KR100767195B1 - Thermosetting resin composition for over coat film of a color filter and over coat film thereof - Google Patents

Thermosetting resin composition for over coat film of a color filter and over coat film thereof Download PDF

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KR100767195B1
KR100767195B1 KR1020060078550A KR20060078550A KR100767195B1 KR 100767195 B1 KR100767195 B1 KR 100767195B1 KR 1020060078550 A KR1020060078550 A KR 1020060078550A KR 20060078550 A KR20060078550 A KR 20060078550A KR 100767195 B1 KR100767195 B1 KR 100767195B1
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color filter
resin composition
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김명구
박주현
임영택
이종범
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금호석유화학 주식회사
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract

A thermosetting composition for a color filter overcoat film, and a color filter overcoat film prepared by using the composition are provided to improve leveling property and to enhance hardness, adhesion, transparency, heat resistance, light resistance, acid resistance, alkali resistance and chemical resistance. A thermosetting composition comprises 0-40 parts by weight of an epoxy-containing reactive solvent based on 100 parts by weight of a polymer, wherein the epoxy-containing reactive solvent is at least one selected from the compounds represented by the formulas. In the formulas, A, B and D are a C2-C15 linear, branched or cyclic hydrocarbon group containing or not containing at least one functional group selected from a glycidyl group, a hydroxyl group and a dihydroxyl group, an ether group, a glycol group, a ketone group or an ester group; R1 are identical or different each other and are H, a C1-C5 alkyl group or a C1-C5 alkylether group; R2 are H or a C1-C5 alkyl group; m is an integer of 3-6; and n is an integer of 0-10.

Description

칼라필터 평탄화막용 열경화성 수지 조성물 및 이를 이용한 평탄화막{Thermosetting resin composition for over coat film of a color filter and over coat film thereof}Thermosetting resin composition for over coat film of a color filter and over coat film

도 1은 칼라필터 기판에 평탄화막을 입힌 단면도이다.1 is a cross-sectional view of a flattening film coated on a color filter substrate.

본 발명은 칼라필터 평탄화막용 열경화성 수지 조성물 및 이를 이용한 평탄화막에 관한 것으로서, 더욱 상세하게는 LCD 공정에서의 칼라필터 기판의 평탄화 및 칼라필터 상부를 보호하기 위하여 에폭시기 함유 반응성 용매를 더 포함하는 열경화성 수지 조성물과 이를 이용해 형성되는 평탄화막에 관한 것이다. The present invention relates to a thermosetting resin composition for a color filter flattening film and a flattening film using the same, and more particularly, a thermosetting resin further comprising an epoxy group-containing reactive solvent to flatten the color filter substrate and protect the upper part of the color filter in the LCD process. It relates to a composition and a planarization film formed using the same.

최근 LCD 산업에서 액정 화면이 급속히 대형화되는 추세를 보이고 있으며, 이러한 대형 액정 화면 구현을 위해서는 평탄도가 우수한 칼라필터 평탄화막이 필요하다. 이러한 평탄화막은 LCD 제조공정 중에 고온, 유기 용제, 산 용액, 알칼리 용액, 광 조사, 배향막 러빙 등의 처리 과정을 거친다. Recently, the LCD industry is rapidly increasing in size in the LCD industry, and in order to realize such a large LCD screen, a color filter flattening film having excellent flatness is required. The planarization film is subjected to high temperature, organic solvent, acid solution, alkali solution, light irradiation, alignment film rubbing and the like during the LCD manufacturing process.

따라서 평탄화막은 상기와 같은 조건들에서 내성을 가지는 동시에 강도, 타층과의 접착성, 투명성, 평탄화성 등이 우수한 물성이 요구된다. 특히나 평탄화막 공정 후 평탄화막 위에 컬럼 스페이서나 ITO, 배향막 등이 도포되게 되는데 평탄화막의 평탄성이 떨어질 경우 평탄화막과 상기의 타층과의 접착성 불량 및 평탄성 불량으로 인하여 얼룩현상, 배선불량, 액정배향불량 등이 발생하므로 대형화면 일수록 평탄화막의 고평탄화성이 요구되어진다.Therefore, the planarization film is required to be resistant under the above conditions and to have excellent physical properties such as strength, adhesion to other layers, transparency, planarization, and the like. In particular, after the planarization process, column spacers, ITO, and alignment layers are coated on the planarization film. If the planarization film becomes poor, unevenness, poor wiring, and poor liquid crystal orientation due to poor adhesion and poor planarity between the planarization film and the other layers. And the like, the larger the screen, the higher the flatness of the planarization film is required.

이러한 평탄화막을 형성하기 위한 재료로는 열경화성 중합체, 보조경화제, 경화제, 첨가제, 용매등으로 구성된 조성물이 많이 사용되고 있다. 이러한 종래의 조성물의 경우 고평탄화성을 구현하는데 한계가 있는 단점이 있다.As a material for forming such a planarization film, a composition composed of a thermosetting polymer, an auxiliary curing agent, a curing agent, an additive, a solvent, and the like is frequently used. In the case of such a conventional composition, there is a disadvantage in that there is a limit in implementing high flatness.

이에 본 발명에서는 상기와 같은 단점을 보완하기 위해 에폭시기 함유 반응성 용매를 사용한 결과, 평탄화막으로서 종래로부터 요구되는 물성을 만족하는 동시에, 평탄화도를 효과적으로 향상시켜 고평탄화성을 갖는 칼라필터 평탄화막용 열경화성 조성물 및 이를 이용한 평탄화막을 제공할 수 있음을 알게 되어 본 발명에 도달하게 되었다. Accordingly, in the present invention, as a result of using an epoxy group-containing reactive solvent in order to compensate for the above disadvantages, the thermosetting composition for color filter planarizing films having high flattenability by satisfying the physical properties required in the past as a planarizing film and effectively improving the planarization degree And it was found that it can provide a flattening film using the same has led to the present invention.

따라서, 본 발명의 목적은 평탄화막으로서 종래부터 요구되는 물성을 만족함과 동시에, 평탄화도를 효과적으로 향상시켜 고평탄화성을 갖는 칼라필터 평탄화막용 열경화성 조성물 및 이를 이용한 평탄화막을 제공하는 데 있다. Accordingly, an object of the present invention is to provide a thermosetting composition for a color filter planarizing film having a high leveling property by satisfying the conventionally required physical properties as a planarizing film and effectively improving the planarization degree, and a planarizing film using the same.

상기와 같은 목적을 달성하기 위하여 본 발명은 칼라필터 평탄화막용 열경화성 수지 조성물에 있어서, 에폭시기 함유 반응성 용매를 더 포함하는 것을 그 특징으로 한다.In order to achieve the above object, the present invention is characterized by further comprising an epoxy group-containing reactive solvent in the thermosetting resin composition for a color filter flattening film.

이하, 본 발명을 더욱 상세하게 설명하면 다음과 같다. Hereinafter, the present invention will be described in more detail.

본 발명의 칼라필터 평탄화막용 열경화성 수지 조성물은 중합체, 보조경화제, 경화용 촉매, 용매, 및 기타첨가제를 포함하며, 여기에 특별히 에폭시기 함유 반응성 용매를 첨가한 데 특징이 있다. The thermosetting resin composition for a color filter flattening film of the present invention contains a polymer, an auxiliary curing agent, a curing catalyst, a solvent, and other additives, and is particularly characterized by adding an epoxy group-containing reactive solvent.

이러한 본 발명의 칼라필터 평탄화막용 열경화성 수지 조성물에 포함되는 구체적인 성분들을 설명하면 다음과 같다.The specific components included in the thermosetting resin composition for a color filter flattening film of the present invention are as follows.

