KR101082494B1 - Photosensitive resin composition which has advanced pattern adhesion and developing property - Google Patents
Photosensitive resin composition which has advanced pattern adhesion and developing property Download PDFInfo
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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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- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/285—Polyhydroxy dicarboxylic acids having five or more carbon atoms, e.g. saccharic acids
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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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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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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- 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
- G03F7/027—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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- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
Abstract
본 발명은 알칼리 가용성 바인더 수지, 다관능성 모노머, 착색제, 광 중합 개시제, 및 용매를 포함하는 감광성 수지 조성물에 대한 것으로, 구체적으로는 상기 다관능성 모노머들에 있어서, 불포화 이중결합의 개수가 다른 다관능성 모노머를 조성비를 달리하여 포함함으로써 패턴 밀착성과 현상성이 개선된 감광성 수지 조성물에 대한 것이다. 본 발명에 따른 감광성 수지 조성물은 빠른 현상 특성을 가짐과 동시에 하부 기판과의 밀착성이 뛰어나고 표면 조도 및 착색제 조성물의 분산 안정성을 개선하는 효과가 있다. The present invention relates to a photosensitive resin composition comprising an alkali-soluble binder resin, a polyfunctional monomer, a colorant, a photopolymerization initiator, and a solvent. Specifically, in the above polyfunctional monomers, the number of unsaturated double bonds is different. The present invention relates to a photosensitive resin composition in which pattern adhesiveness and developability are improved by including monomers in different ratios. The photosensitive resin composition according to the present invention has an effect of improving the surface roughness and dispersion stability of the colorant composition while having fast developing characteristics and excellent adhesion to the lower substrate.
Description
본 발명은 알칼리 가용성 바인더 수지, 다관능성 모노머, 착색제, 광 중합 개시제, 및 용매를 포함하는 감광성 수지 조성물에 대한 것으로, 구체적으로는 상기 다관능성 모노머들에 있어서, 불포화 이중결합의 개수가 다른 다관능성 모노머를 조성비를 달리하여 포함함으로써 패턴 밀착성과 현상성이 개선된 감광성 수지 조성물에 대한 것이다. The present invention relates to a photosensitive resin composition comprising an alkali-soluble binder resin, a polyfunctional monomer, a colorant, a photopolymerization initiator, and a solvent. Specifically, in the above polyfunctional monomers, the number of unsaturated double bonds is different. The present invention relates to a photosensitive resin composition in which pattern adhesiveness and developability are improved by including monomers in different ratios.
LCD는 상하 투명 절연 기판 사이에 이방성 유전율을 가지는 액정을 주입한 후 액정층에 주어지는 전압의 차이로 액정층의 배열을 조절하여 이를 투과하는 빛의 양을 조절함으로써 원하는 화상을 얻는 표시 장치이다. The LCD is a display device that obtains a desired image by injecting a liquid crystal having an anisotropic dielectric constant between the upper and lower transparent insulating substrates, and then controlling the arrangement of the liquid crystal layers by controlling the arrangement of the liquid crystal layers due to the difference in voltage applied to the liquid crystal layer.
상기 LCD에 포함되는 컬러필터 제조방법에는 염색법, 안료 분산법, 전착법 및 인쇄법 등이 있으며, 이중에서 생산성, 품질 및 비용 등에서 장점을 갖는 안료 분산법이 주로 사용되고 있다. 이러한 안료분산법에 사용되는 안료 분산 감광성 조성물(color resist)은 용매, 안료, 안료 분산제, 바인더 폴리머, 다관능성 모노머, 광 개시제 및 첨가제로 구성된다. The color filter manufacturing method included in the LCD includes a dyeing method, a pigment dispersion method, an electrodeposition method and a printing method, among which a pigment dispersion method having advantages in productivity, quality and cost is mainly used. The pigment dispersion photosensitive composition (color resist) used in such a pigment dispersion method consists of a solvent, a pigment, a pigment dispersant, a binder polymer, a polyfunctional monomer, a photoinitiator, and an additive.
최근 액정 디스플레이(LCD)의 용도가 노트북 모니터에서 데스크탑 모니터, LCD TV 등으로 확대됨에 따라 색 재현율이 우수하며 콘트라스트가 높은 컬러필터가 요구되고 있으며, 이러한 요구에 맞추어 향상된 색 특성을 위하여 색 재현율을 높임과 동시에 Color 패턴의 색 두께를 유지하기 위해서는 감광성 조성물에 포함되는 안료 등의 착색제의 함량이 증가하여야 한다.Recently, as the use of liquid crystal displays (LCDs) has been expanded from notebook monitors to desktop monitors and LCD TVs, color filters having excellent color reproducibility and high contrast are required, and color reproducibility is increased for improved color characteristics. At the same time, in order to maintain the color thickness of the color pattern, the content of colorants such as pigments included in the photosensitive composition should be increased.
하지만 착색제의 함량이 증가함에 따라 패턴 막 하부까지 도달할 수 있는 조사 에너지의 양이 줄어들고, 알칼리 현상액에 잘 녹지 않는 안료 분산제의 함량 또한 증가하므로 현상 속도도 느려지게 된다. 따라서 패턴 밀착성 저하와 현상시간 증가를 모두 보완할 수 있는 감광성 수지 조성물의 개발이 요구되고 있다.However, as the amount of the colorant increases, the amount of irradiation energy that can reach the bottom of the pattern film decreases, and the content of the pigment dispersant that is hardly soluble in the alkaline developer also increases, thereby lowering the development speed. Therefore, the development of the photosensitive resin composition which can compensate for both the decline in pattern adhesion and the increase in development time is required.
