoxy-hexene, 1,2-epoxy-9-decene.
또한, 상기 알칼리 가용성 수지의 산가는 50~300 KOH mg/g이고, 중량 평균 분자량은 1,000~200,000인 것일 수 있다.In addition, the acid value of the alkali-soluble resin is 50 ~ 300 KOH mg / g, the weight average molecular weight may be 1,000 to 200,000.
본 발명에 의한 감광성 수지 조성물은 본 발명에 의한 알칼리 가용성 수지 중에서 1종 이상 선택되는 알칼리 가용성 수지와, 에틸렌성 불포화 결합을 갖는 중합성 화합물과, 광개시제와, 용매를 포함한다.The photosensitive resin composition which concerns on this invention contains alkali-soluble resin selected from the alkali-soluble resin by this invention, the polymeric compound which has an ethylenically unsaturated bond, a photoinitiator, and a solvent.
전체 감광성 수지 조성물 중 상기 알칼리 가용성 수지는 5~20중량%, 상기 에틸렌성 불포화 결합을 갖는 중합성 화합물은 1~20중량%,상기 광개시제는 1~30중량%,상기 용매는 10~93중량%인 것을 특징으로 하는 감광성 수지 조성물.The alkali-soluble resin is 5 to 20% by weight of the total photosensitive resin composition, 1 to 20% by weight of the polymerizable compound having the ethylenically unsaturated bond, 1 to 30% by weight of the photoinitiator, 10 to 93% by weight of the solvent It is a photosensitive resin composition characterized by the above-mentioned.
또한, 경화촉진제, 열중합억제제, 가소제, 접착촉진제, 충진제, 계면활성제 중에서 1종 이상 선택되는 첨가제를 더 포함할 수 있다.In addition, it may further include an additive selected from at least one of a curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, a surfactant.
본 발명에 의한 컬럼 스페이서는 본 발명에 의한 감광성 수지 조성물에 의해 제조된다.The column spacer according to the present invention is produced by the photosensitive resin composition according to the present invention.
본 발명에 의하면 분자량에 비해 점도가 높고, 감도가 우수하며, 현상시간을 단축시킬 수 있다. 이에 따라 우수한 품질의 박막의 생산 단가를 낮출 수 있다.According to the present invention, the viscosity is higher than the molecular weight, the sensitivity is excellent, and the development time can be shortened. Accordingly, the production cost of the thin film of excellent quality can be lowered.
본 발명에 의한 알칼리 가용성 수지는 다음의 화학식 1의 구조를 갖는 모노머와, 산기를 포함하는 모노머와, 상기 산기를 포함하는 모노머와 공중합이 가능한 모노머와의 공중합체이다.(알칼리 가용성 수지 1)Alkali-soluble resin which concerns on this invention is a copolymer of the monomer which has a structure of following General formula (1), the monomer containing an acidic radical, and the monomer copolymerizable with the monomer containing the said acidic radical. (Alkali-soluble resin 1)
화학식 1Formula 1
R은 수소, 메틸기, 에틸기 중에서 선택되고,R is selected from hydrogen, methyl group, ethyl group,
X는 탄소와 수소의 비가 1:2인 유기체인이며,X is an organism with a carbon to hydrogen ratio of 1: 2,
Y는 OH이다.Y is OH.
또한, 상기 유기체인은 탄소수 1~3인 알킬렌기, -CH2-CHOH-CH2- 중에서 선택될 수 있다.In addition, the organism may be selected from an alkylene group having 1 to 3 carbon atoms, -CH 2 -CHOH-CH 2- .
또한, 본 발명에 의한 알칼리 가용성 수지는 상기의 화학식 1의 구조를 갖는 모노머와, 산기를 포함하는 모노머와, 상기 산기를 포함하는 모노머와 공중합이 가능한 모노머 및 에폭시기를 함유한 에틸렌성 불포화 화합물과의 고분자 반응에 의해 제조된 것일 수 있다.(알칼리 가용성 수지 2)In addition, the alkali-soluble resin according to the present invention includes a monomer having the structure of Formula 1, a monomer containing an acid group, a monomer copolymerizable with the monomer containing an acid group, and an ethylenically unsaturated compound containing an epoxy group. It may be prepared by a polymer reaction (alkali soluble resin 2).
또한, 본 발명에 의한 알칼리 가용성 수지는 상기 알칼리 가용성 수지 1과 상기 알칼리 가용성 수지 2를 단독으로 사용할 수도 있고, 두 가지를 섞어서 사용할 수도 있다.The alkali-soluble resin according to the present invention may be used alone or in combination with the alkali-soluble resin 1 and the alkali-soluble resin 2.
코팅 공정시 박막의 두께는 도포되는 조성물의 점도에 영향을 받는데, 최근액정표시 소자와 같은 재료에 대한 제조비 의존성이 높은 감광성 포토 레지스트의 제조시 단가 절감을 위해 적은 고형분 함량으로도 원하는 특성의 박막을 제조하려 하고 있다. 예를 들어 스핀 코팅 방식을 사용하는 경우 점도가 10cp이상은 되어야 박막을 형성할 수 있다. The thickness of the thin film during the coating process is influenced by the viscosity of the applied composition. In order to reduce the cost of manufacturing a photosensitive photoresist having high manufacturing cost dependence on a material such as a liquid crystal display device, a thin film having a desired characteristic with a small solid content is required. I'm trying to manufacture. For example, in the case of using a spin coating method, the viscosity must be at least 10 cp to form a thin film.
