KR20090030178A - Uv-curable and alkali-developable modified (co)polymer and process for preparing the same - Google Patents
Uv-curable and alkali-developable modified (co)polymer and process for preparing the same Download PDFInfo
- Publication number
- KR20090030178A KR20090030178A KR1020070095564A KR20070095564A KR20090030178A KR 20090030178 A KR20090030178 A KR 20090030178A KR 1020070095564 A KR1020070095564 A KR 1020070095564A KR 20070095564 A KR20070095564 A KR 20070095564A KR 20090030178 A KR20090030178 A KR 20090030178A
- Authority
- KR
- South Korea
- Prior art keywords
- ethylenically unsaturated
- compound
- polymer
- modified
- functional group
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title description 7
- -1 glycidyl compound Chemical group 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 42
- 125000000524 functional group Chemical group 0.000 claims abstract description 38
- 238000007259 addition reaction Methods 0.000 claims abstract description 19
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 37
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- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 9
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- 239000007795 chemical reaction product Substances 0.000 claims description 7
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- UMILHIMHKXVDGH-UHFFFAOYSA-N Triethylene glycol diglycidyl ether Chemical compound C1OC1COCCOCCOCCOCC1CO1 UMILHIMHKXVDGH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- LSURRKWOANERMF-UHFFFAOYSA-N butyl 2-(hydroxymethyl)prop-2-enoate Chemical compound CCCCOC(=O)C(=C)CO LSURRKWOANERMF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KBPPPUZMFQKLNP-UHFFFAOYSA-N dill ether Natural products C1=C(C)CCC2C(C)COC21 KBPPPUZMFQKLNP-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- SYGAXBISYRORDR-UHFFFAOYSA-N ethyl 2-(hydroxymethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)CO SYGAXBISYRORDR-UHFFFAOYSA-N 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 229960005237 etoglucid Drugs 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- RFUCOAQWQVDBEU-UHFFFAOYSA-N methyl 2-(hydroxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)CO RFUCOAQWQVDBEU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001062 red colorant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Optical Filters (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
본 발명은 광경화형 알칼리 가용성 변성 (공)중합체 및 그의 제조방법에 관한 것으로서, 더욱 상세하게는, 산 작용기(acid functional group), 에틸렌성 불포화결합, 및 부가반응에 의해 도입된, 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 잔기를 포함하며, 컬럼 스페이서, 칼라 필터, 칼라 레지스트, 포토레지스트 등의 평면 디스플레이용 포토리소그래픽 소재에 적용시 현상성이 우수할 뿐만 아니라, 타 유기바인더 및 안료와의 혼화성과 분산성이 우수하고, 강도와 탄성 등의 물성이 개선된 변성 (공)중합체 및 그의 제조방법에 관한 것이다.The present invention relates to a photocurable alkali-soluble modified (co) polymer and a method for preparing the same, and more particularly, to an ethylenically unsaturated bond introduced by an acid functional group, an ethylenically unsaturated bond, and an addition reaction. It contains a glycidyl compound residue that does not have a high molecular weight, and is excellent in developability when applied to flat display photolithographic materials such as column spacers, color filters, color resists, photoresists, and the like, and with other organic binders and pigments. The modified (co) polymer excellent in miscibility and dispersibility, and improved physical properties, such as strength and elasticity, and its manufacturing method.
컬러 필터의 제조법으로는 염색법, 전착법, 인쇄법, 안료 분산법 등 다양한 방법이 알려져 있지만, 생산성, 품질, 비용 등을 종합적으로 고려할 때 현재로는 안료 분산법이 가장 우수하고, 따라서 현재 주로 사용되고 있다.Various methods such as dyeing method, electrodeposition method, printing method and pigment dispersion method are known as the manufacturing method of the color filter. However, in consideration of productivity, quality, cost and the like comprehensively, the pigment dispersion method is the best at present, and is currently mainly used. have.
안료 분산법은 유기 안료를 분산 및 착색시킨 감광성 수지인 컬러 레지스트를 이용하고, 포토리소그래피에 의하여 유리 등의 투명 기판상에 미세한 착색 화상을 형성하고 컬러필터를 제조하는 방법이다. 컬러 필터에는 적, 녹, 청의 3원색의 패턴이 필요하고, 포토리소그래피를 되풀이하는 것에 의해 형성된다. 컬러 필터의 생산성은 포토리소그래피의 효율에 크게 영향을 받기 때문에 재료인 컬러 레지스트에 대한 고감도화와 현상효율성이 강하게 요구된다. 컬러 레지스트로는 여러 가지 원리에 의해 제조되는 감광성 수지를 이용하는 것이 제안되고 있지만, 고감도화의 관점으로부터 연쇄반응을 이용한 래디칼 중합타입의 광경화형 감광성 수지가 주로 사용되고 있다.The pigment dispersion method is a method of forming a fine colored image on a transparent substrate such as glass by photolithography using a color resist which is a photosensitive resin obtained by dispersing and coloring an organic pigment and manufacturing a color filter. The color filter requires a pattern of three primary colors of red, green, and blue, and is formed by repeating photolithography. Since the productivity of the color filter is greatly influenced by the efficiency of photolithography, high sensitivity and development efficiency of the color resist, which is a material, are strongly required. Although it is proposed to use photosensitive resin manufactured according to various principles as a color resist, radical polymerization type photocurable photosensitive resin using the chain reaction from the viewpoint of high sensitivity is mainly used.
상기 래디칼 중합 타입의 광경화를 실현하기 위해, 컬러 레지스트 바인더의 경우 알칼리 가용성 고분자 측쇄 구조에 감광성 불포화결합을 도입하는 기술이 널리 알려져 있으며, 감도와 경화성을 향상시키기 위해 다관능 아크릴레이트류의 에틸렌성 불포화 화합물 단량체 또는 올리고머가 주로 사용되고 있다. In order to realize the photopolymerization of the radical polymerization type, a technique of introducing photosensitive unsaturated bonds into the alkali-soluble polymer side chain structure in the case of a color resist binder is widely known, and the ethylenic properties of polyfunctional acrylates are improved in order to improve sensitivity and curability. Unsaturated compound monomers or oligomers are mainly used.
