KR101144736B1 - Negative resist compositions with high heat resistance - Google Patents
Negative resist compositions with high heat resistance Download PDFInfo
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- KR101144736B1 KR101144736B1 KR1020080138357A KR20080138357A KR101144736B1 KR 101144736 B1 KR101144736 B1 KR 101144736B1 KR 1020080138357 A KR1020080138357 A KR 1020080138357A KR 20080138357 A KR20080138357 A KR 20080138357A KR 101144736 B1 KR101144736 B1 KR 101144736B1
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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Abstract
본 발명은 고내열성 음성 레지스트 조성물에 관한 것이다. 본 발명의 음성 레지스트 조성물은, 특정 화학식으로 표시되는 바인더 수지 3 내지 40중량%; 다관능성 아크릴 단량체 2 내지 40 중량%; 광개시제 0.01 내지 10 중량%; 및 유기용매 10 내지 94 중량%를 포함한다. 본 발명의 음성 레지스트 조성물은 고온에서 내열성이 우수하고, 평탄성, 패턴안정성, 투과율 및 내화학성이 우수하다.The present invention relates to a high heat resistant negative resist composition. The negative resist composition of the present invention, 3 to 40% by weight of the binder resin represented by the specific formula; 2 to 40 weight percent of the multifunctional acrylic monomer; 0.01 to 10% by weight photoinitiator; And 10 to 94% by weight of organic solvent. The negative resist composition of this invention is excellent in heat resistance at high temperature, and excellent in flatness, pattern stability, transmittance | permeability, and chemical resistance.
음성, 레지스트 Voice, resist
Description
본 발명은 고내열성 음성 레지스트 조성물에 관한 것이다. 보다 상세하게는, 고온에서 내열성이 우수하여 각종 미세 패턴 형성이 용이한 고내열성 음성 레지스트 조성물에 관한 것이다.The present invention relates to a high heat resistant negative resist composition. More specifically, the present invention relates to a high heat resistant negative resist composition which is excellent in heat resistance at high temperature and which is easy to form various fine patterns.
반도체 집적 회로의 고도화는 끊임없이 이를 뒷받침할 뛰어난 성능의 재료를 요구하게 된다. 최근 들어 각광받는 박막 트랜지스터 액정 표시소자(TFT-LCD)의 경우 역시 관련 업계에서 대화면화, 고휘도화, 고정밀화, 고속 응답화를 이룩하기 위한 다양한 노력을 시도하고 있고, 이에 따라 액정 표시소자의 구조도 점점 더 복잡해지고 있다. 그 때문에 TFT-LCD 등에 사용되는 유기절연막, R.G.B., 포토스페이서, UV 오버코트 등의 구성 요소를 형성하는 재료는 보다 미세한 패턴 형성을 위한 높은 해상도를 지원할 수 있는 재료가 바람직하다. 따라서, TFT-LCD 소자의 제조 공정에서 상기 구성요소 등을 생성하는 패턴 공정은 미세한 패턴 형성을 위해 포토리소그래피 처리를 통하여 이루어지는 것이 일반적이며, 그에 따라 감광성 재료가 널리 사용되고 있다. 그리고, 이러한 패턴 제조공정에 사용되는 감광성 수지 는 평탄성, 투과성 및 내열성이 우수한 재료가 요구된다. Advances in semiconductor integrated circuits are constantly demanding superior performance materials to support them. Recently, the thin-film transistor liquid crystal display device (TFT-LCD), which has been in the spotlight, has also made various efforts to achieve large screen, high brightness, high precision, and high speed response in the related industry. Is also becoming more and more complex. Therefore, the material which forms components, such as an organic insulating film, R.G.B., a photospacer, UV overcoat, etc. used for TFT-LCD etc., is a material which can support the high resolution for finer pattern formation. Therefore, the pattern process for producing the above components and the like in the manufacturing process of the TFT-LCD device is generally performed through a photolithography process for forming a fine pattern, and thus photosensitive materials are widely used. And the photosensitive resin used for such a pattern manufacturing process requires the material excellent in flatness, permeability, and heat resistance.
하지만, 유기절연막, R.G.B., 블랙 매트릭스, 포토스페이서, UV 오버코트 등에 사용되고 있는 종래의 아크릴계 감광성 수지는 220 ℃ 이하의 공정에서는 visible 영역에서 95%이상의 높은 투과도를 나타내는 반면, 220 ℃ 이상의 고온 공정에서는 열 안정성이 취약하여 열에 의해 수지의 일부가 분해되고 이로 인해 visible 영역에서의 투과도가 감소하는 경향이 있다. 또한, 고온 공정 중에 분해된 분자들에 의해 액정이 오염되는 등의 문제가 있다.However, conventional acrylic photosensitive resins used in organic insulating films, RGB, black matrices, photospacers, UV overcoats, and the like exhibit a high transmittance of 95% or more in the visible region in the process below 220 ° C, while thermal stability in the high temperature process above 220 ° C. This fragile tends to decompose some of the resin by heat and thereby reduce the permeability in the visible region. In addition, there is a problem that the liquid crystal is contaminated by molecules decomposed during the high temperature process.
그러나, 아직까지 이러한 문제점의 효과적 해결책이 보고된 바 없으며, 이에 따라 내열성이 우수한 감광성 수지 조성물의 개발이 시급하다.However, no effective solution to this problem has been reported so far, and therefore, there is an urgent need to develop a photosensitive resin composition having excellent heat resistance.
