KR20000019945A - Copolymer for manufacturing chemical amplifying type photoresist and chemical amplifying type positive photoresist composition having the photoresist - Google Patents

Copolymer for manufacturing chemical amplifying type photoresist and chemical amplifying type positive photoresist composition having the photoresist Download PDF

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KR20000019945A
KR20000019945A KR1019980038306A KR19980038306A KR20000019945A KR 20000019945 A KR20000019945 A KR 20000019945A KR 1019980038306 A KR1019980038306 A KR 1019980038306A KR 19980038306 A KR19980038306 A KR 19980038306A KR 20000019945 A KR20000019945 A KR 20000019945A
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copolymer
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acid
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KR100270352B1 (en
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전현표
김성주
박주현
이종범
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박찬구
금호석유화학 주식회사
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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
    • G03F7/039—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C08F212/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Abstract

PURPOSE: A copolymer for manufacturing chemical amplifying type photoresist and chemical amplifying type positive photoresist composition having the photoresist is provided to has an exposure redundancy with a broad extent and has a high sensitivity, a high resolution, an excellent heat resistance, and a pattern stability. CONSTITUTION: A copolymer for manufacturing chemical amplifying type photoresist is Class 1 or compound selected from groups such as a poly(hydroxystyrene/ alkoxyalkoxystyrene/ t-butylcarbonless/ moporinyl carbonless) quadruple copolymer, a poly(hydroxystyrene/ alkoxyalkoxystyrene/ moporinyl carbonless) ternary copolymer, and a poly(hydroxystyrene/ t-butylcarbonless/ moporinyl carbonless) ternary copolymer.

Description

화학 증폭형 포토레지스트 제조용 공중합체 및 이를 함유하는 화학 증폭형 양성 포토레지스트 조성물Copolymer for Chemically Amplified Photoresist Preparation and Chemically Amplified Positive Photoresist Composition Containing the Same

본 발명은 화학 증폭형 포토레지스트 제조용 공중합체 및 이를 함유하는 화학 증폭형 양성 포토레지스트 조성물에 관한 것으로서, 더욱 상세하게는 기판에 관계없이 우수한 패턴을 형성할 수 있고, 노광 전후의 알칼리 용해 콘트라스트가 매우 높으며, 넓은 범위의 노광 여유도를 갖고, 고감도, 고해상성, 고내열성 및 우수한 노출후 안정성을 가지며, 특히 초 LSI 제조용 미세 패턴 형성 재료로서 자외선, 원자외선, 엑시머레이저, X-선, 전자선 등의 방사선에 감응하는 화학증폭형 양성 포토레지스트 조성물에 관한 것이다.The present invention relates to a copolymer for preparing a chemically amplified photoresist and a chemically amplified positive photoresist composition containing the same. More particularly, an excellent pattern can be formed regardless of a substrate, and the alkali dissolution contrast before and after exposure is very high. It has a high range of exposure margins, high sensitivity, high resolution, high heat resistance and excellent post-exposure stability, and is particularly a micro pattern forming material for ultra LSI manufacturing, such as ultraviolet rays, far ultraviolet rays, excimer lasers, X-rays, and electron beams. A chemically amplified positive photoresist composition sensitive to radiation.

최근 반도체 기술에 있어서 반도체 소자의 고집적화가 급속히 진행되고 있으며, 이에 상응하여 초 LSI 등을 제조하기 위한 포토리소그래피 패터닝(photolithography patterning)에서도 쿼터-미크론 이하 영역의 초미세 패턴이 요구되고 있다. 이에 따라 노광 파장도 종래에 사용하는 g-선이나 i-선 영역에서 단파장화되어 원자외선, KrF 엑시머 레이저, X-선 및 전자선을 이용하는 리소그래피에 대한 연구가 주목받고 있다.Recently, high integration of semiconductor devices is rapidly progressing in semiconductor technology, and accordingly, in photolithography patterning for manufacturing ultra-LSI and the like, ultra-fine patterns of sub-quarter-micron regions are required. Accordingly, attention has been paid to lithography using far ultraviolet rays, KrF excimer lasers, X-rays, and electron beams, since the exposure wavelength is shortened in the conventional g-ray or i-ray region.

종래 g-선이나 i-선에 이용되는 포토레지스트는 노볼락-퀴논디아지드계 화합물을 이용한 것으로서, 원자외선이나 KrF 엑시머 레이저 파장에 적용할 경우는 광의 흡수가 많으므로 노볼락-퀴논디아지드계 화합물에 비하여 상대적으로 광흡수가 적은 폴리하이드록시스티렌 유도체를 기초수지로 이용한 화학 증폭형 포토레지스트에 대한 연구가 진행되고 있다.Conventionally, photoresists used for g-rays and i-rays use novolak-quinonediazide-based compounds, and when applied to far-ultraviolet or KrF excimer laser wavelengths, they absorb a lot of light. Research into chemically amplified photoresist using a polyhydroxy styrene derivative having a relatively low light absorption as a base resin compared to the compound is being conducted.

이같은 화학 증폭형 포토레지스트 조성물은 레지스트층이 화학적 선(chemical ray)에 패턴노광될 때 포토레지스트 조성 중 함유된 산발생제가 산을 방출하고, 방출된 산이 수지성분과 촉매 활성 탈보호화 반응을 일으켜 현상액에 대한 용해도를 변경시키는 원리를 이용한다.The chemically amplified photoresist composition is characterized in that the acid generator contained in the photoresist composition releases an acid when the resist layer is pattern-exposed to a chemical ray, and the released acid causes a catalytically active deprotection reaction with the resin component. Use the principle of changing the solubility in water.

특히, 화학 증폭형 포토레지스트 조성물의 경우 산발생제에서 발생된 소량의 산으로도 수지성분에 촉매 활성을 발휘하기 때문에 패턴의 해상도가 높고, 화학적 선에 대한 감광성이 뛰어나다는 점에서 유용하다.In particular, in the case of chemically amplified photoresist compositions, since a small amount of acid generated from an acid generator exhibits catalytic activity to the resin component, it is useful in that the resolution of the pattern is high and the photosensitivity to chemical rays is excellent.

이같은 화학 증폭형 포토레지스트 재료로는 폴리(p-t-부톡시카르보닐옥시스티렌/p-히드록시스티렌)을 사용한 레지스트 재료(미국특허 제4,491,628호), 폴리(p-t-부톡시스티렌/p-히드록시스티렌)을 사용한 레지스트 재료(미국특허 제5,350,660호), 그리고 폴리(p-1-에톡시에톡시스티렌/p-히드록시스티렌)을 사용한 레지스트 재료(일본특허 A-5-249682) 등이 알려져 있다.As such chemically amplified photoresist materials, resist materials using poly (pt-butoxycarbonyloxystyrene / p-hydroxystyrene) (US Pat. No. 4,491,628), poly (pt-butoxystyrene / p-hydroxy Resist materials using styrene) (US Pat. No. 5,350,660), and resist materials using poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) (Japanese Patent A-5-249682) and the like are known. .

그러나, 상기와 같은 포토레지스트 재료의 기초수지 중 보호기가 tert-부틸기, tert-부톡시카르보닐기인 경우에는 이들 보호기가 강산에서 분해되는 특성을 갖는 바, 결과적으로 공기 중의 염기성 화합물과 반응하여 실활되므로 T-top 형상이 되기 쉽고, 기판의 종류에 따라 패턴이 달라지는 문제점을 갖는다. 한편, 아세탈기 또는 케탈기와 같이 약산으로 분해되는 보호기를 갖는 기초수지의 경우는 공기중의 염기성 화합물의 영향은 적지만 노광에서 열처리(PEB)까지의 시간지연에 따라 패턴 형상이 현저히 좁아진다는 결점을 가지며 고해상도에 적합하지 않다.However, when the protecting group in the base resin of the photoresist material as described above is tert-butyl group and tert-butoxycarbonyl group, these protecting groups have the property of decomposing in strong acid, and as a result, they are inactivated by reacting with basic compounds in air. It tends to be a T-top shape and has a problem in that the pattern varies depending on the type of substrate. On the other hand, in the case of the basic resin having a protecting group that decomposes into a weak acid such as an acetal group or a ketal group, the effect of the basic compound in the air is small, but the pattern shape is significantly narrowed due to the time delay from exposure to heat treatment (PEB). It is not suitable for high resolution.

본 발명은 상기와 같은 종래 화학 증폭형 포토레지스트 조성물에 사용할 수 있는 기초수지의 문제점을 해결하기 위한 것으로서, 넓은 범위의 노광 여유도를 가지며, 고감도, 고해상성, 우수한 내열성 및 패턴 안정성을 가질 뿐만 아니라, 기판의 종류에 관계없이 우수한 레지스트 패턴을 얻을 수 있는 새로운 화학 증폭형 포토레지스트 제조용 공중합체를 제공하는 데 그 목적이 있다.The present invention is to solve the problem of the basic resin that can be used in the conventional chemically amplified photoresist composition as described above, and has a wide range of exposure margin, high sensitivity, high resolution, excellent heat resistance and pattern stability It is an object of the present invention to provide a new chemically amplified photoresist copolymer capable of obtaining excellent resist patterns regardless of the type of substrate.

또한, 본 발명은 상기와 같은 특성을 갖는 공중합체를 함유한 화학 증폭형 양성 포토레지스트 조성물을 제공하는 데도 그 목적이 있다.It is also an object of the present invention to provide a chemically amplified positive photoresist composition containing a copolymer having the above characteristics.

상기와 같은 목적을 달성하기 위한 본 발명의 화학 증폭형 포토레지스트 제조용 공중합체는 다음 화학식 1로 표시되는 것임을 그 특징으로 한다.The copolymer for preparing a chemically amplified photoresist of the present invention for achieving the above object is characterized by that represented by the following formula (1).

화학식 1Formula 1

상기 식에서, R1,R2,R3및 R4는 각각 독립적인 것으로서, 수소원자 또는 저급 알킬기이며,Wherein R 1, R 2, R 3 and R 4 are each independently a hydrogen atom or a lower alkyl group,

R5, R6,R7및 R8는 수소원자, 탄소원자수 1∼8의 알킬기, 알콕시기, 알콕시카르보닐기 또는 할로겐 원자이며,R 5 , R 6 , R 7 and R 8 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxycarbonyl group or a halogen atom,

h와 i는 0∼8의 정수이고,h and i are integers from 0 to 8,

k, l, m 및 n은 각각 반복 단위로서, 0.3<k/(k+l+m+n)<0.9, 0≤l/(k+l+m+n)<0.6, 0≤m/(k+l+m+n)<0.6, 그리고 0.01<n/(k+l+m+n)<0.3인 조건을 만족한다. 그리고 k+l+m+n=1을 만족하며, l과 m는 동시에 0이 될 수 없고, 동시에 0이 아닐 수도 있다.k, l, m and n are repeating units, respectively, 0.3 <k / (k + l + m + n) <0.9, 0 ≦ l / (k + l + m + n) <0.6, 0 ≦ m / ( k + l + m + n) <0.6 and 0.01 <n / (k + l + m + n) <0.3 are satisfied. And k + l + m + n = 1, l and m may not be zero at the same time and may not be zero at the same time.

