KR100427263B1 - Calix derivatives as Photoactive compounds - Google Patents
Calix derivatives as Photoactive compounds Download PDFInfo
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- KR100427263B1 KR100427263B1 KR10-2001-0014180A KR20010014180A KR100427263B1 KR 100427263 B1 KR100427263 B1 KR 100427263B1 KR 20010014180 A KR20010014180 A KR 20010014180A KR 100427263 B1 KR100427263 B1 KR 100427263B1
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/76—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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Abstract
본 발명은 감광제로 유용한 칼릭스 유도체에 관한 것으로서, 더욱 상세하게는 다음 화학식 1의 치환기로서 다이아조 나프토퀴논 술포닐(NQD, Diazo naphthoquinone sulfonyl)기가 치환되어 있으며, 노광시 감도가 우수하여 PS 판용 감광제로서 유용한 다음 화학식 1로 표시되는 칼릭스 유도체에 관한 것이다.
상기 화학식 1에서, R1, R2및 R3은 각각 발명의 상세한 설명에서 정의한 바와 같다.In Formula 1, R 1 , R 2 and R 3 are each as defined in the detailed description of the invention.
Description
본 발명은 감광제로 유용한 칼릭스 유도체에 관한 것으로서, 더욱 상세하게는 다음 화학식 1의 치환기로서 다음 화학식 2로 표시되는 다이아조 나프토퀴논 술포닐(Diazo naphthoquinone sulfonyl)기가 치환되어 있으며, 노광시 감도가 우수하여 PS 판용 감광제로서 유용한 다음 화학식 1로 표시되는 칼릭스 유도체에 관한 것이다. 본 발명에 따른 다음 화학식 1로 표시되는 칼릭스 유도체는 고 감도 및 우수한 분해능을 가지고 있어, PS(예비감광)판, 인쇄회로기판, 컬러 음극선관 및 다른 디스플레이관, 스크린인쇄 및 미세화상용 포토레지스트를 포함한 광범위한 영역에서 감광제로서 유용하게 사용될 수 있다.[화학식 1]상기 화학식 1에서, R1은 -OH 또는 다음 화학식 2의 다이아조 나프토퀴논 술포닐기이며, 적어도 하나 이상의 R1은 다이아조 나프토퀴논 술포닐기로 치환되어 있고, R2는 -NO2, -Cl, -F 또는 -CN 이고, R3는 -OH 또는 -H 이다.
일반적으로 PS 판 제조시 감광막을 형성하는 방법은 알루미늄판 위에 감광액을 도포하여 감광층을 형성한 후 자외선에 의해 화상을 형성시키고 이어 알칼리 현상액을 이용하여 미 반응 부분을 제거함으로써 망점을 형성한다. 이때 자외선에 감광된 부위가 현상액에 용해되는지의 여부에 따라 양각형과 음각형으로 나눌 수 있다. 광 조사된 부분이 가교 또는 중합반응이 일어나 현상 시 현상액에 용해되지 않는 형태를 음각형이라고 하고, 이와는 반대로 광 조사된 부분이 분해되어 현상액에 용해되는 형태를 양각형 감광성 수지라 한다.In general, a method of forming a photoresist film in manufacturing a PS plate forms a photoresist by applying a photoresist on an aluminum plate to form a photoresist, followed by forming an image by ultraviolet light, and then removing an unreacted portion using an alkaline developer to form a dot. At this time, it can be divided into an embossed form and an embossed form depending on whether the site exposed to ultraviolet rays is dissolved in the developer. The form in which the light irradiated portion does not dissolve in the developer when developing due to crosslinking or polymerization reaction is called an intaglio type. On the contrary, the form in which the light irradiated portion is decomposed and dissolved in the developer is called embossed photosensitive resin.
대부분의 양각형 감광성 수지는 알칼리 용해성 수지와 감광성 화합물 및 용매의 혼합물로써 제조된다.Most embossed photosensitive resins are prepared as a mixture of alkali soluble resins, photosensitive compounds and solvents.