따라서 본 발명이 해결하고자 하는 과제는, 고온에서 내열성이 뛰어나고, 유기절연막, R.G.B., 블랙 매트릭스, 포토스페이서, UV 오버코트 등의 제조 공정에서 패턴 형성이 용이하며, 평탄성, 패턴안정성, 투과율 및 내화학성이 우수한 음성 레지스트 조성물을 제공하는 것이다.Therefore, the problem to be solved by the present invention is excellent heat resistance at high temperature, easy to form patterns in the manufacturing process of organic insulating film, RGB, black matrix, photospacer, UV overcoat, flatness, pattern stability, transmittance and chemical resistance It is to provide an excellent negative resist composition.
상기 과제를 해결하기 위하여, 본 발명의 음성 레지스트 조성물은, 하기 화학식 1로 표시되는 바인더 수지 3 내지 40 중량%; 다관능성 아크릴 단량체 2 내지 40 중량%; 광개시제 0.01 내지 10 중량%; 및 유기용매 10 내지 94 중량%를 포함하는 음성 레지스트 조성물을 제공한다:In order to solve the above problems, the negative resist composition of the present invention, 3 to 40% by weight of the binder resin represented by the formula (1); 2 to 40 weight percent of the multifunctional acrylic monomer; 0.01 to 10% by weight photoinitiator; And it provides a negative resist composition comprising 10 to 94% by weight of an organic solvent:
상기 화학식 1에서,In Chemical Formula 1,
R1 및 R2는 각각 독립적으로 수소 또는 메틸기이고, R 1 and R 2 are each independently hydrogen or a methyl group,
R3는 수소, 탄소원자수 1 ~ 14인 알킬기, 시클로알킬기 또는 아릴기이고,R 3 is hydrogen, an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group or an aryl group,
R4는 탄소원자수가 1 ~ 14인 히드록시기로 치환되거나 비치환된 알킬기, 아릴기, 알킬옥시, 아릴옥시, 니트릴 또는 알킬옥시카르보닐기이며, R 4 is an alkyl, aryl, alkyloxy, aryloxy, nitrile or alkyloxycarbonyl group unsubstituted or substituted with a hydroxy group having 1 to 14 carbon atoms,
R5는 탄소원자수가 1~14인 알코올 또는 카르복시산으로 치환되거나 비치환된 비시클로알케닐(bicycloalkenyl)기이고 R 5 is a bicycloalkenyl group unsubstituted or substituted with an alcohol or carboxylic acid having 1 to 14 carbon atoms
x는 0.01~0.55, y는 0.10~0.50, z는 0.03~0.60, m은 0.01~0.50이다.x is 0.01 to 0.55, y is 0.10 to 0.50, z is 0.03 to 0.60, and m is 0.01 to 0.50.
본 발명의 음성 레지스트 조성물은 접착보조제로서 에폭시기 또는 아민기를 포함하는 실리콘계 화합물 0.0001 내지 3 중량%를 더 포함할 수 있다.The negative resist composition of the present invention may further comprise 0.0001 to 3% by weight of a silicon-based compound containing an epoxy group or an amine group as an adhesion aid.
본 발명에 따른 음성 레지스트 조성물은 내열성이 우수할 뿐만 아니라, 평탄성 및 패턴안정성이 매우 양호하다. The negative resist composition according to the present invention not only has excellent heat resistance, but also has very good flatness and pattern stability.
또한, 투과율이 우수하여 백라이트(back light)의 밝기의 조절이 가능하여 배터리 효율을 증가시킬 수 있고, 색감이상, 색차계 변화에 대한 영향을 최소화할 수 있다. In addition, the transmittance is excellent, the brightness of the backlight (back light) can be adjusted to increase the battery efficiency, the color abnormality, it is possible to minimize the influence on the color difference change.
또한, 본 발명의 음성 레지스트 조성물은 본 발명에서 정해진 범위 내에서 바인더 수지의 구조 및 조성비를 변화시키면 요구되는 특정의 물성을 갖는 레지스트로서 다양한 용도로 용이하게 사용될 수 있다.In addition, the negative resist composition of the present invention can be easily used in various applications as a resist having a specific physical properties required by changing the structure and composition ratio of the binder resin within the range defined in the present invention.
이하, 본 발명을 상세히 설명하기로 한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
본 발명의 음성 레지스트 조성물에 포함되는 바인더 수지는 경화반응을 일으키며, 본 발명의 음성 레지스트 조성물이 경화되어 형성되는 레지스트막에 내열성을 부여한다. The binder resin contained in the negative resist composition of the present invention causes a curing reaction and imparts heat resistance to the resist film formed by curing the negative resist composition of the present invention.
본 발명에 따른 바인더 수지를 나타내는 상기 화학식 1에서, R1 및 R2는 각각 독립적으로 수소 또는 메틸기이다. In Formula 1 representing the binder resin according to the present invention, R 1 and R 2 are each independently hydrogen or a methyl group.
상기 화학식 1에서, R3는 수소, 탄소원자수 1 ~ 14인 알킬기, 시클로알킬기 또는 아릴기이다. R3의 구체적인 예를 들면, 수소, 메틸, 에틸, 프로필, 이소프로 필, 부틸, t-부틸, 이소부틸, 펜틸, 헥실, 시클로헥실, 페닐, 벤질, 나프틸, 아다만틸, 4-히드록시페닐, 데실, 도데실 등이 있으나, 이에 한정되는 것은 아니다.In Formula 1, R 3 is hydrogen, an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group, or an aryl group. Specific examples of R 3 are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, cyclohexyl, phenyl, benzyl, naphthyl, adamantyl, 4-hydrate Oxyphenyl, decyl, dodecyl, and the like, but is not limited thereto.