중합체polymer

본 발명 조성에 포함되는 중합체는 기존에 공지되어 있는 국내공개특허 제2005-0050348호, 제2005-0075197호의 중합 방법에 의하여 제조된 것으로, 주쇄에 올레핀 유도체인 단량체와 하이드록시알킬기, 하이드록시기, 글리시딜기 또는 알킬기 중에서 선택된 기능기를 가진 아크릴 또는 메타아크릴 단량체를 포함하고, 측쇄에는 하이드록시기 또는 에폭시기 등과 같은 경화가 가능한 관능기를 포함하는 다음 화학식 2로 표시되는 다원 공중합체이다. The polymer included in the composition of the present invention is prepared by the polymerization method of the previously known Korean Patent Publication Nos. 2005-0050348 and 2005-0075197, and a monomer, a hydroxyalkyl group, a hydroxy group, It is an acrylic or methacrylic monomer having a functional group selected from a glycidyl group or an alkyl group, the side chain is a multi-component copolymer represented by the following formula (2) containing a curable functional group such as a hydroxyl group or an epoxy group.

Figure 112006059085018-pat00001
Figure 112006059085018-pat00001

상기 화학식 2에서, X는 올레핀 유도체; 또는 하이드록시기, 카르복실산기, 에테르기, 나이트릴기 및 에스테르로부터 선택된 관능기를 갖는 올레핀 단량체로부터 유래된 것이고, In Formula 2, X is an olefin derivative; Or derived from an olefin monomer having a functional group selected from a hydroxyl group, a carboxylic acid group, an ether group, a nitrile group and an ester,

R3과 R5는 서로 다른 것으로, 각각 수소원자 또는 메틸기이며, R 3 and R 5 are different from each other, each of a hydrogen atom or a methyl group,

R4와 R6는 서로 다른 것으로, 각각 수소원자; 글리시딜메틸기; 하이드록시알킬기; 또는 탄소수 1 내지 33인 알킬기이고, R 4 and R 6 are different from each other, each hydrogen atom; Glycidylmethyl group; Hydroxyalkyl group; Or an alkyl group having 1 to 33 carbon atoms,

Y는 케톤, 에스테르, 하이드록시, 에테르, 할로겐, 니트릴 및 알콕시로부터 선택된 관능기를 갖거나 또는 갖지 않는 올레핀 화합물; 스타이렌 유도체; 또는 아크릴로나이트릴 단량체로부터 유래된 화합물이며,Y is an olefin compound with or without a functional group selected from ketones, esters, hydroxy, ethers, halogens, nitriles and alkoxy; Styrene derivatives; Or a compound derived from an acrylonitrile monomer,

o, p, q 및 r은 중합체의 반복단위로서, o는 0<o/(o+p+q+r)<0.7, p는 0.1<p/(o+p+q+r)<0.7, q는 0≤q/(o+p+q+r)<0.5 및 r은 0≤r/(o+p+q+r)<0.5인 조건을 만족한다.o, p, q and r are repeating units of the polymer, where o is 0 <o / (o + p + q + r) <0.7, p is 0.1 <p / (o + p + q + r) <0.7, q satisfies the condition that 0 ≦ q / (o + p + q + r) <0.5 and r is 0 ≦ r / (o + p + q + r) <0.5.

또한 본 중합체는 일반적으로 강산이나 라디칼에 의해 경화될 수 있는 관능기를 포함하지만, 경우에 따라서는 포함하지 않을 수도 있다.In addition, the present polymer generally contains a functional group that can be cured by a strong acid or a radical, but may not be included in some cases.

보조경화제Auxiliary hardener

본 발명의 상기 화학식 2로 표시되는 중합체 중 자체 내에 경화 반응이 진행될 수 있는 작용기가 없는 경우나, 작용기가 있는 경우라도 평탄화막의 경도조절, 접착력 향상, 평탄도 향상 등을 위한 수단으로 보조 경화제를 첨가할 수 있다. Addition of an auxiliary curing agent as a means for adjusting the hardness of the flattening film, improving adhesion, improving flatness, etc., even when there is no functional group capable of undergoing a curing reaction in the polymer represented by Formula 2 of the present invention, or even when there is a functional group can do.

이러한 보조경화제의 구체적인 예로는, 비스페놀 A, 1,1,1-트리스(4-하이드록시페닐)에탄 및 폴리하이드록시스티렌과 같은 하이드록시페닐기가 있는 단량체 또는 중합체; 비스페놀 A 디글리시딜 에테르, 비스페놀 A 프로폭실레이트 디글리시딜 에테르, 및 트리페닐올메탄 트리글리시딜 에테르로 이루어진 그룹으로부터 선택된 글리시딜기가 2개 이상 치환된 폴리올류의 단량체 또는 중합체; 또는 에틸렌성 불포화 관능기가 2 내지 6인 다관능성 모노머가 있다. Specific examples of such co-curing agents include monomers or polymers having hydroxyphenyl groups such as bisphenol A, 1,1,1-tris (4-hydroxyphenyl) ethane and polyhydroxystyrene; Monomers or polymers of polyols having two or more glycidyl groups selected from the group consisting of bisphenol A diglycidyl ether, bisphenol A propoxylate diglycidyl ether, and triphenylolmethane triglycidyl ether; Or polyfunctional monomers having 2 to 6 ethylenically unsaturated functional groups.

상기 에틸렌성 불포화 관능기가 2 내지 6인 화합물의 구체적인 예를 들면, 1,6-헥산디올 디아크릴레이트, 1,6-헥산디올(에톡시레이티드)디아크릴레이트, 1,4-부탄디올 디아크릴레이트, 히드록시 피발릭엑시드 네오펜틸 글리콜 디아크릴레이트, 네오펜틸 글리콜 디아크릴레이트, 트리프로필렌 글리콜 디아크릴레이트, 디프로필렌 글리콜 디아크릴레이트, 트리시클로데칸 디메탄올 디아크릴레이트, 테트라에틸렌 글리콜 디아크릴레이트, 트리메틸올프로판 트리아크릴레이트, 트리메틸올프로판 에톡시레이티드 트리아크릴레이트, 글리세린 프로폭시레이티드 트리아크릴레이트, 펜타에리트리톨 트리아크릴레이트, 디(트리메틸올프로판)테트라아크릴레이트, 펜타에리트리톨 테트라아크릴레이트, 펜타에리트리톨 프로폭시레이티드 트리아크릴레이트, 디펜타에이트리톨 펜타아크릴레이트, 디펜타에리트리톨 헥사아크릴레 이트, 펜타에리트리톨 에톡시레이티드 테트라아크릴레이트, 1,4-부탄올 디메타아크릴레이트, 1,6-헥산디올 디메타아크릴레이트, 에틸렌글리콜 디메타아크릴레이트, 디에틸렌글리콜 디메타아크릴레이트, 트리에틸렌글리콜 디메타아크릴레이트, 알콕시레이티드 디메타아크릴레이트, 및 트리메틸올프로판 트리메타아크릴레이트로 이루어진 그룹으로부터 선택된 것이다. Specific examples of the compound having 2 to 6 ethylenically unsaturated functional groups include 1,6-hexanediol diacrylate, 1,6-hexanediol (ethoxylated) diacrylate, and 1,4-butanediol diacryl Latex, hydroxy pivalic acid neopentyl glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, tetraethylene glycol diacrylate , Trimethylolpropane triacrylate, trimethylolpropane ethoxylated triacrylate, glycerin propoxylated triacrylate, pentaerythritol triacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylic Latex, pentaerythritol propoxylated triacrylate, diphene Erythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol ethoxylated tetraacrylate, 1,4-butanol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol di Methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, alkoxylated dimethacrylate, and trimethylolpropane trimethacrylate.