본 발명에 의한 알칼리 가용성 수지는 체인의 길이가 길고 분자내 또는 분자간 수소 결합이 많으며 탄소 체인의 길이가 길어져 분자량에 비해 점도가 높다. 따라서, 적은 고형분 함량만으로도 원하는 점도의 조성물을 제공할 수 있고, 이것은 원가 절감으로 연결된다.Alkali-soluble resins according to the present invention have a long chain length, many intramolecular or intermolecular hydrogen bonds, and a long carbon chain length, and thus have a high viscosity compared to molecular weight. Thus, even a small solids content can provide a composition of the desired viscosity, which leads to cost savings.
상기 산기를 포함하는 모노머는 (메타)아클리산, 크로톤산, 이타콘산, 말레인산, 이소프렌 술폰산, 스티렌 술폰산, 5-노보넨-2-카르복실산, 모노-2-((메타)아크릴로일옥시)에틸 프탈레이트, 모노-2-((메타)아크릴로옥시)에틸숙시네이트, ω-카르복시 폴리카프로락톤 모노(메타)아크릴레이트 또는 이들의 혼합물 등에서 1종 이상 선택될 수 있다.Monomers containing the acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid, mono-2-((meth) acryloyl jade C) ethyl phthalate, mono-2-((meth) acrylooxy) ethylsuccinate,? -Carboxy polycaprolactone mono (meth) acrylate, or mixtures thereof, and the like.
또한, 상기 산기를 포함하는 모노머와 공중합 가능한 모노머는, 스티렌, 클로로 스티렌, α-메틸 스티렌, 비닐 톨루엔, 2-에틸헥실(메타)아크릴레이트, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 벤질(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 2-페녹 시에틸(메타)아크릴레이트, 테트라히드로퍼프릴(메타)아크릴레이트, 2-히드록시-3-클로로프로필(메타)아크릴레이트, 디메틸아미노메틸(메타)아크릴레이트, 디에틸아미노(메타)아크릴레이트, 아실옥틸옥시-2-히드록시프로필(메타)아크릴레이트, 에틸헥실아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 3-메톡시부틸(메타)아크릴레이트, 부톡시에틸(메타)아크릴레이트, 에톡시디에틸렌글리콜(메타)아크릴레이트, 메톡시트리에틸렌글리콜(메타)아크릴레이트, 메톡시트리프로필렌글리콜(메타)아크릴레이트, 메톡시폴리에틸렌글리콜(메타)아크릴레이트, 페녹시디에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리프로필렌글리콜(메타)아크릴레이트, 테트라플루오로프로필(메타)아크릴레이트, 1,1,1,3,3,3,-헥사플루오로이소프로필(메타)아크릴레이트, 옥타플루오로펜틸(메타)아크릴레이트, 헵타데카플루오로데실(메타)아크릴레이트, 트리브로모페닐(메타)아크릴레이트, β-(메타)아실올옥시에틸히드로겐수시네이트, N-페닐말레이미드, N-(4-클로로페닐)말레이미드 또는 이들의 혼합물 등이 있다.Moreover, the monomer copolymerizable with the monomer containing the said acid group is styrene, chloro styrene, (alpha) -methyl styrene, vinyl toluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. , Butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, 2-hydroxy -3-chloropropyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylamino (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2 -Me Cethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, meth Oxytripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene Glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3, -hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate , Heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, β- (meth) acyloloxyethylhydrogensusinate, N-phenylmaleimide, N- (4-chlorophenyl) Maleimides or their Mixtures and the like.
상기 에폭시기를 함유한 에틸렌성 불포화 화합물은, 알릴글리시딜 에테르, 글리시딜(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트, 글리시딜 5-노보덴-2-메틸-카복실레이트(엔도, 엑소 혼합물), 1,2-에폭시-헥센, 1,2-에폭시-9-데센 중에서 1종 이상 선택될 수 있다.The ethylenically unsaturated compound containing the said epoxy group is allyl glycidyl ether, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl methyl (meth) acrylate, glycidyl 5-norbodene-2- One or more of methyl-carboxylate (endo, exo mixture), 1,2-epoxy-hexene, 1,2-epoxy-9-decene can be selected.
상기 알칼리 가용성 수지의 산가는 50~300 KOH mg/g이고, 중량 평균 분자량은 1,000~200,000인 것이 바람직하다.It is preferable that the acid value of the said alkali-soluble resin is 50-300 KOH mg / g, and a weight average molecular weight is 1,000-200,000.
산가가 50 미만인 경우에는 알칼리 현상액에 대한 용해도가 낮아 현상시간이 길어지고 기판상에 잔사가 남을 우려가 있으며, 산가가 300을 초과하는 경우에는 패턴의 탈착이 일어나고 패턴의 직진성을 확보할 수 없으며 패턴의 테이퍼각이 90도를 넘은 역테이퍼를 보이게 된다. If the acid value is less than 50, the solubility in the alkaline developer is low, so that the development time may be long, and residues may remain on the substrate. If the acid value is more than 300, the pattern may be desorbed and the pattern may not be straight. The taper angle of is shown to be inverse taper over 90 degrees.
