KR20030018153A - Acid sensitive Polyamides having a crosslinkable end group, and heat-resistant photoresist composition therefrom - Google Patents

Acid sensitive Polyamides having a crosslinkable end group, and heat-resistant photoresist composition therefrom Download PDF

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KR20030018153A
KR20030018153A KR1020010051727A KR20010051727A KR20030018153A KR 20030018153 A KR20030018153 A KR 20030018153A KR 1020010051727 A KR1020010051727 A KR 1020010051727A KR 20010051727 A KR20010051727 A KR 20010051727A KR 20030018153 A KR20030018153 A KR 20030018153A
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acid
polymer
sensitive
polyamide
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KR100435517B1 (en
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진문영
최길영
김대겸
박동원
오재민
이무영
동현수
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한국화학연구원
제일모직주식회사
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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • 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
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Abstract

PURPOSE: An acid liable polyamide polymer and a photosensitive heat resisting insulator composition containing the polymer are provided, which are improved in the photosensitivity, the resolution, the mechanical properties and the flatness of coating. CONSTITUTION: The acid liable polyamide polymer has a repeating unit represented by the formula 1, and contains an acetal or carbonate side group as an acid liable group and a terminal group containing an acetylene group, wherein Ar1 is a tetravalent aromatic group; Ar2 is a divalent aromatic group; R1 and R2 are the same or different each other and are an acid liable group comprising carbonate or acetal; T1 and T2 are the same or different each other and are a terminal group comprising acetylene group; and m and n are an integer of 5-100, respectively. The acid liable polyamide polymer can be a homopolymer or a copolymer according to the combination of Ar1 and Ar2. The photosensitive heat resisting insulator composition comprises the polyamide polymer; and 0.3-15 wt% of a photoacid generator.

Description

가교 가능한 말단기를 가지는 산민감성 폴리아미드 중합체와 이를 포함하는 감광성 내열절연체 조성물{Acid sensitive Polyamides having a crosslinkable end group, and heat-resistant photoresist composition therefrom}Acid sensitive polyamide polymer having a crosslinkable end group and a photosensitive heat-insulating composition comprising the same {Acid sensitive polyamides having a crosslinkable end group, and heat-resistant photoresist composition therefrom}

본 발명은 가교 가능한 말단기를 가지는 산민감성 폴리아미드 중합체와 이를 포함하는 감광성 내열절연체 조성물에 관한 것으로, 더욱 상세하게는 아세탈 또는 카르보네이트기를 측쇄로 가지며 중합체 말단에 가교가 가능한 아세틸렌기를 포함하는 특수구조의 산민감성 폴리아미드 중합체와, 상기한 신규의 산민감성 폴리아미드 중합체와 광산발생제가 함유된 감광성 내열절연체 조성물에 관한 것이다.The present invention relates to an acid-sensitive polyamide polymer having a crosslinkable end group and a photosensitive heat-insulator composition comprising the same. More particularly, the present invention relates to a special polymer comprising an acetal or carbonate group as a side chain and including an acetylene group capable of crosslinking at the polymer end. A photosensitive heat resistant insulator composition containing an acid sensitive polyamide polymer having a structure and the above-described novel acid sensitive polyamide polymer and a photoacid generator.

내열절연체는 반도체의 패시베이션 막(passivation layer), 완충막(buffer coat) 또는 복합 다층인쇄회로기판의 층간 절연막 형성을 목적으로 사용되고 있다. 또한, 상하층의 전기적 연결 또는 다층배선을 위해 내열절연체의 박막 위에 다시 포토레지스트 코팅, 프리베이크(prebake), UV 조사, 현상, 에칭, 탈막 등과 같은 복잡한 리소(lithography) 공정을 행하고 있다.Heat-resistant insulators have been used for the purpose of forming interlayer insulating films of passivation layers, buffer coats or composite multilayer printed circuit boards of semiconductors. In addition, a complicated lithography process such as photoresist coating, prebake, UV irradiation, development, etching, film removal, etc., is performed again on the thin film of the heat resistant insulator for electrical connection of the upper and lower layers or multilayer wiring.

그러나, 내열절연체의 박막재료가 감광기를 보유하게 되면, 상기한 바와 같은 포토레지스트 공정 없이 내열절연층 제막 공정시 전기적 연결에 필요한 구멍의 제조가 가능하여 공정이 대폭 단순화될 수 있으며, 또한, 사용 레지스트 및 화학약품 사용량의 저감, 공정 단축 등으로 생산성의 증가가 가능하다. 그리고 리소공정에서 재현된 패턴이 내열절연체의 에칭공정을 수행함으로써 발생하게 되는 재현성과 해상력의 떨어짐도 방지할 수 있다. 그러므로, 포토레지스트의 기능과 내열절연체 기능을 복합화한 감광성 내열절연체를 사용한다면 공정을 대폭 단순화시킬 수 있다.However, if the thin film material of the heat resistant insulator has a photosensitive device, it is possible to manufacture the holes necessary for the electrical connection in the heat resistant insulation film forming process without the photoresist process as described above, and the process can be greatly simplified, and the resist used And productivity can be increased by reducing the amount of chemicals used, process shortening, and the like. In addition, it is possible to prevent the reproducibility and resolution degradation caused by the pattern reproduced in the litho process by performing the etching process of the heat resistant insulator. Therefore, the process can be greatly simplified by using the photosensitive heat resistant insulator which combines the function of the photoresist and the heat resistant insulator.

한편, 포토레지스트의 경우 노광, 현상, 에칭 등의 패턴형성 공정이 끝난 후에 탈막시켜 제거하게 되지만, 감광성 내열절연체의 경우는 영구히 반도체 소자 내에 존재하게 되기 때문에 감광성, 해상력, 투명성, 현상성 등의 감광기능 재료로서의 특성들과 함께 절연, 내열, 기계, 저유전 특성 등과 같은 반도체 및 전자 공정재료로서 요구되는 특성이 함께 요구된다.On the other hand, the photoresist is removed by removing the film after the pattern forming process such as exposure, development, etching, etc., but the photosensitive heat insulator is permanently present in the semiconductor element, so the photosensitive, resolution, transparency, developability, etc. Along with the properties as functional materials, properties required as semiconductor and electronic processing materials such as insulation, heat resistance, mechanical, low dielectric properties, and the like are required.

이러한 감광성 내열절연체는 박막형태의 저유전 재료가 사용되는 모든 분야에 적용이 가능하며, 주로 반도체 소자의 패시베이션 막(passivation layer), 완충막(buffer coat) 또는 다층인쇄회로기판 등에 사용되어진다.The photosensitive heat insulator is applicable to all fields in which a thin dielectric material is used, and is mainly used in a passivation layer, a buffer coat, or a multilayer printed circuit board of a semiconductor device.

산민감기를 포함하는 포토레지스트의 기술로서는,J. Photopolymer Science and ThechnologyVol. 9, No, 4, pp. 611, (1996)에는 히드록시폴리스티렌 고분자에 아세탈기를 산민감기로 도입한 감광성 조성물에 대한 자세한 내용이 수록되어 있다. 이 문헌에 기재된 내용은 포토레지스트로의 응용에 한정된 것으로, 내열성 및 기계적 강도가 매우 열악하여 감광성 내열 절연제로의 사용은 곤란하다.As a technique of the photoresist including acid sensitivity, J. Photopolymer Science and Thechnology Vol. 9, No, 4, pp. 611, (1996), describe details of photosensitive compositions in which acetal groups are introduced as acid sensitive groups in hydroxypolystyrene polymers. The content described in this document is limited to the application to photoresist, and its heat resistance and mechanical strength are very poor, making it difficult to use as a photosensitive heat resistant insulation.

지금까지의 감광성 내열절연체는 독일특허 제2,437,348호 또는J. Macromolecluar ScienceA21, 1641(1984) 등에 기재된 것과 같이 에스테르기나 이온성기가 측쇄로 도입된 광가교형 폴리이미드 전구체를 이용한 네가티브형 감광성 폴리이미드가 주로 개발되었다. 그러나 네가티브형 내열절연체는 포토마스크상에 존재할 수 있는 입자나 균열 등에 의한 잘못된 형상 패턴이 나타날 수 있고, 유기용매를 현상액으로 사용하기 때문에 현상시의 팽윤에 의한 해상력의 감소가 일어날 수 있다.Until now, the photosensitive heat insulator has a negative photosensitive polyimide resin using a photocrosslinked polyimide precursor having an ester group or an ionic group introduced into a side chain, as described in German Patent No. 2,437,348 or J. Macromolecluar Science A21, 1641 (1984). Mainly developed. However, in the negative type heat resistant insulator, an incorrect shape pattern due to particles or cracks that may exist on the photomask may appear, and since the organic solvent is used as the developer, a reduction in resolution due to swelling during development may occur.

반면에 포지티브형 감광성 내열 저유전체와 관련하여 미국특허 제4,927,736호에서는 나프토퀴논디아지드(naphtoquinone diazide: 이하 NQ로 표시함) 등의 감광제를 히드록시기를 포함하는 방향족 폴리이미드에 유기결합 또는 블랜딩한 바 있다. 히드록시기를 포함하는 방향족 폴리이미드는 광흡수가 커서 결국 양자수율이 낮아지므로, 이에 양자수율을 향상시키기 위해서는 많은 양의 감광제를 사용하여야 한다. 그러나, 비노광부분을 가열하여 내열고분자로 전환하는 과정에서는 사용된 감광제의 극성 열분해물이 필름내에 다량 존재하게 될 뿐 아니라, 고분자 주사슬에 극성기(예: -OH기)가 그대로 잔존하여 유전율을 높이고 내열성을 떨어뜨리는 원인이 된다.On the other hand, in connection with the positive photosensitive heat-resistant low dielectric, US Patent No. 4,927,736 shows that a photosensitive agent such as naphtoquinone diazide (hereinafter referred to as NQ) is organically bonded or blended to an aromatic polyimide containing a hydroxyl group. have. Since the aromatic polyimide containing a hydroxy group has a large light absorption and eventually has a low quantum yield, a large amount of photosensitive agent should be used to improve the quantum yield. However, in the process of heating the non-exposed part and converting it into a heat-resistant polymer, not only a large amount of polar pyrolysates of the used photosensitive agent exist in the film, but also a polar group (for example, -OH group) remains in the polymer main chain to maintain the dielectric constant. It raises and lowers heat resistance.

또 다른 예로서, 감광성과 해상력을 개량하기 위하여 화학증폭형 산민감성기를 히드록시기를 포함하는 방향족 폴리이미드[Polymers for Advanced Technology,vol. 4, 277, 287, 1992년] 또는 아믹산 tert-부틸 에스테르 전구체[유럽특허공개 제0502400A1호]에 도입함으로써 -OH, 또는 -COOH를 블록킹하여 현상제인 염기성 수용액에 대한 용해도를 낮추고, 광산발생제의 광반응 후 발생하는 양성자산에 의해 산민감기가 분해되고 -OH 또는 -COOH가 재생되어 현상제에 가용화되는 기술이 알려져 있다. 그러나 이 경우에는 양자효율을 증가시키는 화학증폭형의 감광효과는 얻을 수 있으나, 전자의 경우는 최종단계인 열처리과정에서 산민감기가 분해되면서 생성된 -OH가 필름 내에 잔존하는 단점이 있으며, 유럽특허공개 제0502400A1호의 경우에서는 혼합하여 사용하는 광산발생제의 양이 너무 많아 유전율을 높이고 내열성을 떨어뜨리는 원인이 된다.As another example, in order to improve photosensitivity and resolution, an aromatic polyimide containing a hydroxy group as a chemically amplified acid-sensitive group [ Polymers for Advanced Technology , vol. 4 , 277, 287, 1992] or amic acid tert-butyl ester precursor [European Patent Publication No. 0502400A1] to block -OH or -COOH to lower the solubility in the basic aqueous solution as a developer, A technique is known in which acid sensitization is decomposed by a positive asset generated after photoreaction, and -OH or -COOH is regenerated and solubilized in a developer. However, in this case, the photosensitization effect of the chemical amplification type which increases the quantum efficiency can be obtained, but in the former case, -OH generated by decomposing the acid sensitizer in the final heat treatment process remains in the film. In the case of Publication No. 0502400A1, the amount of photoacid generators used in a mixture is too high, which causes a high dielectric constant and a low heat resistance.

한편, 미국특허 제5,449,584호와 제5,037,720호에서는 폴리벤조옥사졸로의 열적전환이 가능한 히드록시기를 포함한 폴리아미드를 감광기와 혼합 또는 유기결합한 바도 있다. 이때 사용된 감광기는 나프토퀴논디아지드(NQ) 유도체로서 화학증폭형의 감광제를 사용하고 있지 않기 때문에 다량의 감광제를 사용하여야 하며, 비노광 부분의 전구체를 내열고분자로 전환하는 과정에서는 사용된 감광제의 극성 열분해물이 필름내에 다량 존재하게 되어 유전율을 높이고 기계적 물성을 떨어뜨리는 원인이 된다.On the other hand, U.S. Patent Nos. 5,449,584 and 5,037,720 may have mixed or organically bonded a polyamide including a hydroxyl group capable of thermally converting to polybenzoxazole. At this time, the photosensitive device is a naphthoquinone diazide (NQ) derivative, so it does not use a chemically amplified photosensitive agent. Therefore, a large amount of photosensitive agent should be used. Due to the large amount of polar pyrolysates present in the film, the dielectric constant is increased and mechanical properties are degraded.

또한, 본 발명자들은 기존의 감광성 내열절연체가 열처리 후에 발생하는 -OH로 인하여 유전율을 증가시키고 내열성이 감소되는 등의 문제점을 개선하기 위한 방안으로서, 빛에 의해 감광된 부분은 현상액에 의해 용해되어 제거되고 빛을 받지 않은 부분은 남아 있다가 후공정인 가열공정에 의해 내열성 고분자로 전환이 가능한 기능을 가진 산민감기를 측쇄로 포함하는 폴리아미드 중합체와, 이를 포함하는 감광성 내열절연체 조성물을 개발하여 특허출원한 바도 있다[한국특허공개 제2001-4433호 및 제2001-11635호].In addition, the inventors of the present invention as a way to improve the problem of increasing the dielectric constant and heat resistance due to the -OH generated after the heat treatment of the conventional photosensitive heat insulating material, the portion exposed by light is dissolved and removed by the developer The patent application was developed by developing a polyamide polymer containing acid-sensitive groups as side chains and having a function capable of converting them into heat-resistant polymers by a post-heating process. There is also one [Korean Patent Publication No. 2001-4433 and 2001-11635].

