WO2015194822A1 - Negative photosensitive resin composition comprising photoreactive silane coupling agent - Google Patents

Negative photosensitive resin composition comprising photoreactive silane coupling agent Download PDF

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WO2015194822A1
WO2015194822A1 PCT/KR2015/006059 KR2015006059W WO2015194822A1 WO 2015194822 A1 WO2015194822 A1 WO 2015194822A1 KR 2015006059 W KR2015006059 W KR 2015006059W WO 2015194822 A1 WO2015194822 A1 WO 2015194822A1
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resin composition
photosensitive resin
negative photosensitive
weight
formula
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PCT/KR2015/006059
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French (fr)
Korean (ko)
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윤주표
윤혁민
정종호
이자영
한승진
박주형
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주식회사 동진쎄미켐
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Priority to CN201580032043.0A priority Critical patent/CN106462070A/en
Publication of WO2015194822A1 publication Critical patent/WO2015194822A1/en

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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
    • 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
    • G03F7/038—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G03F7/0005—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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • 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
    • 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
    • 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
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives

Abstract

The present invention relates to a negative photosensitive resin composition and, more specifically, to a negative photosensitive resin composition comprising a photoreactive silane coupling agent including a vinyl or an acrylic group. The composition of the present invention not only ensures a developing adhesive property, but also has superior prebake margin and hole pattern properties by comprising the photoreactive silane coupling agent, and thereby the composition is suitable to be used in a large area display which uses an insulating layer.

Description

광반응성 실란 커플링제를 포함하는 네거티브 감광성 수지 조성물 Negative photosensitive resin composition containing photoreactive silane coupling agent
본 발명은 네거티브 감광성 수지 조성물에 관한 것으로, 더욱 상세하게는 비닐 또는 아크릴기를 포함하는 광반응성 실란 커플링제를 포함함으로써 현상 접착성을 확보하면서도 프리베이크 마진 및 홀 패턴 특성이 우수한 네거티브 감광성 수지 조성물에 관한 것이다.The present invention relates to a negative photosensitive resin composition, and more particularly, to a negative photosensitive resin composition having an excellent prebak margin and hole pattern properties while securing development adhesiveness by including a photoreactive silane coupling agent containing a vinyl or acrylic group. will be.
TFT형 액정표시소자나 집적회로소자에는 층간에 배치되는 배선의 사이를 절연하기 위한 패시베이션(Passivation) 절연막 및 게이트 절연막, 평탄화막 등 뿐 아니라, 컬럼스페이서, 격벽, 오버코드, 컬러레지스트 형성을 위해 네거티브 감광성 수지 조성물이 주로 사용되어진다.In TFT type liquid crystal display devices or integrated circuit devices, not only passivation insulating films, gate insulating films, planarization films, etc. to insulate the wirings arranged between layers, but also negatives for forming column spacers, barrier ribs, overcodes, and color resists. The photosensitive resin composition is mainly used.
상기 네거티브 감광성 수지 조성물은 미세패턴 및 하프톤패턴에서의 접착력을 확보하기 위하여 열가교제를 포함하는데, 기존의 에폭시기 또는 아민기를 포함하는 멜라민계 또는 실란계 열가교제를 반응시키기 위해서는, 프리베이크 공정을 높은 온도에서 진행을 하여야 하지만, 프리베이크 공정을 높은 온도에서 진행할 경우, 홀 패턴(Hole Pattern)의 해상도가 저하가 발생하며, 프리베이크 공정에서 사용되어지는 핫플레이트 위치별 온도 편차에 따른 접착력 편차와 홀 패턴 CD 편차가 발생하여 공정 마진이 떨어지는 문제가 발생한다.The negative photosensitive resin composition includes a thermal crosslinking agent to secure adhesion in a fine pattern and a halftone pattern, and in order to react a melamine-based or silane-based thermal crosslinking agent containing an existing epoxy group or an amine group, a high prebaking process is performed. However, when the prebaking process is performed at a high temperature, the resolution of the hole pattern decreases, and the adhesion force variation and the hole according to the temperature deviation for each hot plate position used in the prebaking process are performed. There is a problem that the process margin falls due to pattern CD deviation.
또한 멜라민계 가교제 또는 실란계 가교제를 포함하는 조성물을 이용하여 미세패턴을 형성하는 경우, 특히 하프톤 마스크를 사용하는 경우에는 막두께가 매우 얇아짐에 따라 접착력이 감소될 수 있으며, 이로 인해 미세화된 패턴의 현상공정시 유실이 발생하거나, 후공정시 패턴의 무너짐이 발생될 수 있으므로 hexamethyldisilazane(HMDS) 분무공정을 통해서 접착력을 확보해야만 했다.In addition, when the micropattern is formed using a composition including a melamine-based crosslinking agent or a silane-based crosslinking agent, particularly when using a halftone mask, the adhesion may be reduced as the film thickness becomes very thin. Since the pattern may be lost during the developing process, or the pattern may be collapsed during the later process, it is necessary to secure adhesion through the hexamethyldisilazane (HMDS) spraying process.
이에, HMDS 분무공정을 사용하지 않고, 높은 온도에서 프리베이크 공정을 수행하는 경우에도 현상 접착성을 확보하면서도 프리베이크 마진 및 홀 패턴 특성이 우수한 네거티브 감광성 수지 조성물이 절실히 요구되고 있다.Thus, even when the prebaking process is performed at a high temperature without using the HMDS spraying process, there is an urgent need for a negative photosensitive resin composition having excellent prebaking margin and hole pattern characteristics while securing development adhesiveness.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명의 목적은 비닐 또는 아크릴기를 포함하는 광반응성 실란 커플링제를 포함함으로써 현상 접착성을 확보하면서도 프리베이크 마진 및 홀 패턴 특성이 우수한 네거티브 감광성 수지 조성물을 제공하는 것이다.In order to solve the problems of the prior art as described above, an object of the present invention is to provide a negative photosensitive resin composition having excellent prebak margin and hole pattern characteristics while ensuring development adhesiveness by including a photoreactive silane coupling agent containing a vinyl or acrylic group To provide.
본 발명의 또 다른 목적은 상기 네거티브 감광성 수지 조성물을 이용한 디스플레이 소자의 패턴 형성방법을 제공하는 것이다.Still another object of the present invention is to provide a method for forming a pattern of a display device using the negative photosensitive resin composition.
본 발명의 또 다른 목적은 상기 패턴 형성방법에 의하여 형성된 네거티브 감광성 수지 조성물 경화체를 포함하는 디스플레이 소자를 제공하는 것이다.Still another object of the present invention is to provide a display element comprising a cured negative photosensitive resin composition formed by the pattern forming method.