또한, 상기 알칼리 가용성 수지의 중량 평균 분자량이 1,000 미만인 경우에는 바인더 폴리머로서 요구되는 구성 성분간의 바인딩 능력이 약하고, 현상시의 물리적 외력에 견딜 수 없어 패턴이 소실되며 기본적인 내열성 및 내화학성 등의 물성을 만족할 수 없다. 중량 평균 분자량이 200,000을 초과하는 경우에는 알칼리 현상액에 대한 현상성이 과도하게 적어 현상공정 특성이 저하되고 현상이 불가능해진다. 또한 흐름성이 나빠져서 코팅 두께의 제어나 두께의 균일성 확보가 어려워진다.In addition, when the weight average molecular weight of the alkali-soluble resin is less than 1,000, the binding ability between the constituents required as the binder polymer is weak, and the pattern is lost because it cannot withstand the physical external force during development, and the physical properties such as basic heat resistance and chemical resistance Can't be satisfied When the weight average molecular weight exceeds 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, poor flowability makes it difficult to control the coating thickness and ensure uniformity of the thickness.
본 발명에 의한 감광성 수지 조성물은, 상기 알칼리 가용성 수지 1 및 상기 알칼리 가용성 수지 2 중에서 1종 이상 선택되는 알칼리 가용성 수지와, 에틸렌성 불포화 결합을 갖는 중합성 화합물과, 광개시제 및 용매를 포함한다.The photosensitive resin composition which concerns on this invention contains alkali-soluble resin chosen from 1 or more types of the said alkali-soluble resin 1 and said alkali-soluble resin 2, the polymeric compound which has an ethylenically unsaturated bond, a photoinitiator, and a solvent.
전체 감광성 수지 조성물 중 상기 알칼리 가용성 수지는 5~20중량%인 것이 바람직한데 5중량%미만일때에는 가교가 잘 이루어지 지지 않고 현상 공정시 기판에서 패턴이 유실되는 문제가 있고, 20중량% 초과일 때에는 점도가 너무 높아 코팅성에 문제가 생기며 기판의 현상에도 문제가 있다. When the alkali-soluble resin of the total photosensitive resin composition is preferably 5 to 20% by weight, when the content is less than 5% by weight, crosslinking does not occur well, and there is a problem in that the pattern is lost in the substrate during the development process. Too high a viscosity causes a problem in the coating property and a problem in the development of the substrate.
상기 에틸렌성 불포화 결합을 갖는 중합성 화합물은, 분자중에 적어도 1개 이상의 부가중합 가능한 불포화기를 갖는 모노머를 사용할 수 있다.As the polymerizable compound having an ethylenically unsaturated bond, a monomer having an unsaturated group capable of at least one addition polymerization in a molecule can be used.
이들의 비제한적인 예로는 에틸렌글리콜 디(메타)아크릴레이트, 에틸렌기의 수가 2~14인 폴리에틸렌글리콜 디(메타)아크릴레이트, 트리메틸올프로판 디(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메틸)아크릴레이트, 프로필렌기의 수가 2~14인 프로필렌 글리콜 디(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트 등의 다가 알코올 α,β-불포화 카르복실산으로 에스테르화하여 얻어지는 화합물 ; 트리메틸올프로판 트리글리시딜에테르아크릴산 부가물, 비스페놀 A 디글리시딜에테르아크릴산 부가물, 등의 글리시딜기를 함유하는 화합물에 (메타)아크릴산을 부가하여 얻어지는 화합물 ; β-히드록시에틸(메타)아크릴레이트의 프탈산디에스테르, β-히드록시에틸(메타)아크릴레이트의 톨루엔 디이소시아네이트 부가물 등의 수산기 또는 에틸렌성 불포화 결합을 가지는 화합물과 다가 카르복실산과의 에스테르 화합물, 또는 폴리이소시아네이트와의 부가물 ; 및 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트 등의 (메타)아크릴산 알킬에스테르 또는 이들의 혼합물 등이 있다.Non-limiting examples thereof include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylic Polyvalents, such as the rate, pentaerythritol tetra (methyl) acrylate, propylene glycol di (meth) acrylate with the number of propylene groups 2-14, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Compounds obtained by esterifying with an alcohol α, β-unsaturated carboxylic acid; Compounds obtained by adding (meth) acrylic acid to a compound containing glycidyl groups such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; Ester compound of the compound which has hydroxyl group or ethylenically unsaturated bond, such as phthalic acid diester of (beta) -hydroxyethyl (meth) acrylate and toluene diisocyanate adduct of (beta) -hydroxyethyl (meth) acrylate, and polyhydric carboxylic acid Or adducts with polyisocyanates; And (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and mixtures thereof.
상기 에틸렌성 불포화 결합을 갖는 중합성 화합물의 함량은 전체 감광성 수지 조성물 중 1 내지 20중량%가 바람직하다. 1 중량% 미만인 경우 가교가 불충분하여 현상시 패텬 유지가 어려워지며, 20 중량%를 초과하는 경우 현상성이 저하되는 문제점이 발생한다The content of the polymerizable compound having an ethylenically unsaturated bond is preferably 1 to 20% by weight of the total photosensitive resin composition. If it is less than 1% by weight, crosslinking is insufficient, making it difficult to maintain the pattern during development, and if it exceeds 20% by weight, developability is deteriorated.