상기한 감광성 내열 절연체 기술들에서 사용하는 산민감성 중합체의 경우에는 최종 경화 공정 후에도 충분한 기계적 강도를 유지하기 위하여서는, 높은 분자량의 산민감성 중합체를 감광성 조성물에 사용하지 않으면 곤란하다. 일반적으로 반도체의 패시베이션이나 완충막의 경우에는 10 ㎛ 이상의 두께를 요구하고 있기 때문에 고형분 농도가 30% ∼ 50% 정도 이어야만 스핀 코팅에 의해 이러한 두께의 피막형성이 가능하다. 그러나, 기계적 강도를 확보하기 위해 분자량이 높은 중합체를 고 농도로 사용할 경우에는 그 조성물의 용액점도가 매우 높게 되어 스핀코팅시에 균일한 코팅막의 형성이나 평활화가 낮아지는 단점이 있다. 또한 노광후 현상시의 현상속도가 떨어져 해상력의 저하를 가져온다. 반면에, 분자량이 낮은 산민감성 중합체를 사용하는 경우에는 고형분의 농도가 높아도 용액점도가 낮아 충분한 두께의 박막 형성이 가능하지만, 전기한 바와 같이 기계적 강도가 낮아 반도체 소자내에서 크랙의 발생과 같은 치명적인 문제가 발생할 수 있다.In the case of acid-sensitive polymers used in the above-mentioned photosensitive heat insulator technologies, it is difficult to use high molecular weight acid-sensitive polymers in the photosensitive composition in order to maintain sufficient mechanical strength even after the final curing process. In general, in the case of a semiconductor passivation or a buffer film, a thickness of 10 μm or more is required, so that a film having such a thickness can be formed by spin coating only when the solid content concentration is about 30% to 50%. However, when high molecular weight polymers are used at high concentrations to ensure mechanical strength, the solution viscosity of the composition is very high, resulting in the formation or smoothing of a uniform coating film during spin coating. In addition, the developing speed during post-exposure development is lowered, resulting in a lower resolution. On the other hand, in the case of using a low molecular weight acid sensitive polymer, even if the solid concentration is high, the solution viscosity is low, so that a thin film can be formed with a sufficient thickness.However, as described above, the mechanical strength is low. Problems may arise.

이에, 본 발명자들은 기존의 감광성 내열절연체가 가지는 문제점 즉, 높은 분자량의 산민감성 중합체를 사용함에 따라 발생하는 높은 용액점도로 인한 문제 및 낮은 분자량의 산민감성 중합체를 사용함에 따라 발생하는 기계적 강도의 저하 문제를 근본적으로 해결할 수 있는 새로운 구조의 신규 산민감성 중합체를 개발하고자 지속적으로 연구 노력하였다.Therefore, the present inventors have problems of the conventional photosensitive heat insulating material, that is, a problem due to high solution viscosity caused by using a high molecular weight acid sensitive polymer and a decrease in mechanical strength caused by using a low molecular weight acid sensitive polymer. Research has continued to develop new acid-sensitive polymers with new structures that can fundamentally solve the problem.

그 결과, 아세탈 또는 카르보네이트기를 측쇄로 가지는 폴리아미드 중합체의 말단부분에 가교 가능한 기능기(T)를 추가로 부착함으로써, 코팅시에는 낮은 분자량을 가지고 있어 충분한 두께의 균일한 스핀코팅 피막 형성이 가능하고, 고온 경화시에는 가교 가능한 말단기의 작용으로 가교결합의 형성이 가능하여 기계적 강도 또한 우수한 감광성 패턴을 제공하는 열가교형 산민감성 폴리아미드 중합체와 이를 포함하는 감광성 조성물에 관한 기술을 완성함으로써 본 발명을 완성하기에 이르렀다.As a result, by additionally attaching a crosslinkable functional group (T) to the terminal portion of the polyamide polymer having acetal or carbonate group as a side chain, it has a low molecular weight during coating and forms a uniform spin coating film of sufficient thickness. By completing the technology of the thermal crosslinking acid-sensitive polyamide polymer and the photosensitive composition including the same, which can form crosslinks under the action of crosslinkable end groups at high temperature curing, thereby providing a photosensitive pattern with excellent mechanical strength. The present invention has been completed.

따라서, 본 발명은 높은 고형분을 가지면서도 용액점도가 낮아 균일한 도포가 가능하고, 기제 위에 도포하여 사용할 경우 광반응에 의해 노광부는 용해되어 제거됨으로서 광패턴화가 가능하고, 패턴화된 비노광부를 가열함에 따라 내열화 반응으로 유도하여 열적으로 더욱 안정한 벤조옥사졸기로 전환이 가능할 뿐 아니라, 이 열적 전환공정시 말단기의 가교결합이 동반되어 우수한 기계적 강도를 가지는 패턴화된 박막의 제조가 가능한 신규의 산민감성 폴리아미드 중합체를 제공하는데 그 목적이 있다.Accordingly, the present invention has a high solid content and low solution viscosity, so that uniform coating is possible, and when used on a substrate, the exposed portion is dissolved and removed by photoreaction, thereby enabling light patterning, and heating the patterned non-exposed portion. As a result, it is possible not only to convert into a more stable benzoxazole group by inducing a heat-resistant reaction, but also to produce a patterned thin film having excellent mechanical strength due to crosslinking of end groups in this thermal conversion process. It is an object to provide an acid sensitive polyamide polymer.

또한, 본 발명은 상기한 산민감성 폴리아미드 중합체에 최소량의 광산발생제를 함유시켜 낮은 유전율을 보유하도록 하는 신규의 감광성 내열절연체 조성물을 제공하는데 또 다른 목적이 있다.It is another object of the present invention to provide a novel photosensitive heat resistant insulator composition which contains a minimum amount of photoacid generator in the above acid sensitive polyamide polymer so as to have a low dielectric constant.

본 발명은 다음 화학식 1을 반복단위로 하는 것으로, 산민감기로서 아세탈또는 카르보네이트기가 측쇄기로 결합되어 있고, 중합체 말단에는 아세틸렌기를 포함하는 말단기가 결합되어 있는 산민감성 폴리아미드 중합체를 그 특징으로 한다.The present invention has the following general formula (1) as a repeating unit, and is characterized by an acid-sensitive polyamide polymer having an acetal or carbonate group bonded to a side chain group as an acid sensitive group, and a terminal group including an acetylene group bonded to a polymer terminal. .

상기 화학식 1에서 :In Formula 1 above:

Ar1은 4가의 방향족기로서,,,및중에서 선택되고, 이때 X1은 -CH2-, -O-, -S-, -SO2-. -CO-, -NHCO-, -C(CH3)2-, -C(CF3)2-,또는을 나타내며;Ar 1 is a tetravalent aromatic group , , , And Wherein X 1 is —CH 2 —, —O—, —S—, —SO 2 —. -CO-, -NHCO-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , or Represents;

Ar2는 2가의 방향족기로서,,,,,,,,,,,,및중에서 선택되고,이때 X1은 상기에서 정의한 바와 같으며;Ar 2 is a divalent aromatic group , , , , , , , , , , , , And Is selected from X 1 wherein X 1 is as defined above;

R1및 R2은 서로 같거나 다른 산민감기로서, 카르보네이트 또는 아세탈 구조를 갖으며; 아세탈기인 경우, R1및 R2둘 중에 적어도 하나 이상이 C1∼C10의 직쇄, 분쇄 또는 고리형 탄화수소계 에테르기로서 구체적으로 그 구조는또는를 나타내며(이때, R'는 C1∼C6의 저급알킬기로서 구체적으로는 에틸기, 프로필기, 이소프로필기, 부틸기, 이소부틸기, t-부틸기, 시클로헥실기를 나타내며, z는 1∼5의 정수를 나타냄); 카르보네이트기인 경우, 그 구조는를 나타내며, 이때 R" 및 R'"는 C1∼C4의 저급알킬기, 페닐기, 또는 니트로 및 할로겐원자 중에서 선택된 치환기로 치환된 페닐기를 나타내며;R 1 and R 2 are the same or different acid sensitive groups and have a carbonate or acetal structure; In the case of an acetal group, at least one of R 1 and R 2 is a C 1 to C 10 linear, pulverized or cyclic hydrocarbon ether group, specifically, the structure is or Wherein R 'is a lower alkyl group having 1 to 6 carbon atoms, specifically an ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, cyclohexyl group, and z is 1 An integer of -5); In the case of a carbonate group, the structure Wherein R ″ and R ′ ″ represent a C 1 to C 4 lower alkyl group, a phenyl group, or a phenyl group substituted with a substituent selected from nitro and halogen atoms;

T1및 T2는 서로 같거나 다른 중합체 말단기로서 아세틸렌기를 포함하며 구체적으로 아래와 같은 구조를 갖으며;T 1 and T 2 are the same or different polymer end groups and include an acetylene group, and specifically have the following structure;

,,,,, , , , , ,

이때, T1의 경우 Y는이며, T2의 경우 Y는 -NH-기를 나타내며, ;In this case, for T 1 Y is And in the case of T 2 , Y represents a —NH— group;

m과 n은 각각 5부터 100사이의 정수를 나타내며;m and n each represent an integer between 5 and 100;

상기한 Ar1과 Ar2의 조합에 의해 상기 화학식 1을 반복단위로 하는 산민감성 폴리아미드 중합체는 단일중합체 또는 공중합체일 수 있다.The acid-sensitive polyamide polymer having Formula 1 as a repeating unit by the combination of Ar 1 and Ar 2 may be a homopolymer or a copolymer.

이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명에 따른 신규 폴리아미드 중합체는 상기 화학식 1에 나타낸 바와 같이 -OH 또는 산민감기를 측쇄로 포함하고 중합체 말단에는 아세틸렌 유도체들을 포함되어 있는 낮은 중합도의 폴리아미드 구조를 가진다. 이러한 분자 구조적 특이성으로 인하여 본 발명의 산민감성 폴리아미드 중합체는 광산발생제와 혼합하여 사용할 경우에 포지티브형 감광성 내열 저유전체로서의 이용이 가능하다. 즉, 산민감성 폴리아미드 중합체와 광산발생제를 혼합하여 얻은 감광성 내열절연체 조성물을 기재 위에 박막으로 도포한 후에 가시광 또는 자외선으로 패턴이 새겨진 포토마스크를 통하여 노광 및 열처리하게 되면, 노광부에서는 산민감기가 광 및 열분해 반응하여 히드록실기(-OH)로 전환되어 사메틸암모늄 히드록사이드 (tetramethylammonium hydroxide: 이하 'TMAH'로 표기함) 등의 염기성 수용액에 의해 용해된다. 반면에, 빛을 수광하지 않은 비노광부는 염기성 수용액에 대한 용해도가 낮기 때문에 폴리아미드 중합체의 포지티브 패턴의 형성이 가능하다. 이 패턴화된 비노광부를 가열함에 따라 폴리아미드 중합체내의 산민감기가 열분해반응하여 히드록시기(-OH)가 생성되고, 더욱 높은 온도로 가열하면 -OH가 이웃 반응기인 아미드기와 결합하여 내열성이 매우 우수한 저유전체기인 벤조옥사졸기로 전환되어 내열 패턴이 형성된다. 또한, 이 열처리 과정에서는 아세틸렌기의 가교반응이 동반되어, 낮은 분자량의 폴리아미드 또는 열적 전환된 폴리벤조옥사졸이 가교 또는 분자량 증가반응에 의해 기계적으로 안정한 패턴화 된 내열성 박막으로의 전환이 가능하여 지는 것이다. 폴리벤조옥사졸은 내열성이 매우 우수하여 500 ℃ 이상의 내열성을 나타내며, 이를 녹일 수 있는 유기용매가 거의 없을 정도의 매우 안정한 물질일 뿐 아니라, 유전율과 흡수율 또한 일반적인 폴리이미드보다 낮다. 뿐만 아니라 산민감기로서 측쇄로 도입되어 있는 아세탈 또는 카르보네이트 유도체는 분해되어 휘발성 저분자량의 화학물질(예: 에틸비닐에테르, 3,4-디히드로-2H-피란, 또는 이산화탄소, 이소부틸렌)로 기체화되어 피막 내부에는 아무런 분해물질이 남지 않는 바, 종래의 나프토퀴논디아지드(NQ)를 사용한 감광성 폴리이미드(PSPI) 또는 tert-부톡시기를 측쇄로 하는 폴리이미드를 사용하는 것에 비하여 훨씬 낮은 유전상수를 나타낸다. 즉, 저유전특성, 내열특성 그리고 전기적특성을 열악하게 하는 원인인 -OH를 고분자내에서 제거할 뿐 아니라, 더 나아가 이를 내열화 반응에 응용한 것이다. 그리고 감광성 조성물로서는 화학증폭형 개념의 광산발생제와 산민감기를 사용하기 때문에 광 또는 산에 의해 분해될 때 다량의 산이 발생하여 산민감기의 분해를 촉진시킨다. 따라서 양자효율이 높아 광산발생제의 사용량을 최소화할 수 있으며, 광산발생제에 의한 유전율 증가 및 제반 물성의 저하를 최소화 할 수 있다.The novel polyamide polymer according to the present invention has a low degree of polymerization polyamide structure containing -OH or acid sensitive groups as side chains and acetylene derivatives at the polymer ends, as shown in Chemical Formula 1. Due to such molecular structural specificity, the acid-sensitive polyamide polymer of the present invention can be used as a positive photosensitive heat-resistant low dielectric when used in combination with a photoacid generator. That is, when the photosensitive heat insulating composition obtained by mixing the acid sensitive polyamide polymer and the photoacid generator is applied to the substrate as a thin film, and then subjected to exposure and heat treatment through a photomask engraved with visible light or ultraviolet light, It is converted to a hydroxyl group (-OH) by light and pyrolysis, and dissolved by a basic aqueous solution such as tetramethylammonium hydroxide (hereinafter referred to as TMAH). On the other hand, since the non-exposed portion that does not receive light has low solubility in the basic aqueous solution, it is possible to form a positive pattern of the polyamide polymer. As the patterned non-exposed part is heated, the acid sensitive groups in the polyamide polymer thermally decompose to form a hydroxyl group (-OH), and when heated to a higher temperature, -OH is combined with the amide group, which is a neighboring reactor, and has excellent heat resistance. It converts into the benzoxazole group which is a dielectric group, and a heat resistant pattern is formed. In addition, the heat treatment process is accompanied by a crosslinking reaction of the acetylene group, the low molecular weight polyamide or thermally converted polybenzoxazole can be converted into a mechanically stable patterned heat-resistant thin film by crosslinking or molecular weight increase reaction To lose. Polybenzoxazole has excellent heat resistance and shows heat resistance of 500 ° C. or higher, and is not only a very stable material having almost no organic solvent capable of dissolving it, but also has a low dielectric constant and water absorption rate than general polyimides. In addition, acetal or carbonate derivatives introduced into the side chain as acid-sensitive groups are decomposed to volatile low molecular weight chemicals (e.g. ethyl vinyl ether, 3,4-dihydro-2 H -pyran, or carbon dioxide, isobutylene). And no decomposition products remain inside the coating due to the gasification thereof, as compared with the use of photosensitive polyimide (PSPI) or tert-butoxy group side chains using conventional naphthoquinone diazide (NQ). Much lower dielectric constant. That is, -OH, which is a cause of low dielectric properties, heat resistance and electrical properties, is not only removed from the polymer, but also applied to the heat-resistant reaction. And since the photosensitive composition uses a photo-acid generator and acid sensitizer of the chemically amplified concept, a large amount of acid is generated when decomposed by light or acid to promote the decomposition of acid sensitizer. Therefore, the high quantum efficiency can minimize the amount of photoacid generator used, it is possible to minimize the increase in dielectric constant and deterioration of physical properties by the photoacid generator.

