KR100759442B1 - Photoresist polymer and photoresist composition and phosphor composition comprising the same - Google Patents
Photoresist polymer and photoresist composition and phosphor composition comprising the same Download PDFInfo
- Publication number
- KR100759442B1 KR100759442B1 KR1020010048308A KR20010048308A KR100759442B1 KR 100759442 B1 KR100759442 B1 KR 100759442B1 KR 1020010048308 A KR1020010048308 A KR 1020010048308A KR 20010048308 A KR20010048308 A KR 20010048308A KR 100759442 B1 KR100759442 B1 KR 100759442B1
- Authority
- KR
- South Korea
- Prior art keywords
- photoresist
- polymer
- composition
- fluorescent film
- phosphor
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
-
- 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
- G03F7/038—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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
-
- 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 포토레지스트 중합체 및 이를 포함하는 포토레지스트 조성물과 형광막 조성물에 관한 것으로서, 상기 포토레지스트 중합체는 하기 화학식 1을 갖는다.The present invention relates to a photoresist polymer and a photoresist composition and a fluorescent film composition comprising the same, wherein the photoresist polymer has the following Chemical Formula 1.
[화학식 1][Formula 1]
(상기 식에서,(Wherein
R1은 (R)α(CH2)βR' 또는 (R)α((CH2) mO)γR'(여기에서, R은 CO, CO2, O, OCO 또는 OCO2이고, R'은 O, CO2 또는 OCO2이고, α는 0 또는 1이며, β는 0 내지 5이고, m은 1 또는 2이고, γ는 1 내지 5임)이고, R 1 is (R) α (CH 2 ) β R 'or (R) α ((CH 2 ) m O) γ R' where R is CO, CO 2 , O, OCO or OCO 2 , and R 'Is O, CO 2 or OCO 2 , α is 0 or 1, β is 0 to 5, m is 1 or 2, and γ is 1 to 5),
R2, R3 및 R4는 각각 수소, 탄소수 1 내지 5인 포화 알킬, 불포화 알킬, 방향족, 에테르, 카르보닐, 아민 또는 알콜기이고,R 2 , R 3 and R 4 are each hydrogen, saturated alkyl, unsaturated alkyl, aromatic, ether, carbonyl, amine or alcohol group having 1 to 5 carbon atoms,
X는 0 내지 5이고,X is from 0 to 5,
a, b, c는 각 단량체의 몰비율이고, a는 0.6 내지 0.99의 값을 가지며, b는 0 내지 0.1의 값을 가지며, c는 0.01 내지 0.3의 값을 가지며, a+b+c=1이고, a, b, c are the molar ratios of each monomer, a has a value of 0.6 to 0.99, b has a value of 0 to 0.1, c has a value of 0.01 to 0.3, a + b + c = 1 ego,
n은 고분자 중합도로서 2 이상의 값을 가진다.)n is a polymer degree of polymerization and has a value of 2 or more.)
포토레지스트, 네가티브, 수용성, 아세탈Photoresist, Negative, Water Soluble, Acetal
Description
[산업상 이용 분야][Industrial use]
본 발명은 포토레지스트 중합체 및 이를 포함하는 포토레지스트 조성물과 형광막 조성물에 관한 것으로서, 더욱 상세하게는 환경 오염을 유발하지 않으면서, 저장 안정성이 우수하고, 고감도를 갖는 포토레지스트 중합체 및 이를 포함하는 포토레지스트 조성물과 형광막 조성물에 관한 것이다.The present invention relates to a photoresist polymer and a photoresist composition and a fluorescent film composition comprising the same, more particularly, a photoresist polymer having excellent storage stability and high sensitivity without causing environmental pollution, and a photo comprising the same It relates to a resist composition and a fluorescent film composition.
[종래 기술][Prior art]
음극선관의 형광막은 전자빔의 에너지를 광에너지로 변환시키는 것으로, 전자빔이 음극선관 패널에 형성된 형광막의 형광체에 충돌함으로써 발광한다. 음극선관의 형광막의 제조 공정은 다음과 같다. 우선 패널 내면에 블랙 매트릭스 패턴을 형성한 다음 형광막 패턴을 형성한다. 형광막 성형 공정은 블랙 매트릭스 패턴이 형성된 패널 내면에 형광체 슬러리를 도포하고 건조 후, 마스크를 장착하고 고압 수은등을 이용하여 노광한 다음 순수를 이용하여 현상하여 형광막을 형성한다. 이와 같은 과정을 적색, 녹색 및 청색 형광체로 반복하여 3색의 형광체 패턴을 형성한다. 상기 형광체 슬러리는 감광성 고분자인 포토레지스트 수지, 광 가교제, 형광체와 접착력 증가제, 분산제 등과 같은 기타 첨가제를 포함한다. 또한, 상기 형광체 슬러리를 도포하기 전에 포토레지스트 수지와 광 가교제를 포함하는 포토레지스트 조성물을 하도액 조성물로 사용하여 패널에 도포하여, 형광체의 접착력을 증가시킬 수도 있다. The fluorescent film of a cathode ray tube converts the energy of an electron beam into light energy, and an electron beam emits light by colliding with the fluorescent substance of the fluorescent film formed in the cathode ray tube panel. The manufacturing process of the fluorescent film of a cathode ray tube is as follows. First, a black matrix pattern is formed on the inner surface of the panel, and then a fluorescent film pattern is formed. In the fluorescent film forming process, a phosphor slurry is coated on an inner surface of a panel on which a black matrix pattern is formed, dried, a mask is mounted, exposed using a high pressure mercury lamp, and then developed using pure water to form a fluorescent film. This process is repeated with red, green, and blue phosphors to form three phosphor patterns. The phosphor slurry includes other additives such as a photoresist resin, a photocrosslinking agent, a phosphor and an adhesion increasing agent, a dispersant, and the like which are photosensitive polymers. In addition, before applying the phosphor slurry, a photoresist composition including a photoresist resin and an optical crosslinking agent may be applied to the panel using the undercoating solution composition to increase adhesion of the phosphor.