상기 목적을 달성하기 위하여 본 발명은The present invention to achieve the above object
a) 아크릴계 공중합체;a) acrylic copolymer;
b) 하기 화학식 1의 광반응성 실란 커플링제;b) a photoreactive silane coupling agent of formula (1);
c) 광개시제; c) photoinitiators;
d) 에틸렌성 불포화 결합을 가지는 다관능성 모노머; 및d) polyfunctional monomers having ethylenically unsaturated bonds; And
e) 잔량의 용매e) residual solvent
를 포함하는 네거티브 감광성 수지 조성물을 제공한다:It provides a negative photosensitive resin composition comprising:
[화학식 1][Formula 1]
Figure PCTKR2015006059-appb-I000001
Figure PCTKR2015006059-appb-I000001
상기 식에서, Where
R1은 아크릴, 메타아크릴 또는 비닐이고,R 1 is acrylic, methacryl or vinyl,
R2는 메톡시, 에톡시 또는 메틸이며,R 2 is methoxy, ethoxy or methyl,
R3는 메톡시 또는 에톡시이다.R 3 is methoxy or ethoxy.
바람직하게는, 상기 네거티브 감광성 수지 조성물은 Preferably, the negative photosensitive resin composition
a) 아크릴계 공중합체 100 중량부;a) 100 parts by weight of the acrylic copolymer;
b) 하기 화학식 1의 광반응성 실란 커플링제 0.1 내지 20 중량부;b) 0.1 to 20 parts by weight of the photoreactive silane coupling agent of Formula 1;
c) 광개시제 0.1 내지 30 중량부; c) 0.1 to 30 parts by weight of photoinitiator;
d) 에틸렌성 불포화 결합을 가지는 다관능성 모노머 10 내지 200 중량부; 및d) 10 to 200 parts by weight of a multifunctional monomer having an ethylenically unsaturated bond; And
e) 용매 150 내지 800 중량부e) 150 to 800 parts by weight of solvent
를 포함하는 것을 특징으로 한다.Characterized in that it comprises a.
또한 본 발명은 상기 네거티브 감광성 수지 조성물을 이용한 디스플레이 소자의 패턴 형성방법을 제공한다.In another aspect, the present invention provides a method of forming a pattern of a display device using the negative photosensitive resin composition.
또한 본 발명은 상기 패턴 형성방법에 의하여 형성된 네거티브 감광성 수지 조성물 경화체를 포함하는 디스플레이 소자를 제공한다.In addition, the present invention provides a display device comprising a cured negative photosensitive resin composition formed by the pattern forming method.
본 발명에 따른 네거티브 감광성 수지 조성물은 비닐기 또는 아크릴기를 포함하는 광반응성 실란 커플링제를 포함함으로써 HMDS 공정 없이도 하프톤 패턴에서 접착력이 우수하며, 프리베이크 공정을 80 내지 130℃ 에서 진행하여도 홀 패턴 CD 감소가 기존 열가교제 대비 적으며, 핫플레이트 위치별 온도 편가에 따른 접착력 및 홀 패턴 CD 편차가 없어 공정 마진 확보가 가능하다. 또한 공정비용을 감소시켜서 패널의 제조비용 절감을 이룰 수 있다.Since the negative photosensitive resin composition according to the present invention includes a photoreactive silane coupling agent containing a vinyl group or an acrylic group, the adhesive force is excellent in the halftone pattern without the HMDS process, and the hole pattern is performed even when the prebaking process is performed at 80 to 130 ° C. CD reduction is less than that of existing thermal crosslinking agents, and process margins can be secured because there is no variation in adhesive force and hole pattern CD according to temperature deviation by hot plate location. In addition, the manufacturing cost of the panel can be reduced by reducing the process cost.
따라서 본 발명의 네거티브 감광성 수지 조성물은 대면적 디스플레이 소자 및 다양한 디스플레이 소자, 예를 들어, TFT-LCD, TSP, OLED, 또는 O-TFT 등의 대면적 디스플레이의 절연막, 게이트 절연막, 평탄화막, 컬럼스페이서, 오버코트 또는 컬러레지스트의 형성에 사용할 수 있다.Therefore, the negative photosensitive resin composition of the present invention is an insulating film, a gate insulating film, a planarizing film, a column spacer of a large area display device and various display devices, for example, a large area display such as TFT-LCD, TSP, OLED, or O-TFT. It can be used for forming overcoat or color resist.
이하에서 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 네거티브 감광성 수지 조성물은 a) 아크릴계 공중합체; b) 하기 화학식 1의 광반응성 실란 커플링제; c) 광개시제; d) 에틸렌성 불포화 결합을 가지는 다관능성 모노머; 및 e) 잔량의 용매를 포함하는 것을 특징으로 한다:The negative photosensitive resin composition of this invention is a) acrylic copolymer; b) a photoreactive silane coupling agent of formula (1); c) photoinitiators; d) polyfunctional monomers having ethylenically unsaturated bonds; And e) a residual amount of solvent:
[화학식 1][Formula 1]
Figure PCTKR2015006059-appb-I000002
Figure PCTKR2015006059-appb-I000002
상기 식에서, Where
R1은 아크릴, 메타아크릴 또는 비닐이고,R 1 is acrylic, methacryl or vinyl,
R2는 메톡시, 에톡시 또는 메틸이며,R 2 is methoxy, ethoxy or methyl,
R3는 메톡시 또는 에톡시이다.R 3 is methoxy or ethoxy.
본 발명에 사용되는 상기 a)의 아크릴계 공중합체는 현상할 때에 스컴이 발생하지 않는 소정의 패턴을 용이하게 형성할 수 있도록 하는 작용을 한다.The acrylic copolymer of a) used in the present invention serves to easily form a predetermined pattern in which scum does not occur when developing.
상기 a)의 아크릴계 공중합체로는 네가티브 감광성 수지 조성물에 사용되는 공지의 아크릴계 공중합체를 사용할 수 있으며, 조성물 총 중량에 대하여 100 중량부의 양으로 포함할 수 있다.As the acrylic copolymer of a), a known acrylic copolymer used in the negative photosensitive resin composition may be used, and may be included in an amount of 100 parts by weight based on the total weight of the composition.
상기 a) 아크릴계 공중합체는 폴리스티렌 환산중량평균분자량(Mw)이 3,000 내지 30,000인 것이 바람직하다. 상기 폴리스티렌 환산중량평균분자량이 3,000 미만인 유기절연막의 경우 현상성, 잔막율 등이 저하되거나, 패턴 현상, 내열성 등이 뒤떨어진다는 문제점이 있으며, 상기 폴리스티렌 환산중량평균분자량이 30,000을 초과하는 층간절연막의 경우에는 패턴 현상이 뒤떨어진다는 문제점이 있다.Preferably, the a) acrylic copolymer has a polystyrene reduced weight average molecular weight (Mw) of 3,000 to 30,000. In the case of the organic insulating film having a polystyrene reduced weight average molecular weight of less than 3,000, there is a problem in that developability, residual film ratio, or the like is inferior to pattern development, heat resistance, and the like, and that the polystyrene reduced weight average molecular weight exceeds 30,000. In this case, there is a problem that the pattern phenomenon is inferior.
본 발명에 사용되는 상기 b)의 광반응성 실란 커플링제는 노광 공정의 UV광에 의해 가교반응이 가능하며, 하부 기판과의 접착력 향상을 위해 사용하며, 하기 화학식 1의 구조를 가질 수 있다:The photoreactive silane coupling agent of b) used in the present invention may be crosslinked by UV light in an exposure process, and used to improve adhesion to a lower substrate, and may have a structure of Formula 1 below:
[화학식 1][Formula 1]
Figure PCTKR2015006059-appb-I000003
Figure PCTKR2015006059-appb-I000003
상기 식에서, Where
R1은 아크릴, 메타아크릴 또는 비닐이고,R 1 is acrylic, methacryl or vinyl,
R2는 메톡시, 에톡시 또는 메틸이며,R 2 is methoxy, ethoxy or methyl,
R3는 메톡시 또는 에톡시이다.R 3 is methoxy or ethoxy.