감광성 화합물은 비노광 부위의 알카리 용액에 대한 용해 억제제로서 작용하고, 광원에 노출되면 감광성 화합물 자체가 현상액에 대하여 용해성 물질로 변환된다. 종래 대부분의 양각형 감광성 수지 조성물들은 막 형성 성분으로서 알카리 가용성 노블락 수지와 광분해 성분으로서 퀴논디아자이드 화합물을 혼합하여 사용하였다. 일반적 형태의 인쇄판용 감광성 조성물로 o-퀴논 디아지드 또는 p-퀴논 디아지드 화합물, 나프토퀴논 디아자이드술폰산 및 1 개 이상의 페놀성 수산기를 가지는 화합물간에 생성되는 술폰산 에스테르류와 에스테르류가 있다. 감광성 수지 조성물 중의 막 형성 성분으로서 전형적인 것으로서는 알카리 가용성 노블락 수지가 있으며 페놀-포름알데히드 노블락 수지와 크레졸 노블락 수지를 비롯한 각종의 노블락 수지들이 제안되어 있다.The photosensitive compound acts as a dissolution inhibitor for the alkali solution at the non-exposed site, and upon exposure to a light source, the photosensitive compound itself is converted into a soluble material for the developer. Most of the conventional embossed photosensitive resin compositions were used by mixing an alkali soluble noblock resin as a film forming component and a quinone diazide compound as a photolysis component. Typical types of photosensitive compositions for printing plates include sulfonic acid esters and esters produced between o-quinone diazide or p-quinone diazide compounds, naphthoquinone diazide sulfonic acid and compounds having at least one phenolic hydroxyl group. Typical examples of the film-forming component in the photosensitive resin composition include alkali-soluble noblock resins and various noblock resins have been proposed, including phenol-formaldehyde noblock resins and cresol noblock resins.
또한, 크레졸 노블락 수지의 제조에 사용되는 크레졸 이성체들의 비율을 적당히 선택함으로써 막 형성 성분으로서의 크레졸 노블락 수지로 구성되는 포지티브형 감광성 수지 조성물의 물성을 개선한 예가 일본특허공보 소45-9610호에 기술되어 있다.Further, an example of improving the physical properties of the positive photosensitive resin composition composed of the cresol noblock resin as the film forming component by appropriately selecting the proportion of the cresol isomers used in the production of the cresol noblock resin is described in Japanese Patent Publication No. 45-9610. have.
그러나, 상기 퀴논 디아지드류를 단독으로 사용하는 감광성 조성물에서는 결정이 석출되므로 화상이 기계적 강도가 약해지고 많은 인쇄를 하기가 어려운 문제점이 있다. 또한 망점의 크기가 수 미크론 이하로 내려가면서 망점 둘레 부분의 현상성이 나빠져 해상도가 저하되는 문제가 있다. 특히 감광성 수지를 사용하여 2 미크론 이하의 망점을 형성할 때에는 이러한 점이 큰 장해 요인이 된다.However, in the photosensitive composition using the quinone diazide alone, crystals are precipitated, so that the image is weak in mechanical strength and difficult to print a lot. In addition, as the size of the dot is lowered to a few microns or less, there is a problem that the developability of the portion around the dot is deteriorated and the resolution is reduced. In particular, when forming a dot of 2 microns or less using a photosensitive resin, such a point becomes a major obstacle.
본 발명은 다이아조 나프토퀴논 술포닐(Diazo naphthoquinone sulfonyl)기가 치환되어 있으며, 노광시 감도가 우수하므로 다음 화학식 1로 표시되는 칼릭스 유도체를 PS 판용 감광제로 사용하는 용도를 제공하는데 그 목적이 있다.The present invention is a diazo naphthoquinone sulfonyl (substituted diazo naphthoquinone sulfonyl) group is substituted, and excellent sensitivity during exposure, it is an object to provide a use of the Kalix derivative represented by the following formula (1) as a photosensitive agent for PS plate .
본 발명은 다음 화학식 1로 표시되는 칼릭스 유도체를 PS판용 감광제로 사용하는 용도를 그 특징으로 한다.The present invention is characterized by the use of the Kalix derivative represented by the following Chemical Formula 1 as a photosensitive agent for PS plates.
[화학식 1][Formula 1]
상기 화학식 1에서, R1, R2및 R3은 각각 상기에서 정의한 바와 같다. In Chemical Formula 1, R 1 , R 2, and R 3 are each as defined above.