종래의 칼라음극선관(Cathode Ray Tube: CRT)의 형광면의 제조 공정에 사용되는 형광체 슬러러와 하도액에 사용되는 포토레지스트 수지 및 광가교제로는 폴리비닐알콜(PVA)과 소디움 디크로메이트(SDC) 또는 암모늄 디크로메이트(ADC)를 사용하는 것이 일반적이다. 이 밖에도 포토레지스트 수지로서 미국특허 제3,558,310호, 미국특허 제4,556,626호와 일본특허 평5-173331호에 기재된 바와 같이 폴리비닐알콜(PVA)을 변형시킨 형태나 폴리비닐알콜(PVA)과 폴리비닐피롤리돈(PVP)이 도입된 형태가 사용되기도 한다. 폴리비닐알콜(PVA)과 소디움 디크로메이트(SDC) 또는 암모늄 디크로메이트(ADC) 슬러리는 감도가 뛰어나고 색잔이 없어 깨끗하게 형광체가 형성되나 생성되는 형광체의 도트(dot) 폭 조절이 어렵고 보관시 온도 및 습도에 영향을 받고 특히 암반응이 일어나므로 보관하기가 어렵다. 또한 광 가교제인 소디움 디크로메이트(SDC)가 중금속인 크롬을 함유하고 있어 환경오염의 문제를 유발한다는 단점을 갖고 있다.As the photoresist resin and photocrosslinker used in phosphor slurries and undercoat liquids, which are used in the manufacturing process of fluorescent surfaces of conventional cathode ray tubes (CRT), polyvinyl alcohol (PVA) and sodium dichromate (SDC) are used. Or ammonium dichromate (ADC). In addition, as the photoresist resin, polyvinyl alcohol (PVA) or polyvinyl alcohol (PVA) and polyvinyl film as described in US Pat. No. 3,558,310, US Pat. No. 4,556,626, and Japanese Patent No. Hei 5-173331. Forms with the introduction of rolidone (PVP) may also be used. Polyvinyl alcohol (PVA) and sodium dichromate (SDC) or ammonium dichromate (ADC) slurries are highly sensitive and have no color residue to form phosphors cleanly, but it is difficult to control the dot width of the resulting phosphors and to store temperature and humidity It is difficult to store because it is affected by cancer, especially cancer reactions. In addition, since sodium dichromate (SDC), an optical crosslinking agent, contains chromium, which is a heavy metal, it has a disadvantage of causing environmental pollution.
크롬이 없는 포토레지스트 수지와 광가교제를 이용한 것으로는 수용성 고분자-비스아지드(bisazide)계 포토레지스트와 수용성 고분자-디아조(diazo)계 포토레 지스트가 있다. 미국특허 제4,086,090호, 미국특허 제4,332,874호, 미국특허 제4,241,161호와 일본특허공개 평5-216219호에는 수용성 고분자로는 폴리비닐알콜(PVA)계, 폴리비닐프로필렌(PVP)계 또는 폴리아크릴아미드(PAD)계 등의 중합체를 이용하고, 광 가교제로는 비스아지드계 화합물을 이용한 수용성 고분자-비스아지드계 포토레지스트가 기재되어 있다. 상기 비스아지드계 광가교제로는 4,4'-디아지도벤잘아세토페논-2-설포네이트, 4,4'-디아지도스틸벤-2,2'-디설포네이트, 4,4'-디아지도스틸벤-γ-카르복실산 등에 관하여 소개하고 있다. 미국특허 제3,965,278호, 미국특허 제4,123,276호와 대한민국특허 공개번호 제1999-085157호에는 수용성 고분자-디아조계 포토레지스트가 기재되어 있다. 상기 디아조계 광가교제로는 비닐아지도벤질리덴아세토페논술폰산알카리염, 비닐아지도벤질리덴아세토페논카르복실산알카리염, 비닐아지도신나밀리덴아세토페논술폰산알카리염과 비닐아지도신나밀리덴아세토페논카르복실산알카리염 등의 단량체로부터 합성한 고분자 등이 사용된다.Examples of the chromium-free photoresist resin and the photocrosslinker include a water-soluble polymer-bisazide-based photoresist and a water-soluble polymer-diazo-based photoresist. US Pat. No. 4,086,090, US Pat. No. 4,332,874, US Pat. No. 4,241,161 and Japanese Patent Laid-Open No. 5-216219 include water-soluble polymers such as polyvinyl alcohol (PVA), polyvinylpropylene (PVP) or polyacrylamide. A water-soluble polymer-bisazide-based photoresist using a bisazide-based compound is described as a photocrosslinking agent using a polymer such as (PAD) -based. As the bisazide-based photocrosslinking agent, 4,4'-diazidobenzalacetophenone-2-sulfonate, 4,4'-diazidostilben-2,2'-disulfonate, 4,4'-dia It introduces about dozilbene- (gamma) -carboxylic acid. US Pat. No. 3,965,278, US Pat. No. 4,123,276 and Korean Patent Publication No. 1999-085157 describe water-soluble polymer-diazo photoresists. The diazo-based photocrosslinking agents include vinyl azidobenzylideneacetophenonesulfonic acid alkali salts, vinyl azidobenzylideneacetophenonecarboxylic acid alkali salts, vinyl azidocinnamilideneacetophenonesulfonic acid alkali salts and vinyl azidocinnamilideneaceto Polymers synthesized from monomers such as phenonecarboxylic acid alkali salts and the like are used.
그러나 상기 크롬이 없는 포토레지스트 수지와 광가교제를 포함하는 슬러리는 폴리비닐알콜-소디움 디크로메이트(PVA-SDC) 포토레지스트에 비해 노광 감도와형광체의 패널에 대한 접착력이 떨어지는 문제점이 있다.However, the slurry containing the chromium-free photoresist resin and the photocrosslinking agent has a problem in that the exposure sensitivity and the adhesion of the phosphor to the panel are inferior to those of the polyvinyl alcohol-sodium dichromate (PVA-SDC) photoresist.
크롬이 없는 포토레지스트 수지와 광가교제로 제안된 또 다른 형태는 미국특허 제4,990,4417호, 미국특허 제5,506,087호, 일본특허 소55-24126호와 대한민국특허 공개번호 제1999-015235호에 소개된 바 있는 폴리비닐알콜-스틸바졸륨(PVA-SbQ)이다. 이 형태는 폴리비닐알콜(PVA)에 스틸바졸륨(SbQ)기를 도입한 것으로 감광 특성이 좋고, 저장 안정성이 뛰어난 것으로 알려져 있다. 그러나 폴리비닐알콜-스틸바졸륨(PVA-SbQ) 포토레지스트를 이용하여 형광막을 형성하게 되면 수용성 고분자-비스아지드계 포토레지스트와 수용성 고분자-디아조계 포토레지스트와 동일한 결과, 즉 상기한 노광 감도와 형광체의 패널에 대한 접착성이 나빠 사용상의 문제점을 갖고 있는 것으로 나타났다.Other forms proposed as chromium-free photoresist resins and photocrosslinkers are described in US Pat. No. 4,990,4417, US Pat. No. 5,506,087, Japanese Patent No. 55-24126, and Korean Patent Publication No. 1999-015235. Bar polyvinyl alcohol-steelbazolium (PVA-SbQ). This form introduce | transduces a stilbazolium (SbQ) group into polyvinyl alcohol (PVA), and it is known that it is excellent in photosensitive characteristic and is excellent in storage stability. However, when the fluorescent film is formed by using a polyvinyl alcohol-stilbazolium (PVA-SbQ) photoresist, the same result as that of the water-soluble polymer-bisazide-based photoresist and the water-soluble polymer-diazo-based photoresist It was found that the adhesiveness to the panel of the phosphor was poor, and thus there was a problem in use.