상기 화학식 1에서, R4는 탄소원자수가 1 ~ 14인 히드록시기로 치환되거나 비치환된 알킬기, 아릴기, 알킬옥시, 아릴옥시, 니트릴 또는 알킬옥시카르보닐기이다. R4의 구체적인 예를 들면, 메톡시카르보닐, 에톡시카르보닐, 프로필옥시카르보닐, 이소프로필옥시카르보닐, 글리시딜옥시카르보닐, 부톡시카르보닐, t- 부톡시카르보닐, 이소부톡시카르보닐, 펜틸옥시카르보닐, 헥실옥시카르보닐, 시클로헥실옥시카르보닐, 페닐옥시카르보닐, 벤질옥시카르보닐, 나프틸옥시카르보닐, 이소보닐옥시카르보닐, 2-옥소옥사펜틸옥시카르보닐, 아다만틸옥시카르보닐, 디사이클로펜타닐옥시카르보닐, 디사이클로펜테닐옥시카르보닐, 디사이클로펜타닐에틸옥시카르보닐, 디사이클로펜테닐에틸옥시카르보닐, 히드록시에틸옥시카르보닐, 디메틸아미노에틸옥시카르보닐, 메톡시, 에톡시, 페닐옥시, 페닐, 나프틸, 히드록시페닐, 니트릴 등이 있으나, 이에 한정되는 것은 아니다.In Formula 1, R 4 is an alkyl group, aryl group, alkyloxy, aryloxy, nitrile or alkyloxycarbonyl group unsubstituted or substituted with a hydroxy group having 1 to 14 carbon atoms. Specific examples of R 4 include methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, glycidyloxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, isobutoxy Carbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, naphthyloxycarbonyl, isobornyloxycarbonyl, 2-oxooxapentyloxycarbon Carbonyl, adamantyloxycarbonyl, dicyclopentanyloxycarbonyl, dicyclopentenyloxycarbonyl, dicyclopentanylethyloxycarbonyl, dicyclopentenylethyloxycarbonyl, hydroxyethyloxycarbonyl, dimethylamino Ethyloxycarbonyl, methoxy, ethoxy, phenyloxy, phenyl, naphthyl, hydroxyphenyl, nitrile and the like, but are not limited thereto.
상기 화학식 1에서, R5는 탄소원자수가 1~14인 알코올 또는 카르복시산으로 치환되거나 비치환된 비시클로알케닐기이다. R5를 형성하는 단량체의 구체적인 예를 들면, 5-노보넨-2,3-디카르복시언하이드라이드, 5-노보넨-2-메탄올, 5-노보넨-2-카르복시산, 노보넨, 5-노보넨-2,2-디메탄올, 5-노보넨-2,3-디메탄올 등이 있으나, 이에 한정되는 것은 아니다.In Formula 1, R 5 is a bicycloalkenyl group unsubstituted or substituted with an alcohol or carboxylic acid having 1 to 14 carbon atoms. Specific examples of the monomer forming R 5 include 5-norbornene-2,3-dicarboxylic hydride, 5-norbornene-2-methanol, 5-norbornene-2-carboxylic acid, norbornene, 5- Norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, and the like, but is not limited thereto.
상기 화학식 1의 x, y, z, m은 각 중합단위의 몰비로서, x는 0.01~0.55, y는 0.10~0.50, z는 0.03~0.60, m은 0.01~0.50이다. 상기 화학식 1의 바인더 수지는 각 중합단위의 배열순서에 제한되지 않으며, 예를 들면 랜덤 공중합체일 수 있다.X, y, z, m in the formula (1) is a molar ratio of each polymerized unit, x is 0.01 ~ 0.55, y is 0.10 ~ 0.50, z is 0.03 ~ 0.60, m is 0.01 ~ 0.50. The binder resin of Chemical Formula 1 is not limited to the arrangement order of each polymer unit, and may be, for example, a random copolymer.
본 발명에 따른 바인더 수지는 조성물 전체 중량 대비 3 내지 40중량%가 포함된다. 상기 함량이 3중량% 미만이면 코팅성과 기계적 물성이 저하되고, 40중량%를 초과하면 패턴 형성이 잘 이루어지지 않으므로 그 함량이 상기 범위내일 경우가 바람직하다.The binder resin according to the present invention contains 3 to 40% by weight based on the total weight of the composition. When the content is less than 3% by weight, the coating properties and mechanical properties are lowered, and when the content is more than 40% by weight, the pattern is not formed well, and the content is preferably within the above range.
바인더 수지의 평균 분자량은 2,000 내지 300,000, 분산도는 1.0 내지 10.0, 산가는 10 내지 400 KOH mg/g인 것을 사용하는 것이 바람직하며, 보다 바람직하게는 평균 분자량 4,000 내지 100,000이고, 분산도는 1.5 내지 3.0이고, 산가는 20 내지 200 KOH mg/g인 것을 사용할 수 있다.The average molecular weight of the binder resin is preferably 2,000 to 300,000, the dispersity is 1.0 to 10.0, the acid value is 10 to 400 KOH mg / g, more preferably the average molecular weight of 4,000 to 100,000, the dispersion degree is 1.5 to 3.0 and an acid value of 20-200 KOH mg / g can be used.