본 발명이 이루고자 하는 기술적 과제는 착색제의 함량 증가에 따른 상기 문제점을 해결하기 위한 것으로, 우수한 패턴 밀착성을 가지며 동시에 현상성이 뛰어난 감광성 수지 조성물을 제공하는 것이다.The technical problem to be achieved by the present invention is to solve the above problems caused by the increase in the content of the colorant, and to provide a photosensitive resin composition having excellent pattern adhesion and at the same time excellent developability.
상기 과제를 해결하기 위한 수단으로 본 발명은, 감광성 수지 조성물에 있어서, 다관능성 모노머로서 불포화 이중결합의 개수가 1 내지 4인 다관능성 모노머를 20-80 중량% 포함하고, 불포화 이중결합의 개수가 5 내지 6인 다관능성 모노머를 80-20중량%로 포함하는 것을 특징으로 한다. As a means for solving the above problems, the present invention, in the photosensitive resin composition, 20 to 80% by weight of a polyfunctional monomer having a number of unsaturated
또한, 상기 불포화 이중결합의 개수가 5 내지 6인 다관능성 모노머는 펜타에리스리톨 테트라(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트 중에서 선택되는 1종 이상인 것을 특징으로 한다. The polyfunctional monomer having a number of unsaturated double bonds of 5 to 6 may be one selected from pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. It is characterized by the above.
또한, 상기 불포화 이중결합의 개수가 1 내지 4인 다관능성 모노머는 하기 [화학식 1]로 표시되는 다관능성 모노머 외에 폴리에틸렌 글리콜 디(메타)아크릴레이트, 트리메틸올프로판 디(메타)아크릴레이트, 트리메틸올프로판 트리(메타)아크릴레이드, 펜타에리스리톨 트리(메타)아크릴레이트 중에서 선택되는 1종 이상인 것을 특징으로 한다.In addition, the polyfunctional monomer having the number of the unsaturated
[화학식 1] [Formula 1]
R1, R2, R3는 각각 에틸렌계 탄화수소 중의 하나이고, 3≤a+b+c≤10이다.R1, R2 and R3 are each one of the ethylene hydrocarbons, and 3 ≦ a + b + c ≦ 10.
또한, 상기 다관능성 모노머는 전체 감광성 수지 조성물에 대해 1 ~ 30 중량부로 포함되는 것을 특징으로 하며, In addition, the multifunctional monomer is characterized in that it is included in 1 to 30 parts by weight based on the total photosensitive resin composition,
상기 감광성 수지 조성물은 알칼리 가용성 바인더 수지, 착색제, 중합개시제 및 용매를 더 포함하는 것을 특징으로 한다. The photosensitive resin composition is characterized by further comprising an alkali-soluble binder resin, a colorant, a polymerization initiator and a solvent.
또한, 감광성 수지 조성물 100 중량부를 기준으로 알칼리 가용성 수지 5 ~ 30 중량부; 광개시제 0.5 ~ 5 중량부; 착색제 3 ~ 30 중량부; 및 용매 10 ~ 90 중량부로 포함하는 것을 특징으로 한다. In addition, based on 100 parts by weight of the photosensitive resin composition, 5 to 30 parts by weight of alkali-soluble resin; 0.5-5 parts by weight of photoinitiator; 3 to 30 parts by weight of colorant; And 10 to 90 parts by weight of the solvent.
본 발명에 따른 감광성 수지 조성물은 빠른 현상 특성을 가짐과 동시에 하부 기판과의 밀착성이 뛰어나고 표면 조도 및 착색제 조성물의 분산 안정성을 개선하는 효과가 있다. The photosensitive resin composition according to the present invention has an effect of improving the surface roughness and dispersion stability of the colorant composition while having fast developing characteristics and excellent adhesion to the lower substrate.
도 1은 실시예 1의 수지BM 상 패턴의 패턴 유실정도를 광학현미경을 이용하여 200배 배율로 관찰한 모습이다.
도 2은 실시예 2의 수지BM 상 패턴의 패턴 유실정도를 광학현미경을 이용하여 200배 배율로 관찰한 모습이다.
도 3은 비교예 1의 수지BM 상 패턴의 패턴 유실정도를 광학현미경을 이용하여 200배 배율로 관찰한 모습이다.
도 4은 비교예 2의 현상 후 유리기판 상 패턴의 유실정도를 광학현미경을 이용하여 50배 배율로 관찰한 모습이다.
도 5은 비교예 2의 현상 후 Cr-BM기판 상 패턴의 유실정도를 광학현미경을 이용하여 50배 배율로 관찰한 모습이다.
도 6은 실시예 3의 현상 후 유리기판 상 패턴의 유실정도를 광학현미경을 이용하여 50배 배율로 관찰한 모습이다.
도 7은 실시예 3의 현상 후 Cr-BM기판 상 패턴의 유실정도를 광학현미경을 이용하여 50배 배율로 관찰한 모습이다.1 is a view of the pattern loss degree of the resin BM phase pattern of Example 1 observed at 200 times magnification using an optical microscope.
2 is a view of the pattern loss degree of the resin BM phase pattern of Example 2 observed at 200 times magnification using an optical microscope.