본 발명에 따른 산민감성 폴리아미드 중합체의 분자량은 고유점도(inherent viscosity: 0.50 g/dL의 농도의 N-메틸피롤리돈 용액에서 30℃에서 측정)가 0.07 ∼ 0.35 dL/g 으로서, 이 산민감성 폴리아미드를 40 중량%를 포함하는 감광성 조성물인 경우의 용액점도는 7,000 cps를 넘지 않아 스핀 코팅이 가능한 점도를 나타낸다. 고유점도의 크기가 이 보다 높을 경우에는 용액점도가 너무 커 스핀코팅이 곤란하거나 평활한 피막의 형성이 불가능하다.The molecular weight of the acid sensitive polyamide polymer according to the present invention has an inherent viscosity (measured at 30 ° C. in an N-methylpyrrolidone solution at a concentration of 0.50 g / dL) of 0.07 to 0.35 dL / g. The solution viscosity in the case of the photosensitive composition containing 40 weight% of polyamide does not exceed 7,000 cps, and shows the viscosity which can be spin-coated. If the intrinsic viscosity is higher than this, the solution viscosity is so large that it is difficult to spin coating or to form a smooth film.

특히, 본 발명에 따른 산민감성 폴리아미드 중합체는 가교 가능한 말단기가 결합되어 있고, 이러한 말단기로는 아세틸렌을 가지는 다양한 방향족 유도체의 사용이 가능하고, 경우에 따라서는 두 개의 아세틸렌이 한 개의 벤젠핵에 치환된 화합물의 사용이 가능하다. 본 발명에 따른 폴리아미드 중합체의 아세틸렌 말단기로 도입되는 화합물의 열적 가교온도는 150 ∼ 400 ℃ 범위가 적당하며, 이 보다 높은 반응온도를 요구하는 아세틸렌 화합물의 경우에는 폴리아미드 또는 폴리벤조옥사졸의 열화를 일으킬 가능성이 있으므로 본 발명에서는 배제한다.In particular, the acid-sensitive polyamide polymer according to the present invention has a crosslinkable end group bonded thereto, and as such end groups, various aromatic derivatives having acetylene can be used, and in some cases, two acetylenes are substituted for one benzene nucleus. The use of these compounds is possible. The thermal crosslinking temperature of the compound introduced into the acetylene end group of the polyamide polymer according to the present invention is preferably in the range of 150 to 400 ° C., and in the case of the acetylene compound requiring a higher reaction temperature, the polyamide or polybenzoxazole Since this may cause deterioration, it is excluded in the present invention.

또한, 본 발명에 따른 산민감성 폴리아미드 중합체내에 포함된 산민감기(-OR1또는 -OR2)의 농도 [n/(m+n)]는 1% ∼ 90%, 좋기로는 3% ∼ 70%의 범위를 가지도록 한다. 산민감기의 농도가 너무 클 경우에는 현상속도가 떨어지며 장시간의 노광시간 또는 많은 양의 광산발생제의 사용이 필요하게 되며, 산민감기의 농도가 너무 작을 경우에는 해상력의 부족과 두께의 감소 등의 문제점들이 나타날 수 있다.Further, the concentration [n / (m + n)] of the acid sensitive group (-OR 1 or -OR 2 ) contained in the acid sensitive polyamide polymer according to the present invention is 1% to 90%, preferably 3% to 70%. Have a range of%. If the concentration of acid-sensitizer is too high, the development speed will be slow and a long exposure time or the use of a large amount of photoacid generator will be required. If the concentration of the acid-sensitizer is too small, problems such as lack of resolution and thickness decrease May appear.

또한, 상기 화학식 1의 반복단위를 가지는 산민감성 폴리아미드 중합체는 Ar1과 Ar2의 조합으로 구성되는 단일 중합체와 공중합체를 모두 포함한다.In addition, the acid-sensitive polyamide polymer having a repeating unit of Formula 1 includes both a homopolymer and a copolymer composed of a combination of Ar 1 and Ar 2 .

이상에서 설명한 바와 같은 본 발명의 산민감성 폴리아미드 중합체는 디히드록시기를 갖는 방향족 디아민과 방향족 디카르복시산 또는 그의 유도체로부터 제조하며, 그 과정을 간략히 나타내면 다음 반응식 1과 같다.As described above, the acid-sensitive polyamide polymer of the present invention is prepared from an aromatic diamine having an dihydroxy group, an aromatic dicarboxylic acid or a derivative thereof, and the process thereof is briefly represented by the following Scheme 1.

상기 반응식 1에서 : Ar1, Ar2, X1, X2,R1, R2, T1, T2, n 및 m은 각각 상기에서 정의한 바와 같다.In Scheme 1: Ar 1 , Ar 2 , X 1 , X 2 , R 1 , R 2 , T 1 , T 2 , n and m are as defined above, respectively.

상기 반응식 1에 따른 폴리아미드 중합체의 중합방법으로는 산클로라이드에 의한 중합법, 실릴 클로라이드를 이용한 중합법, 에스테르 치환반응, 그리고 직접중합법 등에 의해 중합이 가능하다. 제조된 산민감성 폴리아미드 중합체의 분자량은 고유점도로 0.07∼ 0.35 dL/g 까지를 나타낸다. 중합반응온도는 50 ℃이하, 바람직하기로는 30 ℃ 이하의 저온을 유지시키는 것이 바람직한 바, 중합반응온도가 너무 높은 경우에는 과도한 반응이 일어나 용매에 불용인 폴리벤조옥사졸이 생성되기 쉽고 분자량이 낮은 중합체가 형성된다.As a polymerization method of the polyamide polymer according to Scheme 1, polymerization by acid chloride, polymerization using silyl chloride, ester substitution reaction, direct polymerization and the like can be carried out. The molecular weight of the produced acid sensitive polyamide polymer has an intrinsic viscosity of 0.07 to 0.35 dL / g. It is preferable to maintain the polymerization temperature at 50 ° C. or lower, preferably 30 ° C. or lower. If the polymerization temperature is too high, excessive reactions occur and polybenzoxazoles which are insoluble in the solvent are formed easily and the molecular weight is low. The polymer is formed.

현상속도의 조절 및 감광성의 부여를 위하여, 이상의 중합방법으로 제조된 말단기가 부착된 폴리아미드 중합체에 산민감기를 도입한다.In order to control the development speed and impart photosensitivity, an acid-sensitive group is introduced into the polyamide polymer having end groups prepared by the above polymerization method.

아세탈기를 산민감기로 도입할 경우에 사용될 수 있는 화합물은 C1∼C10의 직쇄, 분쇄 또는 고리형의 불포화탄화수소계 에테르 화합물로서, 예컨대또는로 표시될 수 있다. 상기한 산민감기 도입 화합물의 구체적인 예로는 에틸비닐에테르, 프로필비닐에테르, 이소프로필비닐에테르, n-부틸비닐에테르, tert-부틸비닐에테르, 시클로헥실비닐에테르, 2,3-디히드로퓨란, 3,4-디히드로-2H-피란 등이 포함된다. 이들 산민감기 화합물은 1종 또는 2종 이상을 혼합 사용할 수도 있다. 아세탈 계열의 산민감기를 고분자에 결합시키는 방법으로는 상기한 산민감기 화합물을 과량 사용하여 산 촉매 조건으로 반응시키는 방법이 좋다. 이때, 산 촉매로서는 바람직하기로, p-톨루엔설폰산, 인산, 염산 등과 같은 강산성 물질을 사용한다. 산민감기 도입 반응은 가능하다면 상온 또는 그 이하에서 진행시키는 것이 바람직하며, 반응 온도가 높은 경우에는 산민감기의 열적분해반응과 폴리벤조옥사졸의 형성이 일어날 수 있다.Compounds which may be used when introducing an acetal group as an acid sensitive group are C 1 to C 10 linear, pulverized or cyclic unsaturated hydrocarbon ether compounds, for example or It may be represented as. Specific examples of the acid sensitive group introducing compound include ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, 2,3-dihydrofuran, 3, 4-dihydro-2H-pyran and the like. These acid sensitive compounds can also be used 1 type or in mixture of 2 or more types. As a method of binding the acetal-based acid-sensitive group to the polymer, a method in which an acid-sensitized compound is used in an excess amount and reacted under an acid catalyst condition is preferable. At this time, a strong acid substance such as p-toluenesulfonic acid, phosphoric acid, hydrochloric acid or the like is preferably used as the acid catalyst. The acid sensitivity introduction reaction is preferably carried out at room temperature or lower if possible. If the reaction temperature is high, thermal decomposition reaction of the acid sensitivity and formation of polybenzoxazole may occur.

카르보네이트기를 산민감기로 도입할 경우에 사용될 수 있는 화합물은 알킬옥시카르보닐옥시기를 포함하는 산무수물 또는 클로라이드이며, 이들 산민감기 화합물은 과잉으로 사용하여 염기성 용액내에서 반응시킨다. 이때, 반응촉매로서 피리딘, 칼륨 tert-부톡사이드, 트리에틸아민, 디메틸아미노피리딘, 1,4-디아자비시클로[2,2,2]옥탄 등과 같은 염기성 물질을 사용한다.Compounds which can be used when introducing a carbonate group as an acid sensitive group are acid anhydrides or chlorides containing alkyloxycarbonyloxy groups, and these acid sensitive compounds are used in excess to react in a basic solution. At this time, a basic substance such as pyridine, potassium tert-butoxide, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo [2,2,2] octane and the like is used as the reaction catalyst.

말단기를 부착하는 방법으로서, 중간체 폴리아미드의 반응말단이 방향족 아민의 경우에는 말단기 유도체로는 아세틸렌을 포함한 유도체의 산클로라이드를 사용하고, 중간체 폴리아미드의 반응말단이 산 또는 산클로라이드인 경우에는 아세틸렌을 포함한 아미노 화합물을 말단기 유도체로 사용한다. 바람직하로는 상기 반응식 1에 나타낸 중간체 폴리아미드의 합성이 종결된 후 같은 반응기내에 과잉의 가교형 말단기를 포함하는 화합물을 투입하여 말단기를 부착시킨다.As a method for attaching the end group, when the reaction end of the intermediate polyamide is an aromatic amine, an acid chloride of a derivative including acetylene is used as the end group derivative, and when the reaction end of the intermediate polyamide is an acid or an acid chloride An amino compound including acetylene is used as the end group derivative. Preferably, after the synthesis of the intermediate polyamide shown in Scheme 1 is terminated, a compound including an excess of crosslinked end groups is introduced into the same reactor to attach the end groups.

한편, 본 발명은 상기 화학식 1을 반복단위로 하는 산민감성 폴리아미드 중합체와 광산발생제가 함유되어 있는 감광성 내열절연체 조성물을 포함한다.On the other hand, the present invention includes a photosensitive heat-resistant insulator composition containing an acid-sensitive polyamide polymer having a repeating unit of Formula 1 and a photoacid generator.

본 발명에 따른 감광성 내열절연체 조성물중에 포함되는 광산발생제는 노광에 의해 산을 발생하는 물질로서 문헌을 통하여 알려진 다양한 광산발생제의 사용이 가능하다. 바람직하기로는 함께 사용된 산민감성 폴리아미드 중합체의 흡광영역보다 긴 흡광영역(300 nm 이상)의 빛을 흡수하여 산을 발생하는 물질을 사용하는 것이다. 이러한 광산발생제를 구체적으로 예시하면 다음과 같은 바, 본 발명에서의 광산발생제가 다음에서 예시된 물질로 한정되는 것은 아니다.Photoacid generators included in the photosensitive heat-resistant insulator composition according to the present invention can be used a variety of photoacid generators known through the literature as a material for generating an acid by exposure. Preferably, a material that generates an acid by absorbing light in an absorption region (300 nm or more) longer than the absorption region of the acid-sensitive polyamide polymer used together is used. Specific examples of such a photoacid generator are as follows, and the photoacid generator in the present invention is not limited to the materials exemplified below.

,,, , , ,

상기에서 :From above:

R3, R4및 R6는 각각 수소원자 또는 C1∼C10의 알콕시기를 나타내고, 구체적으로는 수소원자, 메톡시기, 에톡시기, 프로폭시기, 부톡시기 등을 나타내며;R 3 , R 4 and R 6 each represent a hydrogen atom or an alkoxy group having 1 to 10 carbon atoms, and specifically, a hydrogen atom, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or the like;

R5는 C1∼C10의 알킬기, C1∼C10의 할로알킬기, 알킬기로 치환 또는 치환된 페닐기, 또는 캄포닐기를 나타내고, 구체적으로는 메틸기, 에틸기, 트리플로오로메틸기, 페닐기, 4-메틸페닐기, 캄포닐기 등을 나타낸다.R 5 represents a C 1 -C 10 alkyl group, a C 1 -C 10 haloalkyl group, a phenyl group substituted or substituted with an alkyl group, or a camphoryl group, and specifically, a methyl group, an ethyl group, a trifluoromethyl group, a phenyl group, 4- Methylphenyl group, camphoryl group, etc. are shown.

상기한 바와 같은 광산발생제는 폴리아미드 중합체에 대하여 0.3 ∼ 15 중량% 범위로 함유시킨다. 광산발생제의 사용량이 너무 많을 경우에는 필름내의 유전특성과 기계적 강도, 내열성을 떨어뜨릴 뿐만 아니라 광투과도가 떨어져 완전한 구멍의 형성이 곤란해지고, 그 사용량이 너무 작을 경우에는 충분한 산이 존재하지 않아 산발생제로서의 역할을 충분히 발휘할 수가 없어 해상도가 나빠진다.The photoacid generator as described above is contained in the range of 0.3 to 15% by weight based on the polyamide polymer. If the amount of photoacid generator is used too much, not only the dielectric properties, mechanical strength and heat resistance of the film may be lowered, but also the light transmittance may be difficult to form a complete hole. If the amount of the photoacid generator is too small, sufficient acid may not be present. It can't fully play its role as zero, resulting in poor resolution.