광개시제는 본 발명이 속하는 분야에서 알려진 광중합 개시제 및 광증감제를 사용할 수 있다. 이의 비제한적인 예로는 2,4-트리클로로메틸-(4´-메톡시페닐)-6-트리아진, 2,4-트리클로로메틸-(4´-메톡시스티릴)-6-트리아진, 2,4-트리클로로메 틸-(피플로닐)-6-트리아진, 2,4-트리클로로메틸-(3´,4´-디메톡시페닐)-6-트리아진, 3-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}프로판산 등의 트리아진 화합물; 2,2´-비스(2-클로로페닐)-4,4´,5,5´-테트라페닐 비이미다졸, 2,2´-비스(2,3-디클로로페닐)-4,4´,5,5´-테트라페닐비이미다졸 등의 비이미다졸 화합물; 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-(4-이소프로필페닐)-2-하이드록시-2-메틸프로판-1-온, 4-(2-히드록시에톡시)-페닐(2-히드록시)프로필 케톤, 1-히드록시시클로헥실 페닐 케톤, 벤조인메틸 에테르, 벤조인에틸 에테르, 벤조인이소부틸 에테르, 벤조인부틸에테르, 2,2-디메톡시-2-페닐 아세토페논, 2-메틸-(4-메틸티오페닐)-2-몰폴리노-1-프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-몰폴리노페닐)-부탄-1-온, 등의 아세토페논계 화합물; 벤조페논, 4,4´-비스(디메틸아미노)벤조페논, 4,4´-비스(디에틸아미노)벤조페논, 2,4,6-트리메틸아미노벤조페논, 메틸-o-벤조일벤조에이트, 3,3-디메틸-4-메톡시벤조페논, 3,3´,4,4´-테트라(t-부틸퍼옥시카르보닐)벤조페논 등의 벤조페논계 화합물; 9-플로레논, 2-클로로-9-플로레논, 2-메틸-9-플로레논 등의 플로레논계 화합물; 티옥산톤, 2,4-디에틸 티옥산톤, 2-콜로로 티옥산톤, 1-클로로-4-프로필옥시 티옥산톤, 디이소프로필 티옥산톤 등의 티옥산톤계 화합물; 크산톤, 2-메틸크산통 등의 크산톤계 화합물; 안트라퀴논, 2-메틸 안트라퀴논, 2-에틸 안트라퀴논, t-부틸 안트라퀴논, 2,6-디클로로-9,10-안트라퀴논 등의 안트라퀴논계 화합물; 9-페닐아크리딘, 1,7-비스(9-아크리디닐)헵탄, 1,5-비스(9-아크리디닐)펜탄, 1,3-비스(9-아크리디닐)프로판 등의 아크리딘계 화합물; 벤질, 1,7,7-티리메틸-비스클로로[2,2,1]헵탄-2,3-디온, 9,10-펜안트렌퀴논 등의 디카르보닐 화합물; 2,4,6-트리메틸벤조일 디페닐포스핀 옥사이드, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸 포스핀 옥사이드, 비스(2,6-디클로로벤조일)프로필 포스핀 옥사이드 등의 포스핀 옥사이드계 화합물; 메틸 4-(디메틸아미노)벤조에이트, 에틸-4-(디메틸아미노)벤조에이트, 2-n-부톡시에틸 4-(디메틸아미노)벤조에이트, 2,5-비스(4-디에틸아미노벤잘)시클로펜타논, 2,6-비스(4-디에틸아미노벤잘)시클로헥사논, 2,6-비스(4-디에틸아미노벤잘)-4-메틸-시클로헥사논 등의 아민계 시너지스트; 3,3´-카르보닐비닐-7-(디에틸아미노)쿠마린, 3-(2-벤조티아졸일)-7-(디에틸아미노)쿠마린, 3-벤조일-7-(디에틸아미노)쿠마린, 3-벤조일-7-메톡시-쿠마린, 10,10´-카르보닐비스[1,1,7,7-테트라메틸-2,3,6,7-테트라하이드로-1H,5H,11H-C1]-벤조피라노[6,7,8-ij]-퀴놀리진-11-온 등의 쿠마린계 화합물; 4-디에틸아미노 칼콘, 4-아지드벤잘아세토페논 등의 칼콘 화합물; 2-벤조일메틸렌, 3-메틸-β-나프토티아졸린 또는 이들의 혼합물 등이 있다.Photoinitiators may use photoinitiators and photosensitizers known in the art. Non-limiting examples thereof include 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine , 2,4-trichloromethyl- (pipelonyl) -6-triazine, 2,4-trichloromethyl- (3 ′, 4′-dimethoxyphenyl) -6-triazine, 3- {4- Triazine compounds such as [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazole compounds such as 5′-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy- 2-phenylacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl Acetophenone-based compounds such as) -butan-1-one; Benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3 Benzophenone compounds such as 3,3-dimethyl-4-methoxybenzophenone and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; Fluorene compounds such as 9-fluorenone, 2-chloro-9-fluorenone and 2-methyl-9-fluorenone; Thioxanthone-based compounds such as thioxanthone, 2,4-diethyl thioxanthone, 2-cholo thioxanthone, 1-chloro-4-propyloxy thioxanthone and diisopropyl thioxanthone; Xanthone compounds such as xanthone and 2-methylxanthine; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane, and the like. Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-thirimethyl-bischloro [2,2,1] heptane-2,3-dione, 9,10-phenanthrenequinone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as these; (Dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) Amine-based synergists such as cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, and 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclohexanone; 3,3′-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-C1] Coumarin-based compounds such as -benzopyrano [6,7,8-ij] -quinolizin-11-one; Chalcone compounds such as 4-diethylaminokalone and 4-azidobenzalacetophenone; 2-benzoylmethylene, 3-methyl-β-naphthothiazoline or mixtures thereof, and the like.
상기 광개시제는 전체 감광성 수지 조성물 중 1~30중량%인 것이 바람직한데, 특히 5~20 중량%인 것이 바람직하다.The photoinitiator is preferably 1 to 30% by weight of the total photosensitive resin composition, particularly preferably 5 to 20% by weight.