3 is a view of the pattern loss degree of the resin BM phase pattern of Comparative Example 1 observed at 200 times magnification using an optical microscope.
4 is a view of the degree of loss of the pattern on the glass substrate after the development of Comparative Example 2 at 50 times magnification using an optical microscope.
5 is a view of the degree of loss of the pattern on the Cr-BM substrate after the development of Comparative Example 2 at 50 times magnification using an optical microscope.
6 is a view of the degree of loss of the pattern on the glass substrate after the development of Example 3 at 50 times magnification using an optical microscope.
FIG. 7 shows the degree of loss of the pattern on the Cr-BM substrate after developing in Example 3 at 50 times magnification using an optical microscope.
본 발명은, 불포화 이중결합의 개수가 1 내지 4인 모노머 20중량% 내지 80중량%, 불포화 이중결합의 개수가 5 내지 6인 모노머 80중량% 내지 20중량%로 구성된 다관능성 모노머를 포함하는 감광성 수지 조성물을 제공함으로써 빠른 현상 특정 및 우수한 기판 밀착성, 표면 조도 및 착색제 조성물의 분산 안정성을 제공할 수 있다.
The present invention provides a photosensitive composition comprising a polyfunctional monomer composed of 20 wt% to 80 wt% of monomers having 1 to 4 unsaturated double bonds and 80 wt% to 20 wt% of monomers having 5 to 6 unsaturated double bonds. Providing a resin composition can provide fast development and excellent substrate adhesion, surface roughness and dispersion stability of the colorant composition.
상기 불포화 이중결합의 개수가 1 내지 4인 모노머로는, 하기 [화학식 1]로 표시되는 다관능성 모노머 외에 폴리에틸렌 글리콜 디(메타)아크릴레이트, 트리메틸올프로판 디(메타)아크릴레이트, 트리메틸올프로판 트리(메타)아크릴레이드, 펜타에리스리톨 트리(메타)아크릴레이트로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.Examples of the monomer having 1 to 4 unsaturated unsaturated bonds include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri, in addition to the polyfunctional monomer represented by the following [Formula 1]. One or more types selected from the group consisting of (meth) acrylate and pentaerythritol tri (meth) acrylate can be used.
[화학식 1][Formula 1]
상기 화학식 1에서 R1, R2, R3는 각각 에틸렌계 탄화수소 중의 하나일 수 있다. 구체적으로 예를 들면, 에틸렌, 프로필렌, 이소프로필렌, 부틸렌 등이 적용될 수 있으나, 이에 한정하지 아니하며, 바람직하게는 에틸렌 일 수 있다. 또한, 3≤a+b+c≤10이다. In Formula 1, R1, R2, and R3 may each be one of ethylene hydrocarbons. Specifically, for example, ethylene, propylene, isopropylene, butylene, etc. may be applied, but is not limited thereto, and may preferably be ethylene. 3? A + b + c? 10.
상기 불포화 이중결합의 개수가 1 내지 4인 다관능성 모노머는 전제 다관능성 모노머의 중량 대비 20 내지 80 중량%로 포함됨이 바람직하다. It is preferable that the polyfunctional monomer having the number of the unsaturated double bonds of 1 to 4 is included in 20 to 80% by weight relative to the weight of the total polyfunctional monomer.
상기 불포화 이중결합의 개수가 1 내지 4인 다관능성 모노머가 20중량% 미만으로 너무 적게 포함되는 경우에는 현상특성 개선 등 모노머 혼합에 따른 개선이 미비한 문제점이 있으며, 반대로 80중량%를 초과하여 포함되는 경우에는 오히려 패턴 밀착성이 저하되는 문제가 있다. When the polyfunctional monomer having 1 to 4 polyunsaturated double bonds is contained in an amount of less than 20% by weight, there is a problem in that the improvement due to the mixing of the monomers is insufficient. In this case, there is a problem in that the pattern adhesion is lowered.
한편, 불포화 이중결합의 개수가 5 내지 6인 다관능성 모노머로는 펜타에리스리톨 테트라(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트 등으로 이루어진 군에서 선택되는 1종 이상을 사용할 수 있다. On the other hand, the polyfunctional monomer having a number of unsaturated double bonds of 5 to 6 in the group consisting of pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. One or more kinds selected may be used.
상기 불포화 이중결합의 개수가 5 내지 6인 다관능성 모노머는 전제 다관능성 모노머의 중량 대비 80 중량% 내지 20 중량%로 포함됨이 바람직하다. The polyfunctional monomer having the number of unsaturated double bonds of 5 to 6 is preferably included in 80 to 20% by weight relative to the weight of the total polyfunctional monomer.
상기 불포화 이중결합의 개수가 5 내지 6인 다관능성 모노머가 20 중량% 미만으로 너무 적게 포함되는 경우에는 충분한 패턴 밀착성을 얻을 수 없으며, 반대로 80 중량%를 초과하여 포함되는 경우에는 모노머 혼합에 따른 개선효과가 미비한 문제가 있다. If the number of polyunsaturated polyfunctional monomers having 5 to 6 unsaturated double bonds is less than 20% by weight, sufficient pattern adhesion may not be obtained. There is a problem that is ineffective.