본 발명에 따른 감광성 내열절연체 조성물은 용액 상태로 제조하여 사용할 수 있는 바, 용매로는 디메틸설포옥사이드, 헥사메틸포스포아미드, 디메틸아세트아미드, 디메틸포름아미드, N-메틸-2-피롤리돈, 감마-부티로락톤, 디그라임, 부톡시에탄올, 프로필렌글리콜메틸에테르아세테이트(PGMEA) 등의 용매가 사용 가능하나 특정용매로 한정하지는 않는다. 또한, 이들 용매는 박막의 균일도, 두께조절 그리고 접착력 향상을 위하여, 2가지 이상의 용매를 혼합하여 사용할 수도 있다. 감광성 내열절연체 조성물은 10 ∼ 70 중량% 농도로 제조하며, 원하는 코팅 두께에 따라 조절하여 사용이 가능하다.The photosensitive heat insulator composition according to the present invention can be prepared and used in a solution state, and as a solvent, dimethylsulfooxide, hexamethylphosphoamide, dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, Solvents such as gamma-butyrolactone, diglyme, butoxyethanol and propylene glycol methyl ether acetate (PGMEA) may be used but are not limited to specific solvents. In addition, these solvents may be used by mixing two or more solvents in order to improve the uniformity, thickness control and adhesion of the thin film. The photosensitive heat insulating composition is prepared at a concentration of 10 to 70% by weight, and can be used by adjusting it according to a desired coating thickness.

또한, 감광성 내열절연체 조성물을 사용한 박막의 형성은 전자산업에서 많이 사용하고 있는 스핀 코팅이나 바코팅, 덕터블레이드를 사용하는 방법 등 어느 것이나 적용이 가능하다. 박막형성을 위한 건조온도는 40 ∼ 150 ℃가 적당하며, 건조온도가 너무 낮을 경우는 건조시간이 길어지게 되고, 건조온도가 너무 높을 경우에는 산민감기의 열분해 그리고 벤조옥사졸기의 형성에 의해 진한색으로 전환되기 때문에 투과도의 감소가 일어난다.In addition, the formation of a thin film using the photosensitive heat insulating insulator composition can be applied to any method such as spin coating, bar coating, and duct blades, which are widely used in the electronics industry. Drying temperature for forming a thin film is suitable for 40 ~ 150 ℃, if the drying temperature is too low, the drying time is long, if the drying temperature is too high, dark color due to pyrolysis of acid sensitivity and the formation of benzoxazole group Because of the conversion, the decrease in transmittance occurs.

노광은 자외선을 사용하여 200 ∼ 500 nm 파장의 가시광 또는 자외선을 나타내는 노광장치를 사용하면 좋으나, 좋기로는 단색파장을 나타낼 수 있는 필터가 장착된 노광기의 사용이 해상력이나 공정성의 측면에서 더욱 유리하다. 본 발명에서는 특정한 장비나 노광장비를 한정하지는 않는다.An exposure apparatus may be an exposure apparatus that displays visible light or ultraviolet rays having a wavelength of 200 to 500 nm using ultraviolet rays. However, it is preferable to use an exposure apparatus equipped with a filter capable of displaying monochromatic wavelengths in terms of resolution and fairness. . The present invention does not limit specific equipment or exposure equipment.

노광시간은 실험조건에 따라 변화가 가능하며, 본 발명에서 사용한 365 nm의 필터가 장착된 자외선 노광장치를 사용할 때는 노광시간은 10 ∼ 200초까지 변화하여 측정하였을 때 패턴의 형성이 가능하였으며, 보다 강력한 노광장치를 사용하는 경우 노광시간은 더욱 짧아질 수 있다. 노광에너지는 에너지미터를 사용하여정량하며, 해상력은 프로파일로미터를 이용하여 깊이와 폭으로 확인하고, 박막의 단면은 전자현미경으로써 확인한다.The exposure time can be changed according to the experimental conditions. When using the ultraviolet exposure apparatus equipped with the 365 nm filter used in the present invention, the exposure time was changed from 10 to 200 seconds, and the pattern was formed. When a powerful exposure apparatus is used, the exposure time can be shorter. The exposure energy is quantified using an energy meter, the resolution is checked by depth and width using a profilometer, and the cross section of the thin film is confirmed by an electron microscope.

이상에서 설명한 바와 같은 본 발명은 다음의 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 이에 한정되는 것은 아니다.The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.

본 발명의 실시예에서 말단기 도입에 사용하는 화합물 중 3-에티닐아닐린(이하, '3-EA'라 함)은 상용제품을 구입하여 사용하였으며, 3-에티닐벤조산 클로라이드(이하, '3-EB'라 함)는 3-에티닐벤조산을 촉매량의 디메틸포름아미드 존재하에서 티오닐클로라이드와 반응시켜 제조하였다. 3-클로로포르밀-N-(3-에티닐페닐)-프탈이미드(이하, '3-EI'라 함)는 트리멜릭틱산 무수물과 3-에티닐아닐린으로부터 제조된 N-(3-에티닐페닐)트리멜리틱이미드를 촉매량의 디메틸포름아미드 존재하에서 티오닐클로라이드와 반응시켜 제조하였다. 그리고, 3-클로로포르밀-N-(3,4-디에티닐페닐)-프탈이미드(이하, 'DEI'라 함)는 3,4-디에티닐아닐린을 트리멜릭틱산 무수물과 반응시켜 N-(3,4-디에티닐페닐)트리멜리틱이미드를 제조하고, 이를 다시 촉매량의 디메틸포름아미드 존재하에서 티오닐클로라이드와 반응시켜 제조하였다. 제조된 화합물들은 각각 NMR, mass 등으로 확인하였다.In the embodiment of the present invention, 3-ethynylaniline (hereinafter, referred to as '3-EA') among the compounds used to introduce end groups was purchased from commercially available products, and 3-ethynylbenzoic acid chloride (hereinafter, '3' -EB ') was prepared by reacting 3-ethynylbenzoic acid with thionylchloride in the presence of a catalytic amount of dimethylformamide. 3-Chloroformyl-N- (3-ethynylphenyl) -phthalimide (hereinafter referred to as '3-EI') is an N- (3-e) prepared from trimellitic anhydride and 3-ethynylaniline. Tinylphenyl) trimeliticimide was prepared by reacting with thionylchloride in the presence of a catalytic amount of dimethylformamide. In addition, 3-chloroformyl-N- (3,4-diethynylphenyl) -phthalimide (hereinafter referred to as 'DEI') is reacted with 3,4-diethynylaniline with trimellitic anhydride to give N- (3,4-Diethynylphenyl) trimeliticimide was prepared and prepared by reacting with thionyl chloride in the presence of a catalytic amount of dimethylformamide. The prepared compounds were identified by NMR and mass, respectively.

그리고 본 발명의 실시예에서 사용하는 광산발생제로서 p-니트로벤질-9,10-디메톡시안트라센-2-술포네이트(이하, 'NBAS'라 함)는 문헌에 알려진 방법에 의해 제조하였다. 한편, N-트리플로로메탄술포닐옥시-4-메톡시-1,8-나프틸이미드(이하, 'CF-PAG'라 함), N-캄파설포닐옥시-4-메톡시-1,8-나프틸이미드(이하, 'camphor-PAG'라 함)는 각각 제조예 1과 제조예 2에 기재한 방법으로 제조하여 사용하였다.In addition, p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (hereinafter referred to as 'NBAS') as a photoacid generator used in the examples of the present invention was prepared by a method known in the literature. Meanwhile, N-trifluoromethanesulfonyloxy-4-methoxy-1,8-naphthylimide (hereinafter referred to as 'CF-PAG') and N-campasulfonyloxy-4-methoxy-1 , 8-naphthylimide (hereinafter referred to as 'camphor-PAG') was prepared and used in the methods described in Preparation Example 1 and Preparation Example 2, respectively.

제조예 1Preparation Example 1

질소분위기하에서 100 mL 플라스크에 하이드록시아민 염산염 1.37 g(0.020 mol)을 넣고 피리딘에 용해시키고 온도를 90 ℃로 올렸다. 이 반응 용액에 4-브로모-1,8-나프틸산 무수물 5 g(0.018 mol)을 소량씩 첨가하고 90 ℃를 유지하면서 4시간 반응시켰다. 이 반응 용액을 증류수에 부어 무수 아세트산으로 침전을 잡고 여과하여 메탄올로 세척을 한 후에 50 ℃의 진공오븐에서 건조를 시켰다. 얻어진 합성물을 질소분위기하에서 100 mL 플라스크에 넣고 디메틸포름아미드에 용해시키고 90 ℃로 온도를 상승시켰다. 이 반응 용액에 나트륨메톡사이드 1.66 g(0.030 mol)을 첨가하고 90 ℃를 유지하면서 2시간동안 반응시켰다. 이 반응 용액을 차가운 증류수에 침전을 시키고 여과하여 수 차례에 걸쳐 물과 메탄올로 세척 건조하였다. 얻어진 합성물을 질소 분위기하에서 50 mL 플라스크에 넣고 테트라히드로퓨란에 용해시킨 후 이미다졸 1.175 g (0.0173 mol)을 넣고 0 ℃로 유지시켰다. 이 반응 용액에 트리플루오로메탄설포닐 클로라이드 2.91 g (0.01726 mol)를 천천히 투입하고 상온에서 1시간 동안 반응시켰다. 이 반응물을 여과하고 여액을 무수 아세트산으로 침전을 잡아 다시 여과하고 증류수로 수 차례에 걸쳐 세척을 하여 상온의 진공오븐에서 건조를 하여 'CF-PAG'를 합성하였다.Under a nitrogen atmosphere, 1.37 g (0.020 mol) of hydroxyamine hydrochloride was added to a 100 mL flask, dissolved in pyridine, and the temperature was raised to 90 ° C. 5 g (0.018 mol) of 4-bromo-1,8-naphthic anhydrides were added to this reaction solution little by little, and it was made to react for 4 hours, maintaining 90 degreeC. The reaction solution was poured into distilled water, precipitated with acetic anhydride, filtered and washed with methanol, and dried in a vacuum oven at 50 ° C. The obtained compound was placed in a 100 mL flask under nitrogen atmosphere, dissolved in dimethylformamide, and the temperature was raised to 90 ° C. 1.66 g (0.030 mol) of sodium methoxide was added to the reaction solution and reacted for 2 hours while maintaining at 90 ° C. The reaction solution was precipitated in cold distilled water, filtered and washed several times with water and methanol. The obtained compound was placed in a 50 mL flask under nitrogen atmosphere, dissolved in tetrahydrofuran, and then 1.175 g (0.0173 mol) of imidazole was added thereto and maintained at 0 ° C. 2.91 g (0.01726 mol) of trifluoromethanesulfonyl chloride was slowly added to the reaction solution, and reacted at room temperature for 1 hour. The reaction product was filtered, the filtrate was precipitated with acetic anhydride, filtered again, washed with distilled water several times, and dried in a vacuum oven at room temperature to synthesize 'CF-PAG'.

1H-NMR : δ8.64, 8.60, 8.57, 7.88, 7.39, 4.15 ppm 1 H-NMR: δ 8.64, 8.60, 8.57, 7.88, 7.39, 4.15 ppm

제조예 2Preparation Example 2

질소분위기하에서 100 mL 플라스크에 하이드록시아민 염산염 1.37 g (0.020 mol)을 넣고 피리딘에 용해시키고 온도를 90 ℃로 올렸다. 이 반응 용액에 4-브로모-1,8-나프틸산 무수물 5 g (0.018 mol)을 소량씩 첨가하고 90℃를 유지하면서 4시간 반응시켰다. 이 반응 용액을 증류수에 부어 무수 아세트산으로 침전을 잡고 여과하여 메탄올로 세척을 한 후에 50 ℃의 진공오븐에서 건조를 시켰다. 얻어진 연노란색의 물질을 질소분위기하에서 100 mL 플라스크에 넣고 디메틸포름아미드에 용해시키고 90 ℃로 온도를 상승시켰다. 이 반응 용액에 나트륨메톡사이드 1.66 g(0.030 mol)을 첨가하고 90 ℃를 유지하면서 2시간동안 반응시켰다. 이 반응 용액을 차가운 증류수에 침전을 시키고 여과하여 수 차례에 걸쳐 물과 메탄올로 세척 건조하였다. 얻어진 합성물을 질소분위기하에서 50 mL 플라스크에 넣고 테트라히드로퓨란에 용해시킨 후 이미다졸 1.175 g (0.0173 mol)을 넣고 0 ℃로 유지시켰다. 이 반응 용액에 10-캄파술포닐 클로라이드 4.33 g (0.01726 mol)를 천천히 투입하고 상온에서 12시간 동안 반응시켰다. 반응 용매를 제거하고 클로로포름으로 추출을 실시하여 상온의 진공오븐에서 건조를 하여 'Camph-PAG'을 얻었다.Under a nitrogen atmosphere, 1.37 g (0.020 mol) of hydroxyamine hydrochloride was added to a 100 mL flask, dissolved in pyridine, and the temperature was raised to 90 ° C. 5 g (0.018 mol) of 4-bromo-1,8-naphthic anhydride was added to this reaction solution little by little, and it was made to react for 4 hours, maintaining 90 degreeC. The reaction solution was poured into distilled water, precipitated with acetic anhydride, filtered and washed with methanol, and dried in a vacuum oven at 50 ° C. The obtained pale yellow material was placed in a 100 mL flask under nitrogen atmosphere, dissolved in dimethylformamide, and the temperature was increased to 90 ° C. 1.66 g (0.030 mol) of sodium methoxide was added to the reaction solution and reacted for 2 hours while maintaining at 90 ° C. The reaction solution was precipitated in cold distilled water, filtered and washed several times with water and methanol. The obtained compound was placed in a 50 mL flask under nitrogen atmosphere, dissolved in tetrahydrofuran, and then 1.175 g (0.0173 mol) of imidazole was added thereto and maintained at 0 ° C. 4.33 g (0.01726 mol) of 10-camphorsulfonyl chloride was slowly added to the reaction solution and reacted at room temperature for 12 hours. The reaction solvent was removed, extracted with chloroform, and dried in a vacuum oven at room temperature to obtain 'Camph-PAG'.

1H-NMR : δ8.65, 8.62, 8.60, 8.57, 8.55, 7.87, 7.40, 7.37, 7.35, 4.15, 4.03, 4.01, 1.07, 0.86 ppm 1 H-NMR: δ 8.65, 8.62, 8.60, 8.57, 8.55, 7.87, 7.40, 7.37, 7.35, 4.15, 4.03, 4.01, 1.07, 0.86 ppm

비교예 1Comparative Example 1

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol)과 이소프탈릭산 디클로라이드 15.63 g(0.076 mol)을 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 12시간 반응시켰다. 얻어진 점성의 액체를 0℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 43.3 g의 중간체 폴리아미드를 얻었다. 얻어진 흰색의 중간체 폴리아미드 38.8 g을 다시 테트라히드로퓨란 (THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 46.76 g을 p-톨루엔설폰산 1.51 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 폴리아미드 중합체 분말 43.19 g을 얻었다. 얻어진 고분자의 고유점도는 0.22 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는 바, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.1 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 15.63 g (0.076 mol) of isophthalic acid dichloride were added. The solution was dissolved in dimethylacetamide while stirring and reacted for 12 hours while maintaining 0 ° C. The resulting viscous liquid was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 43.3 g of intermediate polyamide. 38.8 g of the obtained white intermediate polyamide was again dissolved in tetrahydrofuran (THF), and 46.76 g of 7-equivalent 3,4-dihydro-2H-pyran was 1.51 p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and bound to acid-sensitized polyamide polymer powder 43.19 g was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.22 dL / g. The substitution rate of acid sensitivity isOneH-NMR spectroscopy showed that the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, As a result of comparing the integral areas of 3.52, 1.77, and 1.47 ppm), the concentration of the substituted acid sensitivity was [n / (n + m)] of 48.1 mol%.