바람직하기로, 상기 실란 커플링제는 하기 화학식 2 내지 6의 구조를 가질 수 있다:Preferably, the silane coupling agent may have a structure of Formulas 2 to 6:
[화학식 2][Formula 2]
Figure PCTKR2015006059-appb-I000004
Figure PCTKR2015006059-appb-I000004
[화학식 3][Formula 3]
Figure PCTKR2015006059-appb-I000005
Figure PCTKR2015006059-appb-I000005
[화학식 4][Formula 4]
Figure PCTKR2015006059-appb-I000006
Figure PCTKR2015006059-appb-I000006
[화학식 5][Formula 5]
Figure PCTKR2015006059-appb-I000007
Figure PCTKR2015006059-appb-I000007
[화학식 6][Formula 6]
Figure PCTKR2015006059-appb-I000008
Figure PCTKR2015006059-appb-I000008
상기 실란 커플링제의 함량은 상기 a) 아크릴계 공중합체 100 중량부에 대하여 0.1 내지 20 중량부, 바람직하게는 1 내지 10 중량부로 포함하는 것이 좋다. 그 함량이 0.1 중량부 미만일 경우에는 하부 기판과의 접착력이 저하되고, 그 함량이 20 중량부를 초과할 경우에는, 저장안정성 및 현상성이 떨어지고, 해상도가 저하된다는 문제점이 있다. The content of the silane coupling agent may be 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the a) acrylic copolymer. If the content is less than 0.1 parts by weight, the adhesive strength with the lower substrate is lowered, if the content is more than 20 parts by weight, there is a problem that the storage stability and developability is lowered, the resolution is lowered.
본 발명에 사용되는 상기 c)의 광개시제는 네가티브 감광성 수지 조성물에 사용되는 공지의 광개시제가 사용될 수 있으며, 바람직하게는 옥심에스테르계 화합물을 사용 할 수 있다.As the photoinitiator of c) used in the present invention, a known photoinitiator used in the negative photosensitive resin composition may be used, and an oxime ester compound may be preferably used.
상기 광개시제의 함량은 상기 a) 아크릴계 공중합체 100 중량부에 대하여 0.1 내지 30 중량부로 포함하는 것이 좋다. 그 함량이 0.1 중량부 미만일 경우에는 낮은 감도로 인해 잔막율이 나빠지게 된다는 문제점이 있으며, 그 함량이 30 중량부를 초과할 경우에는, 현상성이 떨어지고, 해상도가 저하된다는 문제점이 있다. The photoinitiator may be included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the a) acrylic copolymer. If the content is less than 0.1 parts by weight, there is a problem that the residual film ratio is deteriorated due to low sensitivity. If the content is more than 30 parts by weight, there is a problem that developability is lowered and resolution is lowered.
본 발명에 사용되는 상기 d)의 에틸렌성 불포화 결합을 가지는 다관능성 모노머는 디펜타에리스리톨헥사아크릴레이트, 및 펜타에리스리톨디아크릴레이트, 펜타에리스리톨트리아크릴레이트, 펜타에리스리톨테트라아크릴레이트, 프탈릭다이아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 트리사이클로데칸디메탄올디아크릴레이트, 트리글리세롤디아크릴레이트, 트리스아크릴옥시에틸이소시아뉴레이트, 트리메틸올프로판트리아크릴레이트 유도체 및 이들의 메타크릴레이트류로 이루어진 군에서 선택되는 1종 이상의 모노머의 혼합물을 사용할 수 있다.The polyfunctional monomer having the ethylenically unsaturated bond of d) used in the present invention is dipentaerythritol hexaacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and phthalic diacrylate. , Polyethylene glycol diacrylate, tetraethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, triglycerol diacrylate, trisacryloxyethyl isocyanurate, trimethylolpropane triacrylate derivatives and methacryl thereof Mixtures of one or more monomers selected from the group consisting of lates can be used.
상기 에틸렌성 불포화 결합을 가지는 다관능성 모노머의 함량은 상기 a) 아크릴계 공중합체 100 중량부에 대하여 1 내지 200 중량부로 포함하는 것이 좋다. 그 함량이 1 중량부 미만일 경우에는 낮은 감도로 인해 잔막율이 나빠지게 된다는 문제점이 있으며, 그 함량이 200 중량부를 초과할 경우에는, 현상성이 떨어지고, 해상도가 저하된다는 문제점이 있다. The content of the polyfunctional monomer having an ethylenically unsaturated bond may be included in an amount of 1 to 200 parts by weight based on 100 parts by weight of the a) acrylic copolymer. If the content is less than 1 part by weight, there is a problem that the residual film ratio is deteriorated due to low sensitivity. If the content is more than 200 parts by weight, developability is lowered and resolution is lowered.
본 발명에 사용되는 상기 e)의 용매는 층간절연막의 평탄성과 코팅얼룩을 발생하지 않게 하여 균일한 패턴 프로파일(pattern profile)을 형성하게 한다.The solvent of e) used in the present invention does not generate flatness and coating stain of the interlayer insulating film, thereby forming a uniform pattern profile.
상기 용매로는 메탄올, 에탄올 등의 알코올류; 테트라히드로퓨란 등의 에테르류; 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르 등의 글리콜에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트 등의 에틸렌글리콜알킬에테르 아세테이트류; 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜디메틸에테르 등의 디에틸렌글리콜류; 프로필렌글리콜메틸에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르 등의 프로필렌글리콜모노알킬에테르류; 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜부틸에테르아세테이트 등의 프로필렌글리콜알킬에테르아세테이트류; 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르프로피오네이트, 프로필렌글리콜부틸에테르프로피오네이트 등의 프로필렌글리콜알킬에테르아세테이트류; 톨루엔, 크실렌 등의 방향족 탄화수소류; 메틸에틸케톤, 시클로헥사논, 4-히드록시 4-메틸 2-펜타논 등의 케톤류; 또는 초산메틸, 초산에틸, 초산프로필, 초산부틸, 2-히드록시 프로피온산 에틸, 2-히드록시 2-메틸프로피온산 메틸, 2-히드록시 2-메틸프로피온산 에틸, 히드록시초산메틸, 히드록시초산에틸, 히드록시초산부틸, 유산메틸, 유산에틸, 유산프로필, 유산부틸, 3-히드록시프로피온산메틸, 3-히드록시프로피온산에틸, 3-히드록시프로피온산프로필, 3-히드록시프로피온산부틸, 2-히드록시 3-메틸부탄산 메틸, 메톡시초산메틸, 메톡시초산에틸, 메톡시초산프로필, 메톡시초산부틸, 에톡시초산메틸, 에톡시초산에틸, 에톡시초산프로필, 에톡시초산부틸, 프로폭시초산메틸, 프로폭시초산에틸, 프로폭시초산프로필, 프로폭시초산부틸, 부톡시초산메틸, 부톡시초산에틸, 부톡시초산프로필, 부톡시초산부틸, 2-메톡시프로피온산메틸, 2-메톡시프로피온산에틸, 2-메톡시프로피온산프로필, 2-메톡시프로피온산부틸, 2-에톡시프로피온산메틸, 2-에톡시플피온산에틸, 2-에톡시프로피온산프로필, 2-에톡시프로피온산부틸, 2-부톡시프로피온산메틸, 2-부톡시프로피온산에틸, 2-부톡시프로피오산프로필, 2-부톡시프로피온산부틸, 3-메톡시프로피온산메틸 3-메톡시프로피온산에틸, 3-메톡시프로피온산프로필, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸, 3-에톡시프로피온산프로필, 3-에톡시프로피온산부틸, 3-프로폭시프로피온산메틸, 3-프로폭시프로피온산에틸, 3-프로폭시프로피온산프로필, 3-프로폭시프로피온산부틸, 3-부톡시프로피온산메틸, 3-부톡시프로피온산에틸, 3-부톡시프로피온산프로필, 3-부톡시프로피온산부틸 등의 에스테르류 등을 사용할 수 있으며, 이들은 필요에 따라 1종 이상 혼합 사용이 가능하다.As said solvent, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; Or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl hydroxypropionate, 2-hydroxy 3 Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate Ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2 Ethyl butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-part Ester, such as methyl oxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate, etc. can be used, These can be mixed 1 or more types as needed.