따라서, 노광 감도 및 형광체의 패널에 대한 접착력이 뛰어나면서 보관 안정성이 우수한 환경친화적인 포토레지스트 조성물이 요구되어 지고 있다.Therefore, there is a need for an environmentally friendly photoresist composition that is excellent in exposure sensitivity and adhesion of the phosphor to the panel and excellent in storage stability.
본 발명은 상기 문제점을 해결하기 위하여 안출된 것으로서, 본 발명의 목적은 환경 오염을 유발하지 않으면서, 저장 안정성이 우수하고, 고감도를 가지는 포토레지스트 중합체를 제공하는 것이다.The present invention has been made to solve the above problems, and an object of the present invention is to provide a photoresist polymer having excellent storage stability and high sensitivity without causing environmental pollution.
본 발명의 다른 목적은 상기 중합체를 포함하는 환경 오염을 유발하지 않으면서, 저장 안정성이 우수하고, 고감도인 포토레지스트 조성물을 제공하는 것이다.It is another object of the present invention to provide a photoresist composition having excellent storage stability and high sensitivity without causing environmental pollution including the polymer.
본 발명의 또 다른 목적은 상기 중합체를 포함하는 환경 오염을 유발하지 않으면서, 저장 안정성이 우수하고, 고감도인 형광막 조성물을 제공하는 것이다.Still another object of the present invention is to provide a fluorescent film composition having excellent storage stability and high sensitivity without causing environmental pollution including the polymer.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1의 포토레지스트 중합체를 제공한다. In order to achieve the above object, the present invention provides a photoresist polymer of the formula (1).
[화학식 1][Formula 1]
(상기 식에서,(Wherein
R1은 (R)α(CH2)βR' 또는 (R)α((CH2) mO)γR'(여기에서, R은 CO, CO2, O, OCO 또는 OCO2이고, R'은 O, CO2 또는 OCO2이고, α는 0 또는 1이며, β는 0 내지 5이고, m은 1 또는 2이고, γ는 1 내지 5임)이고, R 1 is (R) α (CH 2 ) β R 'or (R) α ((CH 2 ) m O) γ R' where R is CO, CO 2 , O, OCO or OCO 2 , and R 'Is O, CO 2 or OCO 2 , α is 0 or 1, β is 0 to 5, m is 1 or 2, and γ is 1 to 5),
R2, R3 및 R4는 각각 수소, 탄소수 1 내지 5인 포화 알킬, 불포화 알킬, 방향족, 에테르, 카르보닐, 아민 또는 알콜기이고,R 2 , R 3 and R 4 are each hydrogen, saturated alkyl, unsaturated alkyl, aromatic, ether, carbonyl, amine or alcohol group having 1 to 5 carbon atoms,
X는 1 내지 5이고,X is 1 to 5,
a, b, c는 각 단량체의 몰비율이고, a는 0.6 내지 0.99의 값을 가지며, b는 0 내지 0.1의 값을 가지며, c는 0.01 내지 0.3의 값을 가지며, a+b+c=1이고,a, b, c are the molar ratios of each monomer, a has a value of 0.6 to 0.99, b has a value of 0 to 0.1, c has a value of 0.01 to 0.3, a + b + c = 1 ego,
n은 고분자 중합도로서 2 이상의 값을 가진다.)n is a polymer degree of polymerization and has a value of 2 or more.)
본 발명은 또한 상기 화학식 1의 중합체를 포함하는 포토레지스트 조성물을 제공한다. 상기 포토레지스트 조성물에 형광체를 더욱 포함시키면 형광막 조성물로 사용할 수 있다. The present invention also provides a photoresist composition comprising the polymer of Formula 1. If the phosphor is further included in the photoresist composition, it can be used as a fluorescent film composition.
이하 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 환경 오염을 유발하지 않으면서, 저장 안정성이 우수하고, 고감도인 신규의 포토레지스트 중합체 및 이를 포함하는 포토레지스트 조성물과 형광막 조성물에 관한 것이다. The present invention relates to a novel photoresist polymer having excellent storage stability and high sensitivity without causing environmental pollution, and a photoresist composition and a fluorescent film composition comprising the same.
본 발명의 포토레지스트 중합체는 촉매 역할을 하는 산의 존재 하에서 열을 가하면 가교 반응을 일으켜 현상액에 불용상태가 되는 아세탈기를 갖는 비닐계 중합체이다. 상기 산은 광산 발생제가 노광시 빛을 받으면 생성되며 이 생성된 산은 포토레지스트 중합체의 가교 반응을 촉진한다. 본 발명의 포토레지스트 중합체의 가교 반응은 화학증폭(chemically amplification)형 방식으로 이루어진다. 화학증폭에서는 한번의 광화학적 반응에 의해 발생된 활성종이 탈보호(deprotection), 가교 반응과 같은 화학 반응들이 연속적으로 일어날 수 있도록 촉매로서 작용하여 이들 반응들의 총 양자 수율(quantum yield)이 초기 촉매 생성의 양자 수율보다 크게 증폭되어 고감도의 포토레지스트 특성을 갖게 한다.The photoresist polymer of the present invention is a vinyl-based polymer having an acetal group which, when heated in the presence of an acid serving as a catalyst, causes crosslinking reaction and becomes insoluble in the developer. The acid is produced when the photoacid generator receives light upon exposure and the acid generated promotes the crosslinking reaction of the photoresist polymer. The crosslinking reaction of the photoresist polymer of the present invention takes place in a chemically amplification type manner. In chemical amplification, the active species generated by a single photochemical reaction act as a catalyst so that chemical reactions, such as deprotection and crosslinking, can occur continuously so that the total quantum yield of these reactions produces an initial catalyst. It is amplified to be greater than the quantum yield of to have a high sensitivity photoresist characteristics.