R9는 다음 화학식 2로 표시되는 것이고,R 9 is represented by the following formula (2),

화학식 2Formula 2

상기 식에서, R10와 R11는 각각 독립적으로 수소원자 또는 탄소원자수 1∼6의 직쇄상 또는 분지쇄상의 알킬기이고,In the above formula, R 10 and R 11 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,

R12는 탄소원자수 1∼10의 직쇄상, 분지쇄상 또는 환상의 알킬기이며, 이때 직쇄상, 분지쇄상 또는 환상의 알킬기로의 구체적인 예로는 메틸기, 에틸기, 프로필기, 이소프로필기, n-부틸기, 이소부틸기, t-부틸기이며, 환상의 알킬기는 사이클로 헥실기이다.R 12 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and specific examples of the linear, branched or cyclic alkyl group include methyl, ethyl, propyl, isopropyl and n-butyl groups. , Isobutyl group and t-butyl group, and the cyclic alkyl group is a cyclohexyl group.

상기 화학식 2로 표시되는 산 불안정기의 구체적인 예는 메톡시에틸기, 에톡시에틸기, n-부톡시에틸기, 사이클로헥실기 또는 메톡시프로필기이다.Specific examples of the acid labile group represented by the formula (2) are methoxyethyl group, ethoxyethyl group, n-butoxyethyl group, cyclohexyl group or methoxypropyl group.

Am은 -NR13R14(여기서 R13과 R14은 각각 독립적인 것으로서, 수소원자, 탄소원자수 1∼8인 알킬기, 아릴기 또는 페닐기이다), 고리형 2가 아민류, 및 산소 또는 황원자가 포함된 고리형 2가 아민류이다.Am is —NR 13 R 14 wherein R 13 and R 14 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or a phenyl group, cyclic divalent amines, and oxygen or sulfur atoms Cyclic divalent amines.

또한, 본 발명의 화학 증폭형 양성 포토레지스트 조성물은 상기 화학식 1로 표시되는 공중합체, 산발생제 및 첨가제를 용매에 녹여 제조된 것임을 그 특징으로 한다.In addition, the chemically amplified positive photoresist composition of the present invention is characterized in that it is prepared by dissolving the copolymer, acid generator and additive represented by the formula (1) in a solvent.

이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명에서 사용되는 상기 화학식 1로 표시되는 기초수지 중 바람직한 예로는 다음과 같다;Preferred examples of the basic resin represented by Formula 1 used in the present invention are as follows;

(A)폴리(하이드록시스티렌/알콕시알콕시스티렌/t-부틸카르보닐알콕시스티렌/몰포리닐카르보닐알콕시스티렌)의 4원 공중합체이면서, k, l, m 및 n 이 각각 0.3<k/(k+l+m+n)<0.9, 0≤l/(k+l+m+n)<0.6, 0≤m/(k+l+m+n)<0.6, 그리고 0.01<n/(k+l+m+n)<0.3인 조건을 만족하는 수지,(A) is a quaternary copolymer of poly (hydroxystyrene / alkoxyalkoxystyrene / t-butylcarbonylalkoxystyrene / morpholinylcarbonylalkoxystyrene), wherein k, l, m and n are each 0.3 <k / ( k + l + m + n) <0.9, 0 ≦ l / (k + l + m + n) <0.6, 0 ≦ m / (k + l + m + n) <0.6, and 0.01 <n / (k resin which satisfies the condition of + l + m + n) <0.3,

(B)폴리(하이드록시스티렌/알콕시알콕시스티렌/몰포리닐카르보닐알콕시스티렌)의 3원 공중합체이면서, k, l, m 및 n이 각각 0.3<k/(k+l+m+n)<0.9, 0≤l/(k+l+m+n)<0.6, m=0, 그리고 0.01<n/(k+l+m+n)<0.3인 조건을 만족하는 수지,(B) a terpolymer of poly (hydroxystyrene / alkoxyalkoxystyrene / morpholinylcarbonylalkoxystyrene), wherein k, l, m and n are each 0.3 <k / (k + l + m + n) Resin satisfying the condition of <0.9, 0≤l / (k + l + m + n) <0.6, m = 0, and 0.01 <n / (k + l + m + n) <0.3,

(C)폴리(하이드록시스티렌/t-부틸카르보닐알콕시스티렌/몰포리닐카르보닐알콕시스티렌)의 3원 공중합체이면서, k, l, m 및 n이 각각 0.3 < k/(k+l+m+n) < 0.9, l=0, 0 ≤ m/(k+l+m+n) < 0.6 그리고 0.01 < n/(k+l+m+n) < 0.3 을 만족하는 수지로서,(C) a terpolymer of poly (hydroxystyrene / t-butylcarbonylalkoxystyrene / morpholinylcarbonylalkoxystyrene), wherein k, l, m and n are each 0.3 <k / (k + l + m + n) <0.9, l = 0, 0 <m / (k + l + m + n) <0.6 and 0.01 <n / (k + l + m + n) <0.3,

상기 (A), (B) 및 (C) 수지 중 선택하여 1종만을 포토레지스트의 기초수지로 사용할 수도 있고, 필요에 따라 상기 (A), (B) 및 (C) 수지 중 2종 이상을 혼합하여 사용할 수도 있다.Only one of the above (A), (B) and (C) resins may be selected and used as the base resin of the photoresist, and if necessary, two or more of the above (A), (B) and (C) resins may be used. It can also be mixed and used.

상기 화학식 1로 표시되는 공중합체에 있어서, 하이드록시기는 접착력, 내열성 및 감도를 향상시켜주는 역할을 하며, t-부톡시카르보닐메톡시기는 노광할 때 산의 작용에 의해 탈보호화 반응이 일어나 카르복실산 또는 하이드록시기로 변환되고, 에톡시에톡시기는 노광할 때 산의 작용에 의해 탈보호화 반응이 일어나 하이드록시기로 변환되어 용해속도를 증진시킴으로써 해상성을 높여주는 역할을 한다. 에톡시에톡시기는 노광후 베이킹온도(PEB)가 110℃인 프로세스에서도 탈보호화 반응이 잘 일어나므로 쉽게 용해도 차에 의해서 패턴을 형성시키는 장점이 있고, t-부톡시카르보닐메톡시기는 패턴 형상이 좋고, 해상도가 뛰어난 장점이 있으므로 이 두 치환기를 적절히 배합하면 낮은 베이킹온도 프로세스에서도 고해상성을 갖고, 미세패턴 형성이 유리한 포토레지스트를 조성할 수 있다. 그리고, 아미드기는 노광시 발생된 산과의 친화력을 유지시켜 대기중에 있는 염기성 성분이 산과 접촉하는 것을 막아주면서, 또한 인접 거리로 산이 확산되는 것을 방지하고, 노광후 시간 지연에 의한 패턴의 좁아짐 현상을 방지해 준다. 아미드기는 산의 작용에 의해 변화되지 않고 산을 안정화시켜주는 역할을 한다.In the copolymer represented by Chemical Formula 1, the hydroxy group serves to improve adhesion, heat resistance and sensitivity, and the t-butoxycarbonylmethoxy group is deprotected due to the action of an acid when exposed to carbon. The ethoxyethoxy group is converted into an acid or a hydroxyl group, and when exposed, a deprotection reaction occurs due to the action of an acid, which is converted into a hydroxyl group to enhance the dissolution rate. The ethoxyethoxy group has an advantage of easily forming a pattern by the difference in solubility because the deprotection reaction occurs well even in a process where the baking temperature (PEB) is 110 ° C after exposure, and the t-butoxycarbonylmethoxy group has a pattern shape. Because of the advantages of good resolution and excellent resolution, by combining these two substituents properly, a photoresist having high resolution and favorable micropattern formation can be formed even at low baking temperature processes. In addition, the amide group maintains affinity with acid generated during exposure to prevent basic components in the air from contacting the acid, and also prevents acid from diffusing at adjacent distances and prevents narrowing of the pattern due to time delay after exposure. Do it. The amide group plays a role of stabilizing the acid without being changed by the action of the acid.

상기 화학식 1로 표시되는 공중합체에 있어서, t-부톡시카르보닐메톡시기와 에톡시에톡시기의 치환양은 10∼50%인 것이 적절하고, 아미드기의 치환양은 1∼30%인 것이 적절하다. t-부톡시카르보닐메톡시기나 에톡시에톡시기로 너무 많이 치환되면 감도가 낮아지고, 치환양이 너무 적으면 노광부위와 비노광부위의 용해속도 차이가 적어지게 된다. 이같은 점을 고려해 볼 때 바람직한 t-부톡시카르보닐메톡시기와 에톡시에톡시기의 치환양은 20∼40%이며, 아미드기의 치환양은 5∼10% 정도가 가장 적절하다.In the copolymer represented by the formula (1), the substitution amount of the t-butoxycarbonylmethoxy group and the ethoxyethoxy group is appropriately 10 to 50%, and the substitution amount of the amide group is suitably 1 to 30%. . When too much of the t-butoxycarbonylmethoxy group or the ethoxyethoxy group is substituted, the sensitivity becomes low, and when the amount of substitution is too small, the difference in dissolution rate between the exposed and non-exposed sites becomes small. In view of such a point, the substitution amount of the preferable t-butoxycarbonylmethoxy group and the ethoxyethoxy group is 20 to 40%, and the substitution amount of the amide group is about 5 to 10% most appropriate.

이와같이 t-부톡시카르보닐메톡시기 및 아미드기를 도입하는 방법은 폴리하이드록시스티렌과 알킬할로겐 화합물의 치환반응을 통해 이루어지는 바, 이때 반드시 염기성 화합물로서 테트라메틸암모늄하이드록시드를 첨가하여야 한다.Thus, the method of introducing the t-butoxycarbonylmethoxy group and the amide group is carried out through the substitution reaction of the polyhydroxystyrene and the alkylhalogen compound, and at this time, tetramethylammonium hydroxide must be added as the basic compound.

이때, 알킬할로겐 화합물의 일예로는 몰포리닐 브로모아세테이트, t-부틸 브로모아세테이트 등을 들 수 있다.In this case, examples of the alkylhalogen compound include morpholinyl bromoacetate, t-butyl bromoacetate, and the like.