특히, 상기 용매는 용해성, 각 성분과의 반응성, 및 도포막 형성이 용이한 글리콜에테르류, 에틸렌알킬에테르아세테이트류, 및 디에틸렌글리콜류로 이루어지는 군으로부터 1종 이상 선택하여 사용하는 것이 바람직하다.In particular, it is preferable to select and use at least 1 type of said solvent from the group which consists of solubility, reactivity with each component, and easy to form a coating film, glycol ethers, ethylene alkyl ether acetates, and diethylene glycols.
상기 용매는 전체 네거티브 감광성 수지 조성물의 고형분 함량이 10 내지 50 중량%가 되도록 포함되는 것이 바람직하며, 바람직하게는 상기 a)의 아크릴계 공중합체 100 중량부에 대하여 150 내지 800 중량부의 양으로 포함될 수 있다.The solvent is preferably included so that the solid content of the entire negative photosensitive resin composition is 10 to 50% by weight, and preferably may be included in an amount of 150 to 800 parts by weight based on 100 parts by weight of the acrylic copolymer of a). .
본 발명의 감광성 조성물은 0.1 내지 0.2㎛ 의 밀리포아필터 등으로 여과한 뒤 사용하는 것이 좋다. 더욱 바람직하게는, 고형분 함량이 15 내지 40 중량%가 되도록 용매를 포함시키는 것이 좋다. 상기 전체 네거티브 감광성 수지 조성물의 고형분 함량이 10 중량% 미만일 경우에는 코팅두께가 얇게 되고, 코팅평판성이 저하된다는 문제점이 있으며, 50 중량%를 초과할 경우에는 코팅두께가 두꺼워지고, 코팅시 코팅장비에 무리를 줄 수 있다는 문제점이 있다.It is preferable to use the photosensitive composition of this invention after filtering by the Millipore filter of 0.1-0.2 micrometer. More preferably, it is preferable to include the solvent so that the solid content is 15 to 40% by weight. When the solids content of the entire negative photosensitive resin composition is less than 10% by weight, there is a problem that the coating thickness becomes thin and the coating flatness is lowered. When the content exceeds 50% by weight, the coating thickness becomes thick, and the coating equipment is coated. There is a problem that can be overwhelming.
본 발명은 또한 감광성 조성물의 도포성이나 현상성을 향상시키기 위해 다양한 첨가제를 사용할 수 있으며, 바람직하게 상기 첨가제는 계면활성제일 수 있다.The present invention may also use various additives to improve the applicability or developability of the photosensitive composition, preferably the additive may be a surfactant.
상기 계면 활성제로는 실리콘계 또는 불소계 계면활성제를 사용할 수 있으며, 바람직하게는 실리콘계 계면활성제를 사용할 수 있다. 상기 계면 활성제의 사용량은 상기 a) 아크릴계 공중합체 100 중량부에 대하여 0.01 내지 5 중량부로 사용하는 것이 바람직하다.As the surfactant, a silicone-based or fluorine-based surfactant may be used, and preferably a silicone-based surfactant may be used. The amount of the surfactant is preferably used in 0.01 to 5 parts by weight based on 100 parts by weight of the a) acrylic copolymer.
또한 본 발명은 상기와 같은 네거티브 감광성 수지 조성물을 이용한 디스플레이 소자의 패턴 형성방법을 제공한다.In another aspect, the present invention provides a pattern forming method of the display device using the negative photosensitive resin composition as described above.
바람직하게, 본 발명은 기판 상에 본 발명의 네거티브 감광성 수지 조성물을 코팅하고 열처리 후, 현상하는 단계를 포함하는 디스플레이 소자의 패턴 형성방법을 제공한다.Preferably, the present invention provides a method of forming a pattern of a display device, comprising the step of coating the negative photosensitive resin composition of the present invention on a substrate, followed by heat treatment and developing the same.
본 발명에 있어서, 상기 열처리는 네거티브 감광성 수지 조성물을 대상으로 하는 통상적인 온도에서 수행될 수 있다.In the present invention, the heat treatment may be carried out at a conventional temperature for the negative photosensitive resin composition.
상기 패턴은 TFT-LCD, TSP, OLED, 또는 O-TFT 등의 대면적 디스플레이의 절연막, 게이트 절연막, 평탄화막, 컬럼스페이서, 오버코트 또는 컬러레지스트로 사용할 수 있다.The pattern can be used as an insulating film, a gate insulating film, a planarizing film, a column spacer, an overcoat or a color resist of a large area display such as TFT-LCD, TSP, OLED, or O-TFT.
또한 본 발명은 상기 디스플레이 소자의 패턴 형성방법에 의하여 형성된 네거티브 감광성 수지 조성물 경화체를 포함하는 디스플레이 소자를 제공할 수 있다.In addition, the present invention can provide a display device comprising a cured negative photosensitive resin composition formed by the pattern forming method of the display device.
이때, 상기 방법으로 형성되는 패턴의 두께 및 각 조건 등은 특별히 한정되지 않고, 통상의 소자 제작에 사용되는 범위로 설정될 수 있다. 따라서 상기 네거티브 감광성 수지 조성물을 제외한 나머지 사항은 당업자가 공지의 방법을 적절히 이용할 수 선택하여 적용할 수 있음은 물론이다. 보다 구체적으로 디스플레이 소자에 있어서, 네거티브 감광성 수지 조성물을 이용하여 패턴을 형성하는 방법의 일예는 다음과 같다.At this time, the thickness and the conditions of the pattern formed by the above method is not particularly limited, and may be set in a range used for manufacturing a conventional device. Therefore, other matters except for the negative photosensitive resin composition may be applied to those skilled in the art by appropriately selecting a known method. More specifically, in the display element, an example of a method of forming a pattern using a negative photosensitive resin composition is as follows.