그러나 이러한 에틸렌성 불포화 화합물은 광경화 공정에 의해 고분자화되면서 알칼리 가용성 고분자 바인더와의 혼화성이 저하되어 균일하고 투명한 최종 경화물을 얻기가 어려울 뿐 아니라, 분자구조 내에 알칼리 가용성 관능기를 함유하고 있지 않기 때문에 현상성이 열세하다는 문제를 가지고 있다. However, such an ethylenically unsaturated compound is polymerized by a photocuring process, thereby reducing its miscibility with the alkali-soluble polymer binder, making it difficult to obtain a uniform and transparent final cured product, and does not contain alkali-soluble functional groups in the molecular structure. Therefore, there is a problem that developability is inferior.
이에 따라 현상성이 우수할 뿐만 아니라, 혼화성과 분산성이 우수하고 강도와 탄성 등의 물성이 개선된 광경화성 알칼리 가용성 다관능 올리고머를 포토레지스트용 감광성 수지 조성물에 혼용하는 방법이 제안되고 있으나, 이 경우 올리고머의 저분자량과 높은 친수성도로 인하여 현상성 제어가 어려울 뿐 아니라 알칼리 가용성 바인더와의 균일한 경화반응을 유도하기 어렵다는 단점이 있다.Accordingly, a method of using a photocurable alkali-soluble polyfunctional oligomer having excellent developability, excellent miscibility and dispersibility, and improved physical properties such as strength and elasticity is mixed with the photosensitive resin composition for photoresist. In the case of low molecular weight and high hydrophilicity of the oligomer, not only the development control is difficult but also it is difficult to induce a uniform curing reaction with the alkali-soluble binder.
본 발명은 상기와 같은 종래기술들의 문제점을 해결하고자 하는 것으로서, 본 발명의 목적은, 컬럼 스페이서, 칼라 필터, 칼라 레지스트, 포토레지스트 등의 평면 디스플레이용 포토리소그래픽 소재에 적용시 현상성이 우수할 뿐만 아니라, 타 유기바인더 및 안료와의 혼화성과 분산성이 우수하고, 강도와 탄성 등의 물성이 개선된 광경화형 알칼리 가용성 변성 (공)중합체 및 그의 제조방법을 제공하는 것이다.The present invention is to solve the problems of the prior art as described above, an object of the present invention, when applied to a flat display photolithographic material such as column spacer, color filter, color resist, photoresist, etc. In addition, the present invention provides a photocurable alkali-soluble modified (co) polymer having excellent miscibility and dispersibility with other organic binders and pigments and improved physical properties such as strength and elasticity, and a method of manufacturing the same.
상기 기술적 과제들을 해결하고자, 본 발명은, 산 작용기(acid functional group), 에틸렌성 불포화결합, 및 부가반응에 의해 도입된, 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 잔기를 포함하는 변성 (공)중합체를 제공한다.In order to solve the above technical problems, the present invention, an acid functional group (ethyl functional unsaturated bond, and modified by including a glycidyl compound residue having no ethylenically unsaturated bond, introduced by addition reaction (co) To provide a polymer.
또한, 본 발명의 다른 측면에 따르면, (1) 산 작용기를 포함하는 (공)중합체를 제공하는 단계, 및 (2) 상기 (공)중합체에 (i) 에틸렌성 불포화결합 및 부가반응성 작용기를 갖는 반응성 모노머 및 (ii) 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물을 부가반응시키는 단계를 포함하는 변성 (공)중합체의 제조방법이 제공된다.In addition, according to another aspect of the invention, (1) providing a (co) polymer comprising an acid functional group, and (2) the (co) polymer having (i) ethylenically unsaturated bonds and addition reactive functional groups Provided is a method of preparing a modified (co) polymer comprising the step of reacting a reactive monomer and (ii) a glycidyl compound having no ethylenically unsaturated bond.
또한, 본 발명의 또 다른 측면에 따르면, (1) (a) 산 작용기를 가지는 에틸렌성 불포화 화합물; 및 (b) 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물과 산 작용기를 가지는 에틸렌성 불포화 화합물과의 부가반응 생성물(adduct);을 포함하는 혼합물을 공중합하는 단계, 및 (2) 상기 (1) 단계의 결과 공중합체에 에 틸렌성 불포화결합 및 부가반응성 작용기를 갖는 반응성 모노머를 부가반응시키는 단계를 포함하는 변성 공중합체의 제조방법이 제공된다.Further, according to another aspect of the present invention, (1) (a) an ethylenically unsaturated compound having an acid functional group; And (b) an addition reaction product of a glycidyl compound having no ethylenically unsaturated bond with an ethylenically unsaturated compound having an acid functional group; and (2) copolymerizing a mixture comprising (1) As a result of the step, there is provided a method for producing a modified copolymer comprising the step of adding a reactive monomer having an ethylenically unsaturated bond and an addition reactive functional group to the copolymer.
또한, 본 발명의 또 다른 측면에 따르면, 본 발명의 변성 (공)중합체를 포함하는 포토레지스트 조성물이 제공된다.Furthermore, according to another aspect of the present invention, there is provided a photoresist composition comprising the modified (co) polymer of the present invention.
본 발명에 따르면 컬럼 스페이서, 칼라 필터, 칼라 레지스트, 포토레지스트 등의 평면 디스플레이용 포토리소그래픽 소재에 적용시 현상성이 우수할 뿐만 아니라, 타 유기바인더 및 안료와의 혼화성과 분산성이 우수하고, 강도와 탄성 등의 물성이 개선된 광경화형 알칼리 가용성 변성 (공)중합체를 용이하게 제조할 수 있다. According to the present invention, when applied to flat display photolithographic materials such as column spacers, color filters, color resists, and photoresists, it is not only excellent in developability, but also excellent in miscibility and dispersibility with other organic binders and pigments, A photocurable alkali-soluble modified (co) polymer having improved physical properties such as strength and elasticity can be easily produced.