본 발명에 따른 상기 화학식 1로 표시되는 칼릭스 유도체에 있어, R3위치에 수소원자(-H)가 치환된 화합물은 칼릭스[4] 리소시아렌(Calix[4]resorcinarene)으로 명명하고, R3위치에 히드록시(-OH)기가 치환된 화합물은 칼릭스[4]피로갈렌(Calix[4]pyrogallene)으로 명명한다.또한, 본 발명에 따른 상기 화학식 1로 표시되는 칼릭스 유도체의 제조방법은 당 분야에서 널리 공지되어 있다[Contribution from the chemical laboratories of new york university, Vol 62. Sept., 1940, 2512∼2514; J. Org. Chem., 1980, Vol 45, 4498∼4500; J. Korean Ind. Eng. Chem., Vol. 10, No 8, December 1999, 1169∼1174]. 예컨대, 리소시놀과 해당 알데하이드 화합물간의 축합반응에 의해 칼릭스[4]리소시아렌과 칼릭스[4]피로갈렌을 합성한다. 그런 다음, 2-다이아조-1-나프토퀴논-5-술포닐 클로라이드(NQD-Cl)와의 에스테르화 반응시켜 부분적으로 다이아조 나프토퀴논 술포닐기가 치환되어 있는 본 발명의 칼릭스 유도체를 합성한다. 다이아조 나프토퀴논 술포닐기의 치환율은 NQD-Cl의 사용량으로서 충분히 조절이 가능하다. NQD의 치환율이 높을수록 수지와의 가교도가 증가하여 이미지를 형성할 수 있는 감광성 물질의 상대적인 양이 줄어들며, 감광성 물질의 양이 줄어들수록 감도와 내쇄력은 증가한다.이상에서 설명한 바와 같은, 상기 화학식 1로 표시되는 칼릭스 유도체의 제조방법은 다음의 합성예에 의거하여 더욱 상세히 설명하는 바, 본 발명이 이에 한정되는 것은 아니다.In the Kalix derivative represented by Chemical Formula 1 according to the present invention, a compound in which a hydrogen atom (-H) is substituted at the R 3 position is named Calix [4] lysocyrene (Calix [4] resorcinarene). A compound in which a hydroxy (-OH) group is substituted at the R 3 position is referred to as Calix [4] pyrogallene. In addition, according to the present invention, a preparation of a Kalix derivative represented by Chemical Formula 1 is provided. Methods are well known in the art [Contribution from the chemical laboratories of new york university, Vol 62. Sept., 1940, 2512-2514; J. Org. Chem., 1980, Vol 45, 4498-4500; J. Korean Ind. Eng. Chem., Vol. 10, No 8, December 1999, 1169-1174. For example, by the condensation reaction between lysosinol and the aldehyde compound, calix [4] lysocyanene and calix [4] pyrogalene are synthesized. Subsequently, esterification with 2-diazo-1-naphthoquinone-5-sulfonyl chloride (NQD-Cl) results in the synthesis of the calix derivative of the present invention in which the diazonaphthoquinone sulfonyl group is partially substituted. do. The substitution rate of the diazo naphthoquinone sulfonyl group can fully be controlled as the amount of NQD-Cl used. The higher the substitution rate of NQD, the higher the degree of crosslinking with the resin, so that the relative amount of the photosensitive material capable of forming an image decreases, and as the amount of the photosensitive material decreases, the sensitivity and the breaking strength increase. The method for preparing the calix derivative represented by 1 is described in more detail based on the following synthesis examples, but the present invention is not limited thereto.