실시예 1Example 1

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol)과 이소프탈릭산 디클로라이드 17.71 g(0.087 mol)을 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EA 1.63 g (0.0139 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 3-EA가 결합된 말단기 폴리아미드 49.3 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 41.3 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 50.00 g을 p-톨루엔설폰산 1.61 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 43.21 g을 얻었다. 얻어진 고분자의 고유점도는 0.19 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EA의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.18 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.5 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 17.71 g (0.087 mol) of isophthalic acid dichloride were added. The solution was dissolved in dimethylacetamide while stirring and reacted for 4 hours while maintaining 0 ° C. 1.63 g (0.0139 mol) of 3-EA was added to this viscous solution and reacted again for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 49.3 g of 3-EA-bonded end group polyamide. After dissolving 41.3 g of the obtained white polyamide powder in tetrahydrofuran (THF), 50.00 g of 3,4-dihydro-2H-pyran, which is 7 times equivalent, was added to 1.61 g of p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid-sensitization combined with terminal groups and acid sensitive groups. 43.21 g of polyamide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.19 dL / g. The binding of end group 3-EA to acid-sensitive polyamideOneBy confirming the acetylene peak (4.18 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) As a result of comparing the integrated areas, the concentration of the substituted acid sensitive group [n / (n + m)] was 48.5 mol%.

실시예 2Example 2

상기 실시예 1과 동일한 제조 방법으로 얻어진 3-EA가 결합된 말단기 폴리아미드 42 g을 다시 감마-부티로락톤에 용해한 후 4배 당량인 디-tert-디카보네이트 51.50 g을 피리딘 0.025 g과 함께 용해시키면서 2시간 동안 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 47.52 g을 얻었다. 얻어진 고분자의 고유점도는 0.20 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EA의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.18 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 메틸기의 지방족 수소원자(피크위치: 1.38 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 43.0 mol% 이었다.42 g of 3-EA-bonded end group polyamide obtained by the same preparation method as in Example 1 was dissolved in gamma-butyrolactone again, and 51.50 g of 4-ter equivalent di-tert-dicarbonate was pyridine 0.025. The viscous solution obtained by stirring for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and acid-sensitive poly with a terminal group and an acid sensitivity group. 47.52 g of amide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.20 dL / g. The binding of end group 3-EA to acid-sensitive polyamideOneBy confirming the acetylene peak (4.18 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of the aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the integral area of the aliphatic hydrogen atoms of the methyl group (peak position: 1.38 ppm) were compared. The concentration of acid sensitivity [n / (n + m)] was 43.0 mol%.

실시예 3Example 3

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol)과 이소프탈릭산 디클로라이드 15.65 g(0.07708 mol)을 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EB 2.16 g (0.0131 mol)을넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 3-EB가 결합된 말단기 폴리아미드 45.42 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 40.6 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 47.01 g을 p-톨루엔설폰산 1.52 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 44.99 g을 얻었다. 얻어진 고분자의 고유점도는 0.19 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EB의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.30 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 47.5 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 15.65 g (0.07708 mol) of isophthalic acid dichloride were added. The solution was dissolved in dimethylacetamide while stirring and reacted for 4 hours while maintaining 0 ° C. 2.16 g (0.0131 mol) of 3-EB was added to this viscous solution and reacted again for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 45.42 g of 3-EB-bonded end group polyamide. 40.6 g of the obtained white polyamide powder was again dissolved in tetrahydrofuran (THF), and then 47.01 g of 7-fold equivalent 3,4-dihydro-2H-pyran was dissolved with 1.52 g of p-toluenesulfonic acid for 2 hours. The viscous solution obtained by stirring again was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, and dried to obtain 44.99 g of an acid-sensitive polyamide polymer powder having a terminal group and an acid sensitive group bonded thereto. . The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.19 dL / g. The binding of the end group 3-EB to the acid-sensitive polyamide confirmed that the end group was covalently bonded by checking the acetylene peak (4.30 ppm) in the 1 H-NMR spectral spectrum. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) As a result of comparing the integrated areas, the concentration of the substituted acid sensitive group [n / (n + m)] was 47.5 mol%.

실시예 4Example 4

상기 실시예 3과 동일한 방법으로 제조한 3-EB가 결합된 말단기 폴리아미드 40.6 g을 다시 테트라히드로퓨란(THF)에 용해한 후 4배 당량인 에틸비닐에테르 23.0 g을 p-톨루엔설폰산 1.52 g과 함께 용해시키면서 30분간 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 44.07 g을 얻었다. 얻어진 고분자의 고유점도는 0.21 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는 바, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 아세탈의 지방족 수소원자(피크위치: 5.52, 3.68, 3.66, 3.51, 1.42, 1.04 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.3 mol% 이었다.40.6 g of 3-EB-bonded end group polyamide prepared in the same manner as in Example 3 was dissolved in tetrahydrofuran (THF), and then 23.0 g of 4-vinyl ethyl ether (1.52 g) of p-toluenesulfonic acid was added. The resulting solution was stirred for 30 minutes while being dissolved together, and the viscous solution obtained was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, dried, and acid-sensitive polyamide having a terminal group and an acid sensitivity group. 44.07 g of polymer powder was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.21 dL / g. The substitution rate of the acid sensitive group was confirmed by 1 H-NMR spectroscopy. The integral area of aromatic hydrogen (peak position: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atom of acetal (peak position) : Integral area of [5.52, 3.68, 3.66, 3.51, 1.42, 1.04 ppm) was found to be 48.3 mol%.

실시예 5Example 5

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol)과 이소프탈릭산 디클로라이드 15.65 g(0.077 mol)을 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EI 4.06 g(0.0131 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 3-EI가 결합된 말단기 폴리아미드 47.2 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 42.3 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 46.74 g을 p-톨루엔설폰산 1.51 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 46.48 g을 얻었다. 얻어진 고분자의 고유점도는 0.19 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EI의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.32 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.0 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 15.65 g (0.077 mol) of isophthalic acid dichloride were added. The solution was dissolved in dimethylacetamide while stirring and reacted for 4 hours while maintaining at 0 ° C. 4.06 g (0.0131 mol) of 3-EI was added to this viscous solution and reacted again for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 47.2 g of 3-EI-bonded end group polyamide. 42.3 g of the obtained white polyamide powder was again dissolved in tetrahydrofuran (THF), and then 46.74 g of 7-fold equivalent 3,4-dihydro-2H-pyran was dissolved with 1.51 g of p-toluenesulfonic acid for 2 hours. The viscous solution obtained by stirring was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, and dried to obtain 46.48 g of an acid-sensitive polyamide polymer powder having a terminal group and an acid sensitive group bonded thereto. . The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.19 dL / g. The binding of the terminal group 3-EI to the acid-sensitive polyamide confirmed that the terminal group was covalently bonded by checking the acetylene peak (4.32 ppm) in the 1 H-NMR spectral spectrum. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) As a result of comparing the integrated areas, the concentration of the substituted acid sensitive group [n / (n + m)] was 48.0 mol%.

상기 비교예 1 및 실시예 1 ∼ 5에서 합성한 산민감성 폴리아미드의 특성을 정리하여 나타내면 다음 표 1과 같다.The properties of the acid sensitive polyamides synthesized in Comparative Example 1 and Examples 1 to 5 are collectively shown in Table 1 below.

구 분division 말단기Terminal group 산민감기Acid cold 산민감기 치환율(mol%)Acid sensitivity substitution rate (mol%) 고유점도(dL/g)Intrinsic viscosity (dL / g) 비교예 1Comparative Example 1 -- THPTHP 48.148.1 0.220.22 실시예 1Example 1 3-EA3-EA THPTHP 48.548.5 0.190.19 실시예 2Example 2 3-EA3-EA t-boct-boc 43.043.0 0.200.20 실시예 3Example 3 3-EB3-EB THPTHP 47.547.5 0.190.19 실시예 4Example 4 3-EB3-EB EVEEVE 48.348.3 0.210.21 실시예 5Example 5 3-EI3-EI THPTHP 48.048.0 0.190.19 THP : 테트라히드로피라닐기, t-boc : t-부톡시기, EVE : 에틸비닐에테르기THP: tetrahydropyranyl group, t-boc: t-butoxy group, EVE: ethyl vinyl ether group

비교예 2Comparative Example 2

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 10.71 g(0.0527 mol) 및 옥시디벤조산 클로라이드 6.68 g(0.0226 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50℃의 진공오븐에서 건조하여 중간체 폴리아미드 45.0 g을 얻었다. 얻어진 흰색의 중간체 폴리아미드 분말 40.2 g을 다시 테트라히드로퓨란(THF)에 용해한 후 5배 당량인 3,4-디히드로-2H-피란 33.15 g을 p-톨루엔설폰산 1.50 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 폴리아미드 중합체 분말 44.56 g을 얻었다. 얻어진 고분자의 고유점도는 0.18 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는바, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 36.3 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 10.71 g (0.0527 mol) of isophthalic acid dichloride and 6.68 g (0.0226 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining 0 ° C. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 45.0 g of intermediate polyamide. After dissolving 40.2 g of the obtained white intermediate polyamide powder in tetrahydrofuran (THF) again, 33.15 g of 5, equivalent 3,4-dihydro-2H-pyran was added to 1.50 g of p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and bound to acid sensitive groups 44.56 g was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.18 dL / g. The substitution rate of acid sensitivity isOneAs confirmed by H-NMR spectroscopy, the integral area of aromatic hydrogen (peak position: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atom of cyclized acetal (peak position: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) and the integrated area of the substituted acid sensitizer [n / (n + m)] was 36.3 mol%.

실시예 6Example 6

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드12.53 g(0.0617 mol) 및 옥시디벤조산 클로라이드 7.81 g(0.0265 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EA 1.88 g(0.016 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 3-EA가 결합된 말단기 폴리아미드 49.6 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 44.4 g을 다시 테트라히드로퓨란(THF)에 용해한 후 5배 당량인 3,4-디히드로-2H-피란 36.20 g을 p-톨루엔설폰산 1.64 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 48.51 g을 얻었다. 얻어진 고분자의 고유점도는 0.17 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EA의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.18 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 38.7 mol% 이었다.20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 12.53 g (0.0617 mol) of isophthalic acid dichloride in a 500 mL flask under nitrogen atmosphere and 7.81 g (0.0265 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining 0 ° C. 1.88 g (0.016 mol) of 3-EA was added to this viscous solution and reacted again for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 49.6 g of 3-EA-bonded end group polyamide. 44.4 g of the obtained white polyamide powder was dissolved in tetrahydrofuran (THF) again, and then 36.20 g of 5, equivalent 3,4-dihydro-2H-pyran was dissolved with 1.64 g of p-toluenesulfonic acid for 2 hours. The viscous solution obtained by stirring was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, and dried to obtain 48.51 g of an acid-sensitive polyamide polymer powder having a terminal group and an acid sensitive group bonded thereto. . The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.17 dL / g. The binding of the end group 3-EA to the acid-sensitive polyamide confirmed that the end group was covalently bonded by checking the acetylene peak (4.18 ppm) in the 1 H-NMR spectral spectrum. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) of the integrated area, the concentration of the substituted acid sensitivity group [n / (n + m)] was 38.7 mol%.

실시예 7Example 7

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 10.72 g(0.0528 mol) 및 옥시디벤조산 클로라이드 6.68 g(0.0226 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EB 2.43 g(0.0148 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 3-EB가 결합된 말단기 폴리아미드 47.34 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 42.36 g을 다시 테트라히드로퓨란(THF)에 용해한 후 5배 당량인 3,4-디히드로-2H-피란 33.33 g을 p-톨루엔설폰산 1.50 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 46.57 g을 얻었다. 얻어진 고분자의 고유점도는 0.18 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EB의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.30 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 37.3 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 10.72 g (0.0528 mol) of isophthalic acid dichloride and 6.68 g (0.0226 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining 0 ° C. 2.43 g (0.0148 mol) of 3-EB was added to this viscous solution and reacted again for 12 hours. The resulting viscous liquid was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 47.34 g of 3-EB-bonded end group polyamide. 42.36 g of the obtained white polyamide powder was again dissolved in tetrahydrofuran (THF), and then 33.33 g of 5, equivalent 3,4-dihydro-2H-pyran was dissolved with 1.50 g of p-toluenesulfonic acid for 2 hours. The viscous solution obtained by stirring again was precipitated in a methanol solution cooled to 0 ° C., filtered, washed with methanol and water several times, and dried to obtain 46.57 g of acid-sensitive polyamide polymer powder having a terminal group and an acid sensitive group bonded thereto. . The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.18 dL / g. The binding of the end group 3-EB to the acid-sensitive polyamide confirmed that the end group was covalently bonded by checking the acetylene peak (4.30 ppm) in the 1 H-NMR spectral spectrum. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) of the integrated area was compared, the concentration of the substituted acid sensitivity group [n / (n + m)] was 37.3 mol%.

실시예 8Example 8

상기 실시예 7과 동일한 방법으로 제조한 3-EB가 결합된 말단기 폴리아미드 42.36 g을 다시 테트라히드로퓨란(THF)에 용해한 후 4배 당량인 에틸비닐에테르 22.16 g을 p-톨루엔설폰산 1.50 g과 함께 용해시키면서 30분간 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 45.67 g을 얻었다. 얻어진 고분자의 고유점도는 0.21 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는바, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 아세탈의 지방족 수소원자(피크위치: 5.52, 3.68, 3.66, 3.51, 1.42, 1.04 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 38.0 mol% 이었다.After dissolving 42.36 g of a 3-EB-bonded end group polyamide prepared in the same manner as in Example 7, again in tetrahydrofuran (THF), 22.16 g of 4-vinyl ethyl ether was added to 1.50 p-toluenesulfonic acid. The viscous solution obtained by stirring again for 30 minutes while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and acid-sensitive poly with a terminal group and an acid sensitivity group. 45.67 g of amide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.21 dL / g. The substitution rate of acid sensitivity isOneThe H-NMR spectroscopy showed that the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of acetal (peak positions: 5.52, 3.68, 3.66). , 3.51, 1.42, 1.04 ppm) and the integrated area of the substituted acid sensitive group [n / (n + m)] was 38.0 mol%.