본 발명의 포토레지스트 중합체는 상기 화학식 1에 나타낸 바와 같이 히드록시기, 아세톡시기 및 아세탈기를 갖는 중합체이다. 본 발명의 신규 합성한 포토레지스트 중합체의 조성성분에서 히드록시기는 가교 반응에 참여하면서 유리 패널에 대한 접착성을 향상시키는 역할을 하며, 아세톡시기는 현상성을 조절하는 역할을 하며, 아세탈기는 산의 존재 하에서 열을 가하면 가교 반응을 일으키는 자리가 된다.The photoresist polymer of the present invention is a polymer having a hydroxyl group, an acetoxy group and an acetal group as shown in the general formula (1). In the composition of the newly synthesized photoresist polymer of the present invention, the hydroxyl group participates in the crosslinking reaction and improves the adhesion to the glass panel, the acetoxy group serves to control the developability, and the acetal group If heat is applied in the presence, it becomes a site causing a crosslinking reaction.
본 발명의 포토레지스트 조성물은 상기 화학식 1의 중합체 및 광산 발생제(photoacid generator)를 포함한다. 상기 중합체는 전체 포토레지스트 조성물 기준으로 2 내지 5 중량%의 양으로 사용되는 것이 바람직하다. 2 중량% 미만일 경우에는 가교 성분이 적어서 형광막 형성이 어렵고, 5 중량% 초과일 경우에는 점도의 증가에 따른 균일한 막 형성이 어렵다. The photoresist composition of the present invention comprises a polymer of Formula 1 and a photoacid generator. The polymer is preferably used in an amount of 2 to 5% by weight based on the total photoresist composition. If it is less than 2% by weight, it is difficult to form a fluorescent film due to the small amount of crosslinking components. If it is more than 5% by weight, it is difficult to form a uniform film due to an increase in viscosity.
상기 광산 발생제는 노광 공정에서 광원으로부터 자외선 광을 받으면 산을 발생시키고, 이렇게 발생된 산은 의해 상기 중합체의 알코올기가 아세탈기를 공격하여 가교 반응을 일으키는 촉매제의 역할을 한다. 이런 가교 반응을 통해서 노광된 부분과 노광이 안된 부분이 현상액에 대한 용해도 차이를 갖게 하여 패턴을 형성하게 된다. The photoacid generator generates an acid upon receiving ultraviolet light from a light source in an exposure process, and the generated acid acts as a catalyst that causes an alcohol group of the polymer to attack acetal groups to cause a crosslinking reaction. Through such a crosslinking reaction, the exposed portion and the unexposed portion have a difference in solubility in the developer, thereby forming a pattern.
광산 발생제로는 광을 받으면 산을 발생시킬 수 있으면 사용 가능하며 특별히 제한되지는 않으나, 그 예로는 디페닐요도염 헥사플루오르 포스페이트, 디페닐요도염 헥사플루오르 아르세네이트, 디페닐요도염 헥사플루오르 안티모네이트, 디페닐파라메톡시페닐 트리플레이트, 디페닐파라톨루에틸 트리플레이트, 디페닐파라이소부틸페닐 트리플레이트, 디페닐파라-t-부틸페닐 트리플레이트, 트리페닐설포늄 헥사플루오르 포스페이트, 트리페닐설포늄 헥사플루오르 아르세네이트, 트리페닐설포늄 헥사플루오르 안티모네이트, 트리페닐설포늄 트리플레이트, 디부틸나프틸설포늄 트리플레이트 중에서 1종 또는 2종 이상의 황화염계 또는 오니움계 화합물을 사용할 수 있다.The photoacid generator can be used as long as it can generate an acid upon receiving light, and is not particularly limited. Examples thereof include diphenyl iodo hexafluoro phosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, Diphenylparamethoxyphenyl triflate, diphenylparatoluethyl triflate, diphenylparaisobutylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexa One or two or more sulfide-based or onium-based compounds may be used among fluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate and dibutylnaphthylsulfonium triflate.
상기 광산 발생제는 포토레지스트 조성물에 대하여 0.02 내지 0.25 중량%로 사용되는 것이 바람직하다. 0.02 중량% 미만인 경우 산 발생양이 적어 가교가 충 분히 일어나지 못하며, 0.25 중량% 초과일 경우 광산 발생제 자체의 자외선 흡수량 증가에 의해 감도가 감소한다.The photoacid generator is preferably used at 0.02 to 0.25% by weight based on the photoresist composition. If the amount is less than 0.02% by weight, the amount of acid generated is small, so that crosslinking does not occur sufficiently. If the amount is more than 0.25% by weight, the sensitivity is decreased by increasing the amount of ultraviolet light absorbed by the photoacid generator itself.
본 발명의 포토레지스트 중합체를 포함하는 포토레지스트 조성물은 칼라음극선관 형광막을 형성하는 공정에서 형광체와 패널의 접착력을 증가시키기 위해 사용되는 하도액으로 사용될 수 있다.The photoresist composition comprising the photoresist polymer of the present invention can be used as a coating liquid used to increase the adhesion between the phosphor and the panel in the process of forming a color cathode ray tube fluorescent film.
또한, 본 발명의 포토레지스트 조성물에 형광체를 첨가하면 형광막을 형성하기 위한 형광막 조성물로 제조될 수도 있다. 상기 포토레지스트 조성물과 형광체를 포함하는 형광막 조성물은 포토레지스트 중합체와 광산 발생제를 물에 용해한 후, 칼라음극선관에서 일반적으로 사용되는 적색, 청색 및 녹색 형광체를 각각 첨가하여 제조된다. In addition, when the phosphor is added to the photoresist composition of the present invention, it may be prepared as a fluorescent film composition for forming a fluorescent film. The fluorescent film composition including the photoresist composition and the phosphor is prepared by dissolving the photoresist polymer and the photoacid generator in water, and then adding red, blue, and green phosphors generally used in color cathode ray tubes.
상기 적색, 청색 및 녹색 형광체로는 칼라음극선관에서 일반적으로 사용되는 형광체이면 어떠한 것도 사용할 수 있으며, 그 대표적인 예로 Y2O2S:Eu 또는 Y2 O3:Eu의 적색 형광체, ZnS:Ag, Cl의 청색 형광체, ZnS:Au, Cu, Al의 녹색 형광체 등을 사용할 수 있다. As the red, blue and green phosphors, any phosphor can be used as long as it is a phosphor generally used in color cathode ray tubes, and representative examples thereof include Y 2 O 2 S: Eu or Y 2 O 3 : Eu red phosphors, ZnS: Ag, Blue phosphor of Cl, ZnS: Au, Cu, green phosphor of Al, etc. can be used.