이하에서 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 변성 (공)중합체의 제조에는 산 작용기를 가지는 에틸렌성 불포화 화합물 모노머 (A)가 사용되는데, 이러한 산 작용기를 가지는 에틸렌성 불포화 화합물 모노머 (A)의 예로는 (메타)아크릴 산, 이타콘 산, 말레인 산, 무수말레인산, 푸마르 산 및 말레인산 알킬 에스테르 등을 들 수 있으며, 말레인산 알킬 에스테르의 예로는 모노메틸 말레인 산, 에틸 말레인 산, n-프로필 말레인 산, 이소프로필 말레인 산, n-부틸 말레인 산, n-헥실 말레인 산, n-옥틸 말레인 산, 2-에틸헥실 말레인 산, n-노닐 말레인 산, n-도데실 말레인 산 등의 C1-C20 알킬 말레인산을 들 수 있으나 이에 제한되는 것은 아니며, 이들은 단독 또는 2종 이상 혼합하여 사 용할 수 있다.In the preparation of the modified (co) polymer of the present invention, an ethylenically unsaturated compound monomer (A) having an acid functional group is used. Examples of the ethylenically unsaturated compound monomer (A) having such an acid functional group include (meth) acrylic acid, ita Examples include maleic acid, maleic acid, maleic anhydride, fumaric acid, and maleic acid alkyl esters. Examples of maleic acid alkyl esters include monomethyl maleic acid, ethyl maleic acid, n-propyl maleic acid, and isopropyl malein. C1-C20 such as acid, n-butyl maleic acid, n-hexyl maleic acid, n-octyl maleic acid, 2-ethylhexyl maleic acid, n-nonyl maleic acid, n-dodecyl maleic acid Alkyl maleic acid may be mentioned, but is not limited thereto, and these may be used alone or in combination of two or more thereof.
본 발명의 변성 (공)중합체의 제조에는 상기 산 작용기를 가지는 에틸렌성 불포화 화합물 모노머 (A)와 공중합 가능한 에틸렌성 불포화 화합물 모노머 (B)를 더 사용할 수 있으며, 이러한 에틸렌성 불포화 화합물 모노머 (B)의 구체적인 예로는 벤질 (메타)아크릴레이트, 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 노말부틸 (메타)아크릴레이트, 디메틸아미노에틸 (메타)아크릴레이트, 이소부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, 시클로헥실 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 에틸헥실 (메타)아크릴레이트, 2-페녹시에틸 (메타)아크릴레이트, 테트라히드로퍼푸릴 (메타)아크릴레이트, 히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 2-히드록시-3-클로로프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 아실옥틸옥시-2-히드록시프로필 (메타)아크릴레이트, 글리세롤 (메타)아크릴레이트, 2-메톡시에틸 (메타)아크릴레이트, 3-메톡시부틸 (메타)아크릴레이트, 에톡시디에틸렌글리콜 (메타)아크릴레이트, 메톡시트리에틸렌글리콜 (메타)아크릴레이트, 메톡시트리프로필렌글리콜 (메타)아크릴레이트, 폴리(에틸렌글리콜)메틸에테르 (메타)아크릴레이트, 페녹시디에틸렌글리콜 (메타)아크릴레이트, p-노닐페녹시폴리프로필렌글리콜 (메타)아크릴레이트, 테트라플루오로프로필 (메타)아크릴레이트, 헥사플루오로이소프로필 (메타)아크릴레이트, 옥타플루오로펜틸 (메타)아크릴레이트, 헵타데카플루오로데실 (메타)아크릴레이트, 트리브로모페닐 (메타)아크릴레이트, 메틸α-히드록시메틸아 크릴레이트, 에틸α-히드록시메틸아크릴레이트, 프로필α-히드록시메틸아크릴레이트, 부틸α-히드록시메틸아크릴레이트, 디시클로펜타닐 (메타)아크릴레이트, 디시클로펜테닐 (메타)아크릴레이트, 디시클로펜타닐옥시에틸 (메타)아크릴레이트, 디시클로펜테닐옥시에틸 (메타)아크릴레이트와 같은 불포화 카르복실산 에스테르; 스티렌, α-메틸스티렌, 비닐톨루엔, 메톡시스티렌, 클로로스티렌과 같은 방향족 비닐; 비닐 메틸 에테르, 비닐 에틸 에테르, 알릴 글리시딜 에테르와 같은 불포화 에테르; N-비닐 피롤리돈, N-비닐 카바졸, N-비닐 모폴린과 같은 N-비닐 삼차아민; N-페닐 말레이미드, N-(4-클로로페닐)말레이미드, N-(4-히드록시페닐)말레이미드, N-시클로헥실 말레이미드와 같은 불포화 이미드; 무수말레인산, 무수 메틸 말레인산과 같은 무수 말레인산; 알릴 글리시딜 에테르, 글리시딜 (메타)아크릴레이트, 3,4-에폭시시클로헥실메틸 (메타)아크릴레이트와 같은 불포화 글리시딜 화합물 등을 들 수 있으나 이에 제한되는 것은 아니며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.In the preparation of the modified (co) polymer of the present invention, an ethylenically unsaturated compound monomer (B) copolymerizable with the ethylenically unsaturated compound monomer (A) having the acid functional group can be further used, and such an ethylenically unsaturated compound monomer (B) Specific examples of benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, normal butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isononyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperfuryl (meth ) Acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate , Ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (Meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate , Heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate , Propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, Unsaturated carboxylic esters such as dicyclopentenyloxyethyl (meth) acrylate; Aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, methoxystyrene, and chlorostyrene; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; N-vinyl tertiary amines such as N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl morpholine; Unsaturated imides such as N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexyl maleimide; Maleic anhydride such as maleic anhydride and methyl maleic anhydride; Unsaturated glycidyl compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like, and the like, but are not limited thereto. It can mix and use species.