실시예 9Example 9

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 10.72 g(0.0528 mol) 및 옥시디벤조산 클로라이드 6.68 g(0.0226 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EI 4.58 g(0.0148 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 3-EI가 결합된 말단기 폴리아미드 49.4 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 44.2 g을 다시 테트라히드로퓨란(THF)에 용해한 후 5배 당량의 3,4-디히드로-2H-피란 33.15 g을 p-톨루엔설폰산 1.49 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 48.27 g을 얻었다. 얻어진 고분자의 고유점도는 0.19 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EI의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.32 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 39.2 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 10.72 g (0.0528 mol) of isophthalic acid dichloride and 6.68 g (0.0226 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining at 0 ° C. 4.58 g (0.0148 mol) of 3-EI was added to this viscous solution and reacted again for 12 hours. The resulting viscous liquid was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 49.4 g of 3-EI-bonded end group polyamide. After dissolving 44.2 g of the obtained white polyamide powder in tetrahydrofuran (THF) again, 33.15 g of 5 times equivalent of 3,4-dihydro-2H-pyran was added to 1.49 g of p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid-sensitization combined with terminal groups and acid sensitive groups. 48.27 g of polyamide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.19 dL / g. Bonding of end group 3-EI to acid-sensitive polyamideOneBy confirming the acetylene peak (4.32 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and aliphatic hydrogen atoms of cyclized acetal (5.57, 3.83, 3.52, 1.77, 1.47 ppm) As a result of comparing the integrated area of, the concentration of substituted acid sensitivity was [n / (n + m)] was 39.2 mol%.

실시예 10Example 10

상기 실시예 9과 동일한 제조 방법으로 얻어진 3-EI가 결합된 말단기 폴리아미드 44.2 g을 다시 감마-부티로락톤에 용해한 후 4배 당량인 디-tert-디카보네이트 51.11 g을 피리딘 0.25 g과 함께 용해시키면서 1시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 49.47 g을 얻었다. 얻어진 고분자의 고유점도는 0.18 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EI의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.32 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 메틸기의 지방족 수소원자(피크위치: 1.32 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 38.0 mol% 이었다.After dissolving 44.2 g of 3-EI-bonded end group polyamide obtained by the same preparation method as in Example 9 above in gamma-butyrolactone, 51.11 g of 4-ter equivalent of di-tert-dicarbonate was pyridine 0.25 The viscous solution obtained by stirring for 1 hour while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid-sensitization combined with terminal groups and acid sensitive groups. 49.47 g of polyamide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.18 dL / g. Bonding of end group 3-EI to acid-sensitive polyamideOneBy confirming the acetylene peak (4.32 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the integral area of aliphatic hydrogen atoms of the methyl group (peak position: 1.32 ppm) were compared. As a result, the concentration of substituted acid sensitive group [n / (n + m)] was 38.0 mol%.

상기 비교예 2 및 실시예 6 ∼ 10에서 합성한 산민감성 폴리아미드의 특성을 정리하여 나타내면 다음 표 2와 같다.The properties of the acid sensitive polyamides synthesized in Comparative Example 2 and Examples 6 to 10 are collectively shown in Table 2 below.

구 분division 말단기Terminal group 산민감기Acid cold 산민감기 치환율(mol%)Acid sensitivity substitution rate (mol%) 고유점도(dL/g)Intrinsic viscosity (dL / g) 비교예 2Comparative Example 2 -- THPTHP 36.336.3 0.180.18 실시예 6Example 6 3-EA3-EA THPTHP 38.738.7 0.170.17 실시예 7Example 7 3-EB3-EB THPTHP 37.337.3 0.180.18 실시예 8Example 8 3-EB3-EB EVEEVE 38.038.0 0.210.21 실시예 9Example 9 3-EI3-EI THPTHP 39.239.2 0.190.19 실시예 10Example 10 3-EI3-EI t-boct-boc 38.038.0 0.180.18 THP : 테트라히드로피라닐기, t-boc : t-부톡시기, EVE : 에틸비닐에테르기THP: tetrahydropyranyl group, t-boc: t-butoxy group, EVE: ethyl vinyl ether group

비교예 3Comparative Example 3

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 7.68 g(0.0378 mol) 및 옥시디벤조산 클로라이드 11.16 g(0.0378 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50℃의 진공오븐에서 건조하여 중간체 폴리아미드 45.0 g을 얻었다. 얻어진 흰색의 중간체 폴리아미드 분말 41.5 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 46.289 g을 p-톨루엔설폰산 1.495 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 폴리아미드 중합체 분말 45.71 g을 얻었다. 얻어진 고분자의 고유점도는 0.19 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는바, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 46.2 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 7.68 g (0.0378 mol) of isophthalic acid dichloride and 11.16 g (0.0378 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining at 0 ° C. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 45.0 g of intermediate polyamide. After dissolving 41.5 g of the obtained white intermediate polyamide powder in tetrahydrofuran (THF) again, 46.289 g of 3,4-dihydro-2H-pyran, which is 7-fold equivalent, was converted into p-toluenesulfonic acid 1.495. The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and bound to acid-sensitized polyamide polymer powder 45.71 g was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.19 dL / g. The substitution rate of acid sensitivity isOneAs confirmed by H-NMR spectroscopy, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (5.57, 3.83) , 3.52, 1.77, 1.47 ppm) and the integrated area of the acid-substituted concentration [n / (n + m)] was 46.2 mol%.

실시예 11Example 11

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 9.05 g(0.0446 mol) 및 옥시디벤조산 클로라이드 13.16 g(0.0446 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EA 1.88 g (0.016 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50℃의 진공오븐에서 건조하여 3-EA가 결합된 말단기 폴리아미드 51.4 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 46.0 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 50.64 g을 p-톨루엔설폰산 1.64 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 49.59 g을 얻었다. 얻어진 고분자의 고유점도는 0.20 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EA의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.18 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.5 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9.05 g (0.0446 mol) of isophthalic acid dichloride and 13.16 g (0.0446 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining at 0 ° C. 1.88 g (0.016 mol) of 3-EA was added to this viscous solution and reacted again for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to give 51.4 g of 3-EA-bonded end group polyamide. After dissolving 46.0 g of the obtained white polyamide powder in tetrahydrofuran (THF) again, 50.64 g of 3,4-dihydro-2H-pyran, which is 7 times equivalent, was added to 1.64 p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while dissolving with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid sensitivity combined with terminal groups and acid sensitive groups. 49.59 g of polyamide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.20 dL / g. The binding of end group 3-EA to acid-sensitive polyamideOneBy confirming the acetylene peak (4.18 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) of the integrated area, the concentration of the substituted acid sensitivity group [n / (n + m)] was 48.5 mol%.

실시예 12Example 12

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 7.66 g(0.0377 mol) 및 옥시디벤조산 클로라이드 11.13 g(0.0377 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EB 2.43 g (0.0148 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 3-EB가 결합된 말단기 폴리아미드 48.7 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 43.5 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 46.50 g을 p-톨루엔설폰산 1.50 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 47.68 g을 얻었다. 얻어진 고분자의 고유점도는 0.19 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EB의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.30 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의농도[n/(n+m)]는 49.5 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 7.66 g (0.0377 mol) of isophthalic acid dichloride, and 11.13 g (0.0377 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining 0 ° C. 2.43 g (0.0148 mol) of 3-EB was added to the viscous solution and reacted again for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 48.7 g of a 3-EB bonded terminal group polyamide. After dissolving 43.5 g of the obtained white polyamide powder in tetrahydrofuran (THF) again, 46.50 g of 3,4-dihydro-2H-pyran, which is 7 times equivalent, was added to 1.50 g of p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid-sensitization combined with terminal groups and acid sensitive groups. 47.68 g of polyamide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.19 dL / g. The binding of end group 3-EB to acid-sensitive polyamideOneBy confirming the acetylene peak (4.30 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) showed an integrated area, and the concentration of the substituted acid sensitive group [n / (n + m)] was 49.5 mol%.

실시예 13Example 13

상기 실시예 12과 동일한 제조 방법으로 얻어진 3-EB가 결합된 말단기 폴리아미드 43.5 g을 다시 감마-부티로락톤에 용해한 후 4배 당량인 디-tert-디카보네이트 50.59 g을 피리딘 0.25 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 48.89 g을 얻었다. 얻어진 고분자의 고유점도는 0.18 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EB의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.30 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 메틸기의 지방족 수소원자(피크위치: 1.32 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 47.5 mol% 이었다.43.5 g of 3-EB-bonded end group polyamide obtained by the same preparation method as in Example 12 was dissolved in gamma-butyrolactone again, and then 50.59 g of 4-fold equivalent di-tert-dicarbonate was pyridine 0.25. The viscous solution obtained by stirring again for 2 hours while dissolving with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid sensitivity combined with terminal groups and acid sensitive groups. 48.89 g of polyamide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.18 dL / g. The binding of end group 3-EB to acid-sensitive polyamideOneBy confirming the acetylene peak (4.30 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the integral area of aliphatic hydrogen atoms of the methyl group (peak position: 1.32 ppm) were compared. As a result, the concentration of substituted acid sensitive group [n / (n + m)] was 47.5 mol%.

실시예 14Example 14

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 7.66g(0.0377 mol) 및 옥시디벤조산 클로라이드 11.13 g(0.0377 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 3-EI 4.58 g (0.0148 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 3-EI가 결합된 말단기 폴리아미드 50.7 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 45.4 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 46.54 g을 p-톨루엔설폰산 1.50 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 49.38 g을 얻었다. 얻어진 고분자의 고유점도는 0.20 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 3-EI의 결합여부는1H-NMR 분광 스펙트럼에서의 아세틸렌 피크(4.32 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.5 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 7.66 g (0.0377 mol) of isophthalic acid dichloride and 11.13 g (0.0377 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining 0 ° C. 4.58 g (0.0148 mol) of 3-EI was added to this viscous solution and reacted again for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to give 50.7 g of 3-EI-bonded end group polyamide. After dissolving 45.4 g of the obtained white polyamide powder in tetrahydrofuran (THF) again, 46.54 g of 3,4-dihydro-2H-pyran, which is 7 times equivalent, was added to 1.50 p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid-sensitization combined with terminal groups and acid sensitive groups. 49.38 g of polyamide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.20 dL / g. Bonding of end group 3-EI to acid-sensitive polyamideOneBy confirming the acetylene peak (4.32 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) of the integrated area, the concentration of the substituted acid sensitivity group [n / (n + m)] was 48.5 mol%.

실시예 15Example 15

상기 실시예 14와 동일한 방법으로 제조한 3-EI가 결합된 말단기 폴리아미드 45.4 g을 다시 테트라히드로퓨란(THF)에 용해한 후 4배 당량인 에틸비닐에테르 22.78 g을 p-톨루엔설폰산 1.50 g과 함께 용해시키면서 30분간 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 51.03 g을 얻었다. 얻어진 고분자의 고유점도는 0.19 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는 바, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 아세탈의 지방족 수소원자(피크위치: 5.52, 3.68, 3.66, 3.51, 1.42, 1.04 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 47.0 mol% 이었다.45.4 g of 3-EI-bonded end group polyamide prepared in the same manner as in Example 14 was dissolved again in tetrahydrofuran (THF), and then 22.78 g of 4-vinyl ethyl vinyl ether was added to 1.50 g of p-toluenesulfonic acid. The viscous solution obtained by stirring again for 30 minutes while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and acid-sensitive poly with a terminal group and an acid sensitivity group. 51.03 g of amide polymer powder were obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.19 dL / g. The substitution rate of acid sensitivity isOneThe H-NMR spectroscopy showed that the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of acetal (peak positions: 5.52, 3.68, 3.66). , 3.51, 1.42, 1.04 ppm) and the integrated area of the substituted acid sensitizer [n / (n + m)] was 47.0 mol%.

실시예 16Example 16

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 7.66 g(0.0377 mol) 및 옥시디벤조산 클로라이드 11.13 g(0.0377 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 4시간 반응시켰다. 이 점성의 용액에 DEI 4.75 g (0.0142 mol)을 넣고 다시 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50℃의진공오븐에서 건조하여 DEI가 결합된 말단기 폴리아미드 44.3 g을 얻었다. 얻어진 흰색의 폴리아미드 분말 39.6 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 47.52 g을 p-톨루엔설폰산 1.53 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 말단기와 산민감기가 결합된 산민감성 폴리아미드 중합체 분말 43.06 g을 얻었다. 얻어진 고분자의 고유점도는 0.20 dL/g의 분자량이 얻어졌다. 산민감성 폴리아미드에 말단기 DEI의 결합여부는1H-NMR 분광 스펙트럼에서의 2개의 아세틸렌 피크(4.31 ppm)를 확인함으로써 말단기가 중합체 공유결합 되었음을 확인할 수 있었다. 또한, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.0 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 7.66 g (0.0377 mol) of isophthalic acid dichloride, and 11.13 g (0.0377 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 4 hours while maintaining 0 ° C. 4.75 g (0.0142 mol) of DEI was added to this viscous solution and reacted again for 12 hours. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 44.3 g of a terminal group polyamide having DEI bound thereto. After dissolving 39.6 g of the obtained white polyamide powder in tetrahydrofuran (THF) again, 47.52 g of 3,4-dihydro-2H-pyran, which is 7 times equivalent, was added to 1.53 p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while dissolving with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid sensitivity combined with terminal groups and acid sensitive groups. 43.06 g of polyamide polymer powder was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.20 dL / g. The binding of end group DEI to acid-sensitive polyamideOneBy confirming two acetylene peaks (4.31 ppm) in the H-NMR spectral spectrum, it was confirmed that the end group was covalently bonded to the polymer. In addition, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) of the integrated area was compared, the concentration of the substituted acid sensitivity group [n / (n + m)] was 48.0 mol%.

상기 비교예 3 및 실시예 11 ∼ 16에서 합성한 산민감성 폴리아미드의 특성을 정리하여 나타내면 다음 표 3과 같다.The properties of the acid sensitive polyamides synthesized in Comparative Example 3 and Examples 11 to 16 are collectively shown in Table 3 below.