또한, 본 발명의 음성 레지스트 조성물에 포함되는 다관능성 아크릴 단량체는 음성 레지스트 조성물의 구체적인 용도에 따라 전술한 바인더 수지와의 조성비를 본 발명에 범위 내에서 적절히 조절함으로써 조성물이 경화 후 우수한 내열성 및 패턴안정성을 갖도록 할 수 있다.In addition, the polyfunctional acrylic monomer included in the negative resist composition of the present invention has excellent heat resistance and pattern stability after curing, by appropriately adjusting the composition ratio with the above-described binder resin within the scope of the present invention according to the specific use of the negative resist composition. It can be to have.
본 발명에서 사용될 수 있는 다관능성 아크릴 단량체로는 예를 들면, 에틸렌글리콜디(메타)아크릴레이트, 에틸렌옥사이드기의 수가 2 내지 14인 폴리에틸렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 프로필렌옥사이드기의 수가 2 내지 14인 프로필렌글리콜디(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에 리스리톨헥사(메타)아크릴레이트 및 디펜타에리스리톨트리(메타)아크릴레이트로 이루어진 군으로부터 선택된 다가 알콜과 (메타)아크릴산을 에스테르화하여 얻어지는 화합물; 트리메틸올프로판트리글리시딜에테르 아크릴산 부가물, 비스페놀 A 디글리시딜에테르 아크릴산 부가물 등의 글리시딜기 함유 화합물에 (메타)아크릴산을 부가하여 얻어지는 화합물; β-히드록시에틸(메타)아크릴레이트의 프탈산디에스테르와 같은 수산기 및 아크릴기를 가지는 화합물과 다가 카르복시산과의 에스테르 화합물; β-히드록시에틸(메타)아크릴레이트의 톨루엔 디이소시아네이트 부가물와 같은 수산기 및 아크릴기를 가지는 화합물과 폴리이소시아네이트와의 부가물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트 등의 (메타)아크릴산알킬에스테르 등을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the polyfunctional acrylic monomer that can be used in the present invention include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, and trimethylolpropanedi (meth). Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, di Compounds obtained by esterifying a polyhydric alcohol selected from the group consisting of pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol tri (meth) acrylate with (meth) acrylic acid; Compounds obtained by adding (meth) acrylic acid to glycidyl group-containing compounds such as trimethylolpropanetriglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; ester compounds of a compound having a hydroxyl group and an acryl group such as phthalic acid diester of β-hydroxyethyl (meth) acrylate and a polyhydric carboxylic acid; an adduct of a compound having a hydroxyl group and an acryl group, such as toluene diisocyanate adduct of? -hydroxyethyl (meth) acrylate, and a polyisocyanate; (Meth) acrylic-acid alkylesters, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, etc. can be used individually or in mixture of 2 or more types, respectively Can be.
본 발명에 사용되는 다관능성 아크릴 단량체의 함량은 조성물 전체 중량 대비 2 내지 40 중량%이 바람직하며, 다가 아크릴 모노머의 함량이 2 중량% 미만이면 단량체 첨가의 효과가 미미하며, 40 중량%를 초과하면 필름의 가교도가 높아지고 이로 인해 필름의 물성이 저하되며 열 안정성이 떨어지는 문제점이 있다.The content of the polyfunctional acrylic monomer used in the present invention is preferably 2 to 40% by weight based on the total weight of the composition. When the content of the polyvalent acrylic monomer is less than 2% by weight, the effect of monomer addition is insignificant. There is a problem that the degree of crosslinking of the film is high and thereby the physical properties of the film are lowered and the thermal stability is lowered.
당분야에서 광개시제로는 통상적으로 아세토페논계나 벤조페논계를 사용하는데, 광개시제 자체가 색을 가지면 투명성을 저하시키는 작용을 하므로 노광시 사용하는 파장대에서 적절한 감도를 갖고 광개시제 자체에 색을 갖지 않는 것을 사용함으로써 고투명성을 실현할 수 있다. In the art, photoinitiators typically use acetophenone or benzophenone series. When the photoinitiator itself has a color, the photoinitiator acts to reduce transparency. By using it, high transparency can be achieved.
따라서, 본 발명의 음성 레지스트 조성물에 포함되는 상기 다관능성 아크릴 단량체의 가교반응에는 자외선이 가장 일반적으로 사용되므로, 이를 기준으로 본 발명에 바람직한 광개시제를 선택할 수 있다. 예를 들면, 자외선을 방출하는 가장 일반적인 장치인 수은 램프는 약 310～450nm 영역의 파장을 가지며, 따라서 당업자라면 상기 파장 영역에서 라디칼을 발생시키는 광개시제를 적절하게 선택할 수 있다. Therefore, since ultraviolet rays are most commonly used in the crosslinking reaction of the multifunctional acrylic monomer included in the negative resist composition of the present invention, a photoinitiator suitable for the present invention can be selected based on this. For example, a mercury lamp, the most common device for emitting ultraviolet light, has a wavelength in the region of about 310 to 450 nm, and thus a person skilled in the art can appropriately select a photoinitiator for generating radicals in the wavelength region.