합성예 1: 2-다이아조-1-나프토퀴논-5-술포닐 클로라이드(NQD-Cl)의 합성Synthesis Example 1 Synthesis of 2-diazo-1-naphthoquinone-5-sulfonyl chloride (NQD-Cl)
상기 화학식 1로 표시되는 칼릭스 유도체의 치환기로서 상기 화학식 2의 작용기를 도입하는데 사용되는 물질인 2-다이아조-1-나프토퀴논-5-술포닐 클로라이드(NQD-Cl)의 합성 방법은 다음과 같다.Synthesis method of 2-diazo-1-naphthoquinone-5-sulfonyl chloride (NQD-Cl) which is a substance used to introduce the functional group of Chemical Formula 2 as a substituent of the Kalix derivative represented by Chemical Formula 1 is as follows. Same as
클로로술포닉 산 1000 g을 2000 ㎖ 플라스크에 넣고 7 ℃ 까지 충분히 냉각한다. 이곳에 150 g의 나트륨-2-다이아조-1-나프토퀴논-5-술포네이트를 천천히 넣고 58 ℃ 에서 12시간 동안 환류시키면서 반응한다. 반응물을 상온으로 냉각하고 5 ℓ의 얼음물에 천천히 넣는다. 생성된 침전을 필터링한 후 차가운 증류수로 씻어주고 감압 건조하여 노란색의 파우더를 얻었다.1000 g of chlorosulfonic acid are placed in a 2000 ml flask and cooled sufficiently to 7 ° C. 150 g of sodium-2-diazo-1-naphthoquinone-5-sulfonate was slowly added thereto and reacted at 58 ° C. under reflux for 12 hours. Cool the reaction to room temperature and slowly add to 5 L of ice water. The resulting precipitate was filtered and washed with cold distilled water and dried under reduced pressure to obtain a yellow powder.
합성예 2: 칼릭스[4]리소시아렌(Calix[4]resorcinarene)(R1=OH, R2=NO2, R3=H)의 합성Synthesis Example 2 Synthesis of Calix [4] resorcinarene (R 1 = OH, R 2 = NO 2 , R 3 = H)
상기 화학식 3으로 표시되는 리소시놀 10 g과 상기 화학식 4로 표시되는 3-니트로벤젠알데하이드 13.7 g을 200 ㎖ 메탄올과 함께 500 ㎖ 플라스크에 넣고 교반하면서 환류시킨 후, 25 ㎖의 염산을 천천히 넣어 준다. 그 후 6시간 동안 환류를 하고 상온으로 냉각한 후 용액을 천천히 물에 넣어 생성된 침전을 걸러내고 감압 건조하여 칼릭스[4]리소시아렌을 얻었다.10 g of lysosinol represented by the formula (3) and 13.7 g of 3-nitrobenzenealdehyde represented by the formula (4) were added to a 500 ml flask with 200 ml of methanol, refluxed with stirring, and 25 ml of hydrochloric acid was slowly added thereto. . Thereafter, the mixture was refluxed for 6 hours, cooled to room temperature, and the solution was slowly poured into water to filter out the precipitate formed and dried under reduced pressure to obtain Calix [4] lysocyanene.
합성예 3: 칼릭스[4]피로갈렌(Calix[4]pyrogallene) (R1=OH, R2=NO2, R3=OH)의 합성Synthesis Example 3 Synthesis of Calix [4] pyrogallene (R 1 = OH, R 2 = NO 2 , R 3 = OH)
상기 화학식 5로 표시되는 피로갈렌 10 g과 상기 화학식 4로 표현되는 3-니트로벤젠알데하이드 12 g을 200 ㎖ 메탄올과 함께 500 ㎖ 플라스크에 넣고 교반하면서 환류를 시킨 후, 25 ㎖의 염산을 천천히 넣어준다. 그 후 6시간 동안 환류를 하고 상온으로 냉각한 후 용액을 천천히 물에 넣어 생성된 침전을 걸러내고 감압 건조하여 칼릭스[4]피로갈렌을 얻었다.10 g of pyrogalene represented by Formula 5 and 12 g of 3-nitrobenzenealdehyde represented by Formula 4 were added to a 500 ml flask with 200 ml of methanol, refluxed while stirring, and 25 ml of hydrochloric acid was slowly added thereto. . Thereafter, the mixture was refluxed for 6 hours, cooled to room temperature, and the solution was slowly poured into water to filter out the precipitate formed and dried under reduced pressure to obtain Calix [4] pyrogalene.