상기 형광막 조성물에 접착력 보강제, 소포제 등의 기타 첨가제를 더욱 첨가하여 사용할 수도 있다. 접착력 보강제로는 형광막의 균일성과 분산성을 향상시킬수 있는 물질은 어떠한 것도 사용할 수 있으며, 그 대표적인 예로 소르비탄 모노 라우레이트 계면활성제(Sorbitan mono Laulate Surfactant: SLS)를 사용할 수 있으다. 상기 접착력 보강제는 형광막 조성물에 대하여 0.2 중량% 내지 1.0 중량%가 바 람직하다. 0.2 중량% 미만일 경우에는 형광막 분산성과 균일성이 떨어지는 문제점이 있으며, 1.0 중량%를 초과할 경우에는 형광체의 유리 패널에 대한 접착력이 떨어지는 문제점이 있다.Other additives such as an adhesion reinforcing agent and an antifoaming agent may be further added to the fluorescent film composition. As the adhesion enhancer, any material capable of improving the uniformity and dispersibility of the fluorescent film may be used, and as a representative example, sorbitan mono laurate surfactant (SLS) may be used. The adhesion enhancer is preferably 0.2% to 1.0% by weight based on the fluorescent film composition. If it is less than 0.2% by weight, there is a problem in that the dispersibility and uniformity of the fluorescent film is inferior, and if it is more than 1.0% by weight, there is a problem in that the adhesion of the phosphor to the glass panel is inferior.
소포제로는 형광막의 습윤 및 표면 장력 감소로 분산성을 향상시킬 수 있고 도포성이나 현상성을 향상시키기 위한 물질은 어떠한 것도 사용할 수 있다. 대표적인 예로 프로필렌 옥사이드 에틸렌 옥사이드 계면활성제(Propylene oxide Ethylene oxide Surfactant: PES)를 사용할 수 있고, 디나프탈렌-디설폰산성 소다 계면활성제(diNaphthylen-disulfonic acid Soda Surfactant: NSS)도 사용할 수 있고, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노니에테르 등을 들 수 있다. 이들 계면 활성제의 함량은 형광막 조성물에 대하여 0.2 중량% 내지 1.0 중량%가 바람직하고, 0.2 중량% 미만일 경우에는 도포성이나 형상성이 떨어지는 문제점이 있으며, 1.0 중량%를 초과할 경우에는 형광체의 유리 패널에 대한 접착력이 떨어지는 문제점이 있다.As the antifoaming agent, dispersibility can be improved by wetting of the fluorescent film and reduction of surface tension, and any material for improving applicability or developability can be used. As a representative example, propylene oxide ethylene oxide surfactant (PES) may be used, and diNaphthylen-disulfonic acid Soda Surfactant (NSS) may be used, and polyoxyethylene octyl may be used. Phenyl ether, polyoxyethylene noni ether, etc. are mentioned. The content of these surfactants is preferably 0.2% by weight to 1.0% by weight with respect to the fluorescent film composition, and when the content is less than 0.2% by weight, there is a problem in that applicability or shape is inferior. There is a problem that the adhesion to the panel is inferior.
이하 본 발명의 바람직한 실시예, 적용예 및 비교예를 들어 보다 상세히 설명한다. 그러나 하기한 실시예는 본 발명의 바람직한 일 실시예일 뿐이며 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to preferred examples, applications and comparative examples. However, the following examples are merely preferred embodiments of the present invention and the present invention is not limited to the following examples.
포토레지스트 중합체 제조Photoresist Polymer Manufacturing
(실시예 1) (Example 1)
96% 가수분해된 평균 중합도 2000의 폴리비닐알콜(PVA) 22.9g(0.5 몰)과 정제된 테트라하이드로퓨란(THF) 250㎖를 500㎖의 플라스크에 넣은 후, 정제된 피리 딘 12㎖(0.15몰)을 첨가하였다. 여기에 2-브로모메틸-1,3-다이옥솔란 21.7g(0.13몰)을 넣고 상온에서 24시간 교반시켰다. 반응을 완결시키고 석유 에테르에 반응물을 침전시켜 화학식 2의 중합체를 얻었다.22.9 g (0.5 mole) of polyvinyl alcohol (PVA) and 250 ml of purified tetrahydrofuran (THF) with an average degree of polymerization of 96% hydrolysis in 2000 were placed in a 500 ml flask, followed by 12 ml (0.15 mole) of purified pyridine. ) Was added. 21.7 g (0.13 mol) of 2-bromomethyl-1,3-dioxolane was added thereto, followed by stirring at room temperature for 24 hours. The reaction was completed and the reactant was precipitated in petroleum ether to give the polymer of formula 2.
[화학식 2][Formula 2]
(실시예 2)(Example 2)
실시예 1에서 2-브로모메틸-1,3-다이옥솔란 24g(0.26 몰) 대신 2-(2-브로모에틸)-1,3-다이옥솔란 23.5g(0.13 몰)을 사용한 것 외에는 실시예 1과 동일한 방법으로 하기 화학식 3의 중합체를 얻었다.Example 1 except that 23.5 g (0.13 mol) of 2- (2-bromoethyl) -1,3-dioxolane was used instead of 24 g (0.26 mol) of 2-bromomethyl-1,3-dioxolane. In the same manner as in 1, a polymer of Chemical Formula 3 was obtained.
[화학식 3][Formula 3]
(실시예 3)(Example 3)
실시예 1에서 2-브로모메틸-1,3-다이옥솔란 24g(0.26 몰) 대신 5-클로로-2- 펜타논 에틸렌 케탈 21.4g(0.13 몰)을 사용한 것 외에는 실시예 1과 동일한 방법으로 하기 화학식 4의 중합체를 얻었다.The same procedure as in Example 1 was repeated except that 21.4 g (0.13 mol) of 5-chloro-2-pentanone ethylene ketal was used instead of 24 g (0.26 mol) of 2-bromomethyl-1,3-dioxolane in Example 1. A polymer of formula 4 was obtained.
[화학식 4][Formula 4]
(실시예 4)(Example 4)
실시예 1에서 2-브로모메틸-1,3-다이옥솔란 24g(0.26 몰) 대신 2-(2-브로모에틸)-1,3-다이옥산 25.4g(0.13 몰)을 사용한 것 외에는 실시예 1과 동일한 방법으로 하기 화학식 5의 중합체를 얻었다.Example 1 except that 25.4 g (0.13 mol) of 2- (2-bromoethyl) -1,3-dioxane was used instead of 24 g (0.26 mol) of 2-bromomethyl-1,3-dioxolane in Example 1. In the same manner as in the polymer of Formula 5 was obtained.