먼저 본 발명의 네거티브 감광성 수지 조성물을 스프레이법, 롤코터법, 회전도포법 등으로 기판 표면에 도포하고, 프리베이크에 의해 용매를 제거하여 도포막을 형성한다. 이때, 상기 프리베이크는 80 내지 130℃ 의 온도에서 1 내지 5 분간 실시하는 것이 바람직하다.First, the negative photosensitive resin composition of this invention is apply | coated to the surface of a board | substrate by the spray method, the roll coater method, the rotary coating method, etc., A solvent is removed by prebaking, and a coating film is formed. At this time, the prebaking is preferably carried out for 1 to 5 minutes at a temperature of 80 to 130 ℃.
그 다음, 미리 준비된 패턴에 따라 가시광선, 자외선, 원자외선, 전자선, 엑스선 등을 상기 형성된 도포막에 조사하고, 현상액으로 현상하여 불필요한 부분을 제거함으로써 소정의 패턴을 형성한다.Then, a predetermined pattern is formed by irradiating visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like on the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.
상기 현상액은 알칼리 수용액을 사용하는 것이 좋으며, 구체적으로 수산화나트륨, 수산화칼륨, 탄산나트륨 등의 무기 알칼리류; n-프로필아민 등의 1급 아민류; 디에틸아민, n-프로필아민 등의 2급 아민류; 트리메틸아민, 메틸디에틸아민, 디메틸에틸아민, 트리에틸아민 등의 3급 아민류; 디메틸에탄올아민, 메틸디에탄올아민, 트리에탄올아민 등의 알콜아민류; 또는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드 등의 4급 암모늄염의 수용액 등을 사용할 수 있다. 이때, 상기 현상액은 알칼리성 화합물을 0.1 내지 10 중량%의 농도로 용해시켜 사용되며, 메탄올, 에탄올 등과 같은 수용성 유기용매 및 계면활성제를 적정량 첨가할 수도 있다.The developer is preferably an aqueous alkali solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10% by weight, and may be added an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol, ethanol and the like.
또한, 상기와 같은 현상액으로 현상한 후 초순수로 50 내지 180 초간 세정하여 불필요한 부분을 제거하고 건조하여 패턴을 형성하고, 선택적으로 상기 형성된 패턴에 자외선 등의 빛을 조사한 후, 패턴을 오븐 등의 가열장치에 의해 150 내지 250℃ 의 온도에서 30 내지 90 분간 가열처리하여 최종 패턴을 얻을 수 있다.In addition, after developing with the developer as described above, and then washed with ultrapure water for 50 to 180 seconds to remove the unnecessary portion and dried to form a pattern, and optionally irradiated with light such as ultraviolet rays to the formed pattern, heating the pattern in an oven or the like The final pattern can be obtained by heat treatment at a temperature of 150 to 250 ° C. for 30 to 90 minutes by means of the apparatus.
본 발명의 실시예에 따르면, 노광 공정의 UV광에 의해 가교반응이 가능한 광반응성 실란커플링제를 통해 0.1 ㎛ 내지 10 ㎛의 미세패턴의 접착력 확보가 가능하고, 하프톤 패턴에서 마스크 투과도 5%~95%까지의 수준에서의 막두께 0.01 내지 50 ㎛에서도 HMDS 공정의 유무와 상관없이 접착력이 확보가 가능하였다.According to an embodiment of the present invention, through the photoreactive silane coupling agent capable of crosslinking reaction by UV light of the exposure process, it is possible to secure the adhesive force of the micropattern of 0.1 ㎛ to 10 ㎛, mask transmission in the halftone pattern 5% ~ Even at a film thickness of 0.01 to 50 μm at a level up to 95%, adhesive strength was secured regardless of the presence or absence of the HMDS process.
또한 프리베이크 공정에서 온도를 80 내지 130 ℃로 공정을 진행하여도 홀 패턴 CD 감소가 기존 열가교제 대비 적으며, 핫플레이트 위치별 온도 편가에 따른 접착력 및 홀 패턴 CD 편차가 없어 공정 마진 확보가 가능하였다.In addition, even if the process is carried out at a temperature of 80 to 130 ° C. in the prebaking process, hole pattern CD reduction is less than that of the existing thermal crosslinking agent, and process margin is secured because there is no adhesive force and hole pattern CD deviation according to the temperature deviation by hot plate position. It was.
따라서 비닐 또는 아크릴기를 포함하는 광반응성 실란 커플링제를 포함하는 본 발명의 네거티브 감광성 수지 조성물은 상기 광반응성 실란 커플링제를 포함함으로써 현상 접착성을 확보하면서도 프리베이크 마진 및 홀 패턴 특성이 우수하므로, TFT-LCD, TSP, OLED, 또는 O-TFT 등의 대면적 디스플레이의 절연막, 게이트 절연막, 평탄화막, 컬럼스페이서, 오버코트 또는 컬러레지스트에 사용하기 적합하다.Therefore, the negative photosensitive resin composition of the present invention comprising a photoreactive silane coupling agent containing a vinyl or an acryl group has excellent prebak margin and hole pattern characteristics while securing development adhesiveness by including the photoreactive silane coupling agent. Suitable for use in insulating films, gate insulating films, planarization films, column spacers, overcoats or color resists of large area displays such as LCD, TSP, OLED, or O-TFT.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
실시예 1 내지 15:네거티브 감광성 수지 조성물의 제조 Examples 1-15 : Preparation of Negative Photosensitive Resin Composition
중량평균분자량(Mw)이 5000인 아크릴계 공중합체, 옥심에스테르계 광개시제, 에틸렌성 불포화 다관능 모노머로서 디펜타에리스리톨 헥사아크릴레이트, 하기 화학식 2 내지 6으로 표시되는 본 발명의 광반응성 실란 커플링제 및 실리콘계 계면활성제를 하기 표 1에 기재된 조성에 따라 혼합한 다음, 상기 혼합물에 용매로서 프로필렌글리콜 모노에틸프로피오네이트를 가하여 용해시킨 후, 0.2㎛ 의 밀리포아필터로 여과하여 네거티브 감광성 수지 조성물 코팅 용액을 제조하였다.Acrylic copolymer, oxime ester photoinitiator having weight average molecular weight (Mw) of 5000, dipentaerythritol hexaacrylate as ethylenically unsaturated polyfunctional monomer, photoreactive silane coupling agent of the present invention represented by the following formulas 2 to 6 and silicone The surfactant was mixed according to the composition shown in Table 1 below, propylene glycol monoethyl propionate was added to the mixture as a solvent, dissolved therein, and then filtered through a 0.2 μm millipore filter to prepare a negative photosensitive resin composition coating solution. It was.