광개시제의 사용량이 1 중량% 미만일 때에는 가교가 적게 일어나 패턴 형성이 어려우며, 30 중량%를 초과하는 경우는 오븐 공정 중 승화가 일어나는 등의 문제가 발생한다.When the amount of the photoinitiator is less than 1% by weight, crosslinking occurs less, making it difficult to form a pattern. When the amount of the photoinitiator exceeds 30% by weight, problems such as sublimation during the oven process occur.
용매는, 메틸 에틸 케톤, 메틸셀로솔브, 에틸셀로솔브, 에틸렌글리콜디메틸 에테르, 에틸렌글리콜 디에틸 에테르, 프로필렌글리콜 디메틸 에테르, 프로필렌글리콜 디에틸 에테르, 디에틸렌글리콜 디메틸에테르, 디에틸렌글리콜 디에틸 에테 르, 디에틸렌글리콜 메틸 에틸 에테르, 2-에톡시 프로판올, 2-메톡시프로판올, 3-메톡시 부탄올, 시클로헥사논, 시클로펜타논, 프로필렌글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 3-메톡시부틸 아세테이트, 에틸 3-에톡시프로피오네이트, 에틸 셀로솔브 아세테이트, 메틸 셀로솔브 아세테이트, 부틸 아세테이트, 디프로필렌글리콜 모노메틸 에테르 또는 이들의 2종 이상 혼합물에서 선택될 수 있다. 용매는 10내지 93중량% 함유되는 것이 바람직하다.The solvent is methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, diethylene glycol methyl ethyl ether, 2-ethoxy propanol, 2-methoxypropanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3- Methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene glycol monomethyl ether or mixtures of two or more thereof. The solvent is preferably contained 10 to 93% by weight.
또한, 필요에 따라 경화촉진제, 열중합억제제, 가소제, 접착촉진제, 충진제, 계면활성제 중에서 1종 이상 선택되는 첨가제를 더 포함할 수 있다.In addition, if necessary, it may further include an additive selected from at least one of a curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, and a surfactant.
상기 경화 촉진제의 예로는 2-머캡토벤조이미다졸, 2-머캡토벤조티아졸, 2-머캡토벤조옥사졸, 2,5-디머캡토-1,3,4-티아디아졸, 2-머캡토-4,6-디메틸아미노피리딘, 펜타에리스리톨테트라키스(3-머캡토프로피오네이트), 펜타에리스리톨 트리스(3-머캡토프로피오네이트), 펜타에리스리톨 테트라키스(2-머캡토아세테이트), 펜타에리스리톨 트리스(2-머캡토아세테이트), 트리메틸올프로판 트리스(2-머캡토아세테이트), 트리케틸올프로판 트리스(3-머캡토프로피오네이트), 트리메틸올에탄 트리스(2-머캡토아세테이트) 및 트리메틸옥에탄트리스(3-머캡토프로피오네이트)로 이루어지는 군으로부터 선택되는 1종 이상을 사용할 수 있으나 이들로만 한정되는 것은 아니며 당 기술 분야에 널리 알려진 것들을 사용할 수 있다.Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mer Capto-4,6-dimethylaminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), penta Erythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), triketylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate) and trimethyl One or more kinds selected from the group consisting of octane tris (3-mercaptopropionate) may be used, but are not limited thereto, and those well known in the art may be used.
열 중합 억제제로는 p-아니솔, 히드로퀴논, 피로카테콜, t-부틸카테콜, N-니트로소페닐히드록시아민 암모늄염, N-니트로소페닐히드록시아민 알루미늄염 및 페노티아진으로 이루어지는 군으로부터 선택되는 1종 이상을 사용할 수 있으나, 이들 로만 한정되는 것은 아니며 당 기술 분야에 알려진 것들을 사용할 수 있다.Examples of thermal polymerization inhibitors include p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt and phenothiazine. One or more selected may be used, but is not limited thereto, and those known in the art may be used.
기타 가소제, 접착 촉진제, 충전제 및 계면활성제등도 종래 감광성 수지 조성물에 포함될 수 있는 모든 화합물이 사용될 수 있다.Other plasticizers, adhesion promoters, fillers, surfactants and the like can also be used for all compounds that can be included in conventional photosensitive resin compositions.
본 발명에 따른 감광성 수지 조성물은 당업계에 널리 알려진 방법에 따라 컬럼 스페이서를 제조할 수 있다.The photosensitive resin composition according to the present invention may prepare a column spacer according to methods well known in the art.
먼저 본 발명에 따른 감광성 수지 조성물을 기판에 도포한다. 이때 기판은 금속, 유리, 플라스틱, 실리콘, 폴리카보네이트, 폴리에스테르, 방향족 폴리아미드, 폴리아미드이미드, 폴리이미드 등을 사용할 수 있으며 이들 기판은 목적에 따라 실란 커플링제에 의한 약품 처리, 플라즈마 처리, 이온 플레이팅, 스퍼터링, 기상반응법, 진공 증착 등의 적절한 전처리를 실시할 수 있다. 또한 상기 기판은 선택적으로 구동용박막 트랜지스터가 올려져 있을 수 있으며 질화된 규소막이 스퍼터링되어 있을 수 있다.First, the photosensitive resin composition which concerns on this invention is apply | coated to a board | substrate. At this time, the substrate may be a metal, glass, plastic, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. These substrates may be chemically treated with a silane coupling agent, plasma treatment, ion Appropriate pretreatment such as plating, sputtering, vapor phase reaction, vacuum evaporation can be performed. In addition, the substrate may optionally have a driving thin film transistor mounted thereon and a nitrided silicon film may be sputtered thereon.