[화학식 5][Formula 5]
(실시예 5)(Example 5)
실시예 1에서 2-브로모메틸-1,3-다이옥솔란 24g(0.26 몰) 대신 2-(2-브로모에틸)-2,5,5-트리메틸-1,3-다이옥산 30.8g(0.13 몰)을 사용한 것 외에는 실시예 1 과 동일한 방법으로 하기 화학식 6의 중합체를 얻었다.30.8 g (0.13 mol) of 2- (2-bromoethyl) -2,5,5-trimethyl-1,3-dioxane instead of 24 g (0.26 mol) of 2-bromomethyl-1,3-dioxolane in Example 1 A polymer of the following Chemical Formula 6 was obtained by the same method as Example 1 except for using).
[화학식 6][Formula 6]
이하, 실시예 6 내지 10에서는 실시예 1 내지 5에서 합성한 아세탈기를 가지는 포토레지스트 중합체를 이용하여 포토레지스트 조성물을 제조하고, 감도를 측정하였다.Hereinafter, in Examples 6-10, the photoresist composition was produced using the photoresist polymer which has the acetal group synthesize | combined in Examples 1-5, and the sensitivity was measured.
포토레지스트 조성물을 이용한 형광막 제조Fluorescent Film Preparation Using Photoresist Composition
(실시예 6)(Example 6)
원자외선이 차단된 실험실에서 실시예 1에서 제조한 화학식 2의 중합체를 물에 녹여 만든 8% 용액 340g, 광산 발생제인 트리페닐술포늄트리플레이트 1.36g, 접착력 보강제인 소르비탄 모노 라우레이트(SLS) 5% 용액 7g, 소포제인 프로필렌 옥사이드 에틸렌 옥사이드 계면활성제(PES) 5% 용액 6g, 녹색 형광체 320g과 순수 430g을 혼합하여 슬러리를 제조하였다. 제조한 슬러리를 블랙 매트릭스가 형성된 패널에 스핀 도포하고, 110℃로 설정된 히터에서 2분간 회전 건조하였다. 고압 수은등으로 조도 100mW/㎠에서 17초간 노광한 후, 발생된 산에 의한 가교 반응을 일 으키기 위해 110℃로 설정된 히터에서 2분간 후열처리하였다. 이후 40℃의 고압순수를 이용하여 30초간 현상하였다. 현상 후 110℃로 설정된 히터에서 2분간 회전 건조시켜 폭 120㎛의 녹색 형광막을 형성하였다.340 g of an 8% solution prepared by dissolving the polymer of Formula 2 prepared in Example 1 in a laboratory shielded from ultraviolet rays, 1.36 g of triphenylsulfonium triflate as a photoacid generator, and sorbitan mono laurate (SLS) as an adhesion enhancer A slurry was prepared by mixing 7 g of a 5% solution, 6 g of a 5% solution of a propylene oxide ethylene oxide surfactant (PES) as an antifoaming agent, 320 g of green phosphor, and 430 g of pure water. The prepared slurry was spin-coated on a panel on which a black matrix was formed, and it was spin-dried for 2 minutes by the heater set to 110 degreeC. After 17 seconds exposure at 100mW / cm2 illuminance with a high-pressure mercury lamp, post-heat treatment was performed for 2 minutes in a heater set at 110 ° C to cause crosslinking reaction by the generated acid. After developing for 30 seconds using high pressure pure water of 40 ℃. After the development, rotation drying was performed for 2 minutes in a heater set at 110 ° C. to form a green fluorescent film having a width of 120 μm.
청색 형광막과 적색 형광막도 상기와 동일한 방법으로 폭 120㎛의 형광막을 각각 형성하였다.In the blue fluorescent film and the red fluorescent film, a fluorescent film having a width of 120 µm was formed in the same manner as described above.
(실시예 7)(Example 7)
원자외선이 차단된 실험실에서 실시예 2에서 제조한 화학식 3의 중합체를 이용하여 실시예 6과 동일하게 슬러리를 제조한 후, 15초간 노광한 것을 제외하고는 실시예 6과 동일한 방법으로 폭 120㎛의 녹색, 청색 및 적색 형광막을 형성하였다.120 µm wide in the same manner as in Example 6, except that the slurry was prepared in the same manner as in Example 6 using the polymer of Formula 3 prepared in Example 2 in the laboratory where ultraviolet rays were blocked, and then exposed for 15 seconds. Green, blue and red fluorescent films were formed.
(실시예 8)(Example 8)
원자외선이 차단된 실험실에서 실시예 3에서 제조한 화학식 4의 중합체를 이용하여 실시예 6과 동일하게 슬러리를 제조한 후, 20초간 노광한 것을 제외하고는 실시예 6과 동일한 방법으로 폭 120㎛의 녹색, 청색 및 적색 형광막을 형성하였다.120 μm wide in the same manner as in Example 6, except that the slurry was prepared in the same manner as in Example 6 using the polymer of Chemical Formula 4 prepared in Example 3 in the laboratory where ultraviolet rays were blocked, and then exposed for 20 seconds. Green, blue and red fluorescent films were formed.
(실시예 9)(Example 9)
원자외선이 차단된 실험실에서 실시예 4에서 제조한 화학식 5의 중합체를 이용하여 실시예 6과 동일하게 슬러리를 제조한 후, 15초간 노광한 것을 제외하고는 실시예 6과 동일한 방법으로 폭 120㎛의 녹색, 청색 및 적색 형광막을 형성하였다.120 µm wide in the same manner as in Example 6, except that the slurry was prepared in the same manner as in Example 6 using the polymer of Formula 5 prepared in Example 4 in the laboratory where ultraviolet rays were blocked, and then exposed for 15 seconds. Green, blue and red fluorescent films were formed.
(실시예 10)(Example 10)
원자외선이 차단된 실험실에서 실시예 5에서 제조한 화학식 6의 중합체를 이용하여 실시예 6과 동일하게 슬러리를 제조한 후, 20초간 노광한 것을 제외하고는 실시예 6과 동일한 방법으로 폭 120㎛의 녹색, 청색 및 적색 형광막을 형성하였다.120 μm wide in the same manner as in Example 6, except that the slurry was prepared in the same manner as in Example 6 using the polymer of Chemical Formula 6 prepared in Example 5 in a laboratory where ultraviolet rays were blocked, and then exposed for 20 seconds. Green, blue and red fluorescent films were formed.