[화학식 2][Formula 2]
Figure PCTKR2015006059-appb-I000009
Figure PCTKR2015006059-appb-I000009
[화학식 3][Formula 3]
Figure PCTKR2015006059-appb-I000010
Figure PCTKR2015006059-appb-I000010
[화학식 4][Formula 4]
Figure PCTKR2015006059-appb-I000011
Figure PCTKR2015006059-appb-I000011
[화학식 5][Formula 5]
Figure PCTKR2015006059-appb-I000012
Figure PCTKR2015006059-appb-I000012
[화학식 6][Formula 6]
Figure PCTKR2015006059-appb-I000013
Figure PCTKR2015006059-appb-I000013
표 1
아크릴공중합체(중량부) 광개시제(중량부) 다관능모노머(중량부) 실란커플링제(중량부) 계면활성제(중량부) 용매(중량부)
실시예 1 100 10 100 1(화학식 2) 1 250
실시예 2 100 10 100 5(화학식 2) 1 250
실시예 3 100 10 100 10(화학식 2) 1 250
실시예 4 100 10 100 1(화학식 3) 1 250
실시예 5 100 10 100 5(화학식 3) 1 250
실시예 6 100 10 100 10(화학식 3) 1 250
실시예 7 100 10 100 1(화학식 4) 1 250
실시예 8 100 10 100 5(화학식 4) 1 250
실시예 9 100 10 100 10(화학식 4) 1 250
실시예 10 100 10 100 1(화학식 5) 1 250
실시예 11 100 10 100 5(화학식 5) 1 250
실시예 12 100 10 100 10(화학식 5) 1 250
실시예 13 100 10 100 1(화학식 6) 1 250
실시예 14 100 10 100 5(화학식 6) 1 250
실시예 15 100 10 100 10(화학식 6) 1 250
비교예 1 100 10 100 1(화학식 7) 1 250
비교예 2 100 10 100 5(화학식 7) 1 250
비교예 3 100 10 100 10(화학식 7) 1 250
비교예 4 100 10 100 1(화학식 8) 1 250
비교예 5 100 10 100 5(화학식 8) 1 250
비교예 6 100 10 100 10(화학식 8) 1 250
Table 1
Acrylic copolymer (parts by weight) Photoinitiator (parts by weight) Multifunctional Monomer (parts by weight) Silane coupling agent (parts by weight) Surfactant (parts by weight) Solvent (part by weight)
Example 1 100 10 100 1 (Formula 2) One 250
Example 2 100 10 100 5 (Formula 2) One 250
Example 3 100 10 100 10 (Formula 2) One 250
Example 4 100 10 100 1 (Formula 3) One 250
Example 5 100 10 100 5 (Formula 3) One 250
Example 6 100 10 100 10 (Formula 3) One 250
Example 7 100 10 100 1 (Formula 4) One 250
Example 8 100 10 100 5 (Formula 4) One 250
Example 9 100 10 100 10 (Formula 4) One 250
Example 10 100 10 100 1 (Formula 5) One 250
Example 11 100 10 100 5 (Formula 5) One 250
Example 12 100 10 100 10 (Formula 5) One 250
Example 13 100 10 100 1 (Formula 6) One 250
Example 14 100 10 100 5 (Formula 6) One 250
Example 15 100 10 100 10 (Formula 6) One 250
Comparative Example 1 100 10 100 1 (Formula 7) One 250
Comparative Example 2 100 10 100 5 (Formula 7) One 250
Comparative Example 3 100 10 100 10 (Formula 7) One 250
Comparative Example 4 100 10 100 1 (Formula 8) One 250
Comparative Example 5 100 10 100 5 (Formula 8) One 250
Comparative Example 6 100 10 100 10 (Formula 8) One 250
비교예 1 내지 6:네거티브 감광성 수지 조성물의 제조 Comparative Examples 1 to 6 : Preparation of Negative Photosensitive Resin Composition
하기 화학식 7 및 8로 표시되는 종래의 광반응성 실란 커플링제를 사용한 것을 제외하고는 상기 표 1에 기재된 조성에 따라 상기 실시예 1 내지 15와 동일한 방법으로 네거티브 감광성 수지 조성물 코팅 용액을 제조하였다.A negative photosensitive resin composition coating solution was prepared in the same manner as in Examples 1 to 15, except that the conventional photoreactive silane coupling agents represented by the following Chemical Formulas 7 and 8 were used.
[화학식 7][Formula 7]
Figure PCTKR2015006059-appb-I000014
Figure PCTKR2015006059-appb-I000014
[화학식 8][Formula 8]
Figure PCTKR2015006059-appb-I000015
Figure PCTKR2015006059-appb-I000015
시험예 1Test Example 1
상기 실시예 1 내지 15 및 비교예 1 내지 6에서 제조된 네거티브 감광성 수지 조성물 코팅용액을 이용하여 하기와 같은 방법으로 물성을 평가한 후, 그 결과를 하기 표 2에 나타내었다. After evaluating the physical properties in the following manner using the negative photosensitive resin composition coating solution prepared in Examples 1 to 15 and Comparative Examples 1 to 6, the results are shown in Table 2 below.
네거티브 감광성 수지 조성물 코팅액을 이용하여 글래스(glass) 기판 상에 스핀코팅 후 100℃ 로 2분간 핫플레이트 상에서 프리베이크하여 막을 형성 하였다. 상기에서 얻어진 막에 접착성 평가용 패턴 마스크를 사용하여 365-405 nm의 복합파장 노광기를 이용하여 패턴 노광을 하였다. 이후 테트라메틸 암모늄히드록시드 2.38 중량부의 수용액으로 100초간 현상 후 초순수로 60초간 세정 및 건조 하였다. 패턴이 형성된 기판을 오븐속에서 230℃ 로 30분간 가열하여 경화시켜 최종 패턴 막을 얻었다. The film was formed by spin-coating on a glass substrate using a negative photosensitive resin composition coating solution and then prebaking on a hot plate at 100 ° C. for 2 minutes. Pattern exposure was performed to the film | membrane obtained above using the composite wavelength exposure machine of 365-405 nm using the pattern mask for adhesive evaluation. After developing for 100 seconds in an aqueous solution of 2.38 parts by weight of tetramethyl ammonium hydroxide, and washed with ultrapure water for 60 seconds and dried. The patterned substrate was heated and cured at 230 ° C. for 30 minutes in an oven to obtain a final pattern film.
패턴 접착성과 하프톤 접착성 확보 두께 측정은 다음 방법에 의해 측정을 진행 하였다.The thickness measurement of the pattern adhesiveness and the halftone adhesiveness secured was measured by the following method.
1) 패턴 접착성 : 1-50 um 패턴 마스크를 사용하여 최종 패턴 막을 형성 후 광학현미경(OLS 3000, 올림푸스社)을 통해 뜯김이 발생하지 않은 패턴 사이즈를 측정하였다.1) Pattern adhesiveness: After the final pattern film was formed using a 1-50 um pattern mask, the pattern size without tearing was measured through an optical microscope (OLS 3000, Olympus).
2) 하프톤 접착성 확보 두께 : 5-95 % 까지 5% 단위로 split된 하프톤用 Mask를 이용하여 최종 패턴 막을 형성 후 두께 측정장비인 나노스펙(나노 매트릭스社)을 이용하여 뜯김이 발생하지 않은 패턴의 두께를 측정하였다. 2) Securing Halftone Adhesion Thickness: After forming the final pattern film using halftone mask split by 5% to 5-95%, tearing does not occur by using nano spec (nano matrix). The thickness of the pattern was measured.