제조된 기초수지의 분자량은 폴리스티렌 표준 환산 분자량으로 1,000∼1,000,000, 바람직하게는 5,000∼50,000이 가장 적절하다.The molecular weight of the prepared base resin is most preferably 1,000 to 1,000,000, preferably 5,000 to 50,000 in terms of polystyrene standard molecular weight.

이같은 공중합체를 사용하여 포토레지스트 조성물을 조성하는 경우 산발생제와 적당량의 첨가제를 첨가하는 바, 본 발명에서 산발생제로는 활성 조사선에 노출되었을 때 산을 발생시킬 수 있으면서 레지스트 패턴 형성에 나쁜 영향을 주지않는다면 어떠한 물질이라도 사용할 수 있으나, 보다 바람직하게는 248㎚ 부근의 파장에서 적당한 광흡수도와 레지스트 재료의 투명도를 유지할 수 있는 물질을 사용하는 것이다.When forming a photoresist composition using such a copolymer, an acid generator and an appropriate amount of additives are added. As the acid generator in the present invention, acid can be generated when exposed to active radiation and adversely affect the resist pattern formation. Any material may be used as long as it is not provided, but more preferably, a material capable of maintaining appropriate light absorption and transparency of the resist material at a wavelength around 248 nm is used.

이같은 특성을 갖는 산발생제의 바람직한 예로는 다음 화학식 3으로 표시되는 술포늄 화합물이 있다. 그러나, 본 발명의 포토레지스트 조성에 있어서 산발생제는 다음 화합물에 한정되는 것은 아니다.Preferred examples of acid generators having such characteristics include sulfonium compounds represented by the following formula (3). However, the acid generator in the photoresist composition of the present invention is not limited to the following compounds.

화학식 3Formula 3

상기 식에서, R15는 수소원자, 알킬기 또는 알콕시기이고,Wherein R 15 is a hydrogen atom, an alkyl group or an alkoxy group,

R16은 수소원자, 알킬기, 알콕시알킬기, t-부톡시카르보닐메틸기이며,R 16 is a hydrogen atom, an alkyl group, an alkoxyalkyl group, t-butoxycarbonylmethyl group,

X는 O, S 또는 CH2이고,X is O, S or CH 2 ,

g는 0∼20의 정수이다.g is an integer of 0-20.

상기 화학식 3으로 표시되는 산발생제의 구체적인 화합물의 예는 다음과 같다; 트리페닐술포늄 트리플레이트, 디페닐(4-메틸페닐)술포늄 트리플레이트, 디페닐(4-t-부틸페닐)술포늄 트리플레이트, 디페닐(4-메톡시페닐)술포늄 트리플레이트, 디페닐(4-t-부톡시카르보닐메톡시페닐)술포늄 트리플레이트 등을 들 수 있다.Examples of the specific compound of the acid generator represented by Formula 3 are as follows; Triphenylsulfonium triflate, diphenyl (4-methylphenyl) sulfonium triflate, diphenyl (4-t-butylphenyl) sulfonium triflate, diphenyl (4-methoxyphenyl) sulfonium triflate, diphenyl (4-t-butoxycarbonylmethoxyphenyl) sulfonium triflate etc. are mentioned.

상기 화학식 3으로 표시되는 산발생제 외에 트리페닐술포늄 헥사플루오로안티모네이트, 디페닐요드늄 트리플레이트, 디페닐요드늄 메틸벤젠술포네이트, 페닐(4-t-메톡시페닐)요드늄 캄포어 술포네이트, 페닐(4-t-부톡시카르보닐메톡시페닐)요드늄 캄포어 술포네이트, 비스(시클로헥실술포닐)디아조메탄, 그리고 비스(2,4-디메틸페닐술포닐)디아조메탄 등도 바람직하다.In addition to the acid generator represented by the formula (3), triphenylsulfonium hexafluoroantimonate, diphenyl iodonium triflate, diphenyl iodide methylbenzenesulfonate, phenyl (4-t-methoxyphenyl) iodinium camphor Asulfonate, phenyl (4-t-butoxycarbonylmethoxyphenyl) iodium camphor sulfonate, bis (cyclohexylsulfonyl) diazomethane, and bis (2,4-dimethylphenylsulfonyl) diazo Methane and the like are also preferred.

산발생제로 사용할 수 있는 할로겐 화합물로는 1,1-비스(4-클로로페닐)-2,2,2-트리클로로에탄, 페닐-비스(트리클로로메틸)-s-트리아진, 나프틸-비스(트리클로로메틸)-s-트리아진 등이 있다. 이들 외에 디아조케톤 화합물인 1,3-디케토-2-디아조 화합물, 디아조벤조퀴논 화합물, 디아조나프토퀴논 화합물이 있고, 술폰 화합물, 술폰산 화합물, 그리고 니트로벤질 화합물 등이 있다. 이들 산발생제들 중에서 특히 바람직한 화합물로는 오니움염 화합물과 디아조케톤 화합물이다.Halogen compounds that can be used as acid generators include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (Trichloromethyl) -s-triazine and the like. Besides these, there are 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaptoquinone compounds which are diazoketone compounds, and sulfone compounds, sulfonic acid compounds, nitrobenzyl compounds and the like. Particularly preferred compounds among these acid generators are onium salt compounds and diazoketone compounds.

이같은 산발생제는 전체 포토레지스트 조성에 있어서 총 고체성분 100 중량부에 대해 0.1∼30 중량부로 사용하는 것이 바람직하며, 보다 바람직하게는 0.1∼10 중량부로 사용하는 것이다.Such acid generator is preferably used in an amount of 0.1 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total solid component in the total photoresist composition.

한편, 상기의 산발생제는 단독으로 사용하거나 2종 이상을 혼합하여 사용할 수 있다.In addition, said acid generator can be used individually or in mixture of 2 or more types.

본 발명의 포토레지스트 조성물에 있어서, 필요에 따라서는 산에 의해 분해되어 현상액에 대해 용해를 촉진시켜 주는 화합물을 사용할 수도 있다. 산에 의해 분해되어 현상액에 대해 용해를 촉진시켜 주는 화합물로는 방향족 폴리하이드록시 화합물이 t-부톡시카르복시기로 보호된 화합물, 아세탈기 또는 케탈기로 보호된 화합물 등을 들 수 있다. 이같은 화합물을 포토레지스트 제조시 첨가할 경우 그 함량은 총 고체성분 100 중량부에 대해 5∼80 중량부이고, 바람직하게는 10∼50 중량부이다.In the photoresist composition of the present invention, a compound which decomposes with an acid and promotes dissolution in a developing solution may be used, if necessary. Examples of a compound which is decomposed by an acid to promote dissolution in a developer include a compound in which an aromatic polyhydroxy compound is protected with t-butoxycarboxyl group, a compound protected with an acetal group or a ketal group, and the like. When such a compound is added in preparing the photoresist, the content thereof is 5 to 80 parts by weight, preferably 10 to 50 parts by weight based on 100 parts by weight of the total solid component.

본 발명의 조성물은 필요에 따라 첨가제를 사용할 수 있다. 이러한 첨가제의 예로는 계면활성제, 아조계 화합물, 할레이션(halation) 방지제, 접착조제, 보존 안정제 및 소포제를 들 수 있다.The composition of this invention can use an additive as needed. Examples of such additives include surfactants, azo compounds, antihalation agents, adhesion aids, storage stabilizers, and antifoaming agents.

계면활성제로는 폴리옥시 라우릴 에테르, 폴리옥시에틸렌 스테아릴 에테르, 폴리옥시에틸렌 올레일 에테르, 폴리옥시에틸렌 옥틸 페놀 에테르, 폴리옥시에틸렌 노닐 페놀 에테르 또는 폴리에틸렌 글리콜 디라우레이트 등을 들 수 있다. 이들 계면활성제의 함량은 포토레지스트 조성에 있어서 총 고체성분 100 중량부에 대해 2 중량부 이하로 사용하는 것이 좋다.Examples of the surfactant include polyoxy lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether or polyethylene glycol dilaurate. The content of these surfactants is preferably used in an amount of 2 parts by weight or less based on 100 parts by weight of the total solid component in the photoresist composition.

또한, 본 발명의 양성 포토레지스트 조성물에는 상기 성분 이외에도 감도나 해상성을 향상시키기 위해 흡광제를 사용할 수도 있다. 이같은 흡광제로는 벤조페논류의 화합물이나 나프토퀴논류의 화합물이 바람직하다. 그 함량은 총 고체 성분에 대해 0.2∼30중량부, 바람직하게는 0.5∼10중량부이다.Moreover, in addition to the said component, a light absorber can also be used for the positive photoresist composition of this invention in order to improve a sensitivity and resolution. As such a light absorber, a compound of benzophenones or a compound of naphthoquinones is preferable. The content is 0.2 to 30 parts by weight, preferably 0.5 to 10 parts by weight based on the total solid components.

그리고, 노광후 발생된 산의 확산을 막아주기 위해 염기성 화합물을 사용할 수도 있다. 염기성 화합물로는 아민계 화합물이나 암모늄 화합물을 들 수 있다. 구체적인 예를들면 트리페닐 아민, 테트라메틸암모늄 하이드록시드, 테트라메틸암모늄 아세테이트, 트리에틸 아민, 트리에탄올 아민, 디페닐 아민, 피리딘, 디피리딜 또는 N,N-디메틸 아세트아미드 등이다. 염기성 화합물의 첨가량은 총 고체 성분에 대해 0.05∼5 중량부인 것이 바람직하다. 이보다 첨가량이 많아지면 산의 확산은 줄어드는 반면, 감도가 떨어지는 단점이 있다.In addition, a basic compound may be used to prevent diffusion of acid generated after exposure. Examples of the basic compound include an amine compound and an ammonium compound. Specific examples are triphenyl amine, tetramethylammonium hydroxide, tetramethylammonium acetate, triethyl amine, triethanol amine, diphenyl amine, pyridine, dipyridyl or N, N-dimethyl acetamide and the like. It is preferable that the addition amount of a basic compound is 0.05-5 weight part with respect to a total solid component. If the amount is larger than this, the diffusion of the acid is reduced, but the sensitivity is lowered.