상기 조성물을 기판상에 도포하는 방법으로는 당업계에 알려진 롤 코터, 커튼 코터, 스핀 코터, 슬릿 다이 코터, 각종 인쇄, 침적 등의 방법을 사용할 수 있으나 스핀 코터나 슬릿 다이 코터가 특히 바람직하다. 도포된 두께는 특별한 제한이 없으며 통상적인 범위와 동일하다.As a method of applying the composition on a substrate, a roll coater, a curtain coater, a spin coater, a slit die coater, various printing methods, and deposition methods can be used, but a spin coater or a slit die coater is particularly preferable. The thickness applied is not particularly limited and is the same as the conventional range.
도포된 감광성 수지층에 원하는 패턴을 갖는 포토마스크를 통해 노광을 진행한 후, 노광된 감광성 수지층을 적당한 현상액으로 현상함으로써 컬럼스페이서가 제조된다.After exposing through the photomask which has a desired pattern to the apply | coated photosensitive resin layer, a column spacer is manufactured by developing the exposed photosensitive resin layer with a suitable developing solution.
본 발명의 감광성 수지 조성물을 경화시키기 위한 광원으로는 예컨대 파장이 250내지 450nm의 광을 발산하는 수은 증기 아크, 탄소 아크, 제논 아크 등이 있다.As a light source for hardening the photosensitive resin composition of this invention, a mercury vapor arc, a carbon arc, a xenon arc etc. which emit light of wavelength 250-450 nm are mentioned, for example.
사용가능한 알칼리 현상액의 비제한적인 예로는 탄산타트륨, 수산화나트륨, 수산화칼륨, 테트라메틸암모늄히드록시시드 등의 수용액이 있으며, 상기 현상액에 메탄올, 에탄올 등의 수용성 유기 용매나 계면 활성제 등을 적당량 첨가할 수 있다. 또한 현상 처리법으로는 샤워 현상법, 분무현상법, 딥(침지)현상법, 패들(액담굼)현상법 등을 적용할 수 있다.Non-limiting examples of the alkaline developer that can be used include aqueous solutions such as tartium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxyside, and an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the developer. can do. In addition, as the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid dipping) developing method, and the like can be applied.
이하에서는 다음의 실시예들을 통하여 본 발명을 더욱 상세히 설명한다. 다음의 실시예들은 본 발명을 설명하기 위한 것일 뿐, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. The following examples are merely to illustrate the present invention, but the present invention is not limited thereto.
[실시예1][Example 1]
알칼리 가용성 수지의 제조Preparation of Alkali Soluble Resins
반응용기에 열개시제로서 AIBN 3중량부를 용매인 프로필렌글리콜 모노메틸 에테르 아세테이트에 녹인 후 화학식 1로 표시되는 모노머로서 히드록시 에틸(메타)아크릴레이트와 산기를 포함하는 모노머로서 메타아크릴산과, 상기 산기를 포함하는 모노머와 공중합이 가능한 모노머로서 벤질(메타)아크릴레이트를 각각 35.2 : 31.0 : 33.8의 몰비로 투입한 후 질소 분위기에서 60℃를 유지하면서 12시간 반응시켰다. After dissolving 3 parts by weight of AIBN as a initiator in a reaction vessel in propylene glycol monomethyl ether acetate as a solvent, the monomer represented by the formula (1) includes hydroxyethyl (meth) acrylate and an acid group as methacrylic acid and the acid group. Benzyl (meth) acrylate was added as a monomer which can be copolymerized with the monomer to be included in a molar ratio of 35.2: 31.0: 33.8, respectively, and reacted for 12 hours while maintaining 60 ° C in a nitrogen atmosphere.
상기에서 얻은 반응성 수지의 공중합체 용액을 교반기가 부착된 플라스크에 투입하고 온도를 110℃까지 올리고 글리시딜 메타 아크릴레이트 8mol%를 가한다음, 에폭시기가 완전히 사라질 때까지 반응시켜 알칼리 가용성 수지를 제조하였다. 실험에서 사용한 알칼리 가용성 수지의 분자량은 10000~12000이다.Alkali-soluble resin was prepared by adding the copolymer solution of the reactive resin obtained above to a flask with a stirrer, raising the temperature to 110 ° C, adding 8 mol% of glycidyl methacrylate, and reacting until the epoxy group disappeared completely. . The molecular weight of alkali-soluble resin used in the experiment is 10000-12000.