상기 불포화 이중결합의 개수가 1 내지 4인 다관능성 모노머 20 ~ 80중량%, 불포화 이중결합의 개수가 5 내지 6인 다관능성 모노머 80 ~ 20중량%로 구성된 다관능성 모노머의 함량은 전체 조성물에 대해 1 ~ 30 중량부로 포함되는 것이 바람직하다. 상기 다관능성 모노머가 전체 조성물에 대해 1 중량부 미만인 경우에는 공정 진행 후 패턴이 형성되지 않는 문제가 있으며 30 중량부를 초과하여 포함될 경우에는 충분한 현상특성이 확보되지 않는 문제가 있어 바람직하지 않다.
The content of the polyfunctional monomer composed of 20 to 80% by weight of the polyfunctional monomer having 1 to 4 unsaturated double bonds and 80 to 20% by weight of the polyfunctional monomer having 5 to 6 unsaturated double bonds is included in the total composition. It is preferably included in 1 to 30 parts by weight. When the polyfunctional monomer is less than 1 part by weight based on the total composition, there is a problem in that a pattern is not formed after the process is progressed, and when included in excess of 30 parts by weight, sufficient developing characteristics are not secured.
한편, 본 발명은 유기안료 또는 무기안료를 포함한 착색제; 알카리 가용성 수지; 본 발명에 따른 다관능성 모노머; 광개시제; 및 용매를 포함하는 감광성 수지 조성물을 제공한다.On the other hand, the present invention is a colorant including an organic pigment or an inorganic pigment; Alkaline soluble resins; Multifunctional monomers according to the present invention; Photoinitiators; And it provides a photosensitive resin composition comprising a solvent.
상기 감광성 수지 조성물 100 중량부를 기준으로 상기 착색제를 3~30 중량부; 상기 알카리 가용성 수지를 3 ~30중량부; 상기 다관능성 모노머 1~30 중량부; 상기 광개시제 0.5~5 중량부; 및 상기 용매 10~90 중량부를 포함할 수 있다.3 to 30 parts by weight of the colorant based on 100 parts by weight of the photosensitive resin composition; 3 to 30 parts by weight of the alkali-soluble resin; 1 to 30 parts by weight of the multifunctional monomer; 0.5 to 5 parts by weight of the photoinitiator; And it may include 10 to 90 parts by weight of the solvent.
상기 착색제로는 카민 6B(C.I.12490), 프탈로시아닌 그린(C.I. 74260), 프탈로시아닌 블루(C.I. 74160), 페릴렌 블랙(BASF K0084. K0086), 시아닌 블랙, 리놀옐로우(C.I.21090), 리놀 옐로우GRO(C.I. 21090), 벤지딘 옐로우4T-564D, 빅토리아 퓨어 블루(C.I.42595), C.I. PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36; 58 C.I. PIGMENT blue 15:1, 15:3, 15:4, 15:6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37 등이 있고, 이 밖에 백색 안료, 형광 안료, 무기안료 등도 이용할 수 있다.Carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084. K0086), cyanine black, linol yellow (CI21090), linol yellow GRO (CI) 21090), benzidine yellow 4T-564D, Victoria pure blue (CI42595), CI PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36; 58 C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT
상기 광개시제로는 2,4-트리클로로메틸-(4'-메톡시페닐)-6-트리아진, 2,4-트리클로로메틸-(4'-메톡시스티릴)-6-트리아진, 2,4-트리클로로메틸-(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, 벤조인부틸 에테르, 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-클로로 티옥산톤, 1-클로로-4-프로필옥시 티옥산톤, 이소프로필 티옥산톤, 디이소프로필 티옥산톤 등의 티옥산톤계 화합물; 크산톤, 2-메틸크산톤 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-트리메틸-비스클로[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-Cl]-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.Examples of the photoinitiator include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2 , 4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- {4- [2 Triazine compounds such as, 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, benzoinmethyl ether, benzoinethyl ether, benzoin isobutyl ether, benzoinbutyl 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; Fluorenone compounds such as 9- fluorenone, 2-chloro-9- fluorenone and 2-methyl-9- fluorenone; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bisclo [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; Methyl 4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) Amine 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-Cl] Coumarin-based compounds such as -benzopyrano [6,7,8-ij] -quinolizin-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene, 3-methyl-β-naphthothiazoline or mixtures thereof, and the like.
상기 용매로는 끓는점이 140 내지 159℃ 범위를 갖는 제 1 용매, 끓는점이 160 내지 179℃ 범위를 갖는 제 2 용매 및 끓는점이 180 내지 200℃ 범위를 갖는 제 3 용매를 혼용하는 것이 바람직하다. 전체 용매의 평균 끓는점이 145℃ 미만인 경우 VCD 공정 중 급격한 휘발로 얼룩이 발생하게 되며, 전체 용매의 평균 끓는점이 160℃를 초과하는 경우 VCD 공정에 의해 용매 제거가 잘 이루어지지 않는 문제가 있기 때문이다.As the solvent, it is preferable to use a first solvent having a boiling point of 140 to 159 ° C, a second solvent having a boiling point of 160 to 179 ° C, and a third solvent having a boiling point of 180 to 200 ° C. If the average boiling point of the total solvent is less than 145 ℃ staining occurs due to the rapid volatilization of the VCD process, if the average boiling point of the total solvent exceeds 160 ℃ because of the problem that the solvent is not removed by the VCD process.