또한, 에폭시 아크릴레이트를 사용할 수 있는 바, 특별히 비스페놀 A 에폭시 디아크릴레이트, 비스페놀 A 에폭시 디메타아크릴레이트 등이 바람직하며; 폴리에스테르 아크릴레이트로는 4관능 폴리에스테르 아크릴레이트, 6관능 폴리에스테르 아크릴레이트, 클로리네이티드 폴리에스테르 아크릴레이트 등이 바람직하며; 또한 폴리우레탄 아크릴레이트로 2관능 폴리우레탄 아크릴레이트, 3관능 폴리우레탄 아크릴레이트, 6관능 폴리우레탄 아크릴레이트를 사용할 수 있다.In addition, since epoxy acrylate can be used, bisphenol A epoxy diacrylate, bisphenol A epoxy dimethacrylate, etc. are especially preferable; As the polyester acrylate, a tetrafunctional polyester acrylate, a six functional polyester acrylate, a cloned polyester acrylate, etc. are preferable; Also, as the polyurethane acrylate, bifunctional polyurethane acrylate, trifunctional polyurethane acrylate, and 6 functional polyurethane acrylate can be used.

상기의 보조경화제들은 단독으로 사용하거나 2종 이상을 혼합하여 사용할 수도 있으며, 보조경화제를 첨가하는 경우 그 함량은 경도, 평탄화도, 및 칼라필터와의 접착력 등을 고려하여 상기 중합체 100중량부에 대하여 20중량부 이내로 사용하는 것이 바람직하며, 더욱 바람직하게는 3 내지 20중량부로 사용한다.The auxiliary hardeners may be used alone or in combination of two or more thereof. When the auxiliary hardener is added, the amount of the auxiliary hardener is 100 parts by weight of the polymer in consideration of hardness, flatness, and adhesion to a color filter. It is preferably used within 20 parts by weight, more preferably from 3 to 20 parts by weight.

경화용 촉매Curing Catalyst

본 발명의 경화용 촉매는 산발생제, 라디칼 개시제 도는 아미노플라스트 화합물 중에서 선택하여 단독으로 사용하거나, 또는 2종 이상 혼합하여 사용한다. The curing catalyst of the present invention is selected from an acid generator, a radical initiator, or an aminoplast compound and used alone or in combination of two or more thereof.

산발생제는 화합물의 특성에 따라 열이나 광에 의해 산을 발생시키는 화합물 로서, 오니움계인 요드니움염(iodonium salts), 술포니움염(sulfonium salts), 포스포니움염, 디아조니움염, 피리디니움염, sec-알킬-톨루엔술포네이트 및 아미드류 등이 있다. Acid generators are compounds that generate acids by heat or light, depending on the properties of the compounds, such as onium-based iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinini Um salts, sec-alkyl-toluenesulfonates and amides.

특히 상기 sec-알킬-톨루엔술포네이트 중에서 사이클로헥실-톨루엔술포네이트 또는 사이클로펜틸-톨루엔술포네이트는 150℃ 전후에서 산이 발생되고, 노보넨-톨루엔술포네이트는 110℃ 전후에서 산을 발생시키므로, 반응 공정 중에 사용되는 공정 온도 및 효율을 고려할 때 노보넨이 치환된 톨루엔술포네이트인 톨루엔-4-설포닉엑시드 비시클로[2,2,1]헵트-2-일 에스테르를 사용하는 것이 바람직하며, 보관안정성이나 합성법도 간단하여 용이하게 사용할 수 있다. In particular, in the sec-alkyl-toluenesulfonate, cyclohexyl-toluenesulfonate or cyclopentyl-toluenesulfonate generates an acid at about 150 ° C., and norbornene-toluenesulfonate generates an acid at about 110 ° C., thus causing a reaction process. Considering the process temperature and efficiency used in the process, it is preferable to use toluene-4-sulphonic acid bicyclo [2,2,1] hept-2-yl ester, which is a toluenesulfonate substituted with norbornene. The synthesis method is also simple and can be used easily.

그러나, tert-알킬-톨루엔술폰네이트의 경우 보관안정성이 떨어지고, primary-알킬-톨루엔술폰네이트의 경우에는 열적 안정성이 뛰어나 매우 높은 온도에서 산이 발생되는 단점이 있어, 본 발명에서는 sec-알킬-톨루엔술포네이트를 사용하는 것이 바람직하다.However, tert-alkyl-toluenesulfonate has poor storage stability, and primary-alkyl-toluenesulfonate has a disadvantage of excellent thermal stability and generation of acid at a very high temperature. In the present invention, sec-alkyl-toluenesulfo Preference is given to using nates.

또한, 라디칼 개시제는 중합체의 반응을 개시하는 역할을 수행하며, 2,2'-아조비스 이소부티로니트릴, 디메틸-2,2'-아조비스 이소부티레이트, 2,2'-아조비스-(2,4-디메틸발레로니트릴), 2,2'-아조비스-(2-메틸 부티로 니트릴), 2,2'-아조비스-(4-메톡시-2,4-디메틸발레로니트릴), 및 1,1'-아조비스-1-시클로헥산카보니트릴로 이루어진 그룹으로부터 선택된 아조니트릴 화합물; 벤조일 퍼옥시드, t-부틸 퍼옥시드, 1,1'-비스-(t-부틸 퍼옥시)시클로 헥산, 1,1'-비스-(t-부틸퍼옥시)시클로도데칸, 2,2'-비스-(t-부틸 퍼옥시)부탄, n-부틸-4,4'-비스-(t-부틸퍼옥시)발레라이 트, 2,2'-비스-(4,4-디-t-부틸 퍼옥시-시클로헥실)프로판, 파라-메탄-하이드로퍼옥사이드, 디이소프로필-벤젠-하이드로퍼옥사이드, 1,1',3,3'-테트라메틸부틸-하이드로 퍼옥사이드, 큐멘-하이드로 퍼옥사이드, t-헥실 하이드로 퍼옥사이드, 시클로헥사논 퍼옥사이드, 메틸시클로헥사논 퍼옥사이드, 메틸아세토아세테이트 퍼옥사이드, 아세틸아세톤 퍼옥사이드, 1,1'-비스(t-헥실퍼옥시)3,3,5-트리메틸 시클로헥산, 1,1'-비스(t-헥실퍼옥시)시클로헥산, 1,1'-비스(t-부틸퍼옥시)3,3,5-트리메틸 시클로헥산, 및 디-t-부틸퍼옥시-2-메틸 사이클로헥산으로 이루어진 그룹으로부터 선택된 유기 과산화물 중에서 선택된 것이다. In addition, the radical initiator serves to initiate the reaction of the polymer, 2,2'-azobis isobutyronitrile, dimethyl-2,2'-azobis isobutyrate, 2,2'-azobis- (2 , 4-dimethylvaleronitrile), 2,2'-azobis- (2-methyl butyronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), And 1,1'-azobis-1-cyclohexanecarbonitrile; Benzoyl peroxide, t-butyl peroxide, 1,1'-bis- (t-butyl peroxy) cyclo hexane, 1,1'-bis- (t-butylperoxy) cyclododecane, 2,2'- Bis- (t-butyl peroxy) butane, n-butyl-4,4'-bis- (t-butylperoxy) ballate, 2,2'-bis- (4,4-di-t-butyl Peroxy-cyclohexyl) propane, para-methane-hydroperoxide, diisopropyl-benzene-hydroperoxide, 1,1 ', 3,3'-tetramethylbutyl-hydro peroxide, cumene-hydro peroxide, t-hexyl hydroperoxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetone peroxide, 1,1'-bis (t-hexylperoxy) 3,3,5- Trimethyl cyclohexane, 1,1'-bis (t-hexylperoxy) cyclohexane, 1,1'-bis (t-butylperoxy) 3,3,5-trimethyl cyclohexane, and di-t-butylper Organic selected from the group consisting of oxy-2-methyl cyclohexane It is selected from the oxides.