그러므로, 본 발명의 음성 레지스트 조성물에 포함되는 광개시제로는 Irgacure 651, Irgacure 907, TPO, CGI124, EPD/BMS 혼합계 등의 아세토페논계 및 벤조페논계와 트리아진계를 사용하는 것이 바람직하다. 예를 들면 벤조페논, 페닐비페닐케톤, 1-히드록시-1-벤조일시클로헥산, 벤질, 벤질디메틸케탈, 1-벤질-1-디메틸아미노-1-(4-모폴리노-벤조일)프로판, 2-모폴릴-2-(4-메틸머캅토) 벤조일프로판, 치오잔톤(thioxanthone), 1-클로로-4-프록시치오잔톤, 이소프로필치오잔톤, 디에틸치오잔톤, 에틸안트라퀴논, 4-벤조일-4-메틸디페닐설파이드, 벤조인부틸에테르, 2-히드록시-2-벤조일프로판, 2-히드록시-2-(4-이소프로필)벤조일프로판, 4-부틸벤조일트리클로로메탄, 4-페녹시벤조일디클로로메탄, 벤조일포름산메틸, 1,7-비스(9-아크리디닐)헵탄, 9-n-부틸-3,6-비스(2-모폴리노-이소부틸로일)카바졸, 2-메틸-4,6-비스(트리클로로메틸)-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-나프틸-4,6-비스(트리클로로메틸)-s-트리아진 등이 있다. Therefore, as the photoinitiator included in the negative resist composition of the present invention, it is preferable to use acetophenones such as Irgacure 651, Irgacure 907, TPO, CGI124, EPD / BMS mixed system, benzophenone and triazine. Benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4-morpholino-benzoyl) propane, 2-morpholinyl-2- (4-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4- hydroxy thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethyl anthraquinone, 4-benzoyl 4-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxy Cybenzoyldichloromethane, methyl benzoyl formate, 1,7-bis (9-acridinyl) heptane, 9-n-butyl-3,6-bis (2-morpholino-isobutyloyl) carbazole, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis ( Trichloromethyl) -s-triazine and the like.
본 발명에 따른 광개시제는 투명성을 높이며 첨가량을 최소화하기 위한 함량으로서 조성물 전체 중량 대비 0.01 내지 10 중량%, 바람직하게는 0.5 내지 7 중량%를 사용하는 것이 보다 효과적이다.Photoinitiator according to the present invention is more effective to use 0.01 to 10% by weight, preferably 0.5 to 7% by weight relative to the total weight of the composition as a content to increase the transparency and minimize the amount added.
본 발명의 음성 레지스트 조성물은 용매를 가하여 기판 위에 코팅한 후 마스크를 이용하여 자외선을 조사하여 알칼리 현상액으로 현상하는 방법을 통하여 패턴을 형성하게 된다.The negative resist composition of the present invention is coated with a solvent and then coated on a substrate to form a pattern through a method of developing with an alkaline developer by irradiating ultraviolet rays using a mask.
이러한 용매는 바인더 수지, 광개시제, 아크릴 단량체 및 기타 첨가제을 첨가혼합하여 용해하고, 우수한 코팅성과 투명한 박막을 얻기 위해 사용하는 것으로, 바인더 수지, 광개시제, 아크릴 단량체 및 기타 첨가제와의 상용성을 고려하여 당분야에서 사용되는 적절한 것을 채택할 수 있다.These solvents are used to add and dissolve binder resins, photoinitiators, acrylic monomers and other additives, and to obtain excellent coating properties and transparent thin films. In consideration of compatibility with binder resins, photoinitiators, acrylic monomers and other additives, Adopt the appropriate one used by
구체적인 예를 들면, 에틸아세테이트, 부틸아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디메틸에틸에테르, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트(EEP), 에틸락테이트, 프로필렌글리콜메틸에테르아세테이트(PGMEA), 프로필렌글리콜메틸에테르, 프로필렌글리콜프로필에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜메틸아세테이트, 디에틸렌글리콜에틸아세테이트, 아세톤, 메틸이소부틸케톤, 시클로헥사논, 디메틸포름아미드(DMF), N,N-디메틸아세트아미드(DMAc), N-메틸-2-피롤리돈(NMP), γ-부티로락톤, 디에틸에테르, 에틸렌글리콜디메틸에테르, 다이글라임(Diglyme), 테트라하이드로퓨란(THF), 메탄올, 에탄올, 프로판올, 이소-프로판올, 메틸셀로솔브, 에틸셀로솔브, 디에틸렌글리콜메틸에테르, 디에틸렌글리콜에틸에테르, 디프로필렌글리콜메틸에테르, 톨루엔, 크실렌, 헥산, 헵탄, 옥탄 등을 각각 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.Specific examples include ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, and propylene glycol methyl ether acetate. (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethyl Formamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme ), Tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethyl A glycol ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane and the like alone respectively or in combination of two or more may be mixed.
본 발명에 따른 유기용매는 조성물의 점도가 1 내지 50 cps 범위가 되도록 첨가하는 것이 바람직하며, 이를 위해 그 함량은 조성물 전체 중량 대비 10 내지 94 중량%인 것이 바람직하다.The organic solvent according to the present invention is preferably added so that the viscosity of the composition is in the range of 1 to 50 cps, and the content thereof is preferably 10 to 94% by weight based on the total weight of the composition.