제 1 용매 성분으로는 끓는점이 140 내지 159℃ 범위인 용매를 제한 없이 사용할 수 있으며, 이들의 비제한적인 예로는 에틸렌글리콜 모노메틸 에테르 아세테이트(bp 145℃), 프로필렌글리콜 모노메틸 에테르 아세테이트(bp 146℃), 디부틸 에테르(bp 140℃), 사이클로헥사논(bp 156℃), 2-헵타논(bp 151℃), 2-에톡시에틸 아세테이트(bp 156℃), 프로필렌글리콜 모노에틸 에테르 아세테이트(bp 158℃), 2-메톡시에틸 아세테이트(bp 145℃), 메틸 3-메톡시프로피오네이트(bp 142℃) 또는 이들의 혼합 용매 등이 있다. 특히, 프로필렌글리콜 모노메틸 에테르 아세테이트 또는 사이클로헥사논이 바람직하다. As the first solvent component, a solvent having a boiling point in the range of 140 to 159 ° C. may be used without limitation, and non-limiting examples thereof include ethylene glycol monomethyl ether acetate (bp 145 ° C.) and propylene glycol monomethyl ether acetate (bp 146). ° C), dibutyl ether (bp 140 ° C), cyclohexanone (bp 156 ° C), 2-heptanone (bp 151 ° C), 2-ethoxyethyl acetate (bp 156 ° C), propylene glycol monoethyl ether acetate ( bp 158 ° C.), 2-methoxyethyl acetate (bp 145 ° C.), methyl 3-methoxypropionate (bp 142 ° C.), or a mixed solvent thereof. In particular, propylene glycol monomethyl ether acetate or cyclohexanone is preferred.
제 2 용매 성분으로는 끓는점이 160 내지 179℃ 범위인 용매를 제한 없이 사용할 수 있으며, 이들의 비제한적인 예로는 디프로필렌글리콜 디메틸에테르(bp 175℃), 디에틸렌글리콜 부틸 에테르(bp 162℃), 디에틸렌글리콜 디메틸 에테르(bp 162℃), 3-메톡시부틸 아세테이트(bp 170℃), 에틸 3-에톡시프로피오네이트(bp 170℃) 또는 이들의 혼합 용매 등이 있다. 특히, 에틸 3-에톡시 프로피오네이트, 3-메톡시부틸 아세테이트, 등에서 선택하여 사용하는 것이 바람직하다.As the second solvent component, a solvent having a boiling point in the range of 160 to 179 ° C. may be used without limitation, and non-limiting examples thereof include dipropylene glycol dimethyl ether (bp 175 ° C.) and diethylene glycol butyl ether (bp 162 ° C.). , Diethylene glycol dimethyl ether (bp 162 ° C.), 3-methoxybutyl acetate (bp 170 ° C.), ethyl 3-ethoxypropionate (bp 170 ° C.), or a mixed solvent thereof. In particular, it is preferable to select and use from ethyl 3-ethoxy propionate, 3-methoxybutyl acetate, etc.
제 3 용매 성분으로는 끓는점이 180 내지 200℃ 범위인 용매를 제한 없이 사용할 수 있으며, 이들의 비제한적인 예로는 디프로필렌글리콜 메틸 에테르 아세테이트(bp 200℃), 디프로필렌글리콜 부틸 에테르(bp 190℃), 디프로필렌글리콜 모노메틸 에테르(bp 190℃), 디에틸렌글리콜 디에틸 에테르(bp 180-190℃), 에틸렌글리콜 모노아세테이트(bp 188℃), 에틸렌글리콜 디아세테이트(bp 187℃) 또는 이들의 혼합 용매 등이 있다. 특히, 디프로필렌글리콜 모노메틸 에테르(bp 190℃)가 바람직하다. As the third solvent component, a solvent having a boiling point in the range of 180 to 200 ° C. may be used without limitation, and non-limiting examples thereof include dipropylene glycol methyl ether acetate (bp 200 ° C.) and dipropylene glycol butyl ether (bp 190 ° C. ), Dipropylene glycol monomethyl ether (bp 190 ° C), diethylene glycol diethyl ether (bp 180-190 ° C), ethylene glycol monoacetate (bp 188 ° C), ethylene glycol diacetate (bp 187 ° C) or their Mixed solvents; In particular, dipropylene glycol monomethyl ether (bp 190 degreeC) is preferable.
상기 알카리 가용성 수지는 산기(acid functional group)를 포함하는 고분자 수지로서 당 분야에 일반적으로 사용되는 것이라면 특정 구조에 한정되지 않으며, 단독 또는 둘 이상 혼합하여 사용할 수 있다. The alkali-soluble resin is a polymer resin containing an acid functional group (acid functional group) as long as it is generally used in the art is not limited to a specific structure, can be used alone or in combination of two or more.
다만, 산가는 20-300 KOHmg/g 범위이며, 중량평균 분자량은 1,000-200,000의 범위인 것이 바람직하고, 더욱 바람직하게는 분자량이 5,000-100,000의 범위인 것으로 한다. However, the acid value is in the range of 20-300 KOHmg / g, the weight average molecular weight is preferably in the range of 1,000-200,000, more preferably in the range of 5,000-100,000.
산가가 20 KOH mg/g 미만인 경우, 알칼리 현상액에 대한 용해성이 떨어질 수 있으며, 300 KOH mg/g을 초과하는 경우에는 패턴에 언더컷(undercut) 현상이 발생할 수 있기 때문이다. 분자량이 1,000 미만인 경우에는 노광에 따른 현상성의 차이가 발생하지 않아 광 식각법에 의한 패턴 형성이 불가능해 질 수 있으며, 분자량이 200,000을 초과하는 경우에는 용액의 점도가 높아져 코팅이 원활하게 이루어지지 않을 수 있다.