(비교예 1)(Comparative Example 1)
원자외선이 차단된 실험실에서 폴리비닐알콜(PVA)을 물에 녹여 만든 8% 용액 340g, 5% 소디움 디크로메이트(SDC) 63g, 접착력 보강제인 소르비탄 모노 라우레이트(SLS) 5% 용액 7g, 소포제인 프로필렌 옥사이드 에틸렌 옥사이드 계면활성제(PES) 5% 용액 6g, 녹색 형광체 320g과 순수 430g을 혼합하여 슬러리를 제조하였다. 제조한 슬러리를 블랙 매트릭스가 형성된 패널에 스핀 도포하고, 110℃로 설정된 히터에서 2분간 회전 건조하였다. 고압 수은등으로 조도 100mW/㎠에서 30초간 노광한 후, 40℃의 고압 순수를 이용하여 30초간 현상하였다. 현상 후 110℃로 설정된 히터에서 2분간 회전 건조시켜 폭 120㎛의 녹색 형광막을 형성하였다.340g of 8% solution made by dissolving polyvinyl alcohol (PVA) in water, 63g of 5% sodium dichromate (SDC), 7g of sorbitan mono laurate (SLS) 5g solution A slurry was prepared by mixing 6 g of phosphorus propylene oxide ethylene oxide surfactant (PES) 5% solution, 320 g of green phosphor, and 430 g of pure water. The prepared slurry was spin-coated on a panel on which a black matrix was formed, and it was spin-dried for 2 minutes by the heater set to 110 degreeC. After exposing for 30 seconds at the illumination intensity of 100 mW / cm <2> with a high pressure mercury lamp, it developed for 30 second using the high pressure pure water of 40 degreeC. After the development, rotation drying was performed for 2 minutes in a heater set at 110 ° C. to form a green fluorescent film having a width of 120 μm.
청색 형광막과 적색 형광막도 상기와 동일한 방법으로 폭 120㎛의 형광막을 각각 형성하였다. In the blue fluorescent film and the red fluorescent film, a fluorescent film having a width of 120 µm was formed in the same manner as described above.
(비교예 2)(Comparative Example 2)
소디움 디크로메이트(SDC) 대신에 암모늄 디크로메이트(ADC)를 사용하였고 30초간 노광한 것을 제외하고는 비교예 1과 동일한 방법 및 동일한 노광량으로 폭 120㎛의 녹색, 청색 및 적색 형광막을 형성하였다. Ammonium dichromate (ADC) was used instead of sodium dichromate (SDC) and a green, blue and red fluorescent film having a width of 120 μm was formed in the same method and the same exposure amount as Comparative Example 1 except that the exposure was carried out for 30 seconds.
(비교예 3)(Comparative Example 3)
소디움 디크로메이트(SDC) 대신에 4,4'-디아조도벤잘아세토페논-2-설포네이트를 사용하였고 비교예 1과 동일한 방법을 실시하였으나 가교 반응이 제대로 일어 나지 않아 형광막을 형성하지 못하였다. Instead of sodium dichromate (SDC), 4,4'-diazobenzalacetophenone-2-sulfonate was used, and the same method as in Comparative Example 1 was carried out, but the crosslinking reaction did not occur properly, and thus a fluorescent film was not formed.
(비교예 4)(Comparative Example 4)
소디움 디크로메이트(SDC) 대신에 비닐아지도벤질리덴아세토페논술폰산알카리염을 사용하였고 비교예 1과 동일한 방법을 실시하였으나 가교 반응이 제대로 일어나지 않아 형광막을 형성하지 못하였다. Instead of sodium dichromate (SDC), vinyl azidobenzylideneacetophenonesulfonic acid alkali salt was used, and the same method as in Comparative Example 1 was carried out, but the crosslinking reaction did not occur properly, and thus a fluorescent film was not formed.
(비교예 5)(Comparative Example 5)
소디움 디크로메이트(SDC) 대신에 스틸바졸륨(SbQ)을 사용하고 35 초간 노광한 것을 제외하고는 비교예 1과 동일한 방법으로 폭 120㎛의 녹색, 청색 및 적색 형광막을 형성하였다.A green, blue, and red fluorescent film having a width of 120 μm was formed in the same manner as in Comparative Example 1 except that steel barzolium (SbQ) was used instead of sodium dichromate (SDC) and exposed for 35 seconds.
상기한 실시예를 통하여 합성된 중합체를 이용하여 형광막을 형성하는 과정에 필요한 노광 시간과 비교예에서 필요한 노광 시간을 서로 비교하여 표 1에 나타내었다. Table 1 compares the exposure time required for the process of forming the fluorescent film using the polymer synthesized through the above example and the exposure time required in the comparative example.
표 1에 나타난 바와 같이, 실시예 6 내지 10에서 합성한 화학식 2 내지 6의 중합체를 포함하는 포토레지스트 조성물을 이용하여 형광막을 제조하는 공정에 필요로 하는 노광 시간이 비교예 1 내지 5에서 제조한 포토레지스트 조성물을 이용하 여 형광막을 제조하는 공정에 필요로하는 노광 시간보다 감소함을 알 수 있다. 이는 단축된 노광 시간 만큼 감도가 향상되었다는 것을 의미한다.As shown in Table 1, the exposure time required for the process of producing a fluorescent film using the photoresist composition comprising the polymer of Formulas 2 to 6 synthesized in Examples 6 to 10 was prepared in Comparative Examples 1 to 5 It can be seen that the exposure time required for the process of manufacturing the fluorescent film using the photoresist composition is reduced. This means that the sensitivity is improved by the shorter exposure time.
본 발명에 따른 신규의 합성 중합체를 이용하여 슬러리를 제조하여 형광막을 형성하는 경우, 광산 발생제에 의한 화학증폭형 방식으로 가교 밀도가 높고, 노광부와 비노광부의 현상액에 대한 용해도의 차가 매우 커서 감도가 우수한 형광막을 얻을 수 있고, 상기 슬러리는 온도와 습도에 영향을 받지 않으므로 암반응이 진행되지 않으므로 보관 안정성도 우수하며 또한 환경오염물질인 크롬 등의 중금속을 함유하지 않아 환경친화적인 포토레지스트 조성물을 얻을 수 있다.