본 발명의 변성 (공)중합체에는 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 (C)의 잔기가 부가반응에 의하여 도입되는데, 이는 고분자 측쇄구조에 반복적인 가수분해성 에스테르 결합을 도입하여 포토리소그래픽 공정에서의 현상성, 광학특성, 탄성특성 및 잔사저감율을 개선하기 위해서이다. 상기 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 (C)의 예로는 글리시딜기 함유 에테르계 화합물, 글리시딜기 함유 에스테르계 화합물 등을 들 수 있으며, 보다 구체적으로 는 부틸 글리시딜 에테르, 레조시놀 디글리시딜 에테르(Resorcinol diglycidyl ether), 페닐 글리시딜 에테르, S-트리틸 글리시딜 에테르, 글리세롤 트리글리시딜 에테르, 2,6-디글리시딜페닐 글리시딜 에테르, 1,4-사이클로헥산디메탄올의 디글리시딜 에테르, R-벤질 글리시딜 에테르, S-벤질 글리시딜 에테르, 비스페놀 A의 디글리시딜 에테르, 네오펜틸 글리콜 디글리시딜 에테르, 트리에틸렌 글리콜 디글리시딜 에테르, p-크레실 글리시딜 에테르, 구아이아콜 글리시딜 에테르(Guaiacol glycidyl ether), o-크레실 글리시딜 에테르(o-cresyl glycidyl ether), p-클로로페닐 글리시딜 에테르, 에틸렌 글리콜 디글리시딜 에테르, 디글리시딜 에테르, 하이드로퀴논 디글리시딜 에테르, 1,4-부탄디올 디글리시딜 에테르, n-부틸 글리시딜 에테르, 글리시딜 네오데카노에이트, 2-에틸헥실 글리시딜 에테르, 라우릴 글리시딜 에테르, 글리세롤 폴리글리시딜 에테르, 크레실 글리시딜 에테르 등이 있으나 이들에 한정되는 것은 아니며, 이들을 단독 또는 2종 이상 혼합하여 사용할 수 있고, 이 중에서 글리시딜 네오데카노에이트가 바람직하다.In the modified (co) polymer of the present invention, a residue of a glycidyl compound (C) having no ethylenically unsaturated bond is introduced by an addition reaction, which introduces a repeatable hydrolysable ester linkage into the polymer side chain structure to photolithographic In order to improve developability, optical properties, elastic properties and residual reduction rate in the process. Examples of the glycidyl compound (C) having no ethylenically unsaturated bond include glycidyl group-containing ether compounds, glycidyl group-containing ester compounds, and the like, and more specifically, butyl glycidyl ether and reso. Resorcinol diglycidyl ether, phenyl glycidyl ether, S-trityl glycidyl ether, glycerol triglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1, Diglycidyl ether of 4-cyclohexanedimethanol, R-benzyl glycidyl ether, S-benzyl glycidyl ether, diglycidyl ether of bisphenol A, neopentyl glycol diglycidyl ether, triethylene glycol Diglycidyl ether, p-cresyl glycidyl ether, guaiacol glycidyl ether, o-cresyl glycidyl ether, p-chlorophenyl glycy Dill ether, ethylene Recall diglycidyl ether, diglycidyl ether, hydroquinone diglycidyl ether, 1,4-butanediol diglycidyl ether, n-butyl glycidyl ether, glycidyl neodecanoate, 2- Ethylhexyl glycidyl ether, lauryl glycidyl ether, glycerol polyglycidyl ether, cresyl glycidyl ether, and the like, but are not limited thereto, and these may be used alone or in combination of two or more thereof. Among them, glycidyl neodecanoate is preferred.
또한, 본 발명의 일 구체예에 따르면, 상기 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 (C)의 잔기는, 글리시딜 화합물(C)과 산 작용기를 가지는 에틸렌성 불포화 화합물 (A)과의 부가반응 생성물(adduct)과 에틸렌성 불포화 화합물 모노머 (B)들간의 공중합에 의하여 도입될 수도 있다.In addition, according to one embodiment of the present invention, the residue of the glycidyl compound (C) having no ethylenically unsaturated bond is an ethylenically unsaturated compound (A) having a glycidyl compound (C) and an acid functional group; It may also be introduced by copolymerization between the addition reaction product of adduct and ethylenically unsaturated compound monomer (B).
본 발명의 변성 (공)중합체는 빛 감도와 현상성을 향상시키기 위해 에틸렌성 불포화결합을 포함하는데, 이는 에틸렌성 불포화결합 및 부가반응성 작용기를 함께 가지는 반응성 모노머 (D)의 부가반응에 의하여 도입될 수 있다. 상기 에틸렌성 불포화결합 및 부가반응성 작용기를 함께 가지는 반응성 모노머 (D)의 예로는 글리시딜 (메타)아크릴레이트, 아릴 글리시딜 에테르, α-메틸 글리시딜 아크릴레이트 등과 같이 옥시란(Oxirane)환기와 에틸렌성 불포화결합을 함께 가지는 화합물; 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트 등과 같이 수산(Hydroxyl)기와 에틸렌성 불포화결합을 함께 가지는 화합물; 무수말레인산, 무수메틸말레인산과 같은 무수 말레인산; (메타)아크릴로일옥시알킬이소시아네이트, 구체적으로는 2-아크릴로일옥시에틸이소시아네이트, 2-메타크릴로일옥시에틸이소시아네이트 등과 같이 이소시아네이트(Isocyanate)기와 에틸렌성 불포화 이중결합을 가지는 화합물 등을 들 수 있으나 이에 제한되는 것은 아니며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The modified (co) polymer of the present invention includes ethylenically unsaturated bonds to improve light sensitivity and developability, which can be introduced by addition reaction of a reactive monomer (D) having both ethylenically unsaturated bonds and addition reactive functional groups. Can be. Examples of the reactive monomer (D) having an ethylenically unsaturated bond and an addition reactive functional group together include oxirane such as glycidyl (meth) acrylate, aryl glycidyl ether, α-methyl glycidyl acrylate, and the like. Compound having both ventilation and ethylenically unsaturated bond; Compounds having a hydroxyl group and an ethylenically unsaturated bond together, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like; Maleic anhydride such as maleic anhydride and methyl maleic anhydride; (Meth) acryloyloxyalkyl isocyanate, specifically, the compound which has an isocyanate group and ethylenically unsaturated double bond etc., such as 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate, etc. are mentioned. However, the present invention is not limited thereto, and these may be used alone or in combination of two or more thereof.
상기 열거한 반응성 모노머 (D) 중에서 옥시란기와 에틸렌성 불포화결합을 가지는 화합물은 높은 산가를 가지는 (공)중합체와 부가반응을 하고, 수산기와 에틸렌성 불포화결합을 가지는 화합물은 무수산기를 가지는 (공)중합체와 하프-에스테르화(Half-Esterification) 개환반응을 하며, 무수 말레인산 화합물은 수산기를 가지는 (공)중합체와 에스테르화(Esterification) 개환반응을 하고, 이소시아네이트(Isocyanate)기와 에틸렌성 불포화 이중결합을 가지는 화합물은 수산기를 가지는 (공)중합체와 부가반응을 하여 (공)중합체 구조 내에 광중합 가능한 에틸렌성 불포 화기를 도입하게 된다.Among the reactive monomers (D) listed above, the compound having an oxirane group and an ethylenically unsaturated bond reacts with the (co) polymer having a high acid value, and the compound having a hydroxyl group and an ethylenically unsaturated bond has an anhydride group (co) Half-esterification ring-opening reaction with the polymer, maleic anhydride compound undergoes esterification ring-opening reaction with the (co) polymer having a hydroxyl group, and an isocyanate group and an ethylenically unsaturated double bond The compound having an addition reaction with the (co) polymer having a hydroxyl group introduces a photopolymerizable ethylenically unsaturated group into the (co) polymer structure.