If the acid value is less than 20 KOH mg / g, solubility in an alkaline developer may be inferior, and if the acid value exceeds 300 KOH mg / g undercut (undercut) phenomenon may occur in the pattern. If the molecular weight is less than 1,000, there is no difference in developability due to exposure, and thus pattern formation may not be possible by the optical etching method. If the molecular weight is more than 200,000, the viscosity of the solution may increase and coating may not be performed smoothly. Can be.
이하, 실시예를 통하여 본 발명을 더욱 상세하게 설명하나, 하기의 실시예는 본 발명을 예시하기 위한 것일 뿐이며 이들만으로 본 발명의 범위를 한정하는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only intended to illustrate the present invention and do not limit the scope of the present invention.
<실시예1> 감광성 수지 조성물의 제조Example 1 Preparation of Photosensitive Resin Composition
착색제로 G36/Y138안료 5 중량부, 알카리 가용성 수지 3 중량부, 중합성 화합물로 화학식1로 표시되는 다관능성 모노머(R1, R2, R3 는 각각 에틸렌이며, a=1, b=1, c=1)와 디펜타에리스리톨 헥사아크릴레이트를 1:4 비율로 혼합하여, 전체 총 중량에 대해 5 중량부, 광중합 개시제로 아세토페논계와 트리아진계 개시제 그리고 센시타이저 2 중량부 및 유기 용매로 PGMEA, 3-MBA, DPM 85 중량부를 쉐이커를 이용하여 1시간 반동안 혼합시킨 후 1시간 반 동안 상온에서 방치하여 안정화시켰다.
5 parts by weight of a G36 / Y138 pigment, 3 parts by weight of an alkali-soluble resin, and a polyfunctional monomer represented by the formula (1) as the colorant (R1, R2, R3 are ethylene, respectively, a = 1, b = 1, c = 1) and dipentaerythritol hexaacrylate are mixed at a ratio of 1: 4, 5 parts by weight relative to the total weight, acetophenone and triazine initiators as photopolymerization initiators, 2 parts by weight of sensitizer and PGMEA as an organic solvent, 85 parts by weight of 3-MBA, DPM was mixed for 1 hour and a half using a shaker, and then stabilized by standing at room temperature for 1 and a half hours.
<실시예2> 감광성 수지 조성물의 제조Example 2 Preparation of Photosensitive Resin Composition
착색제로 G36/Y138안료 5 중량부, 알카리 가용성 수지 3 중량부, 중합성 화합물로 화학식1로 표시되는 다관능성 모노머(R1, R2, R3 는 각각 에틸렌이며, a=1, b=1, c=1)와 디펜타에리스리톨 헥사아크릴레이트를 2:3 비율로 혼합하여, 전체 총 중량에 대해 5 중량부, 광중합 개시제로 아세토페논계와 트리아진계 개시제 그리고 센시타이저 2 중량부 및 유기 용매로 PGMEA, 3-MBA, DPM 85 중량부를 쉐이커를 이용하여 1시간 반동안 혼합시킨 후 1시간 반동안 상온에서 방치하여 안정화시켰다.
5 parts by weight of a G36 / Y138 pigment, 3 parts by weight of an alkali-soluble resin, and a polyfunctional monomer represented by the formula (1) as the colorant (R1, R2, R3 are ethylene, respectively, a = 1, b = 1, c = 1) and dipentaerythritol hexaacrylate are mixed in a 2: 3 ratio, 5 parts by weight based on the total weight, acetophenone and triazine initiators as photopolymerization initiator, 2 parts by weight of sensitizer and PGMEA as organic solvent, 85 parts by weight of 3-MBA and DPM were mixed for 1 hour and a half using a shaker, and then allowed to stand at room temperature for 1 and a half hours to stabilize.
<비교예1> 감광성 수지 조성물의 제조Comparative Example 1 Preparation of Photosensitive Resin Composition
착색제로 G36/Y138안료 5 중량부, 알카리 가용성 수지 3 중량부, 중합성 화합물로 디펜타에리스리톨 헥사아크릴레이트만을 전체 총 중량에 대해 5 중량부, 광중합 개시제로 아세토페논계와 트리아진계 개시제 그리고 센시타이저 2 중량부 및 유기 용매로 PGMEA,3-MBA,DPM 85 중량부를 쉐이커를 이용하여 1시간 반동안 혼합시킨 후 1시간 반동안 상온에서 방치하여 안정화시켰다.
5 parts by weight of G36 / Y138 pigment as a colorant, 3 parts by weight of alkali-soluble resin, 5 parts by weight of dipentaerythritol hexaacrylate alone as a polymerizable compound, acetophenone-based and triazine-based initiators as photopolymerization initiators, Low 2 parts by weight and 85 parts by weight of PGMEA, 3-MBA, DPM as an organic solvent was mixed for 1 hour and a half using a shaker and then stabilized by standing at room temperature for 1 and a half hours.