When the slurry is prepared by using the novel synthetic polymer according to the present invention to form a fluorescent film, the crosslinking density is high by a chemical amplification method using a photoacid generator, and the difference in solubility in the developer of the exposed part and the non-exposed part is very large. It is possible to obtain a fluorescent film having excellent sensitivity, and since the slurry is not affected by temperature and humidity, the dark reaction does not proceed, so the storage stability is excellent and it does not contain heavy metals such as chromium, which is an environmental pollutant. You can get it.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010048308A KR100759442B1 (en) | 2001-08-10 | 2001-08-10 | Photoresist polymer and photoresist composition and phosphor composition comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010048308A KR100759442B1 (en) | 2001-08-10 | 2001-08-10 | Photoresist polymer and photoresist composition and phosphor composition comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20030013997A KR20030013997A (en) | 2003-02-15 |
| KR100759442B1 true KR100759442B1 (en) | 2007-10-04 |
Family
ID=27718706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020010048308A KR100759442B1 (en) | 2001-08-10 | 2001-08-10 | Photoresist polymer and photoresist composition and phosphor composition comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100759442B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011145881A2 (en) * | 2010-05-18 | 2011-11-24 | 한국과학기술원 | Method for producing an anti-forgery label using a randomly distributed pattern of fine particles formed on a variety of substrates, and method for determining the authenticity of the label |
| KR101180640B1 (en) * | 2010-05-18 | 2012-09-18 | 한국과학기술원 | Fluorescence pattern of the fluorescent dye incorporated photo-crosslinkable photoresiet |
| KR101210904B1 (en) * | 2012-03-07 | 2012-12-11 | 한국과학기술원 | Fluorescence pattern of the fluorescent dye incorporated photo-crosslinkable photoresiet |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970027127A (en) * | 1995-11-28 | 1997-06-24 | 윤덕용 | Vinyl 4-t-butoxycarbonyloxybenzal-vinyl alcohol-vinyl acetate copolymer and vinyl 4-t-butoxycarbonyloxybenzal-vinyl 4-hydroxybenzal-vinyl alcohol-vinyl acetate copolymer and a manufacturing method thereof |
| KR19980060833A (en) * | 1996-12-31 | 1998-10-07 | 손욱 | Photosensitive resin composition and method for forming fluorescent film pattern using the same |
| KR20000056474A (en) * | 1999-02-22 | 2000-09-15 | 김영환 | Novel photoresist crosslinker and photoresist composition using the same |
| KR20010043752A (en) * | 1998-05-27 | 2001-05-25 | 데머 얀, 당코 제니아 떼. | Water soluble negative-working photoresist composition |
-
2001
- 2001-08-10 KR KR1020010048308A patent/KR100759442B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970027127A (en) * | 1995-11-28 | 1997-06-24 | 윤덕용 | Vinyl 4-t-butoxycarbonyloxybenzal-vinyl alcohol-vinyl acetate copolymer and vinyl 4-t-butoxycarbonyloxybenzal-vinyl 4-hydroxybenzal-vinyl alcohol-vinyl acetate copolymer and a manufacturing method thereof |
| KR19980060833A (en) * | 1996-12-31 | 1998-10-07 | 손욱 | Photosensitive resin composition and method for forming fluorescent film pattern using the same |
| KR20010043752A (en) * | 1998-05-27 | 2001-05-25 | 데머 얀, 당코 제니아 떼. | Water soluble negative-working photoresist composition |
| KR20000056474A (en) * | 1999-02-22 | 2000-09-15 | 김영환 | Novel photoresist crosslinker and photoresist composition using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011145881A2 (en) * | 2010-05-18 | 2011-11-24 | 한국과학기술원 | Method for producing an anti-forgery label using a randomly distributed pattern of fine particles formed on a variety of substrates, and method for determining the authenticity of the label |
| WO2011145881A3 (en) * | 2010-05-18 | 2012-04-19 | 한국과학기술원 | Method for producing an anti-forgery label using a randomly distributed pattern of fine particles formed on a variety of substrates, and method for determining the authenticity of the label |
| KR101180640B1 (en) * | 2010-05-18 | 2012-09-18 | 한국과학기술원 | Fluorescence pattern of the fluorescent dye incorporated photo-crosslinkable photoresiet |
| KR101210904B1 (en) * | 2012-03-07 | 2012-12-11 | 한국과학기술원 | Fluorescence pattern of the fluorescent dye incorporated photo-crosslinkable photoresiet |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030013997A (en) | 2003-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5075199A (en) | Radiation sensitive mixture and production of relief patterns | |
| CA1334059C (en) | Radiation sensitive mixture and production of relief patterns | |
| US5807657A (en) | Polyvinyl alcohol base photosensitive resin, photosensitive composition, and method for pattern-formation using the same | |
| US5213946A (en) | Positive type, photosensitive resinous composition | |
| JP2628692B2 (en) | Pattern forming method and color cathode ray tube manufacturing method | |
| KR20020077948A (en) | Monomer for photoresist, polymer for photoresist, photoresist composition and phosphor composition for color cathode ray tube | |
| KR100759442B1 (en) | Photoresist polymer and photoresist composition and phosphor composition comprising the same | |
| US6140018A (en) | Photosensitive resin and composition thereof derived from saponified poly(vinyl acetate) and pattern formation method | |
| JPH05113661A (en) | Photosensitive composition, pattern forming method using the same, and formation of fluorescent screen | |
| AU772375B2 (en) | Photosensitive compounds, photosensitive resin compositions, and pattern formation method making use of the compounds or compositions | |
| JP2643155B2 (en) | Photosensitive composition and pattern forming method using the same | |
| JPH09185163A (en) | Water-soluble photosensitive resin composition and method for forming black matrix pattern using the same | |
| KR20030035005A (en) | Polymer for chemical amplification negative photoresist and photoresist composition | |
| JPH0426849A (en) | Watersoluble photosensitive compound, method for synthesizing same, photosensitive composition, and pattern forming method | |
| KR100450215B1 (en) | Method for forming fluorescent film and slurry for adhesive strength increasing fluorescent film, especially including fluorescent film slurry | |
| KR100869783B1 (en) | Acrylic monomer and polymer comprising azide group for negative photoresist | |
| JPH0292905A (en) | Photosensitive compound and pattern formation using the compound | |
| JPS60156785A (en) | Pattern formation | |
| JP3507221B2 (en) | Polyvinyl alcohol-based photosensitive resin composition and pattern forming method using the same | |
| KR100380663B1 (en) | Photosensitive compounds, photosensitive resin compositions, and pattern formation method making use of the compounds or compositions | |
| JPH09120159A (en) | Water-soluble photosensitive resin composition and black matrix pattern forming method using the same | |
| JP3351739B2 (en) | Water-soluble negative photosensitive composition and method for forming black matrix pattern using the same | |
| JP3660455B2 (en) | Photopolymerizable composition and pattern forming method using the same | |
| JPH05216219A (en) | Photosensitive composition and method for forming pattern by using same | |
| JPH05197141A (en) | Forming method for photosensitive composition and pattern using the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20100826 Year of fee payment: 4 |
|
| LAPS | Lapse due to unpaid annual fee |