아미노플라스트 화합물로는 글리콜우릴-포름알데히드 레진, 멜라민-포름알데히드 레진, 벤조구아민-포름알데히드 레진, 우레아-포름알데히드 레진이 있으며, 이러한 각 레진의 메틸레이티드나 부틸레이티드 구조가 보관안정성이 뛰어나 바람직하게 사용되며, 특히 바람직하게는 메틸레이트 글리콜우릴-포름알데히드 레진으로 POWDER-LINK 1174(Cytec Industries)와 멜라민-포름알데히드 레진으로 폴리(멜라민-co-포름알데히드)아크릴레이티드, 폴리(멜라민-co-포름알데히드)메틸레이티드, 폴리(멜라민-co-포름알데히드)부틸레이티드, 폴리(멜라민-co-포름알데히드)이소부틸레이티드가 바람직하다.Aminoplast compounds include glycoluril-formaldehyde resins, melamine-formaldehyde resins, benzoguamine-formaldehyde resins, and urea-formaldehyde resins, and the methylated or butylated structures of each of these resins are characterized by storage stability. It is excellent and preferably used, and particularly preferably poly (melamine-co-formaldehyde) acrylate, poly () with POWDER-LINK 1174 (Cytec Industries) and melamine-formaldehyde resin as methylate glycoluril-formaldehyde resin. Preference is given to melamine-co-formaldehyde) methylated, poly (melamine-co-formaldehyde) butylated, and poly (melamine-co-formaldehyde) isobutylated.

본 발명의 경화용 촉매는 상기 중합체 100중량부에 대하여 0.1 내지 10 중량부로 사용하는 것이 경화 반응 및 코팅 물성 등의 측면에서 바람직하다. The curing catalyst of the present invention is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer, in terms of curing reaction and coating properties.

에폭시기 함유 반응성 용매Epoxy Group-Containing Reactive Solvent

본 발명에서는 특별히 에폭시기 함유 반응성 용매를 포함하는 바, 이는 중합체 및 보조경화제에 대하여 열경화에 의하여 가교형성이 될 수 있도록 에폭시기를 함유하고 있으며, 열경화에 의하여 가교가 진행될 수 있는 또 다른 작용기로 글리시딜기, 하이드록시기, 또는 비닐기를 포함할 수 있다. 구체적으로는 다음 화학식으로 표시되는 화합물 중에서 선택된 1종 또는 2종 이상의 것이다. In the present invention, an epoxy group-containing reactive solvent is specifically included, which contains an epoxy group so as to be crosslinked by thermosetting with respect to the polymer and the co-curing agent, and another functional group capable of undergoing crosslinking by thermosetting. It may include a cylyl group, a hydroxyl group, or a vinyl group. Specifically, it is one kind or two or more kinds selected from the compounds represented by the following formulas.

Figure 112006059085018-pat00002
Figure 112006059085018-pat00002

상기 각각의 화학식에서, 상기 A, B, C, D는 글리시딜기, 하이드록시기, 디하이드록시기 중에서 선택된 1종 이상의 관능기를 포함하거나 또는 포함하지 않는 C2-15 직쇄상, 분쇄상, 또는 환상의 탄화수소, 에테르, 글리콜, 케톤, 및 에스테르이고, In each of the above formula, A, B, C, D is C 2-15 linear, pulverized phase, which may or may not include at least one functional group selected from glycidyl group, hydroxy group, dihydroxy group, Or cyclic hydrocarbons, ethers, glycols, ketones, and esters,

상기 화학식에서 각 R1은 서로 같거나 다른 것으로서, 수소원자, C1-5알킬, 또는 C1-5 알킬에테르이고, R2는 각각 수소원자 또는 C1-5알킬이며, m은 3~6인 정수이고, n은 0~10인 정수이다.In the formula, each R 1 is the same as or different from each other, a hydrogen atom, C 1-5 alkyl, or C 1-5 alkyl ether, R 2 is each a hydrogen atom or C 1-5 alkyl, and m is 3-6 Is an integer and n is an integer of 0-10.

이러한 에폭시기 함유 반응성 용매의 요구 물성으로는 중합체, 보조경 화제에 대한 혼화성과 용매에 대한 용해성이 우수해야 하며, 비등점이 높아 휘발되지 않아야 열경화에 의하여 중합체, 보조경화제와 함께 가교형성이 되어 고평탄도를 구현 할 수가 있다.Such epoxy group-containing reactive solvents should have excellent compatibility with polymers and co-curing agents and solubility in solvents, and should not be volatilized due to high boiling point. You can implement

혼화성과 용해성이 떨어질 경우 코팅 후 얼룩이 발생하며 혼화 불량으로 오히려 평탄도가 떨어지는 현상이 발생할 수가 있으며, 비등점이 180℃ 미만인 경우 휘발로 인한 얼룩 및 휘발되지 않고 불균일하게 남아있는 반응성 용매로 인하여 전체적인 평탄도가 떨어지는 현상이 발생한다.If the miscibility and solubility are poor, staining may occur after coating, and poor flatness may occur due to poor miscibility. If the boiling point is lower than 180 ° C, the overall flatness may be due to uneven volatility and stains caused by volatilization. Falling phenomenon occurs.

이러한 물성을 만족하는 본 발명의 에폭시기 함유 반응성 용매의 구체적인 예로는, 1,2,7,8-디에폭시옥탄, 에틸렌글리콜 디글리시딜 에테르, 네오펜틸글리콜 디글리시딜 에테르, 1,4-부탄디올 디글리시딜 에테르, 1,4-시클로헥산 디메탄올 디글리시딜 에테르, 4-비닐-1-시클로헥센 디에폭시드, 글리세롤 트리글리시딜 에테르, 3,4-에폭시시클로헥실메틸-3,4-에폭시시클로헥산 카르복실레이트, 디글리시딜-1,2-시클로헥산디카르복실레이트, 비스(3,4-에폭시시클로헥실메틸)아디페이트, 1,2-에폭시-9-데센, 리모넨 옥시드, 프로필옥시란메탄올, 3-[비스(글리시딜옥시메틸)-메톡시]-1,2-프로판디올, 1,3-비스-옥시레닐 메톡시-프로판-2-올 등이 바람직하지만, 이에 한정되는 것은 아니다.Specific examples of the epoxy group-containing reactive solvent of the present invention satisfying such physical properties include 1,2,7,8-diepoxyoctane, ethylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,4- Butanediol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, 4-vinyl-1-cyclohexene diepoxide, glycerol triglycidyl ether, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, diglycidyl-1,2-cyclohexanedicarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 1,2-epoxy-9-decene, limonene Oxide, propyloxyranmethanol, 3- [bis (glycidyloxymethyl) -methoxy] -1,2-propanediol, 1,3-bis-oxyrenyl methoxy-propan-2-ol and the like are preferred. However, it is not limited thereto.