네거티브 감광성 수지 조성물 코팅액을 이용하여 글래스(glass) 기판 상에 스핀코팅 후 핫플레이트 상에서 100℃ , 120℃ 의 온도에서 각각 2분간 프리베이크를 진행하여 막을 형성 하였다. 상기에서 얻어진 막에 10 um 홀 패턴 마스크를 사용하여 상기의 방법으로 최종 패턴 막을 얻었다.The film was formed by spin-coating on a glass substrate using a negative photosensitive resin composition coating solution, followed by prebaking at a temperature of 100 ° C. and 120 ° C. for 2 minutes on a hot plate, respectively. The final pattern film was obtained by the above method using the 10-um hole pattern mask for the film | membrane obtained above.
3) 프리베이크 구간 홀 패턴 CD 변화 : 100℃ 프리베이크와 120℃ 프리베이크 공정 진행 후 최종 패턴 막에서 주사전자현미경(SEM, Nova 400)을 통해 프리베이크 온도 증가에 따른 홀 패턴 CD를 감소를 측정하였다.3) Change of hole pattern CD in pre-baking section: Measure the decrease of hole pattern CD with increasing pre-baking temperature through scanning electron microscope (SEM, Nova 400) in final pattern film after 100 ℃ prebaking and 120 ℃ prebaking process It was.
표 2
평가항목 패턴 접착성 하프톤 접착성확보 두께 프리베이크100~120℃ 구간 홀 패턴 CD 변화
측정장비 OLS3000(올림푸스) Nano Spec(나노매트릭스) Nova 400(FEI)
실시예 1 6 ㎛ 이하 뜯김 10,000 Å이하 뜯김 2 ㎛ 감소
실시예 2 5 ㎛ 이하 뜯김 9,000 Å이하 뜯김 2 ㎛ 감소
실시예 3 4 ㎛ 이하 뜯김 6,500 Å이하 뜯김 2 ㎛ 감소
실시예 4 11 ㎛ 이하 뜯김 20,000 Å이하 뜯김 2 ㎛ 감소
실시예 5 10 ㎛ 이하 뜯김 18,000 Å이하 뜯김 2 ㎛ 감소
실시예 6 9 ㎛ 이하 뜯김 16,500 Å이하 뜯김 2 ㎛ 감소
실시예 7 5 ㎛ 이하 뜯김 8,000 Å이하 뜯김 2 ㎛ 감소
실시예 8 4 ㎛ 이하 뜯김 6,500 Å이하 뜯김 2 ㎛ 감소
실시예 9 3 ㎛ 이하 뜯김 5,000 Å이하 뜯김 2 ㎛ 감소
실시예 10 15 ㎛ 이하 뜯김 24,500 Å이하 뜯김 2 ㎛ 감소
실시예 11 13 ㎛ 이하 뜯김 23,000 Å이하 뜯김 2 ㎛ 감소
실시예 12 11 ㎛ 이하 뜯김 20,000 Å이하 뜯김 2 ㎛ 감소
실시예 13 8 ㎛ 이하 뜯김 15,000 Å이하 뜯김 2 ㎛ 감소
실시예 14 7 ㎛ 이하 뜯김 13,000 Å이하 뜯김 2 ㎛ 감소
실시예 15 5 ㎛ 이하 뜯김 9,000 Å이하 뜯김 2 ㎛ 감소
비교예 1 20 ㎛ 이하 뜯김 35,000 Å이하 뜯김 2 ㎛ 감소
비교예 2 20 ㎛ 이하 뜯김 30,000 Å이하 뜯김 3 ㎛ 감소
비교예 3 15 ㎛ 이하 뜯김 25,000 Å이하 뜯김 5 ㎛ 감소
비교예 4 30 ㎛ 이하 뜯김 40,000 Å이하 뜯김 2 ㎛ 감소
비교예 5 30 ㎛ 이하 뜯김 40,000 Å이하 뜯김 3 ㎛ 감소
비교예 6 30 ㎛ 이하 뜯김 40,000 Å이하 뜯김 4 ㎛ 감소
TABLE 2
Evaluation item Pattern adhesive Halftone Adhesive Thickness Change of hole pattern CD in pre-baking section 100 ~ 120 ℃
measuring equipment OLS3000 (Olympus) Nano Spec (nano matrix) Nova 400 (FEI)
Example 1 Tear below 6 ㎛ Less than 10,000 Tear 2 μm reduction
Example 2 Tear below 5 ㎛ Less than 9,000 2 μm reduction
Example 3 4 μm or less 6,500 Å or less 2 μm reduction
Example 4 Less than 11 ㎛ 20,000 Å or less 2 μm reduction
Example 5 Less than 10 ㎛ Less than 18,000 2 μm reduction
Example 6 Less than 9 ㎛ Less than 16,500 2 μm reduction
Example 7 Tear below 5 ㎛ 8,000 Å or less 2 μm reduction
Example 8 Less than 4 ㎛ 6,500 Å or less 2 μm reduction
Example 9 Less than 3 ㎛ Less than 5,000 torn 2 μm reduction
Example 10 Less than 15 ㎛ Less than 24,500 2 μm reduction
Example 11 Less than 13 ㎛ Less than 23,000 김 2 μm reduction
Example 12 Less than 11 ㎛ 20,000 Å or less 2 μm reduction
Example 13 Tear below 8 ㎛ Less than 15,000 Tear 2 μm reduction
Example 14 Tear below 7 ㎛ 13,000 하 or less 2 μm reduction
Example 15 Tear below 5 ㎛ Less than 9,000 2 μm reduction
Comparative Example 1 Less than 20 ㎛ Less than 35,000 2 μm reduction
Comparative Example 2 Less than 20 ㎛ Less than 30,000 3 μm reduction
Comparative Example 3 Less than 15 ㎛ 25,000 Å or less 5 μm reduction
Comparative Example 4 Less than 30 ㎛ 40,000 Å or less 2 μm reduction
Comparative Example 5 Less than 30 ㎛ 40,000 Å or less 3 μm reduction
Comparative Example 6 Less than 30 ㎛ 40,000 Å or less 4 μm reduction
상기 표 2에 나타난 바와 같이, 본 발명에 따른 실란 커플링제를 포함하여 제조된 실시예 1 내지 15의 감광성 수지 조성물은 종래의 실란 커플링제를 포함하여 제조된 비교예 1 내지 6의 조성물 대비 패턴 접착성이 매우 우수하고, 고온에서의 프리베이크 후에도 홀 패턴의 CD 변화가 매우 적음을 확인할 수 있었다. As shown in Table 2, the photosensitive resin composition of Examples 1 to 15 prepared by including the silane coupling agent according to the present invention is a pattern adhesion compared to the compositions of Comparative Examples 1 to 6 prepared by including a conventional silane coupling agent It was confirmed that the properties were very excellent, and the CD change of the hole pattern was very small even after prebaking at high temperature.
본 발명에 따른 네거티브 감광성 수지 조성물은 비닐기 또는 아크릴기를 포함하는 광반응성 실란 커플링제를 포함함으로써 HMDS 공정 없이도 하프톤 패턴에서 접착력이 우수하며, 프리베이크 공정을 80 내지 130 ℃에서 진행하여도 홀 패턴 CD 감소가 기존 열가교제 대비 적으며, 핫플레이트 위치별 온도 편가에 따른 접착력 및 홀 패턴 CD 편차가 없어 공정 마진 확보가 가능하다. 또한 공정비용을 감소시켜서 패널의 제조비용 절감을 이룰 수 있다.Since the negative photosensitive resin composition according to the present invention includes a photoreactive silane coupling agent containing a vinyl group or an acrylic group, the adhesive force is excellent in the halftone pattern without the HMDS process, and the hole pattern is performed even when the prebaking process is performed at 80 to 130 ° C. CD reduction is less than that of existing thermal crosslinking agents, and process margins can be secured because there is no variation in adhesive force and hole pattern CD according to temperature deviation by hot plate location. In addition, the manufacturing cost of the panel can be reduced by reducing the process cost.