선택적으로, 본 발명의 음성 레지스트 조성물은 필요에 따라 접착보조제로 에폭시기 또는 아민기를 갖는 실리콘 화합물을 더 포함할 수 있으며, 이러한 실리콘 화합물은 ITO 전극과 음성 레지스트 조성물과의 접착력을 향상시키며, 경화 후 내열 특성을 증대시킨다. 이러한 에폭시기 또는 아민기를 갖는 실리콘계 화합물로는 예를 들면, (3-글리시드옥시프로필)트리메톡시실레인, (3-글리시드옥시프로필)트리에톡시실레인, (3-글리시드옥시프로필)메틸디메톡시실레인, (3-글리시드옥시프로필)메틸디에톡시실레인, (3-글리시드옥시프로필)디메틸메톡시실레인, (3-글리시드옥시프로필)디메틸에톡시실레인, 3,4-에폭시부틸트리메톡시실레인, 3,4-에폭시부틸트리에톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실레인, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실레인, (3-아미노프로필)트리메톡시실레인 등을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 한정되는 것은 아니다. 이러한 실리콘 화합물은 본 발명의 조성물 전체 중량 대비 0.0001 내지 3 중량%로 포함되는 것이 기재와의 접착력 및 내열특성의 증대 측면에서 바람직하다.Optionally, the negative resist composition of the present invention may further comprise a silicone compound having an epoxy group or an amine group as an adhesive aid, if necessary, such a silicone compound improves the adhesion between the ITO electrode and the negative resist composition, heat resistance after curing Increase the properties. As a silicone type compound which has such an epoxy group or an amine group, it is (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) triethoxy silane, (3-glycidoxy oxy), for example. Methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxyoxy) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3, 4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl Ethyltriethoxysilane, (3-aminopropyl) trimethoxysilane, and the like may be used alone or in combination of two or more thereof, but is not limited thereto. Such a silicone compound is preferably contained in an amount of 0.0001 to 3% by weight based on the total weight of the composition of the present invention in terms of increasing adhesion to the substrate and heat resistance.
또한, 본 발명의 조성물은 본 발명의 목적 및 효과를 벗어나지 않는 범위에서 필요에 따라 당분야에서 통상적으로 사용되는 광증감제, 열중합 금지제, 소포제, 레벨링제 등의 상용성이 있는 첨가제를 더 포함할 수 있음은 자명하다.In addition, the composition of the present invention further comprises a compatible additive such as photosensitizers, thermal polymerization inhibitors, antifoaming agents, leveling agents, etc. commonly used in the art as needed without departing from the object and effect of the present invention. It may be included.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예는 여러 가지 다른 형태로 변형될 수 있 으며, 본 발명의 범위가 아래에서 상술하는 실시예에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, embodiments according to the present invention may be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
실시예 1~9Examples 1-9
자외선 차단막과 교반기가 설치되어 있는 반응혼합조에 하기 표 1에 기재된 조성 및 함량에 따라 바인더 수지, 유기용매, 다관능성 아크릴 단량체인 디펜타에리트리톨 헥사아크릴레이트와 디펜타에리트리톨 펜타아크릴레이트의 혼합물(중량비=1:1)을 첨가하고,A mixture of a binder resin, an organic solvent, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate, according to the composition and content shown in Table 1 below, in a reaction mixing tank equipped with a sunscreen and a stirrer ( Weight ratio = 1: 1) is added,
광개시제인 Irgacure 651, 접착보조제인 (3-아미노프로필)트리메톡시실레인, 레벨링제인 3M사의 FC-430을 순차적으로 첨가하여 네가형 레지스트 조성물을 제조한 후 상온에서 교반하였다. 이어서, 조성물에 용매를 가하여 레지스트 조성물의 점도를 15cps로 조절하였다.Irgacure 651, a photoinitiator, (3-aminopropyl) trimethoxysilane, an adhesion aid, and FC-430, a 3M leveling agent, were sequentially added to prepare a negative resist composition, followed by stirring at room temperature. Then, a solvent was added to the composition to adjust the viscosity of the resist composition to 15 cps.
(20중량%)Binder Resin
(20% by weight)
(중량%)Acrylic monomer
(weight%)
(중량%)Silicon compound
(weight%)
(중량%)Photoinitiator
(weight%)
(중량%)additive
(weight%)
Organic solvent
x=0.3, y=0.3, z=0.2, m= 0.2R 1, R 2, R 3, R 4 = methyl, R 5 = 5-norbornene-2-carboxylic acid,
x = 0.3, y = 0.3, z = 0.2, m = 0.2
(20)DPEHA