상기와 같은 본 발명의 에폭시기 함유 반응성 용매는 상기 나열된 화합물 중에 에폭시기를 함유함과 동시에, 반드시 글리시딜기, 히드록시기, 또는 (알킬브랜치드)비닐기 중에서 선택된 1종의 관능기를 포함하는 바, 이는 상기 글리시딜기, 히드록시기, 또는 (알킬브랜치드)비닐기와 같은 관능기들은 중합체 및 보조경화제 와 열에 의한 경화가 일어날 수 있는 관능기들로서, 상기 관능기를 포함하지 않는 용매를 사용할 경우(예를 들어, 에폭시기 하나만 있는 용매) 관능기가 부족하여 경화도가 현저히 저하되어 경도가 저하되고, 물성저하로 이어져 칼라필터 평탄화막을 형성하기 어렵기 때문이다. The epoxy group-containing reactive solvent of the present invention as described above contains one functional group selected from glycidyl, hydroxy, and (alkyl branched) vinyl groups while containing an epoxy group in the compounds listed above. Functional groups such as glycidyl group, hydroxy group, or (alkyl branched) vinyl group are functional groups capable of curing with polymer and co-curing agent and heat, and when using a solvent not containing the functional group (for example, having only one epoxy group) This is because the degree of hardening is remarkably lowered, the hardness is lowered, the physical properties are lowered, and it is difficult to form a color filter flattening film.

본 발명의 에폭시기 함유 반응성 용매는 상기 화학식으로 표시되는 화합물 중에서 선택된 1종 또는 2종 이상을 포함하는 것으로서, 그 함량은 상기 중합체 100중량부에 대하여 40중량부 이내인 것이 바람직하며, 더욱 바람직하게는 3 내지 30중량부를 사용한다. 특별히 40중량부를 초과할 경우, 충분한 경화가 일어나지 않아 경도 저하 및 물성저하의 문제가 발생 할 수 있다. The epoxy group-containing reactive solvent of the present invention includes one or two or more selected from the compounds represented by the above formula, and the content thereof is preferably within 40 parts by weight based on 100 parts by weight of the polymer, more preferably. 3 to 30 parts by weight is used. In particular, when the content exceeds 40 parts by weight, sufficient curing may not occur, which may cause problems of lowering hardness and lowering physical properties.

첨가제additive

첨가제로는 평탄화막의 균일성을 높이거나 용액의 혼화성을 높이기 위해 비이온성 계면활성제나 실리콘계 계면활성제를 사용할 수 있으며, 박막조성물의 보관안정성을 높이기 위해 산화방지제를 포함한 보관안정제를 사용할 수 있다.As an additive, a nonionic surfactant or a silicone-based surfactant may be used to increase the uniformity of the planarization film or the miscibility of the solution, and a storage stabilizer including an antioxidant may be used to increase the storage stability of the thin film composition.

첨가제의 함량은 표면의 균일성, 경도 및 얼룩 발생 문제 등을 고려하여 상기 중합체 100중량부에 대하여 0.1 내지 1 중량부인 것이 바람직하다. The content of the additive is preferably 0.1 to 1 parts by weight based on 100 parts by weight of the polymer in consideration of surface uniformity, hardness and staining problems.

용매menstruum

본 발명의 열경화성 평탄화막 조성물에 사용되는 용매로는 중합체, 보조경화제, 경화용 촉매, 에폭시기 함유 반응성 용매, 및 첨가제와 같은 각 성분을 균일하 게 용해시키며, 이러한 성분들과 반응하지 않는 것으로서 적당한 증발속도와 점성을 가진 용매가 바람직하다. The solvent used in the thermosetting flattening film composition of the present invention uniformly dissolves each component such as a polymer, a co-curing agent, a curing catalyst, an epoxy group-containing reactive solvent, and an additive, and does not react with these components. Preference is given to solvents having speed and viscosity.

이러한 물성을 가진 용매로는, 글리콜 에테르류 용매로서 에틸렌글리콜 모노메틸 에테르, 에틸렌글리콜 모노에틸 에테르, 에틸렌글리콜 모노프로필 에테르, 에틸렌글리콜 에틸 메틸 에테르; 아세테이트류 용매로 메틸셀로솔브 아세테이트, 에틸셀로솔브 아세테이트, 프로필렌글리콜 모노메틸 에테르 아세테이트, 프로필렌글리콜 모노에틸 에테르 아세테이트, 프로필렌글리콜 모노프로필 에테르 아세테이트가 있으며; 케톤류 용매로 메틸 이소프로필 케톤, 시클로헥사논, 2-헵타논이 있으며; 히드록시프로피온네이트류 용매로 메틸-2-히드록시프로피온네이트, 에틸-2-히드록시프로피온네이트이 있고; 카비톨류 용매로 메틸 카비톨, 에틸 카비톨, 프로필 카비톨이 있으며; 락테이트나 락톤류 용매로 에틸락테이트, 감마-부티로락톤 등이 바람직하다.Examples of the solvent having such physical properties include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol ethyl methyl ether as glycol ether solvents; Acetate solvents include methylcellosolve acetate, ethylcellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate; Ketone solvents include methyl isopropyl ketone, cyclohexanone and 2-heptanone; Hydroxypropionate solvents include methyl-2-hydroxypropionate and ethyl-2-hydroxypropionate; Carbitol solvents include methyl carbitol, ethyl carbitol and propyl carbitol; As lactate or lactone solvent, ethyl lactate, gamma-butyrolactone, etc. are preferable.

상기의 용매들은 단독으로 사용하거나 2종 이상을 혼합하여 사용할 수도 있으며, 용매의 함량은 휘발성, 점도 등 용매의 물성에 따라 적당량 사용하여 박막이 균일하게 형성될 수 있도록 조절하는 것이 바람직하며, 더욱 바람직하게는 전체 평탄화막 조성물 중 60 내지 85 중량%로 사용하는 것이 바람직하다. The above solvents may be used alone or in a mixture of two or more thereof, and the content of the solvent is preferably adjusted in an appropriate amount according to the physical properties of the solvent such as volatility and viscosity so that the thin film may be uniformly formed. Preferably it is used at 60 to 85% by weight of the total planarization film composition.

상기와 같은 성분을 포함하는 본 발명의 평탄화막 열경화성 수지 조성물은 0.2㎛ 막 필터로 여과시켜 사용한다. 또한, 이러한 평탄화막 열경화성 수지 조성물로부터 평탄화막을 제조하는 공정을 개략적으로 설명하면 다음과 같다. 상기 제조된 평탄화막 열경화성 수지 조성물을 스핀코팅으로 RGB(Red, Green, Blue) 도포 공 정까지 끝난 칼라필터 기판과, LCD용 투명 유리(Glass)에 도포하고, 100℃에서 120초간 가열하고, 220℃로 30분 소성하여 컬러필터 기판의 RGB를 포함하여 2.8~3.8㎛, LCD용 투명 Glass에서 1~1.5㎛가 되도록 평탄화막을 형성시킨다.The flattening film thermosetting resin composition of this invention containing the above components is used by filtering with a 0.2 micrometer film filter. In addition, the process of manufacturing a planarization film from such a planarization film thermosetting resin composition is briefly described as follows. The flattening film thermosetting resin composition prepared above was coated on a color filter substrate finished with RGB (Red, Green, Blue) coating process by spin coating, a transparent glass for LCD, and heated at 100 ° C. for 120 seconds, and 220 By baking for 30 minutes at 30 ° C., a flattening film is formed to have a color filter substrate of 2.8 to 3.8 μm including RGB, and 1 to 1.5 μm in transparent glass for LCD.

이하 본 발명을 실시예에 의거하여 구체적으로 설명하는 바 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, and the present invention is not limited by Examples.