본 발명에 있어서 포토레지스트 조성물에 선택적으로 산화합물을 첨가할 수 있는 바, 구체적으로는 프탈산, 숙신산, 말론산, 벤조산, 살리실산, m-하이드록시벤조산, p-하이드록시벤조산, o-아세틸벤조산, o-아세틸옥시벤조산, o-니트로벤조산, 티오살리실산 및 티오니코틴산, 살리실알데히드, 살리실하이드록삼산, 숙신이미드, 프탈이미드 및 아스코르브산과 같은 유기산을 사용할 수 있으며, 다음 화학식 4로 표시되는 중합체를 사용할 수도 있다. 산화합물의 첨가량은 총 고체 성분에 대해 0.05∼5 중량부가 적절하다. 만일, 첨가량이 과다하면 패턴 형상이 일그러지는 현상이 나타난다.In the present invention, an acid compound may be selectively added to the photoresist composition. Specifically, phthalic acid, succinic acid, malonic acid, benzoic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-acetylbenzoic acid, Organic acids such as o-acetyloxybenzoic acid, o-nitrobenzoic acid, thiosalicylic acid and thinicotinic acid, salicylicaldehyde, salicylic hydroxamic acid, succinimide, phthalimide and ascorbic acid can be used, and are represented by the following formula (4) Polymers may also be used. The addition amount of the acid compound is appropriately 0.05 to 5 parts by weight based on the total solid components. If the added amount is excessive, a phenomenon in which the pattern shape is distorted appears.

화학식 4Formula 4

상기 식에서, 0.01〈 y／(x+y) ≤0.4 이며, 폴리스티렌 표준 중량 평균 분자량은 500∼50,000, 바람직하게는 5,000∼20,000인 것이다.In the above formula, 0.01 &lt; y / (x + y)? 0.4, and the polystyrene standard weight average molecular weight is 500 to 50,000, preferably 5,000 to 20,000.

본 발명의 포토레지스트 조성물은 통상적으로 적당한 용매에 용해시켜 사용하는 바, 균일하고 평탄한 도포막을 얻기 위해서는 적당한 증발속도와 점성을 가진 용매를 사용하여야 한다. 이러한 물성을 갖는 용매의 구체적인 예는 다음과 같다; 에틸렌 글리콜 모노메틸 에테르, 에틸렌 글리콜 모노에틸 에테르, 에틸렌 글리콜 모노프로필 에테르, 에틸렌 글리콜 모노부틸 에테르, 디에틸렌 글리콜 디메틸 에테르, 디에틸렌 글리콜 디에틸 에테르, 디에틸렌 글리콜 디프로필 에테르, 디에틸렌 글리콜 디부틸 에테르, 프로필렌 글리콜 모노메틸 에테르 아세테이트, 프로필렌 글리콜 모노에틸 에테르 아세테이트, 프로필렌 글리콜 모노프로필 에테르 아세테이트, 메틸 에틸 케톤, 시클로헥사논, 메틸 2-하이드록시프로피오네이트, 에틸 2-하이드록시프로피오네이트, 2-헵타논, N-메틸 피롤리돈, N, N-디메틸포름 아미드, N, N-디메틸아세트 아미드, 에틸 피루베이트, n-아밀 아세테이트, 에틸 락테이트, 감마-부티로락톤 등이며, 경우에 따라서는 이들 단독 또는 2 종 이상의 혼합 용매를 사용한다. 용매의 사용량은 사용 용매의 물성 즉, 휘발성, 점도 등에 따라 적당량 사용하여 웨이퍼 상에 균일하게 형성될 수 있도록 조절한다.Generally, the photoresist composition of the present invention is used by dissolving in a suitable solvent, and in order to obtain a uniform and flat coating film, a solvent having an appropriate evaporation rate and viscosity should be used. Specific examples of the solvent having such physical properties are as follows; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ethyl ketone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2- Heptanone, N-methyl pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl pyruvate, n-amyl acetate, ethyl lactate, gamma-butyrolactone, and the like. Uses these single or 2 or more types of mixed solvents. The amount of the solvent is adjusted to be uniformly formed on the wafer using an appropriate amount depending on the physical properties of the solvent used, that is, volatility and viscosity.

본 발명의 조성물을 용액 형태로 제조하여 웨이퍼 기판 상에 도포하고 건조하므로써 포토레지스트 도막을 형성할 수 있다. 이때 도포 방법으로는 레지스트 용액을 제조하여 여과한 후, 얻어진 용액을 회전 도포, 흘림 도포, 또는 롤 도포 등의 방법으로 기판상에 도포할 수 있다.The composition of the present invention can be prepared in the form of a solution, coated on a wafer substrate, and dried to form a photoresist coating film. At this time, as a coating method, after preparing and filtering a resist solution, the obtained solution can be apply | coated on a board | substrate by methods, such as rotational coating, a shed | coating, or roll coating.

이와 같은 방법에 의해 도포시킨 포토레지스트 막을 통해 미세 패턴을 형성하기 위해서는 부분적으로 방사선을 조사해야 한다. 이때 사용할 수 있는 방사선은 특별히 한정되는 것은 아니며, 구체적으로는 자외선인 i-선, 원자외선인 엑시머 레이저, X-선, 하전 입자선인 전자선 등으로 산 발생제의 종류에 따라서 사용될 수 있다. 이와 같은 방사선 조사 후에 감도를 향상시키기 위해 경우에 따라서는 가열처리를 할 수도 있다.In order to form a fine pattern through the photoresist film coated by this method, radiation must be partially irradiated. The radiation that can be used at this time is not particularly limited, and specifically, may be used depending on the type of acid generator as i-rays, ultraviolet rays, excimer lasers, X-rays, electron beams, charged particle beams, and the like. In order to improve the sensitivity after such irradiation, heat treatment may be performed in some cases.

패턴 형성에 있어서 마지막 단계인 현상시 사용되는 현상액으로는 수산화나트륨, 수산화 칼륨, 탄산나트륨, 규산나트륨, 메타규산나트륨, 암모니아수, 에틸아민, n-프로필아민, 트리에틸아민, 테트라메틸암모늄 하이드록시드, 테트라에틸암모늄 하이드록시드 등을 함유하는 수용액 중에서 선택하여 사용한다. 특히, 이들 중 테트라메틸암모늄 하이드록시드가 바람직하다. 이때, 필요에 따라서는 계면활성제, 수용성 알콜류 등을 첨가제로 사용할 수 있다.The developing solution used during the development, which is the final step in the pattern formation, includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, triethylamine, tetramethylammonium hydroxide, It is used by selecting from an aqueous solution containing tetraethylammonium hydroxide and the like. In particular, tetramethylammonium hydroxide is preferable among these. At this time, surfactant, water-soluble alcohol, etc. can be used as an additive as needed.

이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

합성예 1: 폴리(하이드록시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 1 Preparation of Poly (hydroxystyrene / morpholinylcarbonylmethoxystyrene)

폴리하이드록시스티렌 250g을 2ℓ의 아세톤과 물 혼합용매에 용해시킨 후, 테트라메틸암모늄하이드록시드 25% 수용액을 58g 첨가하고, 여기에 몰포리닐 브로모아세테이트를 22g 부가하여 10 시간 동안 교반하였다. 이 반응물에 염산 33㎖를 첨가하여 중화시킨 후 20ℓ의 증류수에 적하하여 백색고체를 얻었다. 얻어진 고체를 여과하여 증류수로 세척, 탈수시킨 후 다시 아세톤에 용해시켰다. 그리고 나서, 증류수에서 석출, 세척, 탈수 및 건조시켜 폴리하이드록시스티렌의 수산기 중 5%가 몰포리닐카르보닐메톡시기로 치환되었으며, 폴리스티렌 표준 환산 중량평균분자량이 12,500인 폴리(하이드록시스티렌/몰포리닐카르보닐메톡시스티렌)을 253g 얻었다.After 250 g of polyhydroxystyrene was dissolved in a mixed solution of acetone and water of 2 L, 58 g of a 25% aqueous tetramethylammonium hydroxide solution was added thereto, and 22 g of morpholinyl bromoacetate was added thereto, followed by stirring for 10 hours. 33 mL of hydrochloric acid was added to the reaction product to neutralize it, and then dropwise added to 20 L of distilled water to obtain a white solid. The obtained solid was filtered, washed with distilled water, dehydrated and dissolved in acetone again. Then, precipitated, washed, dehydrated and dried in distilled water, and 5% of the hydroxyl groups of polyhydroxystyrene were substituted with morpholinylcarbonylmethoxy groups, and poly (hydroxystyrene / mol having a weight average molecular weight of 12,500 in terms of polystyrene standard. 253g of polyvinylcarbonylmethoxystyrene) was obtained.

합성예 2: 폴리(하이드록시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 2 Preparation of Poly (hydroxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 1과 동일한 방법으로 공중합체를 제조하되, 다만 테트라메틸암모늄하이드록시드 25% 수용액을 58g 첨가하는 대신에 116g 첨가하고, 몰포리닐브로모아세테이트을 22g 첨가하는 대신에 44g 첨가하여 몰포리닐카르보닐메톡시기로 10% 치환된 수지 250g을 합성하였다. 얻어진 수지는 폴리스티렌 표준 환산 중량평균분자량이 13,200인 폴리(하이드록시스티렌/몰포리닐카르보닐메톡시스티렌)이었다.A copolymer was prepared in the same manner as in Synthesis example 1, except that 116 g was added instead of 58 g of tetramethylammonium hydroxide 25% aqueous solution, and 44 g was added instead of 22 g of morpholinyl bromoacetate. 250 g of a resin substituted by 10% with a carbonylmethoxy group was synthesized. The obtained resin was poly (hydroxystyrene / morpholinylcarbonylmethoxystyrene) having a polystyrene standard weight average molecular weight of 13,200.

합성예 3: 폴리(하이드록시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 3 Preparation of Poly (hydroxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene)

폴리하이드록시스티렌 100g을 1.5ℓ의 아세톤과 물 혼합용매에 용해시킨 후, 테트라메틸암모늄하이드록시드 25% 수용액을 90g 첨가하고 t-부틸 브로모아세테이트 16g과 몰포리닐 브로모아세테이트 9g 부가하여 10 시간 동안 교반하였다. 이 반응물에 염산 26㎖를 첨가하여 중화시킨 후 15ℓ의 증류수에 적하하여 백색고체를 얻었다. 이 고체를 여과하여 증류수로 세척, 탈수시킨 후 다시 아세톤에 용해시켰다. 그리고 나서, 증류수에서 석출, 세척, 탈수 및 건조시켜 폴리하이드록시스티렌의 수산기 중 8.4%가 t-부톡시카르보닐메톡시기로, 5%는 몰포리닐카르보닐메톡시기로 치환되었으며, 폴리스티렌 표준 환산 중량평균분자량이 13,500인 폴리(하이드록시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 111g 얻었다.100 g of polyhydroxystyrene was dissolved in a mixture of 1.5 L of acetone and water, and then 90 g of a 25% aqueous tetramethylammonium hydroxide solution was added, 16 g of t-butyl bromoacetate and 9 g of morpholinyl bromoacetate were added thereto. Stir for hours. 26 mL of hydrochloric acid was added to the reaction product to neutralize it, followed by dropwise addition to 15 L of distilled water to obtain a white solid. The solid was filtered, washed with distilled water, dehydrated and dissolved in acetone again. Then, precipitated, washed, dehydrated and dried in distilled water, 8.4% of the hydroxyl groups of polyhydroxystyrene were substituted with t-butoxycarbonylmethoxy group, 5% with morpholinylcarbonylmethoxy group, and polystyrene standard equivalent 111 g of poly (hydroxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene) having a weight average molecular weight of 13,500 was obtained.