따라서 본 발명의 네거티브 감광성 수지 조성물은 대면적 디스플레이 소자 및 다양한 디스플레이 소자, 예를 들어, TFT-LCD, TSP, OLED, 또는 O-TFT 등의 대면적 디스플레이의 절연막, 게이트 절연막, 평탄화막, 컬럼스페이서, 오버코트 또는 컬러레지스트의 형성에 사용할 수 있다.Therefore, the negative photosensitive resin composition of the present invention is an insulating film, a gate insulating film, a planarizing film, a column spacer of a large area display device and various display devices, for example, a large area display such as TFT-LCD, TSP, OLED, or O-TFT. It can be used for forming overcoat or color resist.

Claims (10)

  1. a) 아크릴계 공중합체;a) acrylic copolymer;
    b) 하기 화학식 1의 광반응성 실란 커플링제;b) a photoreactive silane coupling agent of formula (1);
    c) 광개시제; c) photoinitiators;
    d) 에틸렌성 불포화 결합을 가지는 다관능성 모노머;d) polyfunctional monomers having ethylenically unsaturated bonds;
    e) 첨가제; 및e) additives; And
    f) 잔량의 용매f) residual solvent
    를 포함하는 네거티브 감광성 수지 조성물:A negative photosensitive resin composition comprising:
    [화학식 1][Formula 1]
    Figure PCTKR2015006059-appb-I000016
    Figure PCTKR2015006059-appb-I000016
    상기 식에서, Where
    R1은 아크릴, 메타아크릴 또는 비닐이고,R 1 is acrylic, methacryl or vinyl,
    R2는 메톡시, 에톡시 또는 메틸이며,R 2 is methoxy, ethoxy or methyl,
    R3는 메톡시 또는 에톡시이다.R 3 is methoxy or ethoxy.
  2. 제1항에 있어서, The method of claim 1,
    a) 아크릴계 공중합체 100 중량부;a) 100 parts by weight of the acrylic copolymer;
    b) 하기 화학식 1의 광반응성 실란 커플링제 0.1 내지 20 중량부;b) 0.1 to 20 parts by weight of the photoreactive silane coupling agent of Formula 1;
    c) 광개시제 0.1 내지 30 중량부; c) 0.1 to 30 parts by weight of photoinitiator;
    d) 에틸렌성 불포화 결합을 가지는 다관능성 모노머 10 내지 200 중량부;d) 10 to 200 parts by weight of a multifunctional monomer having an ethylenically unsaturated bond;
    e) 첨가제 0.01 내지 5 중량부; 및e) 0.01 to 5 parts by weight of the additive; And
    f) 용매 150 내지 800 중량부f) 150 to 800 parts by weight of solvent
    를 포함하는 것을 특징으로 하는 네거티브 감광성 수지 조성물.Negative photosensitive resin composition comprising a.
  3. 제1항에 있어서, The method of claim 1,
    상기 광반응성 실란 커플링제의 함량이 1 내지 10 중량부인 것을 특징으로 하는 네거티브 감광성 수지 조성물.The negative photosensitive resin composition, characterized in that the content of the photoreactive silane coupling agent is 1 to 10 parts by weight.
  4. 제1항에 있어서, The method of claim 1,
    상기 아크릴계 공중합체의 폴리스티렌 환산중량평균분자량(Mw)이 3,000 내지 30,000인 것을 특징으로 하는 네거티브 감광성 수지 조성물Polystyrene reduced weight average molecular weight (Mw) of the acrylic copolymer is 3,000 to 30,000 negative photosensitive resin composition, characterized in that
  5. 제1항에 있어서, The method of claim 1,
    상기 광반응성 실란 커플링제가 하기 화학식 2 내지 6의 구조를 갖는 것을 특징으로 하는 네거티브 감광성 수지 조성물:A negative photosensitive resin composition, wherein the photoreactive silane coupling agent has a structure of Formulas 2 to 6 below:
    [화학식 2][Formula 2]
    Figure PCTKR2015006059-appb-I000017
    Figure PCTKR2015006059-appb-I000017
    [화학식 3][Formula 3]
    Figure PCTKR2015006059-appb-I000018
    Figure PCTKR2015006059-appb-I000018
    [화학식 4][Formula 4]
    Figure PCTKR2015006059-appb-I000019
    Figure PCTKR2015006059-appb-I000019
    [화학식 5][Formula 5]
    Figure PCTKR2015006059-appb-I000020
    Figure PCTKR2015006059-appb-I000020
    [화학식 6][Formula 6]
    Figure PCTKR2015006059-appb-I000021
    Figure PCTKR2015006059-appb-I000021
  6. 제1항에 있어서, The method of claim 1,
    상기 광개시제가 옥심에스테르계 화합물인 것을 특징으로 하는 네거티브 감광성 수지 조성물.Said photoinitiator is an oxime ester type compound, The negative photosensitive resin composition characterized by the above-mentioned.
  7. 제1항에 있어서, The method of claim 1,
    상기 용매가 고형분 함량이 10 내지 50 중량%가 되도록 포함하는 것을 특징으로 하는 네거티브 감광성 수지 조성물.The negative photosensitive resin composition, characterized in that the solvent comprises a solid content of 10 to 50% by weight.
  8. 기판 상에 제1항 내지 제7항 중 어느 한 항의 네거티브 감광성 수지 조성물을 코팅하고 프리베이크 후, 노광 및 현상하는 단계를 포함하는 디스플레이 소자의 패턴 형성방법.A method of forming a pattern of a display device, comprising the steps of coating the negative photosensitive resin composition of any one of claims 1 to 7 on a substrate, prebaking, and then exposing and developing.
  9. 제8항에 있어서, The method of claim 8,
    상기 패턴이 TFT-LCD, TSP(Touch Screen Panel), OLED, 또는 EPD, EWD, O-TFT의 대면적 디스플레이 절연막, 게이트 절연막, 평탄화막, 컬럼스페이서, 격벽, 오버코트 또는 컬러레지스트로 사용되는 것을 특징으로 하는 디스플레이 소자의 패턴 형성방법.The pattern is used as a TFT-LCD, TSP (Touch Screen Panel), OLED, or a large area display insulating film, gate insulating film, planarization film, column spacer, barrier rib, overcoat or color resist of EPD, EWD, O-TFT. The pattern formation method of a display element made into.
  10. 제1항 내지 제7항 중 어느 한 항의 네거티브 감광성 수지 조성물의 경화체를 포함하는 디스플레이 소자.The display element containing the hardened | cured material of the negative photosensitive resin composition of any one of Claims 1-7.
PCT/KR2015/006059 2014-06-18 2015-06-16 Negative photosensitive resin composition comprising photoreactive silane coupling agent WO2015194822A1 (en)

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