(20)
(2)Irgacure 651
(2)
(to 100)PGMEA
(to 100)
R3=이소프로필, R5=5-노보넨-2-카르복시산,
x=0.3, y=0.3, z=0.2, m=0.2R1, R2, R4 = methyl
R3 = isopropyl, R5 = 5-norbornene-2-carboxylic acid,
x = 0.3, y = 0.3, z = 0.2, m = 0.2
(20)DPEHA
(20)
R3=시클로핵실
R4=히드록시에틸옥시카르보닐,
R5=5-노보넨-2-카르복시산,
x=0.35, y=0.25, z=0.2, m=0.2R1, R2 = methyl
R3 = cyclonuclear chamber
R 4 = hydroxyethyloxycarbonyl,
R 5 = 5-norbornene-2-carboxylic acid,
x = 0.35, y = 0.25, z = 0.2, m = 0.2
(20)DPEHA
(20)
R3=페닐, R5=5-노보넨-2-카르복시산,
x=0.3, y=0.3, z=0.2, m=0.2R1, R2, R4 = methyl
R3 = phenyl, R5 = 5-norbornene-2-carboxylic acid,
x = 0.3, y = 0.3, z = 0.2, m = 0.2
(20)DPEHA
(20)
R3, R4=페닐, R5=5-노보넨-2-카르복시산,
x=0.4, y=0.3, z=0.1, m=0.2R1 = methyl, R2 = H
R3, R4 = phenyl, R5 = 5-norbornene-2-carboxylic acid,
x = 0.4, y = 0.3, z = 0.1, m = 0.2
(20)DPEHA
(20)
R3=에틸
R4=글리시딜옥시카르보닐, R5=5-노보넨-2-카르복시산,
x=0.35, y=0.35, z=0.1, m=0.2R1, R2 = methyl
R3 = ethyl
R4 = glycidyloxycarbonyl, R5 = 5-norbornene-2-carboxylic acid,
x = 0.35, y = 0.35, z = 0.1, m = 0.2
(20)DPEHA
(20)
R2, R3=H,
R4=페닐, R5=5-노보넨-2-카르복시산,
x=0.3, y=0.3, z=0.2, m=0.2R 1 = methyl,
R2, R3 = H,
R4 = phenyl, R5 = 5-norbornene-2-carboxylic acid,
x = 0.3, y = 0.3, z = 0.2, m = 0.2
(20)DPEHA
(20)
R3=부틸
R4=메톡시, R5=5-노보넨-2-카르복시산,
x=0.3, y=0.3, z=0.2, m=0.2R1 = methyl, R2 = H
R3 = butyl
R4 = methoxy, R5 = 5-norbornene-2-carboxylic acid,
x = 0.3, y = 0.3, z = 0.2, m = 0.2
(20)DPEHA
(20)
R3= 디사이클로펜타닐옥시카르보닐, R5=5-노보넨-2-카르복시산,
x=0.35, y=0.35, z=0.1, m=0.2R1, R2, R4 = methyl
R3 = dicyclopentanyloxycarbonyl, R5 = 5-norbornene-2-carboxylic acid,
x = 0.35, y = 0.35, z = 0.1, m = 0.2
(20)DPEHA
(20)
상기 표1에 있어서, DPEHA는 디펜타에리트리톨 헥사아크릴레이트와 디펜타에리트리톨 펜타아크릴레이트의 혼합물(중량비=1:1), APTMS는 (3-아미노프로필)트리메톡시실레인, PGMEA는 프로필렌글리콜메틸에테르아세테이트이다.In Table 1, DPEHA is a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (weight ratio = 1: 1), APTMS is (3-aminopropyl) trimethoxysilane, and PGMEA is propylene. Glycol methyl ether acetate.
표 1에서 일반식 1의 바인더 수지들은 평균분자량 9,000, 분산도 2.1 및 산가 110이다. In Table 1, the binder resins of the general formula 1 have an average molecular weight of 9,000, a dispersity of 2.1, and an acid value of 110.
비교예 1~2Comparative Examples 1 and 2
바인더 수지로서 하기 화학식 2로 표시되는 바인더 수지를 사용하고, 조성물의 성분 및 함량을 하기 표 2에 기재된 조성에 따라서 변화시킨 것을 제외하고는 상기 실시예 1과 동일한 방법으로 음성 레지스트 조성물을 제조하였다. 하기 화학식 2에서 R5는 메틸이다.A negative resist composition was prepared in the same manner as in Example 1, except that the binder resin represented by the following Chemical Formula 2 was used as the binder resin, and the components and contents of the composition were changed according to the composition shown in Table 2 below. In Formula 2, R 5 is methyl.
(20중량%)Binder Resin
(20% by weight)
단량체
(중량%)acryl
Monomer
(weight%)
(중량%)Silicon compound
(weight%)
(중량%)Photoinitiator
(weight%)
(중량%)additive
(weight%)
Organic solvent
(20)DPEHA
(20)
(0.1)FC-430
(0.1)
(to 100)PGMEA
(to 100)
표 2에서 일반식 2의 바인더 수지들은 평균분자량 10,000, 분산도 2.5 및 산가 100이다. In Table 2, the binder resins of Formula 2 have an average molecular weight of 10,000, a dispersion of 2.5, and an acid value of 100.
시험예Test Example
이상의 실시예 및 비교예에 있어서 음성 레지스트 조성물의 평가는 실리콘 웨이퍼 또는 유리판 등의 기판 위에서 실시하였으며, 레지스트 조성물의 열적특성, 투과율(T%, 400 nm에서), 평탄성(Uniformity), 잔막율, 패턴 형성, 내화학성 등의 성능평가를 실시하였으며, 그 결과를 하기 표 3과 4에 나타냈다.In the above Examples and Comparative Examples, the negative resist composition was evaluated on a substrate such as a silicon wafer or a glass plate, and the thermal properties, transmittance (at T%, 400 nm), uniformity, residual film ratio, and pattern of the resist composition were evaluated. Performance evaluation of the formation, chemical resistance and the like was performed, and the results are shown in Tables 3 and 4 below.