감광성 수지 조성물의 제조Preparation of Photosensitive Resin Composition
히드록시에틸(메타)아크릴레이트를 14.1mol%포함한 알칼리 가용성 수지 14.5중량%, 중합성 화합물 디펜타에리스리톨 헥사아키를리에트 14.5 중량%, 광중합 개시제로 TPA 1 중량부, CXE-02 1 중량%, PGMEA 69 중량%를 넣고 3시간 교반시켰다. 이 감광성 수지 조성물을 5마이크론 크기의 필터를 이용하여 여과하고 유리에 스핀 코팅하여 약 100℃로 1분 30초간 전열 처리하면 두께가 약 4μm 되는 균일한 필름이 형성된다. 상기 필름을 포토마스크를 이용하여 고압 수은 램프하에서 노광시킨 후 기판을 pH11.3~11.7의 알칼리 수용액으로 현상하고 탈 이온수로 세척하였다. 현상 시간을 조절하면서 기판을 관찰하였다.14.5% by weight of an alkali-soluble resin containing 14.1 mol% of hydroxyethyl (meth) acrylate, 14.5% by weight of the polymerizable compound dipentaerythritol hexaakilyte, 1 part by weight of TPA as a photopolymerization initiator, 1% by weight of CXE-02, PGMEA 69 wt% was added and stirred for 3 hours. The photosensitive resin composition was filtered using a 5 micron filter, spin-coated to glass, and subjected to electrothermal treatment at about 100 ° C. for 1 minute and 30 seconds to form a uniform film having a thickness of about 4 μm. After exposing the film under a high pressure mercury lamp using a photomask, the substrate was developed with an aqueous alkali solution of pH11.3-11.7 and washed with deionized water. The substrate was observed while adjusting the development time.
[실시예 2][Example 2]
알칼리 가용성 수지의 제조Preparation of Alkali Soluble Resins
반응용기에 열개시제로서 AIBN 3중량부를 용매인 프로필렌글리콜 모노메틸 에테르 아세테이트에 녹인 후 화학식 1로 표시되는 모노머로서 1,3-다이히드록시프로필메타크릴레이트와 산기를 포함하는 모노머로서 메타아크릴산과, 상기 산기를 포함하는 모노머와 공중합이 가능한 모노머로서 벤질(메타)아크릴레이트를 각각 35.2 : 31.0 : 33.8의 몰비로 투입한 후 질소 분위기에서 60℃를 유지하면서 12시간 반응시켰다. 3 parts by weight of AIBN as a thermal initiator in a reaction vessel was dissolved in propylene glycol monomethyl ether acetate as a solvent, and as a monomer represented by the formula (1), 1,3-dihydroxypropyl methacrylate and a monomer containing an acid group were used as methacrylic acid, Benzyl (meth) acrylate as a monomer copolymerizable with the monomer including the acid group was added at a molar ratio of 35.2: 31.0: 33.8, respectively, and reacted for 12 hours while maintaining 60 ° C in a nitrogen atmosphere.
상기에서 얻은 반응성 수지의 공중합체 용액을 교반기가 부착된 플라스크에 투입하고 온도를 110℃까지 올리고 글리시딜 메타 아크릴레이트 8mol%를 가한다음, 에폭시기가 완전히 사라질 때까지 반응시켜 알칼리 가용성 수지를 제조하였다. 실험에서 사용한 알칼리 가용성 수지의 분자량은 10000~12000이다.Alkali-soluble resin was prepared by adding the copolymer solution of the reactive resin obtained above to a flask with a stirrer, raising the temperature to 110 ° C, adding 8 mol% of glycidyl methacrylate, and reacting until the epoxy group disappeared completely. . The molecular weight of alkali-soluble resin used in the experiment is 10000-12000.
감광성 수지 조성물의 제조Preparation of Photosensitive Resin Composition
1,3-다이히드록시프로필(메타)아크릴레이트 7.8 mol%포함한 알칼리 가용성 수지 14.5중량%, 중합성 화합물 디펜타에리스리톨 헥사아키를리에트 14.5 중량%, 광중합 개시제로 TPA 1 중량%, CXE-02 1 중량부, PGMEA 69 중량%를 넣고 3시간 교반시켰다. 이 감광성 수지 조성물을 5마이크론 크기의 필터를 이용하여 여과하고 유리에 스핀 코팅하여 약 100℃로 1분 30초간 전열 처리하면 두께가 약 4μm 되는 균일한 필름이 형성된다. 상기 필름을 포토마스크를 이용하여 고압 수은 램프하에서 노광시킨 후 기판을 pH11.3~11.7의 알칼리 수용액으로 현상하고 탈 이온수로 세척하였다. 현상 시간을 조절하면서 기판을 관찰하였다.14.5% by weight of an alkali-soluble resin containing 7.8 mol% of 1,3-dihydroxypropyl (meth) acrylate, 14.5% by weight of the polymerizable compound dipentaerythritol hexaakilyre, 1% by weight of TPA as a photopolymerization initiator, CXE-02 1 part by weight, PGMEA 69% by weight was added and stirred for 3 hours. The photosensitive resin composition was filtered using a 5 micron filter, spin-coated to glass, and subjected to electrothermal treatment at about 100 ° C. for 1 minute and 30 seconds to form a uniform film having a thickness of about 4 μm. After exposing the film under a high pressure mercury lamp using a photomask, the substrate was developed with an aqueous alkali solution of pH11.3-11.7 and washed with deionized water. The substrate was observed while adjusting the development time.
[비교예 1]Comparative Example 1
알칼리 가용성 수지의 제조Preparation of Alkali Soluble Resins
실시예 1에서 화학식 1로 표시되는 모노머를 투입하지않고, 벤질(메타)아크릴레이트와, 메타아크릴산을 몰비로 54.5:45.5로 투입하는 것을 제외하고는 실시예 1과 동일한 방법으로 알칼리 가용성 수지를 제조하였다.Alkali-soluble resins were prepared in the same manner as in Example 1, except that benzyl (meth) acrylate and methacrylic acid were added at a molar ratio of 54.5: 45.5 without adding the monomer represented by Formula 1 in Example 1. It was.