합성예 4: 폴리(하이드록시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 4 Preparation of Poly (hydroxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene)

폴리하이드록시스티렌 100g을 1.5ℓ의 아세톤과 물 혼합용매에 용해시킨 후, 테트라메틸암모늄하이드록시드 25% 수용액을 120g 첨가하고 t-부틸 브로모아세테이트 40g과 몰포리닐 브로모아세테이트 9g 부가하여 10 시간 동안 교반하였다. 이 반응물에 염산 35㎖를 첨가하여 중화시킨 후 15ℓ의 증류수에 적하하여 백색고체를 얻었다. 이 고체를 여과하여 증류수로 세척, 탈수시킨 후 다시 아세톤에 용해시켰다. 그리고 나서, 증류수에서 석출, 세척, 탈수 및 건조시켜 폴리하이드록시스티렌의 수산기 중 23.5%가 t-부톡시카르보닐메톡시기로, 5%가 몰포리닐카르보닐메톡시기로 치환되었으며, 폴리스티렌 표준 환산 중량 평균분자량이 15,200인 폴리(하이드록시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 117g 얻었다.100 g of polyhydroxystyrene was dissolved in a mixture of 1.5 L of acetone and water, and then 120 g of a 25% aqueous tetramethylammonium hydroxide solution was added, 40 g of t-butyl bromoacetate and 9 g of morpholinyl bromoacetate were added thereto. Stir for hours. 35 ml of hydrochloric acid was added to the reaction product to neutralize it, followed by dropwise addition to 15 L of distilled water to obtain a white solid. The solid was filtered, washed with distilled water, dehydrated and dissolved in acetone again. Then, precipitated, washed, dehydrated and dried in distilled water, 23.5% of the hydroxyl groups of polyhydroxystyrene were substituted with t-butoxycarbonylmethoxy group, 5% with morpholinylcarbonylmethoxy group, and polystyrene standard equivalent. 117 g of poly (hydroxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene) having a weight average molecular weight of 15,200 was obtained.

합성예 5: 폴리(하이드록시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 5 Preparation of Poly (hydroxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 4와 동일한 방법으로 공중합체를 제조하되, 다만 테트라메틸암모늄하이드록시드 25% 수용액을 126g, t-부틸브로모아세테이트를 49g 첨가하여 수산기의 28.5%가 t-부톡시카르보닐메톡시기로, 5%가 몰포리닐카르보닐메톡시기로 치환된 수지를 119g 합성하였으며, 이 수지는 폴리스티렌 표준 환산 중량평균분자량이 15,700인 폴리(하이드록시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)이다.A copolymer was prepared in the same manner as in Synthesis example 4, except that 126 g of tetramethylammonium hydroxide 25% aqueous solution and 49 g of t-butylbromoacetate were added to allow 28.5% of the hydroxyl group to be t-butoxycarbonylmethoxy group. 119g of a resin substituted with 5% morpholinylcarbonylmethoxy group was synthesized, and the resin was poly (hydroxystyrene / t-butoxycarbonylmethoxystyrene / mol having a weight average molecular weight of 15,700 in terms of polystyrene standard. Polyvinylcarbonylmethoxystyrene).

합성예 6: 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 6 Preparation of Poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 1에서 얻은 몰포리닐카르보닐메톡시기로 5% 치환된 폴리(하이드록시스티렌/몰포리닐카르보닐메톡시스티렌) 50g을 디메틸 포름아미드 500㎖에 용해시켰다. 그 다음, 여기에 촉매량만큼의 p-톨루엔술폰산을 첨가하고 20℃에서 교반하면서 에틸비닐 에테르 17g을 첨가하였다. 1시간 반응시킨 후에 피리딘으로 중화하고, 물 5ℓ에 중화 반응액을 적하하여 백색 고체를 얻었다. 이 고체를 여과하여 증류수로 세척, 탈수시킨 후 다시 아세톤에 용해시키고 물 5ℓ에 적하하여 여과한 후 세척, 탈수 및 건조시켜 폴리하이드록시스티렌의 수산기 중 27%가 에톡시에톡시기로 치환되었고, 5%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량평균분자량 14,100인 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 51g 얻었다50 g of poly (hydroxystyrene / morpholinylcarbonylmethoxystyrene) substituted by 5% of the morpholinylcarbonylmethoxy group obtained in Synthesis Example 1 was dissolved in 500 ml of dimethyl formamide. Then, a catalytic amount of p-toluenesulfonic acid was added thereto and 17 g of ethylvinyl ether was added with stirring at 20 ° C. After making it react for 1 hour, it neutralized with pyridine, and the neutralization reaction liquid was dripped at 5 L of water, and the white solid was obtained. The solid was filtered, washed with distilled water, dehydrated, and then dissolved in acetone. The solid was added dropwise to 5 liters of water, filtered, washed, dehydrated and dried to replace 27% of the hydroxyl groups of polyhydroxystyrene with ethoxyethoxy group. 51 g of poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene) having 5% of polystyrene standard weight average molecular weight in terms of polystyrene substituted with morpholinylcarbonylmethoxy group was obtained.

합성예 7: 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 7 Preparation of Poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 6과 동일한 방법으로 공중합체를 제조하되, 다만 에틸비닐 에테르의 첨가량을 18.5g으로 하여 폴리하이드록시스티렌의 수산기 중 32%가 에톡시에톡시기로 치환되었고, 5%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량평균분자량이 14,400인 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 50g 얻었다.A copolymer was prepared in the same manner as in Synthesis example 6, except that 32% of the hydroxyl groups of polyhydroxystyrene were substituted with an ethoxyethoxy group, and 5% was morpholinyl, with 18.5 g of ethyl vinyl ether added. 50g of poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene) having a polystyrene standard weight average molecular weight substituted with a carbonylmethoxy group was 14,400.

합성예 8: 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 8 Preparation of Poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 6과 동일한 방법으로 공중합체를 제조하되, 다만 에틸비닐 에테르의 첨가량을 20g으로 하여 폴리하이드록시스티렌의 수산기 중 37%가 에톡시에톡시기로 치환되었고, 5%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량평균분자량 14,700인 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 52g 얻었다.A copolymer was prepared in the same manner as in Synthesis example 6, except that 37% of the hydroxyl groups of polyhydroxystyrene were substituted with an ethoxyethoxy group, and 5% was morpholinylcar, with 20 g of ethyl vinyl ether added. 52g of poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene) having a polystyrene standard weight average molecular weight of 14,700 substituted with a carbonylmethoxy group was obtained.

합성예 9: 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 9 Preparation of Poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 2에서 얻은 몰포리닐카르보닐메톡시기로 10% 치환된 폴리(하이드록시스티렌/몰포리닐카르보닐메톡시스티렌) 50g을 디메틸 포름아미드 500㎖에 용해시켰다. 그 다음, 여기에 촉매량만큼의 p-톨루엔술폰산을 첨가하고 20℃에서 교반하면서 에틸비닐 에테르 15.5g을 첨가하였다. 1시간 반응시킨 후에 피리딘으로 중화하고, 물 5ℓ에 중화 반응액을 적하하여 백색 고체를 얻었다. 이 고체를 여과하여 증류수로 세척, 탈수시킨 후 다시 아세톤에 용해시키고 물 5ℓ에 적하하여 여과한 후 세척, 탈수 및 건조시켜 폴리하이드록시스티렌의 수산기 중 22%가 에톡시에톡시기로 치환되었고, 10%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량 평균분자량 14,500인 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 51g 얻었다50 g of poly (hydroxystyrene / morpholinylcarbonylmethoxystyrene) substituted by 10% of the morpholinylcarbonylmethoxy group obtained in Synthesis Example 2 was dissolved in 500 ml of dimethyl formamide. Then, a catalytic amount of p-toluenesulfonic acid was added thereto, and 15.5 g of ethylvinyl ether was added with stirring at 20 ° C. After making it react for 1 hour, it neutralized with pyridine, and the neutralization reaction liquid was dripped at 5 L of water, and the white solid was obtained. The solid was filtered, washed with distilled water, dehydrated, and then dissolved in acetone. The solid was added dropwise to 5 L of water, filtered, washed, dehydrated, and dried to replace 22% of the hydroxyl groups of polyhydroxystyrene with ethoxyethoxy group. 51 g of poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene) having 10% of polystyrene standard weight average molecular weight in terms of polystyrene substituted with morpholinylcarbonylmethoxy group was obtained.

합성예 10: 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 10 Preparation of Poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 9와 동일한 방법으로 공중합체를 제조하되, 다만 에틸비닐 에테르 의 첨가량을 16.9g으로 하여 폴리하이드록시스티렌의 수산기 중 26%가 에톡시에톡시기로 치환되었고, 10%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량평균분자량 14,700인 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 50g 얻었다.A copolymer was prepared in the same manner as in Synthesis example 9, except that 26% of the hydroxyl groups of polyhydroxystyrene were substituted with an ethoxyethoxy group, and 10% was morpholinyl, with 16.9 g of ethyl vinyl ether added. 50g of poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene) having a polystyrene standard weight average molecular weight of 14,700 substituted with a carbonylmethoxy group was obtained.

합성예 11 : 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 11 Preparation of Poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 9와 동일한 방법으로 공중합체를 제조하되, 다만 에틸비닐 에테르의 첨가량을 18g으로 하여 폴리하이드록시스티렌의 수산기 중 31%가 에톡시에톡시기로 치환되었고, 10%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량평균분자량 15,100인 폴리(하이드록시스티렌/에톡시에톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 50g 얻었다.A copolymer was prepared in the same manner as in Synthesis example 9, except that 31% of the hydroxyl groups of polyhydroxystyrene were substituted with an ethoxyethoxy group and 10% was morpholinylcar with 18 g of ethyl vinyl ether added. 50g of poly (hydroxystyrene / ethoxyethoxystyrene / morpholinylcarbonylmethoxystyrene) having a polystyrene standard weight average molecular weight of 15,100 substituted with a carbonylmethoxy group was obtained.