본 발명의 변성 (공)중합체 제조시 상기 원료물질들의 상대적 사용량에는 특별한 제한이 없으며, 본 발명의 목적을 달성할 수 있는 범위 내에서 적절히 선택될 수 있다. 예컨대, 상기 산 작용기를 가지는 에틸렌성 불포화 화합물 모노머 (A) 100중량부당 에틸렌성 불포화 화합물 모노머 (B)는 100 내지 250 중량부가 사용가능하고, 상기 모노머 (A)와 모노머 (B)의 총합 100중량부당 상기 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 (C)는 5 내지 50 중량부가, 그리고 상기 반응성 모노머 (D)는 5 내지 50 중량부가 사용가능하나, 이에 특별히 제한되는 것은 아니다.There is no particular limitation on the relative amount of the raw materials used in the preparation of the modified (co) polymer of the present invention, and may be appropriately selected within a range capable of achieving the object of the present invention. For example, 100-250 weight part of ethylenically unsaturated compound monomers (B) per 100 weight part of ethylenically unsaturated compound monomers (A) which have the said acid functional group can be used, and the total weight of the said monomer (A) and monomer (B) is 100 weights 5-50 parts by weight of the glycidyl compound (C) having no ethylenically unsaturated bond and 5 to 50 parts by weight of the reactive monomer (D) may be used, but is not particularly limited thereto.
본 발명에 따른 광경화형 알칼리 가용성 변성 (공)중합체의 산가는 고형분 기준으로 30~300 ㎎KOH/g이 바람직하며, 60~200 ㎎KOH/g이 더욱 바람직하다. 산가가 30 ㎎KOH/g 미만일 경우 알칼리수에 대한 현상성이 낮아지고 기판에 잔사를 남길 우려가 있으며, 산가가 300 ㎎KOH/g을 초과하는 경우에는 패턴의 탈착이 일어날 가능성이 높아진다.As for the acid value of the photocurable alkali-soluble modified (co) polymer which concerns on this invention, 30-300 mgKOH / g is preferable on a solid content basis, and 60-200 mgKOH / g is more preferable. If the acid value is less than 30 mgKOH / g, developability with respect to alkaline water may be lowered and residues may remain on the substrate. If the acid value is more than 300 mgKOH / g, there is a high possibility of desorption of the pattern.
또한, 본 발명에 따른 광경화형 알칼리 가용성 변성 (공)중합체의 중량 평균 분자량은 1,000~100,000의 범위가 바람직하며, 3,000~50,000의 범위가 더욱 바람직하다. 중량 평균 분자량이 1,000 미만일 경우 바인더 폴리머로서 요구되는 구성 성분간의 바인딩 기능이 약해질 우려가 있고 현상시의 물리적 외력에 견디기 어려워 져 패턴이 소실되기 쉬우며, 내열성 및 내용제성 등의 물성이 나빠질 수 있다. 반면 중량 평균 분자량이 100,000을 초과하는 경우, 알칼리 현상액에 대한 현상성이 과도하게 적어져 현상공정 특성이 저하될 수 있고, 심할 경우 현상이 불가능해지며, 흐름성도 나빠져서 코팅막 두께 제어나 균일성(Uniformity) 확보가 어려워진다.In addition, the weight average molecular weight of the photocurable alkali-soluble modified (co) polymer according to the present invention is preferably in the range of 1,000 to 100,000, more preferably in the range of 3,000 to 50,000. If the weight average molecular weight is less than 1,000, there is a fear that the binding function between the components required as the binder polymer may be weakened, and it may be difficult to withstand the physical external force during development, and thus the pattern may be easily lost, and the physical properties such as heat resistance and solvent resistance may be deteriorated. . On the other hand, if the weight average molecular weight is more than 100,000, the developability of the alkaline developer is excessively low, which may result in deterioration of the developing process characteristics, and in severe cases, the development is impossible, and the flowability is also worsened, resulting in poor coating thickness control or uniformity ) It becomes difficult to secure.
본 발명의 일 구체예에 따르면, 본 발명의 광경화형 알칼리 가용성 변성 (공)중합체는 (1) 산 작용기를 포함하는 (공)중합체를 제공하는 단계, 및 (2) 상기 (공)중합체에 (i) 에틸렌성 불포화결합 및 부가반응성 작용기를 갖는 반응성 모노머 및 (ii) 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물을 부가반응시키는 단계를 포함하는 방법에 의하여 제조될 수 있다.According to one embodiment of the invention, the photocurable alkali-soluble modified (co) polymer of the present invention comprises the steps of (1) providing a (co) polymer comprising an acid functional group, and (2) the (co) polymer ( i) reacting a reactive monomer having an ethylenically unsaturated bond and an addition reactive functional group, and (ii) a glycidyl compound having no ethylenically unsaturated bond.
상기 (공)중합체 제조방법의 (1) 단계에서 제공되는 산 작용기를 포함하는 (공)중합체는, 상기 모노머 (A) 단독 또는 모노머 (A)와 모노머 (B)를 함께 중합 용매에 투입하고 적정 온도로 가열한 후, 질소 퍼징 또는 환류 공정을 통해 산소를 제거하면서 라디칼 중합개시제를 투입하고 중합온도를 유지함으로써 제조될 수 있다. 이 때, 필요한 경우 연쇄이동제를 사용하여 (공)중합체의 분자량을 조절할 수 있다.In the (co) polymer including the acid functional group provided in step (1) of the method for preparing the (co) polymer, the monomer (A) alone or the monomer (A) and the monomer (B) are added to a polymerization solvent and titrated. After heating to a temperature, it may be prepared by adding a radical polymerization initiator and maintaining the polymerization temperature while removing oxygen through a nitrogen purge or reflux process. At this time, if necessary, a chain transfer agent may be used to adjust the molecular weight of the (co) polymer.