합성예 4: 칼릭스[4]리소시아렌 비스[다이아조-2,1,5] (Calix[4]resorcinarene bis[Diazo-2,1,5]) (R1=OH와 다이아조 나프토퀴논 술포닐기의 조합, R2=NO2, R3=H)의 합성Synthesis Example 4 Calix [4] lysocyanene bis [diazo-2,1,5] (Calix [4] resorcinarene bis [Diazo-2,1,5]) (R 1 = OH and diazo naphtho Combination of quinone sulfonyl groups, R 2 = NO 2 , R 3 = H)
상기 합성예 2에서 합성한 칼릭스[4]리소시아렌과 상기 합성예 1에서 합성한 2-다이아조-1-나프토퀴논-5-술포닐 클로라이드(NQD-Cl)를 THF에 넣고 5분간 교반한 후, 20 중량%의 탄산나트륨에 천천히 넣어준다. 이때 넣어주는 속도를 적절히 조절하여 pH가 9가 되도록 한다. 반응시간은 1시간이며 헥산에 넣어서 침전을 얻으며 감압건조하여 칼릭스[4]리소시아렌 비스[다이아조-2,1,5]를 얻었다.The calix [4] lysiarene synthesized in Synthesis Example 2 and 2-diazo-1-naphthoquinone-5-sulfonyl chloride (NQD-Cl) synthesized in Synthesis Example 1 were added to THF for 5 minutes. After stirring, slowly add to 20% by weight sodium carbonate. At this time, adjust the rate to put properly so that the pH is 9. The reaction time was 1 hour, and the resultant was put in hexane to obtain a precipitate, and dried under reduced pressure to obtain Calix [4] lysocyanene bis [diazo-2,1,5].
이와 동일한 방법으로 칼릭스[4]리소시아렌과 2-다이아조-1-나프토퀴논-5-술포닐 클로라이드(NQD-Cl)의 양을 변화하여 다양한 치환비율을 가진 칼릭스 유도체를 합성하였으며 결과는 다음 표 1과 같다.다음 표 1은 칼릭스[4]리소시아렌 한 분자당 존재하게 되는 8개의 히드록시기 중 5 내지 7 개를 NQD로 치환하여 얻어진 칼릭스 유도체의 제조수율을 나타낸 것이다.In the same way, the calix derivatives having various substitution ratios were synthesized by varying the amounts of calix [4] lysiarene and 2-diazo-1-naphthoquinone-5-sulfonyl chloride (NQD-Cl). The results are shown in Table 1 below. Table 1 shows the production yields of the Kalix derivatives obtained by substituting NQD for 5 to 7 of the 8 hydroxyl groups present per molecule of Kalix [4] lysocyanene.
합성예 5: 칼릭스[4]피로갈렌 비스[다이아조-2,1,5] (Calix[4]pyrogallene bis[Diazo-2,1,5]) (R1=OH와 다이아조 나프토퀴논 술포닐기의 조합, R2=NO2, R3=OH)의 합성Synthesis Example 5 Calix [4] pyrogallene bis [Diazo-2,1,5]) (R 1 = OH and diazo naphthoquinones) Combination of sulfonyl groups, R 2 = NO 2 , R 3 = OH)
화학식 1에서 R1=[화학식 2로 부부적으로 치환되어 있는 -OH], R2=NO2, R3=OH 가 각각 치환된 칼릭스[4]피로갈렌 비스[다이아조-2,1,5] (Calix[4]pyrogallene bis[Diazo-2,1,5])는 다음과 같이 합성한다.In formula (1), R 1 = [-OH which is covalently substituted with Formula 2, R 2 = NO 2 , and R 3 = OH are each substituted with carlix [4] pyrogalene bis [diazo-2,1, 5] (Calix [4] pyrogallene bis [Diazo-2,1,5]) is synthesized as follows.
상기 합성예 3에서 칼릭스[4]피로갈렌과 상기 합성예 1에서 합성한 2-다이아조-1-나프토퀴논-5-술포닐 클로라이드(NQD-Cl)를 THF에 넣고 5분간 교반한 후, 20 중량%의 탄산나트륨에 천천히 넣어준다. 이때 넣어주는 속도를 적절히 조절하여 pH가 9가 되도록 한다. 반응시간은 1시간이며 헥산에 넣어서 침전을 얻으며 감압건조하여 칼릭스[4]피로갈렌 비스[다이아조-2,1,5]를 얻었다.After putting Calix [4] pyrogalene in Synthesis Example 3 and 2-diazo-1-naphthoquinone-5-sulfonyl chloride (NQD-Cl) synthesized in Synthesis Example 1 into THF and stirring for 5 minutes Slowly add 20% sodium carbonate. At this time, adjust the rate to put properly so that the pH is 9. The reaction time was 1 hour, and the resultant was put into hexane to obtain a precipitate, and dried under reduced pressure to obtain Calix [4] pyrogallene bis [diazo-2,1,5].