합성예 12: 폴리(하이드록시스티렌/에톡시에톡시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 12 Preparation of Poly (hydroxystyrene / ethoxyethoxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 3에서 얻은 t-부톡시카르보닐메톡시기로 8.4%, 몰포리닐카르보닐메톡시기로 5% 치환된 폴리(하이드록시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌) 50g을 디메틸 포름아미드 500㎖에 용해시켰다. 그 다음, 여기에 촉매량만큼의 p-톨루엔술폰산을 첨가하고 20℃에서 교반하면서 에틸비닐 에테르 14g을 첨가하였다. 1시간 반응시킨 후에 피리딘으로 중화하고, 물 5ℓ에 중화 반응액을 적하하여 백색 고체를 얻었다. 이 고체를 여과하여 증류수로 세척, 탈수시킨 후 다시 아세톤에 용해시키고 물 5ℓ에 적하하여 여과한 후 세척, 탈수 및 건조시켜 폴리하이드록시스티렌의 수산기 중 16%가 에톡시에톡시기로 치환되고, 8.4%가 t-부톡시카르보닐메톡시기로 치환되며, 5%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량평균분자량 14,400인 폴리(하이드록시스티렌/에톡시에톡시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌) 52g을 얻었다.Poly (hydroxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcar substituted with 8.4% of the t-butoxycarbonylmethoxy group obtained in Synthesis Example 3 and 5% of the morpholinylcarbonylmethoxy group 50 g of carbonylmethoxystyrene) was dissolved in 500 ml of dimethyl formamide. Then, a catalytic amount of p-toluenesulfonic acid was added thereto, and 14 g of ethylvinyl ether was added with stirring at 20 ° C. After making it react for 1 hour, it neutralized with pyridine, and the neutralization reaction liquid was dripped at 5 L of water, and the white solid was obtained. The solid was filtered, washed with distilled water, dehydrated, dissolved in acetone again, and added dropwise to 5 L of water, filtered, washed, dehydrated and dried to replace 16% of the hydroxyl groups of polyhydroxystyrene with ethoxyethoxy groups. Poly (hydroxystyrene / ethoxyethoxystyrene / t- with a weight average molecular weight of 14,400 in terms of polystyrene standard substituted with 8.4% substituted with t-butoxycarbonylmethoxy group and 5% substituted with morpholinylcarbonylmethoxy group 52 g of butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene) were obtained.

합성예 13: 폴리(하이드록시스티렌/에톡시에톡시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 13: Preparation of poly (hydroxystyrene / ethoxyethoxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 12와 동일한 방법으로 공중합체를 제조하되, 다만 에틸비닐 에테르의 첨가량을 15.5g으로 하여 폴리하이드록시스티렌의 수산기 중 21%가 에톡시에톡시기로 치환되었고, 8.4%가 t-부톡시카르보닐메톡시기로 치환되었으며, 5%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량 평균분자량 14,800인 폴리(하이드록시스티렌/에톡시에톡시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 50g 얻었다.A copolymer was prepared in the same manner as in Synthesis example 12, except that 21% of the hydroxyl groups of the polyhydroxystyrene was substituted with an ethoxyethoxy group with 15.5 g of ethyl vinyl ether added, and 8.4% of t-part. Poly (hydroxystyrene / ethoxyethoxystyrene / t-butoxycarbonylmethoxy with a weight average molecular weight of 14,800 in terms of polystyrene standard substituted by oxycarbonylmethoxy group and 5% substituted by morpholinylcarbonylmethoxy group Styrene / morpholinylcarbonylmethoxystyrene) was obtained 50g.

합성예 14: 폴리(하이드록시스티렌/에톡시에톡시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)의 제조Synthesis Example 14 Preparation of Poly (hydroxystyrene / ethoxyethoxystyrene / t-butoxycarbonylmethoxystyrene / morpholinylcarbonylmethoxystyrene)

상기 합성예 12와 동일한 방법으로 공중합체를 제조하되, 다만 에틸비닐 에테르의 첨가량을 17g으로 하여 폴리하이드록시스티렌의 수산기 중 25%가 에톡시에톡시기로 치환되었고, 8.4%가 t-부톡시카르보닐메톡시기로 치환되었으며, 5%가 몰포리닐카르보닐메톡시기로 치환된 폴리스티렌 표준 환산 중량평균분자량 15,000인 폴리(하이드록시스티렌/에톡시에톡시스티렌/t-부톡시카르보닐메톡시스티렌/몰포리닐카르보닐메톡시스티렌)을 54g 얻었다.A copolymer was prepared in the same manner as in Synthesis example 12, except that 25% of the hydroxyl groups of the polyhydroxystyrene were substituted with an ethoxyethoxy group with 17 g of ethyl vinyl ether added, and 8.4% of t-butoxy Poly (hydroxystyrene / ethoxyethoxystyrene / t-butoxycarbonylmethoxystyrene substituted with a carbonylmethoxy group, 5% of which is a polystyrene standard equivalent weight average molecular weight of 15,000 substituted with a morpholinylcarbonylmethoxy group 54 g of morpholinylcarbonylmethoxystyrene) was obtained.

합성예 15: 산화합물의 제조Synthesis Example 15 Preparation of Acid Compound

폴리하이드록시스티렌 100g을 아세톤과 물 혼합용매 1ℓ에 용해시킨 후, 테트라메틸암모늄하이드록시드 25% 수용액을 120g 첨가하고 브로모아세트산을 40g 부가한 다음 10 시간 동안 교반하였다. 이 반응물에 아세트산을 100㎖ 첨가하여 중화시킨 후 증류수 10ℓ에 적하하여 백색 고체를 얻었다. 이 고체를 여과하여 증류수로 세척, 탈수시킨 후 다시 아세톤에 용해시킨 다음 증류수에서 석출, 세척, 탈수 및 건조시켜 다음 식으로 표시되는 산화합물 1을 얻었다.After dissolving 100 g of polyhydroxystyrene in 1 L of acetone and water mixed solvent, 120 g of tetramethylammonium hydroxide 25% aqueous solution was added, 40 g of bromoacetic acid was added, followed by stirring for 10 hours. 100 mL of acetic acid was added to the reaction product to neutralize it, followed by dropwise addition to 10 L of distilled water to obtain a white solid. The solid was filtered, washed with distilled water, dehydrated, dissolved in acetone, and then precipitated, washed, dehydrated and dried in distilled water to obtain an acid compound 1 represented by the following formula.

산화합물 1Acid compound 1

중량평균분자량(Mw) : 5,000 (폴리스티렌 기준)Weight average molecular weight (Mw): 5,000 (based on polystyrene)

분자량분포(Mw/Mn) : 1.8Molecular weight distribution (Mw / Mn): 1.8

y／(x+y) = 0.35y / (x + y) = 0.35

상기 합성예를 통해 제조된 상기 화학식 1로 표시되는 공중합체의 구체적인 조성비 및 폴리하이드록시스티렌의 분자량분포 및 공중합체의 중량평균분자량은 다음 표 1에 나타낸 바와 같다.Specific composition ratio of the copolymer represented by the formula (1) prepared through the synthesis example and the molecular weight distribution of the polyhydroxy styrene and the weight average molecular weight of the copolymer are as shown in Table 1.

합성예Synthesis Example 조성비(몰비)Creation ratio (molar ratio) 폴리하이드록시스티렌의 분자량 분포(Mw/Mn)Molecular Weight Distribution (Mw / Mn) of Polyhydroxystyrene 공중합체의 중량평균분자량(Mw)Weight average molecular weight (Mw) of the copolymer kk ll mm nn 합성예 4Synthesis Example 4 71.571.5 -- 23.523.5 55 1.151.15 15,20015,200 합성예 5Synthesis Example 5 66.566.5 -- 28.528.5 55 1.151.15 15,70015,700 합성예 6Synthesis Example 6 6868 2727 -- 55 1.151.15 14,10014,100 합성예 7Synthesis Example 7 6363 3232 -- 55 1.161.16 14,40014,400 합성예 8Synthesis Example 8 5858 3737 -- 55 1.161.16 14,70014,700 합성예 9Synthesis Example 9 6868 2222 -- 1010 1.201.20 14,50014,500 합성예 10Synthesis Example 10 6464 2626 -- 1010 1.161.16 14,70014,700 합성예 11Synthesis Example 11 5959 3131 -- 1010 1.101.10 15,10015,100 합성예 12Synthesis Example 12 70.670.6 1616 8.48.4 55 1.101.10 14,40014,400 합성예 13Synthesis Example 13 65.665.6 2121 8.48.4 55 1.101.10 14,80014,800 합성예 14Synthesis Example 14 61.661.6 2525 8.48.4 55 1.161.16 15,00015,000

실시예 1∼18Examples 1-18

상기 표 1에 나타낸 바와 같은 합성예를 통해 얻어진 고분자 화합물을 기초수지로 사용하고, 다음 표 2에 나타낸 바와 같은 광산발생제, 염기성 화합물, 계면활성제 및 방향족 카르복실산 등의 레지스트 재료를 용제에 용해시켜 다음 표 3에 나타낸 바와 같은 조성으로 레지스트액을 조제하였다.The polymer compound obtained through the synthesis example as shown in Table 1 is used as the base resin, and a resist material such as a photoacid generator, a basic compound, a surfactant, and an aromatic carboxylic acid as shown in Table 2 is dissolved in a solvent. The resist liquid was prepared by the composition as shown in following Table 3.

산발생제Acid generator 화학식Chemical formula 산발생제Acid generator 화학식Chemical formula PAG 1PAG 1 PAG 2PAG 2 PAG 3PAG 3 PAG 4PAG 4