상기 중합 용매에는 특별한 제한이 없으며, 예컨대, 크실렌, 톨루엔, 프로필렌글리콜 모노메틸에테르 아세테이트, 에톡시 에틸 프로피오네이트, 에틸 셀로솔브 아세테이트, 디이소프로필 에테르, 프로필 아세테이트, n-부틸 프로피오네이트 등과 같은 용매를 사용할 수 있으나, 이들에 한정되는 것은 아니며, 당 업계에 알려져 있는 것이라면 제한 없이 사용할 수 있다.There is no particular limitation on the polymerization solvent, for example, xylene, toluene, propylene glycol monomethyl ether acetate, ethoxy ethyl propionate, ethyl cellosolve acetate, diisopropyl ether, propyl acetate, n-butyl propionate and the like. Although a solvent can be used, it is not limited to these, If it is known in the art, it can use without limitation.
라디칼 중합 개시제로는 당 기술 분야에 알려져 있는 것을 사용할 수 있으며, 일반적인 예로는 2,2’-아조비스이소부티로니트릴(AIBN), 2,2’-아조비스-(2,4- 디메틸 발레로니트릴), 2,2’-아조비스-(4-메톡시-2,4-디메틸 발레로니트릴), 벤조일퍼옥사이드, 라우로일퍼옥사이드, t-부틸퍼옥시발레이트, t-부틸퍼옥시벤조에이트, t-부틸퍼옥시옥토에이트 등을 들 수 있으나 이에 제한되는 것은 아니며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.As the radical polymerization initiator, those known in the art may be used, and general examples thereof include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4-dimethyl valero Nitrile), 2,2'-azobis- (4-methoxy-2,4-dimethyl valeronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxyvalate, t-butylperoxybenzo Et, t- butyl peroxy octoate, etc. can be mentioned, It is not limited to these, These can be used individually or in mixture of 2 or more types.
상기 중합시, 중합 용매 및 개시제 사용량, 중합온도 및 중합시간 등과 같은 중합조건에는 특별한 제한이 없으며, 사용하는 중합 시스템, 중합개시제의 반감기 등을 고려하여 적절히 선택할 수 있다.In the polymerization, the polymerization conditions such as the amount of the polymerization solvent and the initiator, the polymerization temperature and the polymerization time are not particularly limited and may be appropriately selected in consideration of the polymerization system used, the half-life of the polymerization initiator, and the like.
상기 (공)중합체 제조방법의 (2) 단계에서는, (1) 단계에서 제공된 (공)중합체에 (i) 에틸렌성 불포화결합 및 부가반응성 작용기를 갖는 반응성 모노머 (D) 및 (ii) 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 (C)을 부가반응시킨다.In step (2) of the method for preparing the (co) polymer, (i) reactive monomers (D) and (ii) ethylenically unsaturated groups having (i) ethylenically unsaturated bonds and addition reactive functional groups in the (co) polymers provided in step (1). The reaction of glycidyl compound (C) having no bond is added.
상기 부가반응은 20~150℃의 온도조건에서 수행할 수 있으며, 필요에 따라 적절한 촉매를 투입하여 반응을 촉진할 수 있다.The addition reaction may be carried out at a temperature condition of 20 ~ 150 ℃, if necessary, by adding an appropriate catalyst to promote the reaction.
부가반응용 촉매로는 3급아민류 및 디부틸틴디라울레이트와 같은 금속촉매류를 비롯해서 통상적으로 업계에서 알려진 부가반응용 촉매를 사용할 수 있으며, 특별히 제한되지 않는다.As the catalyst for the addition reaction, catalysts for addition reaction commonly known in the art may be used, including metal catalysts such as tertiary amines and dibutyl tin dilaurate, and are not particularly limited.
또한 에틸렌성 불포화결합 및 부가반응성 작용기를 갖는 반응성 모노머 (D)를 부가시키는 단계에서 광중합성 불포화결합 간의 중합반응에 의해 불포화결합이 소모되거나 분자량 상승으로 인한 무리한 점도 상승 또는 (공)중합체가 겔(Gel)화되는 현상을 방지하기 위해 반응 중에 적절한 중합금지제를 투입할 수 있으며, 대표적인 중합금지제로는 4-메톡시페놀(MeHQ)을 들 수 있다.In addition, in the step of adding the reactive monomer (D) having an ethylenically unsaturated bond and an addition reactive functional group, the unsaturated bond is consumed by the polymerization reaction between the photopolymerizable unsaturated bonds or the excessive viscosity increase due to the molecular weight increase or the (co) polymer may In order to prevent the gelation phenomenon, an appropriate polymerization inhibitor may be added during the reaction, and representative examples of the polymerization inhibitor include 4-methoxyphenol (MeHQ).
한편, 본 발명의 다른 구체예에 따르면, 본 발명의 광경화형 알칼리 가용성 변성 공중합체는 (1) (a) 산 작용기를 가지는 에틸렌성 불포화 화합물 (A); 및 (b) 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 (C)과 산 작용기를 가지는 에틸렌성 불포화 화합물 (A)과의 부가반응 생성물(adduct);을 포함하는 혼합물을 공중합하는 단계, 및 (2) 상기 (1) 단계의 결과 공중합체에 에틸렌성 불포화결합 및 부가반응성 작용기를 갖는 반응성 모노머 (D)를 부가반응시키는 단계를 포함하는 방법에 의하여 제조될 수도 있다.On the other hand, according to another embodiment of the present invention, the photocurable alkali-soluble modified copolymer of the present invention (1) (a) an ethylenically unsaturated compound (A) having an acid functional group; And (b) an addition reaction product of a glycidyl compound (C) having no ethylenically unsaturated bond with an ethylenically unsaturated compound (A) having an acid functional group; and (C) copolymerizing a mixture comprising: 2) The result of step (1) may be prepared by a method comprising the step of adding a reactive monomer (D) having an ethylenically unsaturated bond and an addition reactive functional group to the copolymer.