이와 동일한 방법으로 칼릭스[4]피로갈렌과 2-다이아조-1-나프토퀴논-5-술포닐 클로라이드(NQD-Cl)의 양을 변화하여 다양한 치환비율을 가진 칼릭스 유도체를 합성하였으며 결과는 다음 표 2와 같다.다음 표 2는 칼릭스[4]피로갈렌 한 분자당 존재하게 되는 12개의 히드록시기 중 7 내지 11 개를 NQD로 치환하여 얻어진 칼릭스 유도체의 제조수율을 나타낸 것이다.In the same way, the amount of calix [4] pyrogalene and 2-diazo-1-naphthoquinone-5-sulfonyl chloride (NQD-Cl) was changed to synthesize a carlix derivative having various substitution ratios. Table 2 shows the production yields of the Kalix derivatives obtained by substituting NQD for 7 to 11 of 12 hydroxy groups present per molecule of Kalix [4] pyrogalene.
실시예 1.Example 1.
감광제로서 상기 합성예 4에서 제조한 칼릭스[4]리소시아렌 비스[다이아조-2,1,5]와 노볼락 레진을 각각 100 g 및 400 g, 그리고 염료(green dye) 0.1 g을 혼합하고 용매인 메틸 셀로솔브에 넣고 용융시켜 감광성 수지조성물을 제조하고 여과하였다.As a photosensitizer, 100 g, 400 g of novolak resin and 0.1 g of green dye were mixed with calix [4] lysocyanene bis [diazo-2,1,5] prepared in Synthesis Example 4, respectively. The mixture was added to a methyl cellosolve as a solvent and melted to prepare a photosensitive resin composition and filtered.
상기 제조된 감광액을 표면이 연마된 알루미늄판에 도포하여 120 ℃에서 60초간 건조하면 PS판이 제조된다.The prepared photoresist is applied to an aluminum plate having a polished surface, and dried at 120 ° C. for 60 seconds to produce a PS plate.
상기 제조된 PS판의 감광면에 양각형 원화를 밀착시킨 후 노광시키고 110 ℃에서 60초간 베이킹한 후 현상하였다.An embossed original was brought into close contact with the photosensitive surface of the prepared PS plate, followed by exposure and baking at 110 ° C. for 60 seconds.
노광 시간에 따른 상대적인 감도는 다음 표 3과 같다.The relative sensitivity according to the exposure time is shown in Table 3 below.
a = 최적의 노광시간에서의 step numbera = step number at optimum exposure time
b = 동일한 노광시간(50초)에서의 step numberb = step number at the same exposure time (50 seconds)
c =[화학식 6]c = [Formula 6]
-화학식 6-Formula 6-
실시예 2.Example 2.
감광제로서 상기 합성예 5에서 제조한 칼릭스[4]피로갈렌 비스[다이아조-2,1,5]와 노볼락 레진을 각각 100 g 및 400 g, 그리고 염료(green dye) 0.1 g을 혼합하고 용매인 메틸 셀로솔브에 넣고 용융시켜 감광성 수지조성물을 제조하고 여과하였다.100 g and 400 g of novolak resin and 0.1 g of green dye were respectively mixed with Calix [4] pyrogalene bis [diazo-2,1,5] and novolac resin prepared in Synthesis Example 5 as a photosensitizer. It was put in a methyl cellosolve as a solvent and melted to prepare a photosensitive resin composition and filtered.
상기 제조된 감광액을 표면이 연마된 알루미늄판에 도포하여 120 ℃에서 60초간 건조하면 PS판이 제조된다.The prepared photoresist is applied to an aluminum plate having a polished surface, and dried at 120 ° C. for 60 seconds to produce a PS plate.
상기 제조된 PS판의 감광면에 양각형 원화를 밀착시킨 후 노광시키고 110 ℃에서 60초간 베이킹한 후 현상하였다.An embossed original was brought into close contact with the photosensitive surface of the prepared PS plate, followed by exposure and baking at 110 ° C. for 60 seconds.