<패턴 밀착성 평가 실험><Pattern adhesion evaluation experiment>
실시예1, 실시예2 및 비교예1에서 제조된 감광성 수지 조성물을 수지 BM 기판에 스핀 코팅하여 약 90℃로 100 초 동안 전열 처리하고, 두께가 약 2.5 ㎛인 균등한 필름으로 형성한 다음, 소다라임 마스크로 400um gap, 40mJ/cm2 노광 후 25℃ 0.043% KOH용액으로 현상압 0.2MPa조건에서 120초간 현상을 한 후에 광학현미경을 통하여 패턴이 유실된 정도를 관찰하여 하부기판과 패턴의 밀착성을 판단하였다. The photosensitive resin compositions prepared in Examples 1, 2 and Comparative Example 1 were spin-coated on a resin BM substrate and subjected to electrothermal treatment at about 90 ° C. for 100 seconds, and formed into a uniform film having a thickness of about 2.5 μm. After exposure to 400um gap and 40mJ / cm2 with soda-lime mask, develop at 120 ° C under development pressure of 0.2MPa for 25 seconds with 0.043% KOH solution at 25 ℃ and observe the degree of pattern loss through optical microscope. Judging
평가 결과는 도 1, 도 2, 도 3에 기재하였다.Evaluation results were shown in FIG. 1, FIG. 2, FIG.
하기 도면으로부터 본 발명의 화학식 1을 포함한 감광성 수지 조성물의 경우, 기존 조성물에 비하여 하부기판과 밀착성이 향상됨을 확인할 수 있다.
From the following drawings, in the case of the photosensitive resin composition including
<실시예3> 감광성 수지 조성물의 제조 Example 3 Preparation of Photosensitive Resin Composition
실시예 2에서 착색제로 G36/Y138 안료 5 중량부 대신 8 중량부를 혼합하고, 유기 용매로 PGMEA, 3-MBA, DPM를 85 중량부 대신 82 중량부를 혼합한 것을 제외하고는 실시예 2와 동일하게 하여 감광성 수지 조성물을 제조하였다.
In Example 2, 8 parts by weight of G36 / Y138 pigment was mixed instead of 5 parts by weight of a colorant, and 82 parts by weight of PGMEA, 3-MBA, and DPM were mixed with 85 parts by weight of an organic solvent. To prepare a photosensitive resin composition.
<비교예2> 감광성 수지 조성물의 제조 Comparative Example 2 Preparation of Photosensitive Resin Composition
중합성 화합물로 디펜타에리스리톨 헥사아크릴레이트만을 총 5 중량부로 포함한 것을 제외하고는 상기 실시예 3과 동일하게 하여 감광성 수지 조성물을 제조하였다.
A photosensitive resin composition was prepared in the same manner as in Example 3, except that only 5 parts by weight of dipentaerythritol hexaacrylate was included as the polymerizable compound.
<패턴 밀착성 및 현상성 평가 실험><Pattern adhesion and developability evaluation experiment>
실시예3, 및 비교예2에서 제조된 감광성 수지 조성물을 유리 기판 및 Cr-BM 기판에 스핀 코팅하여 약 90℃로 100 초 동안 전열 처리하고, 두께가 약 2.3 ㎛인 균등한 필름으로 형성한 다음, 쿼츠 마스크로 200㎛ gap, 40mJ/cm2 노광 후 25℃ 0.043% KOH용액으로 현상압 0.1MPa조건에서 60초간 현상을 하며 현상시간을 관찰하고 현상 후 광학현미경을 통하여 패턴이 유실된 정도를 관찰하여 하부기판과 패턴의 밀착성을 판단하였다. The photosensitive resin composition prepared in Example 3 and Comparative Example 2 was spin-coated on a glass substrate and a Cr-BM substrate, followed by electrothermal treatment at about 90 ° C. for 100 seconds, and formed into a uniform film having a thickness of about 2.3 μm. , 200μm gap with quartz mask, 40mJ / cm 2 exposure, 25 ℃ 0.043% KOH solution for 60 seconds under developing pressure of 0.1MPa condition, observe development time and observe the degree of pattern loss through optical microscope after development The adhesion between the lower substrate and the pattern was determined.
평가 결과는 표 1과 도 4, 도 5, 도 6, 도 7 에 기재하였다.Evaluation results were described in Table 1 and Figs. 4, 5, 6, and 7.
8/10
37/60
최소 패턴 두께(㎛)Retained on glass substrates after development
Pattern thickness (μm)
최소 패턴 두께(㎛)Retained on Cr-MB substrate after development
Pattern thickness (μm)
EPD(End point detect)는 1은 현상이 시작되는 시간/ 2는 5*5 기판에서 현상이 끝나는 시간을 가리킨다.End point detect (EPD) indicates that 1 is the time at which development begins and 2 is the time at which the development ends on a 5 * 5 substrate.
현상 후 기판에 유지된 최소 패턴 두께가 얇을수록 패턴 밀착성은 우수한 것으로 판단한다.The thinner the minimum pattern thickness maintained on the substrate after development, the better the pattern adhesion.
상기 표와 하기 도면으로부터 본 발명에 따른 다관능성 모노머를 포함한 감광성 수지 조성물의 경우, 기존 조성물에 비하여 하부기판과 밀착성이 향상되며 빠른 현상 특성을 나타냄을 확인할 수 있다.From the above table and the following drawings, in the case of the photosensitive resin composition including the multifunctional monomer according to the present invention, it can be seen that the lower substrate and the adhesiveness are improved compared to the existing composition, and exhibits rapid development characteristics.