실시예Example 레지스트 조성물 (단위:중량부)Resist composition (unit: parts by weight) 기초수지Basic resin 산발생제Acid generator 염기성 화합물Basic compound 산화합물Acid compounds 유기용제Organic solvent 1One 합성예 6／합성예 5( 60／40 )Synthesis Example 6 / Synthesis Example 5 (60/40) PAG 2(3)PAG 2 (3) 디페닐아민(0.9)Diphenylamine (0.9) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 22 합성예 7／합성예 4( 70／30 )Synthesis Example 7 / Synthesis Example 4 (70/30) PAG 2(3)PAG 2 (3) 트리에틸아민(0.09)Triethylamine (0.09) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 33 합성예 8／합성예 4( 80／20 )Synthesis Example 8 / Synthesis Example 4 (80/20) PAG 2(3)PAG 2 (3) 트리에틸아민(0.09)Triethylamine (0.09) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 44 합성예 9／합성예 5( 60／40 )Synthesis Example 9 / Synthesis Example 5 (60/40) PAG 2(3)PAG 2 (3) 트리에틸아민(0.09)Triethylamine (0.09) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 55 합성예 10／합성예 4( 70／30 )Synthesis Example 10 / Synthesis Example 4 (70/30) PAG 2(3)PAG 2 (3) 디페닐아민(0.9)Diphenylamine (0.9) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 66 합성예 11／합성예 4( 80／20 )Synthesis Example 11 / Synthesis Example 4 (80/20) PAG 2(3)PAG 2 (3) N,N-디메틸아세트아미드(1.0)N, N-dimethylacetamide (1.0) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 77 합성예 12／합성예 5( 50／50 )Synthesis Example 12 / Synthesis Example 5 (50/50) PAG 2(3)PAG 2 (3) N,N-디메틸아세트아미드(1.0)N, N-dimethylacetamide (1.0) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 88 합성예 13／합성예 4( 60／40 )Synthesis Example 13 / Synthesis Example 4 (60/40) PAG 2(3)PAG 2 (3) 디페닐아민(0.9)Diphenylamine (0.9) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 99 합성예 14／합성예 4( 70／30 )Synthesis Example 14 / Synthesis Example 4 (70/30) PAG 2(3)PAG 2 (3) N,N-디메틸아세트아미드(1.0)N, N-dimethylacetamide (1.0) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 1010 합성예 6／합성예 11／합성예 4( 20／50／30 )Synthesis Example 6 / Synthesis Example 11 / Synthesis Example 4 (20/50/30) PAG 1(3)PAG 1 (3) 디페닐아민(0.9)Diphenylamine (0.9) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA／EL(500)PGMEA ／ EL (500) 1111 합성예 7／합성예 10／합성예 4( 35／35／30 )Synthesis Example 7 / Synthesis Example 10 / Synthesis Example 4 (35/35/30) PAG 1(3)PAG 1 (3) 트리에틸아민(0.09)Triethylamine (0.09) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA／EL(500)PGMEA ／ EL (500) 1212 합성예 8／합성예 9／합성예 5( 50／20／30 )Synthesis Example 8 / Synthesis Example 9 / Synthesis Example 5 (50/20/30) PAG 4(3)PAG 4 (3) 트리에탄올아민(0.05)Triethanolamine (0.05) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA／EL(500)PGMEA ／ EL (500) 1313 합성예 6／합성예 14／합성예 4( 30／50／20 )Synthesis Example 6 / Synthesis Example 14 / Synthesis Example 4 (30/50/20) PAG 1(3)PAG 1 (3) 트리에탄올아민(0.05)Triethanolamine (0.05) 산화합물 1(0.05)Acid Compound 1 (0.05) PGMEA(500)PGMEA (500) 1414 합성예 7／합성예 13／합성예 5( 40／30／30 )Synthesis Example 7 / Synthesis Example 13 / Synthesis Example 5 (40/30/30) PAG 4(3)PAG 4 (3) 트리에탄올아민(0.09)Triethanolamine (0.09) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) 1515 합성예 8／합성예 12／합성예 4( 50／20／30 )Synthesis Example 8 / Synthesis Example 12 / Synthesis Example 4 (50/20/30) PAG 4(3)PAG 4 (3) 트리에틸아민(0.09)Triethylamine (0.09) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA／EL(500)PGMEA ／ EL (500) 1616 합성예 9／합성예 14／합성예 5( 20／50／30 )Synthesis Example 9 / Synthesis Example 14 / Synthesis Example 5 (20/50/30) PAG 3(3)PAG 3 (3) N,N-디메틸아세트아미드(1.0)N, N-dimethylacetamide (1.0) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA／EL(500)PGMEA ／ EL (500) 1717 합성예 10／합성예 13／합성예 5( 30／30／40 )Synthesis Example 10 / Synthesis Example 13 / Synthesis Example 5 (30/30/40) PAG 3(3)PAG 3 (3) 디페닐아민(0.9)Diphenylamine (0.9) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA／EL(500)PGMEA ／ EL (500) 1818 합성예 11／합성예 12／합성예 4( 30／30／40 )Synthesis Example 11 / Synthesis Example 12 / Synthesis Example 4 (30/30/40) PAG 3(3)PAG 3 (3) 트리에틸아민(0.09)Triethylamine (0.09) 산화합물 1(1.0)Acid Compound 1 (1.0) PGMEA(500)PGMEA (500) (주)PGMEA : 프로필렌글리콜모노메틸에테르아세테이트PGMEA／EL : 프로필렌글리콜모노메틸에테르아세테이트(350중량부)／에틸락테이트 (150중량부)의 혼합용매PGMEA: Propylene glycol monomethyl ether acetate PGMEA / EL: Mixed solvent of propylene glycol monomethyl ether acetate (350 parts by weight) / ethyl lactate (150 parts by weight)

이들 각 조성물을 0.1㎕막 필터로 여과하여 레지스트액을 얻었다. 스피너를 사용하여 레지스트를 도포하고 90℃에서 90초간 베이킹하여 0.7㎛ 두께의 피막을 얻었다. 이 피막에 248㎚ KrF 엑시머 레이저 스텝퍼를 사용하여 패턴 크롬마스크를 통해 노광시킨 후, 110℃에서 90초간 베이킹하고, 2.38 중량% 테트라메틸암모늄하이드록시드 수용액으로 60초간 현상, 건조하여 포지형 레지스트 패턴을 형성하였다.Each of these compositions was filtered through a 0.1 µl membrane filter to obtain a resist liquid. The resist was applied using a spinner and baked at 90 ° C. for 90 seconds to obtain a 0.7 μm thick film. The film was exposed through a pattern chrome mask using a 248 nm KrF excimer laser stepper, baked at 110 ° C. for 90 seconds, developed and dried for 60 seconds in an aqueous 2.38 wt% tetramethylammonium hydroxide solution, and dried into a positive resist pattern. Formed.

이 레지스트 패턴에서 라인 앤드 스페이스(line and space)의 톱(top)면과 보텀(bottom)면의 크기가 1:1로 같아지는 때의 노광량을 최적 노광에너지(감도)로 하고 이 감도에서 얻을 수 있는 최소 선폭을 해상도로 하여 평가하였다.In this resist pattern, the exposure dose when the size of the top and bottom surfaces of the line and space are equal to 1: 1 can be obtained at this sensitivity with the optimum exposure energy (sensitivity). The minimum line width was evaluated as the resolution.

한편, 해상도의 평가는 상기와 같이 노광한 후 베이킹 시간(PED)를 각각 30분 및 2시간으로 변경하면서도 측정하였다.On the other hand, the evaluation of the resolution was measured while changing the baking time (PED) to 30 minutes and 2 hours, respectively, after exposure as described above.

그리고, 레지스트 패턴은 주사형 전자현미경(SEM)을 사용하여 패턴 형상을 관찰하였다.In addition, the pattern of the resist pattern was observed using the scanning electron microscope (SEM).

상기와 같은 평가 결과를 다음 표 4에 나타내었다.The evaluation results as described above are shown in Table 4 below.

실시예Example 감도(Eop)(mJ/cm2)Sensitivity (Eop) (mJ / cm 2 ) 해상도(㎛)Resolution (μm) 패턴 프로파일Pattern profile 즉시Immediately PED 30분PED 30 minutes PED 2시간PED 2 hours 1One 24.024.0 0.180.18 0.180.18 0.180.18 직사각형Rectangle 22 20.020.0 0.200.20 0.200.20 0.200.20 직사각형Rectangle 33 22.022.0 0.200.20 0.200.20 0.200.20 직사각형Rectangle 44 30.030.0 0.200.20 0.200.20 0.200.20 직사각형Rectangle 55 28.028.0 0.180.18 0.180.18 0.180.18 직사각형Rectangle 66 30.030.0 0.180.18 0.180.18 0.180.18 직사각형Rectangle 77 29.029.0 0.180.18 0.180.18 0.180.18 약간마름모꼴Slightly lozenge 88 26.026.0 0.180.18 0.180.18 0.180.18 약간마름모꼴Slightly lozenge 99 28.028.0 0.180.18 0.180.18 0.180.18 약간마름모꼴Slightly lozenge 1010 40.040.0 0.190.19 0.190.19 0.190.19 직사각형Rectangle 1111 37.037.0 0.190.19 0.190.19 0.190.19 직사각형Rectangle 1212 22.022.0 0.190.19 0.190.19 0.190.19 직사각형Rectangle 1313 40.040.0 0.200.20 0.200.20 0.200.20 직사각형Rectangle 1414 23.023.0 0.200.20 0.200.20 0.200.20 직사각형Rectangle 1515 21.021.0 0.190.19 0.190.19 0.190.19 직사각형Rectangle 1616 32.032.0 0.180.18 0.180.18 0.180.18 약간마름모꼴Slightly lozenge 1717 34.034.0 0.190.19 0.190.19 0.190.19 약간마름모꼴Slightly lozenge 1818 31.031.0 0.200.20 0.200.20 0.200.20 약간마름모꼴Slightly lozenge

상기 표 3의 결과로부터 본 발명에 따른 포토레지스트를 사용하여 패턴을 형성한 결과, 해상도가 우수할 뿐만 아니라 베이킹 시간에 관계없이 패턴의 크기가 변화하지 않는 것으로 보아 안정성이 뛰어남을 알 수 있으며, 패턴 프로파일도 간혹 약간마름모꼴로 형성되기는 하였으나 전반적으로 우수한 형태로 형성됨을 알 수 있다.As a result of forming a pattern using the photoresist according to the present invention from the results of Table 3, it can be seen that not only the resolution is excellent but also the stability of the pattern does not change regardless of the baking time. Although the profile is sometimes formed in a slightly rhombic shape, it can be seen that the overall shape is excellent.

이상에서 상세히 설명한 바와 같이, 본 발명에 따라 특정의 공중합체를 포함하여 조성된 화학 증폭형 양성 레지스트 재료는 원자외선, KrF 엑시머레이저, 전자선 등의 방사선에 대하여 넓은 범위의 노광 여유도를 가지며, 고감도, 고해상성, 우수한 내열성, 노광후 시간 지연에 의해 패턴의 크기가 변하지 않는 안정성이 뛰어나고 기판의 종류에 관계없이 우수한 레지스트 패턴을 얻을 수 있을 뿐만 아니라, 특히 KrF 엑시머레이저의 노광 파장에서 미세한 패턴형성에 용이하므로 초 LSI 제조용 미세패턴 형성 재료로서 적합하다.As described in detail above, the chemically amplified positive resist material including a specific copolymer according to the present invention has a wide range of exposure margins for radiation such as far ultraviolet rays, KrF excimer lasers, electron beams, and the like. High resolution, excellent heat resistance, stability of the pattern does not change due to post-exposure time delay, and excellent resist pattern can be obtained regardless of the type of substrate, and especially for the formation of fine patterns at the exposure wavelength of KrF excimer laser. Since it is easy, it is suitable as a fine pattern formation material for ultra LSI manufacture.