상기 제조방법의 (1) 단계에서 공중합되는 혼합물에는 (a) 산 작용기를 가지는 에틸렌성 불포화 화합물 (A); 및 (b) 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 (C)과 산 작용기를 가지는 에틸렌성 불포화 화합물 (A)과의 부가반응 생성물(adduct) 이외에, (c) 공중합 가능한 에틸렌성 불포화 화합물 모노머 (B)가 더 포함될 수 있다.The mixture copolymerized in step (1) of the preparation method includes (a) an ethylenically unsaturated compound having an acid functional group (A); And (b) an addition reaction product of a glycidyl compound (C) having no ethylenically unsaturated bond with an ethylenically unsaturated compound (A) having an acid functional group, and (c) an ethylenically unsaturated compound monomer copolymerizable. (B) may be further included.
상기 (b) 에틸렌성 불포화결합을 가지지 않는 글리시딜 화합물 (C)과 산 작 용기를 가지는 에틸렌성 불포화 화합물 (A)과의 부가반응 생성물(adduct)의 제조는 중합금지제 사용 조건 하에서 상기 글리시딜 화합물 (C)를 공중합체의 카르복실기와 부가반응시키는 공정과 동일한 조건으로 수행할 수 있다.The preparation of the addition reaction product (b) of the glycidyl compound (C) having no ethylenically unsaturated bond with the ethylenically unsaturated compound (A) having the production vessel is carried out under the conditions of using polymerization inhibitor. The cylyl compound (C) can be carried out under the same conditions as the step of addition reaction of the carboxyl group of the copolymer.
본 발명에 따르면, 본 발명의 변성 (공)중합체를 포함하는 포토레지스트 조성물이 또한 제공된다.According to the invention, there is also provided a photoresist composition comprising the modified (co) polymer of the invention.
본 발명의 포토레지스트 조성물에는 본 발명의 변성 (공)중합체 이외에 필요에 따라 다관능 모노머, 광개시제, 포토레지스트용 용매 등이 더 포함될 수 있다.The photoresist composition of the present invention may further include a polyfunctional monomer, a photoinitiator, a solvent for a photoresist, and the like, in addition to the modified (co) polymer of the present invention.
상기 다관능 모노머로는 예컨대 트리메틸올프로판 트리아크릴레이트(Trimethylolpropane triacrylate, TMPTA)를 들 수 있으나, 이에 제한되는 것은 아니다. The polyfunctional monomer may include, for example, trimethylolpropane triacrylate (TMPTA), but is not limited thereto.
상기 광개시제로는 아세토페논계 광개시제, 벤조인계 광개시제, 벤조페논계 광개시제, 트리아진계 광개시제, 카바졸계 광개시제 및 이미다졸계 광개시제 등을 들 수 있으나, 이에 제한되는 것은 아니다.The photoinitiator may include, but is not limited to, acetophenone photoinitiator, benzoin photoinitiator, benzophenone photoinitiator, triazine photoinitiator, carbazole photoinitiator and imidazole photoinitiator.
상기 포토레지스트용 용매로는 메탄올, 에탄올 등의 알코올 류, 테트라하이드로퓨란 등의 에테르 류, 에틸렌 글리콜 모노메틸 에테르 등의 글리콜 에테르 류, 에틸 셀로솔브 아세테이트 등의 에틸렌 글리콜 알킬 에테르 아세테이트 류, 디에틸렌 글리콜 모노메틸 에테르 등의 디에틸렌 글리콜 알킬 에테르류, 프로필렌 글리콜 모노메틸 에테르 등의 프로필렌 글리콜 알킬 에테르 류, 프로필렌 글리콜 모노메틸 에테르 아세테이트(PGMEA) 등의 프로필렌 글리콜 알킬 에테르 아세테이트 류, 톨루 엔, 크실렌 등의 방향족 탄화수소류, 메틸 에틸 케톤, 시클로헥사논 등의 케톤류 및 초산 메틸, 초산 에틸 등의 에스테르류 등을 들 수 있으나, 이에 제한되는 것은 아니다.Examples of the photoresist solvent include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, and diethylene glycol Diethylene glycol alkyl ethers such as monomethyl ether, propylene glycol alkyl ethers such as propylene glycol monomethyl ether, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), aromatics such as toluene and xylene Ketones, such as hydrocarbons, methyl ethyl ketone, cyclohexanone, and esters, such as methyl acetate and ethyl acetate, are mentioned, but it is not limited to these.
본 발명의 포토레지스트 조성물에 포함되는 본 발명의 변성 (공)중합체의 양에는 특별한 제한이 없으며, 예컨대 5 내지 70 중량%의 범위 내에서 적절히 선택될 수 있다.The amount of the modified (co) polymer of the present invention included in the photoresist composition of the present invention is not particularly limited, and may be appropriately selected within the range of 5 to 70% by weight, for example.
이하, 실시예 및 비교예에 의거하여 본 발명을 더욱 상세하게 설명하나, 본 발명이 이들에 한정되는 것은 아니다.Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to these.
실시예Example 1 One
온도계, 콘덴서, 적하깔대기 및 교반기를 갖춘 4구 플라스크를 반응용기로 사용하였다.A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.
하기 표 1에 기재된 용매를 플라스크에 투입하고 질소 분위기 하에서 120℃로 승온하고, 여기에 하기 표 1에 기재된 성분 A, B, B’ 및 열중합개시제의 혼합물을 3시간 동안 균일하게 가하였다. 그 후 2시간을 유지한 후, 120℃의 반응온도를 유지하면서 하기 표 1에 기재된 중합금지제와 촉매를 플라스크에 가한 다음 질소 대신 산소를 공급하면서 성분 C 및 D의 혼합물을 1시간 동안 균일하게 가하였다. 이후 산소분위기 하에서 120℃의 반응온도를 유지하면서 반응물의 산가를 확인하여 산가가 수지 고형분 기준으로 78~83 mgKOH/g 에 이르렀을 때 반응을 종결시켰 다. The solvent shown in Table 1 below was added to the flask and heated to 120 ° C. under a nitrogen atmosphere, to which a mixture of the components A, B, B ′ and the thermal polymerization initiator described in Table 1 was added uniformly for 3 hours. After holding for 2 hours, the polymerization inhibitor and the catalyst shown in Table 1 were added to the flask while maintaining the reaction temperature of 120 ℃ and then the mixture of components C and D uniformly for 1 hour while supplying oxygen instead of nitrogen Was added. The reaction was terminated when the acid value reached 78-83 mgKOH / g based on the resin solid content by checking the acid value of the reactants while maintaining the reaction temperature of 120 ℃ under oxygen atmosphere.