<실시예 1><Example 1>

냉각관, 교반기, 질소 퍼지장치를 구비한 반응기에 2,2'-아조비스 이소부티로니트릴 5중량부와 3-메틸-3-부텐올 12.5중량부를 프로필렌글리콜 모노메틸 에테르 아세테이트(PGMEA) 200중량부에 녹인 후 반응기를 70℃로 승온하였다. 이 반응기에 글리시딜 메타아크릴레이트 50중량부와 t-부틸 아크릴레이트 25중량부 그리고 스타이렌 12.5중량부를 4시간에 걸쳐 서서히 적하시켰다. 적하가 끝나면 같은 온도에서 4시간 동안 교반 후 감압증류를 통하여 미반응 모노머들을 제거하고 상온으로 냉각시켜 공중합체[A]를 포함하는 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 함량은 40중량%이었다.200 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) 5 parts by weight of 2,2'-azobis isobutyronitrile and 12.5 parts by weight of 3-methyl-3-butenol in a reactor equipped with a cooling tube, a stirrer and a nitrogen purge device After dissolving in the portion, the reactor was heated to 70 ° C. 50 parts by weight of glycidyl methacrylate, 25 parts by weight of t-butyl acrylate and 12.5 parts by weight of styrene were slowly added dropwise to the reactor over 4 hours. After the dropwise addition, the mixture was stirred at the same temperature for 4 hours, and then unreacted monomers were removed by distillation under reduced pressure and cooled to room temperature to obtain a polymer solution containing the copolymer [A]. Solid content of the obtained polymer solution was 40 weight%.

상기 중합체 A 100중량부(고형분 함량), 보조경화제로 비스페놀 A 디글리시딜 에테르 15중량부, 경화용 촉매로 산발생제인 톨루엔-4-설포닉엑시드 비시클로[2,2,1]헵트-2-일 에스테르 1.5중량부와 아미노플라스트인 폴리(멜라민-co-포름알데히드)아크릴레이티드 1.5중량부를 합한 3중량부, 에폭시기 함유 반응성 용매로 에틸렌글리콜 디글리시딜 에테르 20중량부, 첨가제로 계면활성제인 FC-430(3M) 0.1중량부와 보관안정제인 Irganox 1010(스위스 시바가이기사) 0.1중량부를 첨가하여 고형분 농도 25중량%가 되도록 용매 디에틸렌글리콜디메틸에테르에 용해시켜 칼라필터 평탄화막 제조를 위한 열경화성 수지 조성물을 제조하였다.100 parts by weight of the polymer A (solid content), 15 parts by weight of bisphenol A diglycidyl ether as an auxiliary curing agent, and toluene-4-sulphonic acid bicyclo [2,2,1] hept as an acid generator as a curing catalyst. 3 parts by weight of 1.5 parts by weight of 2-yl ester and 1.5 parts by weight of poly (melamine-co-formaldehyde) acrylate, an aminoplast, 20 parts by weight of ethylene glycol diglycidyl ether as an epoxy group-containing reactive solvent, and an interface with additives 0.1 part by weight of FC-430 (3M), an active agent, and 0.1 part by weight of Irganox 1010 (Shiba Seiki Co., Ltd.), a storage stabilizer, were dissolved in solvent diethylene glycol dimethyl ether to obtain a solid concentration of 25% by weight. Thermosetting resin composition was prepared.

<실시예 2 내지 5><Examples 2 to 5>

상기 실시예 1에서 사용한 에폭시기 함유 반응성 용매 대신, 실시예 2에서는 1,4-부탄디올 디글리시딜 에테르를, 실시예 3에서는 1,4-시클로헥산 디메탄올 디글리시딜 에테르를, 실시예 4에서는 디글리시딜-1,2-시클로헥산디카르복실레이트를, 실시예 5에서는 3,4-에폭시 시클로헥실메틸-3,4-에폭시시클로헥산 카르복실레이트를 사용하는 것을 제외하고는, 상기 실시예 1과 동일한 조성을 가진 칼라필터 평탄화막 제조를 위한 열경화성 수지 조성물을 제조하였다.Instead of the epoxy group-containing reactive solvent used in Example 1, 1,4-butanediol diglycidyl ether in Example 2, 1,4-cyclohexane dimethanol diglycidyl ether in Example 3, and Example 4 Except that diglycidyl-1,2-cyclohexanedicarboxylate is used, and in Example 5, 3,4-epoxy cyclohexylmethyl-3,4-epoxycyclohexane carboxylate is used. A thermosetting resin composition for preparing a color filter flattening film having the same composition as in Example 1 was prepared.

<실시예 6 ><Example 6>

냉각관, 교반기, 질소 퍼지장치를 구비한 반응기에 2,2'-아조비스 이소부티로니트릴 5중량부와 3-메틸-3-부텐올 12.5중량부와 노보넨 12.5중량부를 프로필렌글리콜 모노메틸 에테르 아세테이트(PGMEA) 200중량부에 녹인 후 반응기를 70℃로 승온하였다. 이 반응기에 글리시딜 메타아크릴레이트 50중량부와 스타이렌 25중량부를 4시간에 걸쳐 서서히 적하시켰다. 적하가 끝나면 같은 온도에서 4시간동안 교반 후 감압증류를 통하여 미반응 모노머들을 제거하고 상온으로 냉각시켜 공중합체 B를 포함하는 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 함량은 40중량%이었다. 5 parts by weight of 2,2'-azobis isobutyronitrile, 12.5 parts by weight of 3-methyl-3-butenol, and 12.5 parts by weight of norbornene in a reactor equipped with a cooling tube, a stirrer, and a nitrogen purge propylene glycol monomethyl ether After dissolving in 200 parts by weight of acetate (PGMEA), the reactor was heated to 70 ℃. 50 parts by weight of glycidyl methacrylate and 25 parts by weight of styrene were slowly added dropwise to the reactor over 4 hours. After the dropwise addition, the mixture was stirred at the same temperature for 4 hours, and then unreacted monomers were removed by distillation under reduced pressure and cooled to room temperature to obtain a polymer solution containing copolymer B. Solid content of the obtained polymer solution was 40 weight%.

상기 중합체 A 100중량부(고형분 함량), 보조경화제로 디펜타에이트리톨 펜타아크릴레이트 15중량부, 경화용 촉매로서 산발생제인 톨루엔-4-설포닉엑시드 비시클로[2,2,1]헵트-2-일 에스테르 1.5중량부와 라디칼 개시제인 2,2'-비스-(4,4-디-t-부틸 퍼옥시-시틀로헥실)프로판 1.5중량부를 합하여 3중량부, 에폭시기 함유 반응성 용매로 4-비닐-1-시클로헥센 디에폭시드 20중량부, 첨가제로 계면활성제인 FC-430(3M) 0.1중량부, 보관안정제인 Irganox 1010(스위스 시바가이기) 0.1중량부 를 고형분 농도 25중량%가 되도록 용매 디에틸렌글리콜디메틸에테르에 용해시켜 칼라필터 평탄화막 제조를 위한 열경화성 수지 조성물을 제조하였다.100 parts by weight of the polymer A (solid content), 15 parts by weight of dipentaerythritol pentaacrylate as an auxiliary curing agent, and toluene-4-sulphonic acid bicyclo [2,2,1] hept- which is an acid generator as a curing catalyst. 3 parts by weight of 1.5 parts by weight of the 2-yl ester and 1.5 parts by weight of 2,2'-bis- (4,4-di-t-butyl peroxy-cyclohexyl) propane, which is a radical initiator, 20 parts by weight of vinyl-1-cyclohexene diepoxide, 0.1 part by weight of FC-430 (3M) as an additive, and 0.1 part by weight of Irganox 1010 (Shiba Shigaigi), a storage stabilizer, It was dissolved in a solvent diethylene glycol dimethyl ether to prepare a thermosetting resin composition for producing a color filter flattening film.