감광성 수지 조성물의 제조Preparation of Photosensitive Resin Composition
위에서 제조한 알칼리 가용성 수지를 14.5중량%, 중합성 화합물 디펜타에리스리톨 헥사아키를리에트 14.5 중량%, 광중합 개시제로 TPA 1 중량%, CXE-02 1 중량%, PGMEA 69 중량%를 넣고 3시간 교반시켰다. 이 감광성 수지 조성물을 5마이크론 크기의 필터를 이용하여 여과하고 유리에 스핀 코팅하여 약 100℃로 1분 30초간 전열 처리하면 두께가 약 4μm 되는 균일한 필름이 형성된다. 상기 필름을 포토마스크를 이용하여 고압 수은 램프하에서 노광시킨 후 기판을 pH11.3~11.7의 알칼리 수용액으로 현상하고 탈 이온수로 세척하였다. 현상 시간을 조절하면서 기판을 관찰하였다.14.5% by weight of the alkali-soluble resin prepared above, 14.5% by weight of the polymerizable compound dipentaerythritol hexaacrylitol, 1% by weight of TPA, 1% by weight of CXE-02, 69% by weight of PGMEA as a photopolymerization initiator, and stirred for 3 hours. I was. The photosensitive resin composition was filtered using a 5 micron filter, spin-coated to glass, and subjected to electrothermal treatment at about 100 ° C. for 1 minute and 30 seconds to form a uniform film having a thickness of about 4 μm. After exposing the film under a high pressure mercury lamp using a photomask, the substrate was developed with an aqueous alkali solution of pH11.3-11.7 and washed with deionized water. The substrate was observed while adjusting the development time.
[비교예 2]Comparative Example 2
알칼리 가용성 수지의 제조Preparation of Alkali Soluble Resins
실시예 1에서 화학식 1으로 표시되는 모노머를 투입하지 않고, 벤질(메타)아크릴레이트와, 메타아크릴산, 이소보닐(메타)아크릴레이트를 몰비로 35.2 : 31.0 : 33.8로 투입하는 것을 제외하고는 실시예 1과 동일한 방법으로 알칼리 가용성 수지를 제조하였다.Except that the monomer represented by the formula (1) in Example 1, benzyl (meth) acrylate, methacrylic acid, isobonyl (meth) acrylate in a molar ratio of 35.2: 31.0: 33.8 except that Alkali-soluble resin was prepared in the same manner as in 1.
감광성 수지 조성물의 제조Preparation of Photosensitive Resin Composition
위에서 준비한 알칼리 가용성 수지를 14.5중량%, 중합성 화합물 디펜타에리스리톨 헥사아키를리에트 14.5 중량%, 광중합 개시제로 TPA 1 중량%, CXE-02 1 중량%, PGMEA 69 중량%를 넣고 3시간 교반시켰다. 이 감광성 수지 조성물을 5마이크론 크기의 필터를 이용하여 여과하고 유리에 스핀 코팅하여 약 100℃로 1분 30초간 전열 처리하면 두께가 약 4μm 되는 균일한 필름이 형성된다. 상기 필름을 포토마스크를 이용하여 고압 수은 램프하에서 노광시킨 후 기판을 pH11.3~11.7의 알칼리 수용액으로 현상하고 탈 이온수로 세척하였다. 현상 시간을 조절하면서 기판을 관찰하였다.14.5% by weight of the alkali-soluble resin prepared above, 14.5% by weight of the polymerizable compound dipentaerythritol hexaacrylitol, 1% by weight of TPA, 1% by weight of CXE-02, and 69% by weight of PGMEA were added to the photopolymerization initiator, followed by stirring for 3 hours. . The photosensitive resin composition was filtered using a 5 micron filter, spin-coated to glass, and subjected to electrothermal treatment at about 100 ° C. for 1 minute and 30 seconds to form a uniform film having a thickness of about 4 μm. After exposing the film under a high pressure mercury lamp using a photomask, the substrate was developed with an aqueous alkali solution of pH11.3-11.7 and washed with deionized water. The substrate was observed while adjusting the development time.
[실험예 1 : 현상 시간의 측정]Experimental Example 1: Measurement of Developing Time
현상성은 현상액이 토출된 후 기판에 남아있는 막이 벗어지는 시간을 기준으로 하였다. The developability was based on the time when the film remaining on the substrate was released after the developer was discharged.
현상 정도는 숫자로 표시하였으며 1로부터 5로 갈수록 완전히 현상이 된 상태를 의미한다.The degree of development is indicated by numbers and it means that the status is completely developed from 1 to 5.
1 : 패턴은 보이나 기판 전체적으로 얇은 막이 관찰이 되는 상태.1: A pattern is seen but a thin film is observed on the whole board | substrate.
2 : 패턴 부의 유리 기판이 보이기 시작하는 상태.2: The state where the glass substrate of a pattern part starts to be seen.
3 : 패턴 부의 박막이 완전히 제거된 것이 관찰이 되는 상태.3: It is observed that the thin film of a pattern part was removed completely.
4 : 기판의 edge부만 조금 남은 상태4: Only the edge part of the board is left
5 : 완전히 현상된 상태.5: Completely developed state.
[실험예 2 : 점도의 측정]Experimental Example 2 Measurement of Viscosity
알칼리 가용성 수지의 용액 내 동일한 솔리드 함량비에서의 점도를 측정하였다. 온도는 25℃이다. The viscosity at the same solids content ratio in the solution of the alkali soluble resin was measured. The temperature is 25 ° C.
측정기구는 모세관 점도 측정기를 사용하였다.The measuring instrument used a capillary viscosity meter.
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