Claims (7)

다음 화학식 1로 표시되며, 폴리스티렌 환산 중량평균분자량이 1,000∼1,000,000인 화학 증폭형 포토레지스트 제조용 공중합체.A copolymer for preparing a chemically amplified photoresist represented by the following Chemical Formula 1, wherein the polystyrene reduced weight average molecular weight is 1,000 to 1,000,000. 화학식 1Formula 1 상기 식에서,R1,R2,R3및 R4는 각각 독립적인 것으로서, 수소원자 또는 저급 알킬기이며,In the above formula, R 1, R 2, R 3 and R 4 are each independently a hydrogen atom or a lower alkyl group, R5, R6,R7및 R8는 수소원자, 탄소원자수 1∼8의 알킬기, 알콕시기, 알콕시카르보닐기 또는 할로겐 원자이며,R 5 , R 6 , R 7 and R 8 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxycarbonyl group or a halogen atom, h와 i는 0∼8의 정수이고,h and i are integers from 0 to 8, k, l, m 및 n은 각각 반복 단위를 나타내는 수로서, 0.3 < k/(k+l+m+n) < 0.9, 0 ≤l/(k+l+m+n) < 0.6, 0 ≤ m/(k+l+m+n) < 0.6, 그리고 0.01 < n/(k+l+m+n) < 0.3인 조건을 만족한다. 그리고 k+l+m+n=1을 만족하며, l과 m는 동시에 0이 될 수 없고, 동시에 0이 아닐 수도 있다.k, l, m and n are the numbers representing the repeating units, respectively, 0.3 <k / (k + l + m + n) <0.9, 0 ≤ l / (k + l + m + n) <0.6, 0 ≤ m / (k + l + m + n) <0.6 and 0.01 <n / (k + l + m + n) <0.3 are satisfied. And k + l + m + n = 1, l and m may not be zero at the same time and may not be zero at the same time. R9는 다음 화학식 2로 표시되는 화합물이고,R 9 is a compound represented by the following formula (2), 화학식 2Formula 2 상기 식에서, R10와 R11는 각각 독립적으로 수소원자 또는 탄소원자수 1∼6의 직쇄상 또는 분지쇄상의 알킬기이고,In the above formula, R 10 and R 11 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, R12는 탄소원자수 1∼10의 직쇄상, 분지쇄상 또는 환상의 알킬기이다.R 12 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Am은 -NR13R14(여기서, R13과 R14은 각각 독립적인 것으로서 수소원자, 탄소원자수 1∼8의 알킬기, 아릴기 또는 페닐기이다), 고리형 2가 아민류 및 산소 또는 황 원자가 포함된 고리형 2가 아민류 등이다.Am is —NR 13 R 14 (wherein R 13 and R 14 are each independently being a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or a phenyl group), a cyclic divalent amine and an oxygen or sulfur atom Cyclic divalent amines; 제 1 항에 있어서, 화학식 1로 표시되는 공중합체는 다음과 같은 군으로부터 선택된 1종 또는 혼합물인 것임을 특징으로 하는 화학 증폭형 포토레지스트 제조용 공중합체;The method of claim 1, wherein the copolymer represented by the formula (1) is a copolymer for preparing a chemically amplified photoresist, characterized in that one or a mixture selected from the following group; (A)폴리(하이드록시스티렌/알콕시알콕시스티렌/t-부틸카르보닐알콕시스티렌/모폴린닐 카르보닐알콕시스티렌)의 4원 공중합체이면서, k, l, m 및 n은 0.3 < k/(k+l+m+n) < 0.9, 0 ≤l/(k+l+m+n) < 0.6, 0 ≤ m/(k+ℓ+m+n) < 0.6, 그리고 0.01 < n/(k+l+m+n) < 0.3인 조건을 만족하는 수지,(A) a quaternary copolymer of poly (hydroxystyrene / alkoxyalkoxystyrene / t-butylcarbonylalkoxystyrene / morpholinyl carbonylalkoxystyrene), wherein k, l, m and n are 0.3 < k / (k + l + m + n) <0.9, 0 <l / (k + l + m + n) <0.6, 0 <m / (k + l + m + n) <0.6, and 0.01 <n / (k + resin satisfying the condition of l + m + n) <0.3, (B)폴리(하이드록시스티렌/알콕시알콕시스티렌/몰포리닐카르보닐알콕시스티렌) 의 3원 공중합체이면서, k, l, m 및 n은 각각 반복 단위를 나타내는 수로서, 0.3 < k/(k+l+m+n) < 0.9, 0 ≤l/(k+l+m+n) < 0.6, m=0, 그리고 0.01 < n/(k+l+m+n) < 0.3인 조건을 만족하는 수지,(B) is a ternary copolymer of poly (hydroxystyrene / alkoxyalkoxystyrene / morpholinylcarbonylalkoxystyrene), wherein k, l, m and n each represent a repeating unit, and 0.3 <k / (k + l + m + n) <0.9, 0 ≤ l / (k + l + m + n) <0.6, m = 0, and 0.01 <n / (k + l + m + n) <0.3 Resin made, (C)폴리(하이드록시스티렌/t-부틸카르보닐알콕시스티렌/몰포리닐카르보닐알콕시스티렌 )의 3원 공중합체이면서, k, l, m 및 n은 각각 반복 단위를 나타내는 수로서, 0.3 < k/(k+l+m+n) < 0.9, l=0, 0 ≤ m/(k+ℓ+m+n) < 0.6, 그리고 0.01 < n/(k+l+m+n) < 0.3인 조건을 만족하는 수지.(C) a ternary copolymer of poly (hydroxystyrene / t-butylcarbonylalkoxystyrene / morpholinylcarbonylalkoxystyrene), wherein k, l, m and n each represent a repeating unit, where 0.3 < k / (k + l + m + n) <0.9, l = 0, 0 ≤ m / (k + l + m + n) <0.6, and 0.01 <n / (k + l + m + n) <0.3 Resin that meets the conditions. 제 1 항에 있어서, t-부톡시카르보닐메톡시기 및 아미드기는 테트라메틸암모늄하이드록시드를 염기성 화합물로 첨가하여 폴리하이드록시스티렌과 알킬할로겐 화합물의 치환반응을 통해 도입된 것임을 특징으로 하는 화학 증폭형 포토레지스트 제조용 공중합체.The chemical amplification method according to claim 1, wherein the t-butoxycarbonylmethoxy group and the amide group are introduced through a substitution reaction of polyhydroxystyrene and an alkylhalogen compound by adding tetramethylammonium hydroxide as a basic compound. Copolymer for Producing Type Photoresist. 제 1 항의 공중합체, 산발생제 및 첨가제를 용매에 녹여 제조된 화학 증폭형 양성 포토레지스트 조성물.A chemically amplified positive photoresist composition prepared by dissolving the copolymer, acid generator and additive of claim 1 in a solvent. 제 4 항에 있어서, 산발생제는 트리페닐술포니움 헥사플루오로안티모네이트, 디페닐요드늄 트리플레이트, 디페닐요드늄 메틸벤젠술포네이트, 페닐(4-t-메톡시페닐)요드늄 캄포어 술포네이트, 페닐(4-t-부틸아세틸페닐)요드늄 캄포어 술포네이트, 비스(시클로헥실술포닐)디아조메탄, 비스(2,4-디메틸페닐술포닐)디아조메탄, 1,1-비스(4-클로로페닐)-2,2,2-트리클로로에탄, 페닐-비스(트리클로로메틸)-s-트리아진, 나프틸-비스(트리클로로메틸)-s-트리아진 및 다음 화학식 3으로 표시되는 술포늄 화합물 중에서 선택된 1종 이상의 것임을 특징으로 하는 화학 증폭형 양성 포토레지스트 조성물.The acid generator of claim 4, wherein the acid generator is triphenylsulfonium hexafluoroantimonate, diphenyliodnium triflate, diphenyliodium methylbenzenesulfonate, phenyl (4-t-methoxyphenyl) iodium Camphor sulfonate, phenyl (4-t-butylacetylphenyl) iodium camphor sulfonate, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, 1, 1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine and A chemically amplified positive photoresist composition, characterized in that one or more selected from sulfonium compounds represented by the formula (3). 화학식 3Formula 3 상기 식에서, R15는 수소원자, 알킬기 또는 알콕시기이고,Wherein R 15 is a hydrogen atom, an alkyl group or an alkoxy group, R16은 알킬기, 알콕시알킬기, t-부톡시카르보닐메틸기이며,R 16 is an alkyl group, an alkoxyalkyl group, t-butoxycarbonylmethyl group, X는 O, S 또는 CH2이고,X is O, S or CH 2 , g는 0∼20의 정수이다.g is an integer of 0-20. 제 4 항에 있어서, 다음 화학식 4로 표시되는 산화합물을 추가적으로 함유하는 것임을 특징으로 하는 화학 증폭형 양성 포토레지스트 조성물.The chemically amplified positive photoresist composition according to claim 4, further comprising an acid compound represented by the following formula (4). 상기 식에서, 0.01〈 y／(x+y) ≤0.4 이며, 폴리스티렌 표준 중량평균분자량은 500∼50,000, 바람직하게는 5,000∼20,000인 것이다.In the above formula, 0.01 &lt; y / (x + y)? 0.4, and the polystyrene standard weight average molecular weight is 500 to 50,000, preferably 5,000 to 20,000. 제 4 항에 있어서, 첨가제는 계면활성제, 아조계 화합물, 할레이션(halation) 방지제, 접착조제, 보존 안정제 및 소포제인 것임을 특징으로 하는 화학 증폭형 양성 포토레지스트 조성물.The chemically amplified positive photoresist composition according to claim 4, wherein the additive is a surfactant, an azo compound, an antihalation agent, an adhesion aid, a storage stabilizer, and an antifoaming agent.
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JP4554665B2 (en) * 2006-12-25 2010-09-29 富士フイルム株式会社 PATTERN FORMATION METHOD, POSITIVE RESIST COMPOSITION FOR MULTIPLE DEVELOPMENT USED FOR THE PATTERN FORMATION METHOD, NEGATIVE DEVELOPMENT SOLUTION USED FOR THE PATTERN FORMATION METHOD, AND NEGATIVE DEVELOPMENT RINSE SOLUTION USED FOR THE PATTERN FORMATION METHOD
US8530148B2 (en) 2006-12-25 2013-09-10 Fujifilm Corporation Pattern forming method, resist composition for multiple development used in the pattern forming method, developer for negative development used in the pattern forming method, and rinsing solution for negative development used in the pattern forming method
US8637229B2 (en) 2006-12-25 2014-01-28 Fujifilm Corporation Pattern forming method, resist composition for multiple development used in the pattern forming method, developer for negative development used in the pattern forming method, and rinsing solution for negative development used in the pattern forming method

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KR100573819B1 (en) * 2001-05-31 2006-04-26 토쿄오오카코교 가부시기가이샤 Sensitive stacked structure and resist pattern forming method using the same

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