<실시예 7 내지 9><Examples 7 to 9>

상기 실시예 6에서 사용한 에폭시기 함유 반응성 용매 대신, 실시예 7에서는 3-[비스(글리시딜옥시메틸)-메톡시]-1,2-프로판디올을, 실시예 8에서는 1,2-에폭시-9-데센을, 실시예 9에서는 리모넨 옥시드를 사용한 것을 제외하고는, 상기 실시예 6과 동일한 조성을 가진 칼라필터 평탄화막 제조를 위한 열경화성 수지 조성물을 제조하였다.Instead of the epoxy group-containing reactive solvent used in Example 6, 3- [bis (glycidyloxymethyl) -methoxy] -1,2-propanediol was used in Example 7, and 1,2-epoxy- was used in Example 8. 9-decene was prepared in Example 9, except that limonene oxide was used, thereby preparing a thermosetting resin composition for preparing a color filter planarization film having the same composition as in Example 6.

<비교예 1>Comparative Example 1

상기 실시예 1에서 사용한 에폭시기 함유 반응성 용매를 제외하고, 각각의 성분을 고형분 농도 25중량%가 되도록 용매 디에틸렌글리콜디메틸에테르에 용해시 켜, 칼라필터 평탄화막 제조를 위한 열경화성 수지 조성물을 제조하였다. Except for the epoxy group-containing reactive solvent used in Example 1, each component was dissolved in a solvent diethylene glycol dimethyl ether to a solid content concentration of 25% by weight to prepare a thermosetting resin composition for preparing a color filter flattening film.

<비교예 2>Comparative Example 2

상기 실시예 5에서 사용한 에폭시기 함유 반응성 용매를 제외하고 각각의 성분을 고형분 농도 25중량%가 되도록 용매 디에틸렌글리콜디메틸에테르에 용해시켜, 칼라필터 평탄화막 제조를 위한 열경화성 수지 조성물을 제조하였다. Except for the epoxy group-containing reactive solvent used in Example 5, each component was dissolved in a solvent diethylene glycol dimethyl ether to a solid content concentration of 25% by weight to prepare a thermosetting resin composition for preparing a color filter flattening film.

<평탄화막의 형성><Formation of Flattening Film>

상기 실시예와 비교예로부터 얻어진 각각의 열경화성 조성물을 스핀코팅으로 RGB(Red, Green, Blue) 도포 공정까지 끝난 칼라필터 기판과, LCD용 투명 Glass에 도포를 하고, 100℃에서 120초간 가열하고, 220℃로 30분 소성하여 컬러필터 기판의 RGB를 포함하여 2.8~3.8㎛, LCD용 투명 Glass에서 1~1.5㎛가 되도록 평탄화막을 형성하였다. 형성된 평탄화막을 하기의 구체적 평가방법에 의하여 평가하여 그 결과를 하기 표 1에 나타내었다.Each of the thermosetting compositions obtained from the above Examples and Comparative Examples was applied to the color filter substrate and the transparent glass for LCD, which were completed by RGB (Red, Green, Blue) coating process by spin coating, and heated at 100 ° C. for 120 seconds, The film was baked at 220 ° C. for 30 minutes to form a planarization film such that RGB of the color filter substrate was 2.8 to 3.8 μm and 1 to 1.5 μm in transparent glass for LCD. The formed flattening film was evaluated by the following specific evaluation method, and the results are shown in Table 1 below.

<평탄화막의 평가방법><Evaluation Method of Flattening Film>

1.평탄성(%) 1.Flatness (%)

다음 도 1과 하기 평탄화도 계산식에 따라 평탄화도를 평가하였다. 상기 계산식에 의해 10% 이하일 때 평탄화성이 양호한 것으로, 5% 미만일 경우 고평탄화성을 갖는 것으로 판단하였다.Next, the planarization degree was evaluated according to FIG. 1 and the following planarization formula. According to the above formula, it was determined that the flattening property was good when it was 10% or less, and that the flattening property was high when it was less than 5%.

평탄화도=(T2/T1)*100(%)Flatness = (T 2 / T 1 ) * 100 (%)

여기서, T1= 2.8 내지 3.80㎛의 값이다.Here, the value of the T 1 = 2.8 to 3.80㎛.

2.경도2.hardness

연필 경도법에 따라 평탄화막에 대한 연필 스크레치 시험에 의해 평탄화막의 경도를 측정하였으며, 4H 이상일 때 양호한 것으로 판단하였다.The hardness of the flattening film was measured by a pencil scratch test on the flattening film according to the pencil hardness method, and was judged to be good when it was 4H or more.

3.접착성3.Adhesion

LCD용 투명 유리와 ITO가 스퍼터링되어 있는 ITO 유리 위에 형성된 평탄화막을 압력솥 시험장치(온도 120℃, 습도 100%, 시간 12h)에 처리 후 ASTM D 3359-02의 부착성 바둑판 무늬 테이프법에 의해 접착성을 평가하였으며, 그 값이 4B 이상일 때 양호한 것으로 판단하였다.After flattening film formed on transparent glass for LCD and ITO sputtered ITO glass by pressure cooker test device (temperature 120 ℃, humidity 100%, time 12h), it is adhesive by adhesive checkered tape method of ASTM D 3359-02 Was evaluated and judged to be good when the value was 4B or more.

4.투명성(%)4.Transparency (%)

상기에 형성된 평탄화막을 분광 광도계를 이용하여 400~800nm의 가시광선 영역에서의 투과율을 측정하였으며, 95% 이상일 때 양호한 것으로 판단하였다.The transmittance in the visible light region of 400-800 nm was measured for the planarization film formed above using a spectrophotometer, and it was judged that it is favorable when it is 95% or more.

5.내열성(%)5.Heat resistance (%)

상기에 형성된 평탄화막을 240℃ 에서 1시간동안 추가로 가열을 하고, 가열 전후의 투과율의 차이가 3% 미만일 때 양호한 것으로 판단하였다.The flattening film formed above was further heated at 240 ° C. for 1 hour, and was judged to be good when the difference in transmittance before and after heating was less than 3%.

6.내광성(%)6.Light resistance (%)

상기에 형성된 평탄화막에 350W 수은 랩프에서 방출되는 자외선 5000J/㎡를 일정시간 조사한 후, 조사 전후의 투과율의 차이가 3% 미만일 때 양호한 것으로 판 단하였다.After irradiating 5000J / m 2 of ultraviolet rays emitted from the 350W mercury wrap to the planarization film formed for a predetermined time, it was judged to be good when the difference in transmittance before and after irradiation was less than 3%.

7.내산성(nm)7.acid resistance (nm)

상기에 형성된 평탄화막을 20% 염산 수용액에 45℃, 10분간 침지 후 외관의 변화를 관찰하고, 침지 전후의 두께를 측정하여 두께 차가 5nm 미만일 때 양호한 것으로 판단하였다.The flattening film formed above was immersed in a 20% hydrochloric acid aqueous solution at 45 ° C. for 10 minutes, and the appearance change was observed. The thickness before and after the immersion was measured to determine that the thickness was less than 5 nm.

8.내알칼리성(nm)8.alkali resistance (nm)

상기에 형성된 평탄화막을 10% 수산화나트륨 수용액에 25℃, 30분간 침지 후 외관의 변화를 관찰하고, 침지 전후의 두께를 측정하여 두께 차가 5nm 미만일 때 양호한 것으로 판단하였다.The flattening film formed above was immersed in a 10% aqueous sodium hydroxide solution at 25 ° C. for 30 minutes, and then the change in appearance was observed, and the thickness before and after immersion was measured to determine that the thickness was less than 5 nm.