1. 열적특성1. Thermal Characteristics
음성 레지스트 조성물을 기판위에 스핀 코터를 이용하여 800rpm의 속도로 8초간 도포한 후, 100℃에서 1분간 프리베이크(prebake)하였다. 다음으로 365nm에서 15초간 노광시킨 후, 240℃에서 30분간 포스트베이크(postbake)를 실시하여 레지스트 막을 형성시켰다. 이를 오토클레이브(Autoclave)에 넣어 100℃에서 1시간동안 숙성시켰다. 오토클레이브에서 숙성된 시편을 크로스 헤찌 커터(Cross Hatch Cutter)로 기판이 드러나도록 스크레치(Scratch)한 후 접착 테잎으로 부착한 후 탈착했다. 100 셀 중 80셀이 테잎에 붙어 기판으로부터 탈착되지 않으면 '양호' 그렇지 않은 경우를 '불량'으로 판단했다.The negative resist composition was applied onto the substrate using a spin coater for 8 seconds at a speed of 800 rpm, and then prebaked at 100 ° C. for 1 minute. Next, after exposing for 15 second at 365 nm, it post-baked at 240 degreeC for 30 minutes, and formed the resist film. This was put into an autoclave and aged at 100 ° C. for 1 hour. The specimens aged in the autoclave were scratched to expose the substrate with a cross hatch cutter, and then attached with an adhesive tape and then detached. If 80 cells out of 100 cells adhered to the tape and were not detached from the substrate, the result was judged as 'good' or 'bad'.
2. UV투과율2. UV transmittance
음성 레지스트 조성물을 기판 위에 스핀 코터를 이용하여 800rpm의 속도로 8초간 도포한 후, 100℃에서 1분간 프리베이크(prebake)하였다. 다음으로, TMAH 2.38%용액에 60초간 스프레이(spray)현상 후, 순수(DI Water)로 60초간 린스하였다. 압축공기로 불어낸 다음, 250℃에서 30분간 포스트베이크(postbake)를 실시하여 약 3.5 내지 4.0 마이크로미터(um)의 레지스트 막을 형성하였다. 형성된 박에 UV를 투과하여 400nm영역의 투과율을 측정하였다.The negative resist composition was applied to the substrate using a spin coater for 8 seconds at a speed of 800 rpm, and then prebaked at 100 ° C. for 1 minute. Next, after spraying for 60 seconds to the TMAH 2.38% solution, it was rinsed with pure water (DI Water) for 60 seconds. After blowing with compressed air, postbake was performed at 250 ° C. for 30 minutes to form a resist film of about 3.5 to 4.0 micrometers (um). UV was transmitted through the formed foil to measure transmittance in the 400 nm region.
3. 잔막율3. Residual rate
음성 레지스트 조성물을 기판 위에 스핀 코팅하고, 프리베이크(Pre-Bake)를 한 후의 두께와 포스트베이크(Post-Bake)를 하여 용매를 제거한 후 형성된 막의 두께 비율(%)을 측정하였다.The negative resist composition was spin-coated on a substrate, the thickness after pre-baking and post-baking to remove the solvent, and the thickness ratio (%) of the formed film was measured.
4. 패턴 형성4. Pattern Formation
음성 레지스트 패턴을 형성한 실리콘 웨이퍼를 홀(Hole) 패턴의 수직방향에서부터 절단하고, 패턴의 단면 방향에서 전자현미경으로 관찰한 결과를 나타냈다. 패턴 사이드 벽(side wall)이 기판에 대하여 55도 이상의 각도로 세워져 있고, 막이 감소되지 않은 것을 '양호'로 하고, 막의 감소가 인정된 것을 '막감(膜減)'으로 판정하였다.The silicon wafer in which the negative resist pattern was formed was cut from the vertical direction of the hole pattern, and the result which observed with the electron microscope in the cross-sectional direction of the pattern was shown. The pattern side wall was erected at an angle of 55 degrees or more with respect to the substrate, and the film was not reduced.
5. 내화학성5. Chemical resistance
음성 레지스트 조성물을 기판 위에 스핀 코터를 이용하여 도포한 후, 프리베이크(prebake) 및 포스트베이크(postbake) 등의 공정을 거쳐 형성된 레지스트 막을 스트리퍼(Stripper), 에천트(Etchant) 용액에 40℃에서 10분 동안 담근 후 레지스트 막의 투과율 및 두께의 변화가 있는지 살펴보았다. 투과율 및 두께의 변화가 없을 때 '양호'로 하고, 투과율 및 두께의 변화가 있으면 '불량'으로 판정하였다.After the negative resist composition was applied onto the substrate using a spin coater, a resist film formed through a process such as prebake and postbake was applied to a stripper or etchant solution at 40 ° C. at 10 ° C. After soaking for minutes, the transmittance and thickness of the resist film were examined. When there was no change in transmittance and thickness, it was set as 'good', and when there was a change in transmittance and thickness, it was determined as 'poor'.
(400nm) (%)UV transmittance
(400nm) (%)
(%)Residual rate
(%)
(400nm) (%)UV transmittance
(400nm) (%)
(%)Residual rate
(%)
상기 표 3 및 표 4의 시험결과에서 알 수 있듯이, 본 발명의 액정표시소자용 음성 레지스트 조성물은 종래의 레지스트 조성물과는 달리 내열성이 우수할 뿐만 아니라, 금속 및 무기물과의 접착력, UV투과율, 잔막율, 평탄성, 패턴안정성 및 내화학성이 매우 우수함을 알 수 있다.As can be seen from the test results of Tables 3 and 4, the negative resist composition for a liquid crystal display device of the present invention, unlike the conventional resist composition, not only has excellent heat resistance, but also adhesion to metals and inorganic materials, UV transmittance, glass, and the like. It can be seen that the film rate, flatness, pattern stability and chemical resistance are very excellent.
Claims (8)
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| KR100597715B1 (en) | 2004-08-25 | 2006-07-10 | 주식회사 삼양이엠에스 | Negative resist composition |
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