구 분division 말단기Terminal group 산민감기Acid cold 산민감기 치환율(mol%)Acid sensitivity substitution rate (mol%) 고유점도(dL/g)Intrinsic viscosity (dL / g) 비교예 3Comparative Example 3 -- THPTHP 46.246.2 0.190.19 실시예 11Example 11 3-EA3-EA THPTHP 48.548.5 0.200.20 실시예 12Example 12 3-EB3-EB THPTHP 49.549.5 0.190.19 실시예 13Example 13 3-EB3-EB t-boct-boc 47.547.5 0.180.18 실시예 14Example 14 3-EI3-EI THPTHP 48.548.5 0.200.20 실시예 15Example 15 3-EI3-EI EVEEVE 47.047.0 0.190.19 실시예 16Example 16 DEIDEI THPTHP 48.048.0 0.200.20 THP : 테트라히드로피라닐기, t-boc : t-부톡시기, EVE : 에틸비닐에테르기THP: tetrahydropyranyl group, t-boc: t-butoxy group, EVE: ethyl vinyl ether group

비교예 4Comparative Example 4

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol)과 이소프탈릭산 디클로라이드 16.64 g(0.082 mol)을 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50 ℃의 진공오븐에서 건조하여 중간체 폴리아미드 44.3 g을 얻었다. 얻어진 흰색의 중간체 폴리아미드 분말 39.6 g을 다시 테트라히드로퓨란(THF)에 용해한 후 7배 당량인 3,4-디히드로-2H-피란 47.04 g을 p-톨루엔설폰산 1.51 g과 함께 용해시키면서 2시간 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 폴리아미드 중합체 분말 44.0 g을 얻었다. 얻어진 고분자의 고유점도는 0.81 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는바, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.0 mol% 이었다.In a 500 mL flask under nitrogen atmosphere, 20 mL of pyridine, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 16.64 g (0.082 mol) of isophthalic acid dichloride were added. The solution was dissolved in dimethylacetamide while stirring and reacted for 12 hours while maintaining 0 ° C. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 44.3 g of intermediate polyamide. 39.6 g of the obtained white intermediate polyamide powder was dissolved in tetrahydrofuran (THF) again, and 47.04 g of 3,4-dihydro-2H-pyran, which is 7-fold equivalent, was added to 1.51 p-toluenesulfonic acid 1.51. After stirring for 2 hours while dissolving with g, the viscous solution obtained was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and bound with acid-sensitized polyamide polymer powder 44.0 g Got. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.81 dL / g. The substitution rate of acid sensitivity isOneH-NMR spectroscopy showed that the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of cyclized acetal (peak positions: 5.57, 3.83, As a result of comparing the integrated areas of 3.52, 1.77, and 1.47 ppm), the concentration of the substituted acid sensitivity was [n / (n + m)] of 48.0 mol%.

비교예 5Comparative Example 5

상기 비교예 4와 동일한 방법으로 제조한 중간체 폴리아미드 39.6 g을 다시 감마-부티로락톤에 용해한 후 4배 당량인 디-tert-디카보네이트 51.81 g을 피리딘 0.25 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 중간체 폴리아미드 분말 45.21 g을 얻었다. 얻어진 고분자의 고유점도는 0.79 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는 바, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 메틸기의 지방족 수소원자(피크위치: 1.32 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 41.2 mol% 이었다.After dissolving 39.6 g of the intermediate polyamide prepared in the same manner as in Comparative Example 4 again in gamma-butyrolactone, 51.81 g of 4-fold equivalent di-tert-dicarbonate was pyridine 0.25 The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried and the intermediate polyamide powder bound with acid sensitivity was 45.21 g was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.79 dL / g. The substitution rate of acid sensitivity isOneAs confirmed by H-NMR spectroscopy, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the integral of the aliphatic hydrogen atoms of the methyl group (peak position: 1.32 ppm) were determined. As a result of comparing the areas, the concentration of substituted acid sensitive group [n / (n + m)] was 41.2 mol%.

비교예 6Comparative Example 6

상기 비교예 4와 동일한 방법으로 제조한 중간체 폴리아미드 39.6g을 다시 테트라히드로퓨란(THF)에 용해한 후 4배 당량인 에틸비닐에테르 23.05 g을 p-톨루엔설폰산 1.52 g과 함께 용해시키면서 30분간 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 폴리아미드 중합체 분말 43.09 g을 얻었다. 얻어진 고분자의 고유점도는 0.80 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는 바, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 아세탈의 지방족 수소원자(피크위치: 5.52, 3.68, 3.66, 3.51, 1.42, 1.04 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 48.0 mol% 이었다.39.6 g of the intermediate polyamide prepared in the same manner as in Comparative Example 4 was dissolved in tetrahydrofuran (THF) again, and 23.05 g of 4-vinyl ethyl vinyl ether was added to 1.52 p-toluenesulfonic acid 1.52. The viscous solution obtained by stirring again for 30 minutes while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, and dried. Got. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.80 dL / g. The substitution rate of acid sensitivity isOneThe H-NMR spectroscopy showed that the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atoms of acetal (peak positions: 5.52, 3.68, 3.66). , 3.51, 1.42, 1.04 ppm) and the integrated area of the substituted acid sensitive group [n / (n + m)] was 48.0 mol%.

비교예 7Comparative Example 7

질소분위기하에서 500 mL 플라스크에 피리딘 20 mL, 2,2-비스(3-아미노-4-히드록시페닐)헥사플로오로프로판 30 g(0.082 mol), 이소프탈릭산 디클로라이드 11.65 g(0.0574 mol) 및 옥시디벤조산 클로라이드 7.26 g(0.0246 mol)을 혼합하여 넣고 교반하면서 디메틸아세트아미드에 용해시키고 0 ℃를 유지하면서 12시간 반응시켰다. 얻어진 점성의 액체를 0 ℃로 냉각된 메탄올 1 L에서 침전시키고 50℃의 진공오븐에서 건조하여 중간체 폴리아미드 46.4 g을 얻었다. 얻어진 흰색의 전구체 분말 41.5 g을 다시 테트라히드로퓨란(THF)에 용해한 후 5배 당량인 3,4-디히드로-2H-피란 39.27 g을 p-톨루엔설폰산 1.78 g과 함께 용해시키면서 2시간 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 폴리아미드 중합체 분말 45.75 g을 얻었다. 얻어진 고분자의 고유점도는 0.95 dL/g의분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는바, 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 환화 아세탈의 지방족 수소원자(피크위치: 5.57, 3.83, 3.52, 1.77, 1.47 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 36.9 mol% 이었다.20 mL of pyridine in a 500 mL flask under nitrogen atmosphere, 30 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 11.65 g (0.0574 mol) of isophthalic acid dichloride and 7.26 g (0.0246 mol) of oxydibenzoic acid chloride was mixed, dissolved in dimethylacetamide with stirring, and reacted for 12 hours while maintaining 0 ° C. The viscous liquid obtained was precipitated in 1 L of methanol cooled to 0 ° C. and dried in a vacuum oven at 50 ° C. to obtain 46.4 g of intermediate polyamide. 41.5 g of the white precursor powder thus obtained was dissolved in tetrahydrofuran (THF) again, and then 39.27 g of 3,4-dihydro-2H-pyran, which was 5 times equivalent, was added to 1.78 g of p-toluenesulfonic acid. The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and bound with acid-sensitized polyamide polymer powder 45.75 g Got. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.95 dL / g. The substitution rate of acid sensitivity isOneAs confirmed by H-NMR spectroscopy, the integral area of aromatic hydrogen (peak position: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and the aliphatic hydrogen atom of cyclized acetal (peak position: 5.57, 3.83, 3.52, 1.77, 1.47 ppm) and the integrated area of the substituted acid sensitizer [n / (n + m)] was 36.9 mol%.

비교예 8Comparative Example 8

상기 비교예 7과 동일한 방법으로 제조한 중간체 폴리아미드 41.5 g을 다시 감마-부티로락톤에 용해한 후 4배 당량인 디-tert-디카보네이트 60.54 g을 피리딘 0.30 g과 함께 용해시키면서 2시간 동안 다시 교반을 하여 얻어진 점성의 용액을 0℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 폴리아미드 중합체 분말 46.96 g을 얻었다. 얻어진 고분자의 고유점도는 0.80 dL/g의 분자량이 얻어졌다. 산민감기의 치환율은1H-NMR 분광 스펙트럼으로 확인하였는바, 방향족 수소(피크위치: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm)의 적분면적과, 메틸기의 지방족 수소원자(피크위치: 1.32 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 45.2 mol% 이었다.After dissolving 41.5 g of the intermediate polyamide prepared in the same manner as in Comparative Example 7 again in gamma-butyrolactone, 60.54 g of di-tert-dicarbonate having a 4-fold equivalent was pyridine 0.30 The viscous solution obtained by stirring again for 2 hours while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and bound to acid-sensitized polyamide polymer powder 46.96 g was obtained. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.80 dL / g. The substitution rate of acid sensitivity isOneAs confirmed by H-NMR spectroscopy, the integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 7.91, 7.65, 7.28, 7.12, 7.00 ppm) and the integral of the aliphatic hydrogen atoms of the methyl group (peak position: 1.32 ppm) were determined. As a result of comparing the areas, the concentration of substituted acid sensitive group [n / (n + m)] was 45.2 mol%.

비교예 9Comparative Example 9

상기 비교예 7과 동일한 방법으로 제조한 중간체 폴리아미드 41.5 g을 다시 테트라히드로퓨란(THF)에 용해한 후 4배 당량인 에틸비닐에테르 26.93 g을 p-톨루엔설폰산 1.78 g과 함께 용해시키면서 30분간 다시 교반을 하여 얻어진 점성의 용액을 0 ℃로 냉각시킨 메탄올 용액에서 침전시키고 여과하여 수 차례에 걸쳐 메탄올과 물로 세척, 건조하여 산민감기가 결합된 폴리아미드 중합체 분말 44.85 g을 얻었다. 얻어진 고분자의 고유점도는 0.79 dL/g의 분자량이 얻어졌다. 방향족 수소(피크위치: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm)의 적분면적과, 아세탈의 지방족 수소원자(피크위치: 5.52, 3.68, 3.66, 3.51, 1.42, 1.04 ppm)의 적분면적을 비교한 결과, 치환된 산민감기의 농도[n/(n+m)]는 49.0 mol% 이었다.41.5 g of the intermediate polyamide prepared in the same manner as in Comparative Example 7 was again dissolved in tetrahydrofuran (THF), followed by 26.93 g of 4-vinyl ethyl ether (1.78 g) of p-toluenesulfonic acid. The viscous solution obtained by stirring again for 30 minutes while being dissolved together with g was precipitated in a methanol solution cooled to 0 ° C., filtered, washed several times with methanol and water, dried, and then subjected to acid-sensitized polyamide polymer powder 44.85 g Got. The intrinsic viscosity of the obtained polymer was obtained with a molecular weight of 0.79 dL / g. Integral area of aromatic hydrogen (peak positions: 8.50, 8.10, 8.01, 7.91, 7.65, 7.52, 7.28, 7.12, 7.00 ppm) and aliphatic hydrogen atoms of acetal (peak positions: 5.52, 3.68, 3.66, 3.51, 1.42, 1.04) ppm), and the concentration of the substituted acid sensitive group [n / (n + m)] was 49.0 mol%.

상기 비교예 4 ∼ 9에서 합성한 산민감성 폴리아미드의 특성을 정리하여 나타내면 다음 표 4와 같다.The properties of the acid sensitive polyamides synthesized in Comparative Examples 4 to 9 are collectively shown in Table 4 below.

구 분division 말단기Terminal group 산민감기Acid cold 산민감기 치환율(mol%)Acid sensitivity substitution rate (mol%) 고유점도(dL/g)Intrinsic viscosity (dL / g) 비교예 4Comparative Example 4 -- THPTHP 48.048.0 0.810.81 비교예 5Comparative Example 5 -- t-boct-boc 41.241.2 0.790.79 비교예 6Comparative Example 6 -- EVEEVE 48.048.0 0.800.80 비교예 7Comparative Example 7 -- THPTHP 36.936.9 0.950.95 비교예 8Comparative Example 8 -- t-boct-boc 45.245.2 0.800.80 비교예 9Comparative Example 9 -- EVEEVE 49.049.0 0.790.79 THP : 테트라히드로피라닐기, t-boc : t-부톡시기, EVE : 에틸비닐에테르기THP: tetrahydropyranyl group, t-boc: t-butoxy group, EVE: ethyl vinyl ether group

[ 실험예 ]Experimental Example

상기 실시예 1 ∼ 16과 비교예 1 ∼ 9에서 얻은 각각의 폴리아미드 중합체와여러 가지의 광산발생제를 다음 표 5에 나타낸 바와 같은 함량으로 N-메틸-2-피롤리돈(NMP)에 40 중량%로 용해시키고 0.25 ㎛ 필터를 통하여 여과하였다. 이 용액을 실리콘 웨이퍼에 스핀코팅하고 110 ℃에서 5분간 가속건조하여 예시한 두께의의 절연체 박막을 얻었다. 365 nm의 필터가 장착된 자외선 노광장비를 사용하여 포토마스크를 통하여 30초간 노광하였다. 이 후 90 ℃에서 1분간 가열한 후 사메틸암모늄 히드록사이드(TMAH) 2.38 중량%의 현상액에서 현상한 후 물로 세척하였다. 패턴이 형성된 웨이퍼를 150 ℃에서 1시간, 300 ℃의 2시간 가열하여 경화된 패턴을 얻었다. 패턴된 박막의 FT-IR 분광 스펙트럼을 분석한 결과, 경화 전에 존재하였던 1660 cm-1의 아미드 특성피크의 소멸과, 1487 cm-1에서의 벤조옥사졸 특성피크의 생성으로부터 고분자 박막은 100% 폴리벤조옥사졸로 전환되었음을 확인하였다. 해상력은 프로파일로미터를 이용하여 깊이와 폭을 확인하였고, 박막의 단면을 전자현미경으로 관찰하였다.Each of the polyamide polymers obtained in Examples 1 to 16 and Comparative Examples 1 to 9 and various kinds of photoacid generators were added to N-methyl-2-pyrrolidone (NMP) in an amount as shown in Table 5 below. Dissolved in weight percent and filtered through a 0.25 μm filter. The solution was spin-coated on a silicon wafer and accelerated to dry at 110 ° C. for 5 minutes to obtain an insulator thin film of the thickness shown. It was exposed for 30 seconds through a photomask using an ultraviolet exposure equipment equipped with a 365 nm filter. Thereafter, the mixture was heated at 90 ° C. for 1 minute, and then developed in a developer of 2.38 wt% of tetramethylammonium hydroxide (TMAH), followed by washing with water. The patterned wafer was heated at 150 ° C. for 1 hour and 300 ° C. for 2 hours to obtain a cured pattern. Analysis of the FT-IR spectral spectrum of the patterned thin film showed that the polymer thin film was 100% poly from the disappearance of the 1660 cm -1 amide characteristic peak that existed before curing and the formation of the benzoxazole characteristic peak at 1487 cm -1 . It was confirmed that it was converted to benzoxazole. The resolution was checked for depth and width using a profilometer, and the cross section of the thin film was observed with an electron microscope.

각각의 실험 결과는 다음 표 5에 정리하여 나타내었다.Each experimental result is summarized in Table 5 below.