9.내화학성(nm)9.chemical resistance (nm)

상기에 형성된 평탄화막을 아세톤, 이소프로필알코올, N-메틸피롤리디논에 각각 25℃, 30분간 침지 후 외관의 변화를 관찰하고, 침지 전후의 두께를 측정하여 두께 차가 5nm 미만일 때 양호한 것으로 판단하였다.The flattening film formed above was immersed in acetone, isopropyl alcohol, and N-methylpyrrolidinone at 25 ° C. for 30 minutes, and the appearance change was observed, and the thickness before and after the immersion was measured to determine that the thickness difference was less than 5 nm.

(표 1)Table 1

Figure 112006059085018-pat00003
Figure 112006059085018-pat00003

상기 표 1의 결과로부터, 에폭시기 함유 반응성 용매를 포함하는 본 발명의 실시예 1 내지 8의 조성물의 경우 종래의 물성을 만족하는 동시에 특히 평탄성이 개선됨을 알 수 있다.From the results in Table 1, it can be seen that the composition of Examples 1 to 8 of the present invention containing an epoxy group-containing reactive solvent, in particular, satisfies the conventional physical properties and particularly improves the flatness.

이상에서 상세히 설명한 바와 같이, 본 발명에 따라 열경화성 중합체와 보조경화제 그리고 경화용촉매를 비롯하여 첨가제를 포함한 조성물에 중합체와 보조경화제와 열가교를 이룰 수 있는 에폭시기 함유 반응성 용매를 배합한 조성물은 평탄화막으로서 종래로부터 요구되어지는 물성을 만족시키는 동시에, 평탄화도를 효과적으로 향상시켜 고평탄화성을 갖는 칼라필터 평탄화막을 제공할 수 있다.As described in detail above, according to the present invention, a composition comprising an epoxy group-containing reactive solvent capable of thermally crosslinking with a polymer and an auxiliary curing agent in a composition containing an additive including a thermosetting polymer, an auxiliary curing agent, and a curing catalyst is a flattening film. It is possible to provide a color filter flattening film having high flattening property by satisfying the conventionally required physical properties and effectively improving the flattening degree.

Claims (7)

칼라필터 평탄화막용 열경화성 수지 조성물에 있어서, In the thermosetting resin composition for a color filter flattening film, 에폭시기 함유 반응성 용매를 더 포함하고,Further comprising an epoxy group-containing reactive solvent, 상기 에폭시기 함유 반응성 용매는 다음 화학식으로 표시되는 화합물 중에서 선택된 1종 또는 2종 이상인 것을 특징으로 하는 칼라필터 평탄화막용 열경화성 조성물.The epoxy group-containing reactive solvent is a thermosetting composition for a color filter flattening film, characterized in that at least one selected from the compounds represented by the following formula.
Figure 112007047094083-pat00006
Figure 112007047094083-pat00006
상기 각각의 화학식에서, 상기 A, B, C, D는 글리시딜기, 하이드록시기, 디하이드록시기 중에서 선택된 1종 이상의 관능기를 포함하거나 또는 포함하지 않는 C2-15 직쇄상, 분쇄상, 또는 환상의 탄화수소, 에테르, 글리콜, 케톤, 및 에스테르이고, In each of the above formula, A, B, C, D is C 2-15 linear, pulverized phase, which may or may not include at least one functional group selected from glycidyl group, hydroxy group, dihydroxy group, Or cyclic hydrocarbons, ethers, glycols, ketones, and esters, 상기 화학식에서 각 R1은 서로 같거나 다른 것으로서, 수소원자, C1-5알킬, 또는 C1-5 알킬에테르이고, R2는 각각 수소원자 또는 C1-5알킬이며, m은 3~6인 정수이고, n은 0~10인 정수이다.In the formula, each R 1 is the same as or different from each other, a hydrogen atom, C 1-5 alkyl, or C 1-5 alkyl ether, R 2 is each a hydrogen atom or C 1-5 alkyl, and m is 3-6 Is an integer and n is an integer of 0-10.
삭제delete 제 1항에 있어서, 상기 에폭시기 함유 반응성 용매는 상기 열경화성 수지 조성물에 포함되는 중합체 100중량부에 대하여 40 중량부 이내로 포함되는 것을 특징으로 하는 칼라필터 평탄화막용 열경화성 조성물. The thermosetting composition for a color filter flattening film according to claim 1, wherein the epoxy group-containing reactive solvent is contained within 40 parts by weight based on 100 parts by weight of the polymer contained in the thermosetting resin composition. 제 1항에 있어서, 상기 수지 조성물은 경화용 촉매로서 산발생제, 라디칼 개시제 또는 아미노플라스트를 단독으로 사용하거나 또는 2종 이상 혼합하여 사용하는 것을 특징으로 하는 칼라필터 평탄화막용 열경화성 수지 조성물. The thermosetting resin composition for a color filter flattening film according to claim 1, wherein the resin composition is used alone or in combination of two or more acid generators, radical initiators or aminoplasts as a curing catalyst. 제 4항에 있어서, 상기 경화용 촉매는 열경화성 수지 조성물에 포함되는 중합체 100중량부에 대하여 0.1 내지 10중량부로 포함되는 것을 특징으로 하는 칼라필터 평탄화막용 열경화성 수지 조성물. The thermosetting resin composition of claim 4, wherein the curing catalyst is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer contained in the thermosetting resin composition. 제 1항에 있어서, 상기 수지 조성물은 에틸렌성 불포화 관능기를 포함하는 다관능성 모노머, 글리시딜기가 2개 이상 치환된 폴리올류의 단량체 또는 중합체, 하이드록시페닐기가 있는 단량체 또는 중합체, 에폭시 아크릴레이트, 폴리에스테르 아크릴레이트, 또는 폴리우레탄 아크릴레이트 중에서 선택된 1종 이상의 보조경화제를 포함하는 것을 특징으로 하는 칼라필터 평탄화막용 열경화성 수지 조성물. The method of claim 1, wherein the resin composition is a polyfunctional monomer containing an ethylenically unsaturated functional group, monomers or polymers of polyols having two or more glycidyl groups, monomers or polymers having a hydroxyphenyl group, epoxy acrylate, A thermosetting resin composition for a color filter flattening film, comprising at least one auxiliary curing agent selected from polyester acrylate and polyurethane acrylate. 제 1항의 칼라필터 평탄화막용 열경화성 수지 조성물로부터 제조된 칼라필터 평탄화막.The color filter planarization film manufactured from the thermosetting resin composition for color filter planarization films of Claim 1.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11242111A (en) 1998-02-26 1999-09-07 Asahi Glass Co Ltd Composition for color filters protective film, substrate with color filter, its production and liquid crystal display element
KR20040081302A (en) * 2003-03-10 2004-09-21 제이에스알 가부시끼가이샤 Resin Compositions, Protective Films of Color Filters and Process for Forming the Same
KR20060045445A (en) * 2004-04-02 2006-05-17 후지 샤신 필름 가부시기가이샤 Colorant-containing curable composition, color filter and method of producing the same
KR20060086277A (en) * 2005-01-25 2006-07-31 주식회사 엘지화학 Thermally curable resin composition with extended storage stability and good adhesive property

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11242111A (en) 1998-02-26 1999-09-07 Asahi Glass Co Ltd Composition for color filters protective film, substrate with color filter, its production and liquid crystal display element
KR20040081302A (en) * 2003-03-10 2004-09-21 제이에스알 가부시끼가이샤 Resin Compositions, Protective Films of Color Filters and Process for Forming the Same
KR20060045445A (en) * 2004-04-02 2006-05-17 후지 샤신 필름 가부시기가이샤 Colorant-containing curable composition, color filter and method of producing the same
KR20060086277A (en) * 2005-01-25 2006-07-31 주식회사 엘지화학 Thermally curable resin composition with extended storage stability and good adhesive property

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