노광 시간에 따른 상대적인 감도는 다음 표 4와 같다.The relative sensitivity according to the exposure time is shown in Table 4 below.
a = 최적의 노광시간에서의 step numbera = step number at optimum exposure time
b = 동일한 노광시간(50초)에서의 step numberb = step number at the same exposure time (50 seconds)
c =[화학식 6]c = [Formula 6]
본 발명에 따른 상기 화학식 1로 표시되는 칼릭스 유도체는 공지 합성방법에 의하여 용이하게 합성할 수 있고 고순도의 감광제를 쉽게 얻을 수 있다. 또한, 상기 화학식 1로 표시되는 칼릭스 유도체는 발라스트(ballast)로 작용하는 칼릭스[4]리소시렌 또는 칼릭스[4]피로갈렌으로 제조하는 바, 칼릭스[4]리소시렌 또는 칼릭스[4]피로갈렌은 각각 8 또는 12개의 수산화기를 가지고 있기 때문에 2-다이아조-1-나프토퀴논-5-술포닐 클로라이드를 넣어주는 양을 조절함으로써 쉽게 2-다이아조-1-나프토퀴논-5-술포닐기가 치환되는 비율을 조절 할 수 있으며, 이로 인해 용해도 조절이 매우 용이한 장점을 가지고 있다.본 발명에 따른 상기 화학식 1로 표시되는 칼릭스 유도체를 감광제로 사용하여 노광할 경우 기존의 상용화된 물질에 비하여 훨씬 높은 해상도를 나타내며 감도 또한 2배 이상 높이는 효과를 얻었다.따라서, 본 발명에 따른 상기 화학식 1로 표시되는 칼릭스 유도체는 제조하기 간편하고 용해성이 우수하므로, PS(예비감광)판, 인쇄회로기판, 컬러 음극선관 및 다른 디스플레이관, 스크린인쇄 및 미세화상용 포토레지스트에 감광제로서 응용 되어서는 도막을 형성한 후 결정이 석출되는 문제점을 해결 할 수 있다.The calyx derivative represented by Chemical Formula 1 according to the present invention can be easily synthesized by a known synthesis method, and a high purity photosensitive agent can be easily obtained. In addition, the calyx derivative represented by the formula (1) is made of calyx [4] lysorene or calix [4] pyrogalene acting as a ballast (ballast), barium [4] lysoxyrene or calix [ 4] Since pyrogalene has 8 or 12 hydroxyl groups, respectively, it is easy to control 2-diazo-1-naphthoquinone by controlling the amount of 2-diazo-1-naphthoquinone-5-sulfonyl chloride. It is possible to control the rate at which the 5-sulfonyl group is substituted, and thus has the advantage that the solubility is very easy to control. Exposed by using the Kalix derivative represented by the formula (1) according to the present invention as a photosensitive agent Compared to the commercially available materials, it has a much higher resolution and more than twice the sensitivity. Thus, the Kalix derivative represented by Chemical Formula 1 according to the present invention is easy to prepare and has excellent solubility. Therefore, when applied as a photosensitive agent in PS (preliminary photosensitive) plate, printed circuit board, color cathode ray tube and other display tube, screen printing and micro-image photoresist, it is possible to solve the problem that crystals are deposited after forming a coating film.
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| JPH11322656A (en) * | 1998-05-11 | 1999-11-24 | Jsr Corp | New calix arene derivative and calix resorcinarene derivative, and photosensitive composition |
| US6093517A (en) * | 1998-07-31 | 2000-07-25 | International Business Machines Corporation | Calixarenes for use as dissolution inhibitors in lithographic photoresist compositions |
| KR20020017023A (en) * | 2000-08-28 | 2002-03-07 | 주덕영 | Naphthoquinone-diazide calix ester photosensitive compounds and method for preparing them |
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| JPH11322656A (en) * | 1998-05-11 | 1999-11-24 | Jsr Corp | New calix arene derivative and calix resorcinarene derivative, and photosensitive composition |
| US6093517A (en) * | 1998-07-31 | 2000-07-25 | International Business Machines Corporation | Calixarenes for use as dissolution inhibitors in lithographic photoresist compositions |
| KR20020017023A (en) * | 2000-08-28 | 2002-03-07 | 주덕영 | Naphthoquinone-diazide calix ester photosensitive compounds and method for preparing them |
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