Claims (9)
상기 불포화 이중결합의 개수가 1 내지 4인 다관능성 모노머는 하기 [화학식 1]로 표시되는 다관능성 모노머인 것을 특징으로 하는 감광성 수지 조성물.
[화학식 1]
R1, R2, R3는 각각 에틸렌계 탄화수소 중의 하나이고, 3≤a+b+c≤10 이다.
In the photosensitive resin composition, as a polyfunctional monomer, it contains 20-80 weight% of polyfunctional monomers whose number of unsaturated double bonds is 1-4, and 80-20 weight of the polyfunctional monomer whose number of unsaturated double bonds is 5-6. In%,
The polyfunctional monomer having the number of the unsaturated double bonds 1 to 4 is a photosensitive resin composition, characterized in that the polyfunctional monomer represented by the following [Formula 1].
[Formula 1]
R1, R2 and R3 are each one of the ethylene hydrocarbons, and 3 ≦ a + b + c ≦ 10.
The polyfunctional monomer according to claim 1, wherein the polyfunctional monomer having an unsaturated double bond number of 5 to 6 is selected from pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. It is 1 or more types chosen Photosensitive resin composition characterized by the above-mentioned.
The photosensitive resin composition of claim 1, wherein the multifunctional monomer is included in an amount of 1 to 30 parts by weight based on the total photosensitive resin composition.
The photosensitive resin composition of claim 1, wherein the photosensitive resin composition further comprises an alkali-soluble binder resin, a colorant, a polymerization initiator, and a solvent.
According to claim 5, Alkali soluble resin 5 to 30 parts by weight based on 100 parts by weight of the photosensitive resin composition; 0.5-5 parts by weight of photoinitiator; 3 to 30 parts by weight of colorant; And a photosensitive resin composition comprising 10 to 90 parts by weight of the solvent.
6. The photoinitiator of claim 5, wherein the photoinitiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6 -Triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- {4- [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 ', 5,5'-tetraphenylbiimidazole, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -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-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino ) Benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetra (t- Butylperoxycarbonyl) benzophenone, 9-florenone, 2-chloro-9-florenone, 2-methyl-9-florenone, thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thi Oxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone, diisopropyl thioxanthone; Xanthone, 2-methylxanthone, anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, 2,6-dichloro-9,10-anthraquinone, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane, benzyl, 1,7,7- Trimethyl-bisclo [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 , Methyl 4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal ) Cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclohexanone, 3,3'-carr Bonylvinyl-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-Cl] -benzopyrano [6 , 7,8-ij] -quinolinzin-11-one, 4-diethylamino chalcone, 4-azidebenzalacetophenone, and 2-benzoylmethylene, 3-methyl-β-naphthothia The photosensitive resin composition, characterized in that at least one member selected from the group consisting of lean.
디프로필렌글리콜 디메틸에테르(bp 175℃), 디에틸렌글리콜 부틸 에테르(bp 162℃), 디에틸렌글리콜 디메틸 에테르(bp 162℃), 3-메톡시 부틸 아세테이트(bp 170℃), 및 에틸 3-에톡시프로피오네이트(bp 170℃) 로 이루어진 그룹에서 선택되는 1종 이상; 및
디프로필렌글리콜 메틸 에테르 아세테이트(bp 200℃), 디프로필렌글리콜 부틸 에테르(bp 190℃), 디프로필렌글리콜 모노메틸 에테르(bp 190℃), 디에틸렌글리콜 디에틸 에테르(bp 180-190℃), 에틸렌글리콜 모노아세테이트(bp 188℃), 에틸렌글리콜 디아세테이트(bp 187℃) 로 이루어진 그룹에서 선택되는 1종 이상인 것을 특징으로 하는 감광성 수지 조성물.
The method of claim 5, wherein the solvent is ethylene glycol monomethyl ether acetate (bp 145 ℃), propylene glycol monomethyl ether acetate (bp 146 ℃), dibutyl ether (bp 140 ℃), cyclohexanone (bp 156 ℃) , 2-heptanone (bp 151 ° C.), 2-ethoxyethyl acetate (bp 156 ° C.), propylene glycol monoethyl ether acetate (bp 158 ° C.), 2-methoxyethyl acetate (bp 145 ° C.) and methyl 3- At least one member selected from the group consisting of methoxy propionate (bp 142 ° C.);
Dipropylene glycol dimethyl ether (bp 175 ° C.), diethylene glycol butyl ether (bp 162 ° C.), diethylene glycol dimethyl ether (bp 162 ° C.), 3-methoxy butyl acetate (bp 170 ° C.), and ethyl 3- One or more selected from the group consisting of oxypropionate (bp 170 ° C.); And
Dipropylene glycol methyl ether acetate (bp 200 ° C.), dipropylene glycol butyl ether (bp 190 ° C.), dipropylene glycol monomethyl ether (bp 190 ° C.), diethylene glycol diethyl ether (bp 180-190 ° C.), ethylene Photosensitive resin composition, characterized in that at least one member selected from the group consisting of glycol monoacetate (bp 188 ℃), ethylene glycol diacetate (bp 187 ℃).
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| WO2017052131A1 (en) * | 2015-09-21 | 2017-03-30 | 주식회사 엘지화학 | Ultraviolet curable and infrared permeable ink composition for inkjet, having enhanced high temperature resistance |
| KR20190099762A (en) | 2018-02-20 | 2019-08-28 | 동우 화인켐 주식회사 | Curable resin composition and index matching layer formed the same |
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