시료sample 산민감성 폴리아미드Acid Sensitive Polyamide 광산발생제, 중량%a) Photoacid generator, weight% a) 용액점도(cps)Solution viscosity (cps) 코팅성Coating Dose(mJ/㎤)Dose (mJ / cm 3) 두께(㎛)Thickness (㎛) 선폭(㎛)Line width (㎛) 인장강도(㎏f/㎠)Tensile Strength (㎏f / ㎠) 시료 1Sample 1 비교예 1Comparative Example 1 CF-PAG, 1CF-PAG, 1 2680* 2680 * 보통usually 150150 1111 55 brittlebrittle 시료 2Sample 2 비교예 2Comparative Example 2 CF-PAG, 1CF-PAG, 1 2363* 2363 * 보통usually 140140 88 33 brittlebrittle 시료 3Sample 3 비교예 3Comparative Example 3 CF-PAG, 1CF-PAG, 1 2368* 2368 * 좋음good 150150 1111 55 brittlebrittle 시료 4Sample 4 비교예 4Comparative Example 4 CF-PAG, 1CF-PAG, 1 3577** 3577 ** 나쁨Bad 170170 1313 88 11001100 시료 5Sample 5 비교예 5Comparative Example 5 CF-PAG, 1CF-PAG, 1 3560** 3560 ** 나쁨Bad 170170 1313 88 10801080 시료 6Sample 6 비교예 6Comparative Example 6 CF-PAG, 1CF-PAG, 1 3568** 3568 ** 나쁨Bad 170170 1313 88 10501050 시료 7Sample 7 비교예 7Comparative Example 7 CF-PAG, 1CF-PAG, 1 4200** 4200 ** 나쁨Bad 170170 1313 88 11201120 시료 8Sample 8 비교예 8Comparative Example 8 CF-PAG, 1CF-PAG, 1 3560** 3560 ** 나쁨Bad 170170 1313 88 11501150 시료 9Sample 9 비교예 9Comparative Example 9 CF-PAG, 1CF-PAG, 1 3560** 3560 ** 나쁨Bad 170170 1313 88 11501150 시료 10Sample 10 실시예 1Example 1 CF-PAG, 1CF-PAG, 1 2465* 2465 * 보통usually 150150 1111 55 12001200 시료 11Sample 11 실시예 1Example 1 NBAS, 2NBAS, 2 2470* 2470 * 보통usually 400400 1111 55 12001200 시료 12Sample 12 실시예 2Example 2 CF-PAG, 1CF-PAG, 1 2372* 2372 * 보통usually 150150 1111 55 11801180 시료 13Sample 13 실시예 2Example 2 NBAS, 2NBAS, 2 2376* 2376 * 보통usually 400400 1111 55 11501150 시료 14Sample 14 실시예 3Example 3 CF-PAG, 1CF-PAG, 1 2368* 2368 * 보통usually 150150 1111 55 12101210 시료 15Sample 15 실시예 3Example 3 NBAS, 2NBAS, 2 2360* 2360 * 보통usually 400400 1111 66 12001200 시료 16Sample 16 실시예 3Example 3 Camph-PAG, 1.5Camph-PAG, 1.5 2358* 2358 * 보통usually 200200 1111 55 11501150 시료 17Sample 17 실시예 4Example 4 CF-PAG, 1CF-PAG, 1 2605* 2605 * 보통usually 150150 1111 55 12101210 시료 18Sample 18 실시예 5Example 5 Camph-PAG, 1.5Camph-PAG, 1.5 2401* 2401 * 보통usually 200200 1111 55 12101210 시료 19Sample 19 실시예 6Example 6 NBAS, 2NBAS, 2 2355* 2355 * 좋음good 380380 88 66 12401240 시료 20Sample 20 실시예 7Example 7 CF-PAG, 1CF-PAG, 1 2363* 2363 * 좋음good 140140 88 33 12401240 시료 21Sample 21 실시예 7Example 7 NBAS, 2NBAS, 2 2367* 2367 * 좋음good 380380 88 33 12101210 시료 22Sample 22 실시예 7Example 7 Camph-PAG, 1.5Camph-PAG, 1.5 2350* 2350 * 좋음good 190190 88 33 12801280 시료 23Sample 23 실시예 8Example 8 CF-PAG, 1CF-PAG, 1 2355* 2355 * 좋음good 140140 88 33 12401240 시료 24Sample 24 실시예 9Example 9 CF-PAG, 1CF-PAG, 1 2411* 2411 * 좋음good 140140 88 33 12501250 시료 25Sample 25 실시예 10Example 10 CF-PAG, 1CF-PAG, 1 2397* 2397 * 좋음good 140140 88 33 12601260 시료 26Sample 26 실시예 10Example 10 NBAS, 2NBAS, 2 2407* 2407 * 좋음good 380380 88 55 12101210 시료 27Sample 27 실시예 10Example 10 Camph-PAG, 1.5Camph-PAG, 1.5 2368* 2368 * 좋음good 190190 88 33 12401240 시료 28Sample 28 실시예 11Example 11 CF-PAG, 1CF-PAG, 1 2372* 2372 * 좋음good 150150 1111 55 12801280 시료 29Sample 29 실시예 12Example 12 CF-PAG, 1CF-PAG, 1 2396* 2396 * 좋음good 150150 1111 55 12501250 시료 30Sample 30 실시예 12Example 12 NBAS, 2NBAS, 2 2412* 2412 * 좋음good 400400 1111 55 12801280 시료 31Sample 31 실시예 12Example 12 Camph-PAG, 1.5Camph-PAG, 1.5 2391* 2391 * 좋음good 200200 1111 55 12701270 시료 32Sample 32 실시예 13Example 13 CF-PAG, 1CF-PAG, 1 2364* 2364 * 좋음good 150150 1111 66 12801280 시료 33Sample 33 실시예 14Example 14 CF-PAG, 1CF-PAG, 1 2472* 2472 * 좋음good 150150 1111 55 12601260 시료 34Sample 34 실시예 14Example 14 NBAS, 2NBAS, 2 2438* 2438 * 좋음good 400400 1111 66 12301230

시료sample 산민감성폴리아미드Acid Sensitive Polyamide 광산발생제, 중량%a)Photoacid generator, weight% a) 용액점도(cps)Solution viscosity (cps) 코팅성Coating Dose(mJ/㎤)Dose (mJ / cm 3) 두께(㎛)Thickness (㎛) 선폭(㎛)Line width (㎛) 인장강도(㎏f/㎠)Tensile Strength (㎏f / ㎠) 시료 35Sample 35 실시예 14Example 14 Camph-PAG, 1.5Camph-PAG, 1.5 2409* 2409 * 좋음good 200200 1111 55 12601260 시료 36Sample 36 실시예 15Example 15 CF-PAG, 1CF-PAG, 1 2392* 2392 * 좋음good 150150 1111 55 12501250 시료 37Sample 37 실시예 16Example 16 CF-PAG, 1CF-PAG, 1 2402* 2402 * 좋음good 150150 1111 55 12801280 a)산민감성 폴리아미드에 대비되는 사용량임*25℃, 40중량% NMP 용액에서 측정,**25℃, 20중량% NMP 용액에서 측정 a) Consumption relative to acid sensitive polyamide * measured at 25 ° C, 40% by weight NMP solution, ** measured at 25 ° C, 20% by weight NMP solution

이상에서 설명한 바와 같이, 본 발명은 높은 고형분을 가지면서도 용액점도가 낮아 균일한 도포가 가능하고, 기제위에 도포하여 사용할 경우, 광반응에 의해 노광부는 용해되어 제거됨으로서 광패턴화가 가능하고, 패턴화된 비노광부를 가열함에 따라 내열화 반응으로 유도하여 열적으로 더욱 안정한 벤조옥사졸기로 전환시킴이 가능할 뿐 아니라, 이 열적 전환공정시 말단기의 가교결합이 동반되어 우수한 기계적 강도를 가지는 패턴화된 박막의 제조가 가능한 기술을 제공한다.As described above, the present invention has a high solid content and low solution viscosity, so that uniform coating is possible. When applied to a substrate and used, the exposed portion is dissolved and removed by photoreaction, so that light patterning is possible. By heating the non-exposed part, it is not only possible to convert into a more thermally stable benzoxazole group by inducing a heat-resistant reaction, but also a patterned thin film having excellent mechanical strength due to crosslinking of end groups in this thermal conversion process. Provides a technology that can be manufactured.

따라서, 본 발명에 따른 폴리아미드 중합체와 소량의 광산발생제가 포함된 감광성 내열절연체 조성물은 저유전 재료가 사용되는 모든 분야에 사용이 가능하며, 특히 반도체 소자의 패시베이션 막(passivation layer), 완충막(buffer coat) 또는 복합 다층인쇄회로기판의 층간 절연막 재료로 유용하다.Accordingly, the photosensitive heat insulating composition including the polyamide polymer according to the present invention and a small amount of photoacid generator can be used in all fields in which low dielectric materials are used. In particular, a passivation layer and a buffer film of a semiconductor device may be used. It is useful as an interlayer insulating film material for a buffer coat) or a composite multilayer printed circuit board.

Claims (7)

다음 화학식 1을 반복단위로 하는 것으로, 산민감기로서 아세탈 또는 카르보네이트기가 측쇄기로 결합되어 있고, 중합체 말단에는 아세틸렌기를 포함하는 말단기가 결합되어 있는 것임을 특징으로 하는 산민감성 폴리아미드 중합체.An acid-sensitive polyamide polymer having the following formula (1) as a repeating unit, wherein an acetal or carbonate group is bonded as a side chain group as an acid sensitive group, and an end group including an acetylene group is bonded to a polymer terminal. [화학식 1][Formula 1] 상기 화학식 1에서 :In Formula 1 above: Ar1은 4가의 방향족기로서,,,및중에서 선택되고, 이때 X1은 -CH2-, -O-, -S-, -SO2-. -CO-, -NHCO-, -C(CH3)2-, -C(CF3)2-,또는을 나타내며;Ar 1 is a tetravalent aromatic group , , , And Wherein X 1 is —CH 2 —, —O—, —S—, —SO 2 —. -CO-, -NHCO-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , or Represents; Ar2는 2가의 방향족기로서,,,,,,,,,,,,및중에서 선택되고, 이때 X1은 상기에서 정의한 바와 같으며;Ar 2 is a divalent aromatic group , , , , , , , , , , , , And Is selected from X 1 wherein X 1 is as defined above; R1및 R2은 서로 같거나 다른 산민감기로서, 카르보네이트 또는 아세탈 구조를 갖으며;R 1 and R 2 are the same or different acid sensitive groups and have a carbonate or acetal structure; T1및 T2는 서로 같거나 다른 중합체 말단기로서 아세틸렌기를 포함하며, 아래와 같은 구조를 갖으며;T 1 and T 2 include acetylene groups as the same or different polymer end groups, and have a structure as follows; ,,,,, , , , , , 이때, T1의 경우 Y는이며, T2의 경우 Y는 -NH-기를 나타내며;In this case, for T 1 Y is And in the case of T 2 Y represents a —NH— group; m과 n은 각각 5부터 100사이의 정수를 나타내며;m and n each represent an integer between 5 and 100; 상기한 Ar1과 Ar2의 조합에 의해 상기 화학식 1을 반복단위로 하는 산민감성 폴리아미드 중합체는 단일중합체 또는 공중합체일 수 있다.The acid-sensitive polyamide polymer having Formula 1 as a repeating unit by the combination of Ar 1 and Ar 2 may be a homopolymer or a copolymer. 제 1 항에 있어서, 상기 R1및 R2둘 중에 적어도 하나 이상이,또는(이때, R'는 C1∼C6의 저급알킬기를 나타내고, R" 및 R'"는 각각 C1∼C4의 저급알킬기, 페닐기, 또는 니트로 및 할로겐원자 중에서 선택된 치환기로 치환된 페닐기를 나타냄)인 것임을 특징으로 하는 산민감성 폴리아미드 중합체.The method of claim 1, wherein at least one of the two R 1 and R 2 , or (Wherein R 'represents a lower alkyl group of C 1 to C 6 , R "and R'" respectively represent a lower alkyl group of C 1 to C 4 , a phenyl group, or a phenyl group substituted with a substituent selected from nitro and halogen atoms). Acid-sensitive polyamide polymer, characterized in that). 제 1 항에 있어서, 상기 중합체내에 포함된 산민감기(-OR1또는 -OR2)의 농도 [n/(n+m)]가 3% ∼ 70%인 것임을 특징으로 하는 산민감성 폴리아미드 중합체.The acid-sensitive polyamide polymer according to claim 1, wherein the concentration [n / (n + m)] of the acid sensitivity group (-OR 1 or -OR 2 ) contained in the polymer is 3% to 70%. 제 1 항에 있어서, 상기 중합체는 고유점도(N-메틸피롤리돈 용액 농도 0.50 g/dL, 30 ℃) 범위가 0.07 ∼ 0.35 dL/g인 것임을 특징으로 하는 산민감성 폴리아미드 중합체.The acid-sensitive polyamide polymer according to claim 1, wherein the polymer has an intrinsic viscosity (N-methylpyrrolidone solution concentration of 0.50 g / dL at 30 ° C.) of 0.07 to 0.35 dL / g. 다음 화학식 1을 반복단위로 하는 폴리아미드 중합체와, 상기한 폴리아미드중합체에 대하여 0.3 ∼ 15 중량%의 광산발생제가 함유되어 있는 것임을 특징으로 하는 감광성 내열절연체 조성물.A polyamide polymer having a repeating unit represented by the following formula (1) and 0.3 to 15% by weight of a photoacid generator based on the polyamide polymer described above. [화학식 1][Formula 1] 상기 화학식 1에서 : Ar1, Ar2, R1, R2, m 및 n은 각각 청구항 1에서 정의한 바와 같다.In Formula 1: Ar 1 , Ar 2 , R 1 , R 2 , m and n are as defined in claim 1, respectively. 제 5 항에 있어서, 상기 광산발생제는 폴리아미드 중합체의 흡광영역보다 긴 파장(300 nm 이상) 영역의 빛을 흡수하여 산을 발생하는 물질인 것임을 특징으로 하는 감광성 내열절연체 조성물.6. The photosensitive heat insulating composition according to claim 5, wherein the photoacid generator is a material that absorbs light having a wavelength longer than that of the polyamide polymer (300 nm or more) to generate an acid. 제 5 항 또는 제 6 항에 있어서, 상기 광산발생제가 다음에서 예시된 화합물중에서 선택된 것임을 특징으로 하는 감광성 내열절연체 조성물.7. The photosensitive heat insulating composition according to claim 5 or 6, wherein the photoacid generator is selected from the compounds exemplified below. ,,, , , , 상기에서 :From above: R3, R4및 R6는 각각 수소원자 또는 C1∼C10의 알콕시기를 나타내고;R 3 , R 4 and R 6 each represent a hydrogen atom or a C 1 to C 10 alkoxy group; R5는 C1∼C10의 알킬기, C1∼C10의 할로알킬기, 알킬기로 치환 또는 치환된 페닐기, 또는 캄포닐기를 나타낸다.R 5 is C 1 ~C 10 alkyl group represents a group, C 1 ~C 10 of the haloalkyl group, a substituted or substituted phenyl group with an alkyl group, or a camphor carbonyl.
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