상기와 같이 하여 제조된 변성 공중합체 수지는 최종적으로 산가 82 mgKOH/g, 불휘발분 함량 40중량%, 점도 800cps, 및 중량평균 분자량 28,000을 가지는 것으로 확인되었다.The modified copolymer resin prepared as described above was finally confirmed to have an acid value of 82 mgKOH / g, a nonvolatile content of 40% by weight, a viscosity of 800 cps, and a weight average molecular weight of 28,000.
합성예Synthesis Example 1 One
온도계, 콘덴서, 적하깔대기 및 교반기를 갖춘 4구 플라스크를 반응용기로 사용하였다.A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.
하기 표 2에 기재된 성분들을 모두 플라스크에 투입하고 산소 분위기 하에서 120℃로 승온하여 유지하면서, 반응물 산가를 확인하여 산가가 3 mgKOH/g 이하일 때 반응을 종결시켜, 글리시딜 네오데카노에이트-메타아크릴산 어덕트(adduct)를 제조하였다.Put all the components shown in Table 2 to the flask and keep the temperature of the reactant at 120 ℃ under oxygen atmosphere, while checking the acid value of the reactant to terminate the reaction when the acid value is 3 mgKOH / g or less, glycidyl neodecanoate-meta Acrylic acid adducts were prepared.
상기 제조된 글리시딜 네오데카노에이트-메타아크릴산 어덕트는 최종적으로 산가 2 mgKOH/g, 불휘발분 함량 99중량% 이상, 점도 80cps, 및 중량평균 분자량 38,000을 가지는 것으로 확인되었다.The prepared glycidyl neodecanoate-methacrylic acid adduct was finally confirmed to have an acid value of 2 mgKOH / g, a nonvolatile content of 99% by weight or more, a viscosity of 80 cps, and a weight average molecular weight of 38,000.
실시예Example 2 2
온도계, 콘덴서, 적하깔대기 및 교반기를 갖춘 4구 플라스크를 반응용기로 사용하였다.A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.
하기 표 3에 기재된 용매를 플라스크에 투입한 후 질소 분위기 하에서 120℃로 승온하고, 하기 표 3에 기재된 성분 A, B, B’ 합성예 1에서 제조한 글리시딜 네오데카노에이트-메타아크릴산 어덕트 및 열중합개시제의 혼합물을 3시간 동안 균일하게 가하고 2시간을 유지하였다. 120℃의 반응온도를 유지하면서 하기 표 3에 기재된 중합금지제와 촉매를 플라스크에 가한 다음 질소 대신 산소를 공급하면서 성분 D를 1시간 동안 균일하게 가하였다. 이후 산소분위기 하에서 120℃의 반응온도를 유지하면서 반응물 산가를 확인하여 산가가 수지 고형분 기준으로 78~83 mgKOH/g에 이르렀을 때 반응을 종결시켰다.After adding the solvent of Table 3 to a flask, it heated up at 120 degreeC under nitrogen atmosphere, the glycidyl neodecanoate-methacrylic acid fish prepared in the component A, B, B 'synthesis example 1 of Table 3 below The mixture of duct and thermal initiator was added uniformly for 3 hours and maintained for 2 hours. The polymerization inhibitor and the catalyst shown in Table 3 were added to the flask while maintaining the reaction temperature of 120 ° C., and then component D was added uniformly for 1 hour while supplying oxygen instead of nitrogen. The reaction was terminated when the acid value reached 78-83 mgKOH / g based on the resin solid content by checking the acid value of the reactants while maintaining the reaction temperature of 120 ℃ under oxygen atmosphere.
상기 제조된 변성 공중합체 수지는 최종적으로 산가 83 mgKOH/g, 불휘발분 함량 40중량%, 점도 850cps, 및 중량평균 분자량 30,000을 가지는 것으로 확인되었다.The prepared modified copolymer resin was finally confirmed to have an acid value of 83 mgKOH / g, a nonvolatile content of 40% by weight, a viscosity of 850 cps, and a weight average molecular weight of 30,000.
실시예Example 3 및 4 및 3 and 4 and 비교예Comparative example
상기 실시예 1 및 2에서 제조된 변성 공중합체 수지를 각각 사용하여 하기 표 4에 나타낸 바와 같은 실시예 3 및 4의 포토레지스트 조성물을 각각 제조하였다. Using the modified copolymer resins prepared in Examples 1 and 2, respectively, photoresist compositions of Examples 3 and 4 were prepared as shown in Table 4 below.
한편, 하기 화학식 1의 구조를 가지는 일반적인 광경화형 알칼리 가용성 아크릴 공중합체를 사용하여 실시예 3 및 4와 동일한 방법으로 비교예의 포토레지스트 조성물을 제조하였다Meanwhile, a photoresist composition of Comparative Example was prepared in the same manner as in Examples 3 and 4 using a general photocurable alkali-soluble acrylic copolymer having the structure of Formula 1 below.
제조된 포토레지스트 조성물들의 물성 비교를 위해 레지스트 특성을 평가하였으며, 하기 표 4와 같은 결과를 얻었다.The resist properties were evaluated to compare the physical properties of the prepared photoresist compositions, and the results as shown in Table 4 below were obtained.
상기 화학식 1에서 p는 0.15, q는 0.2, r은 0.5, s는 0.15이다.In Formula 1, p is 0.15, q is 0.2, r is 0.5, and s is 0.15.
(내열성 평가)(Heat resistance evaluation)
열중량 분석(Thermogravimetric analysis, TGA)을 이용한 가열감량법으로 열분해온도를 측정하였으며, 시료초기무게 대비 5%가 감소되는 온도로 비교하였다.Pyrolysis temperature was measured by the thermogravimetric analysis (TGA) using a heating loss method, and compared to the initial weight of the sample reduced by 5%.
(현상성 평가)(Evaluation evaluation)
포토레지스트 조성물을 유리 기판상에 스핀코터(MIKASA제 1H-DX2)를 사용하여 1.5㎛ 두께로 도포하고, 100℃에서 3분간 베이킹(Baking)한 다음 소정의 노광 패턴을 형성할 수 있도록 포토마스크를 배치하고 자외선을 100 mJ/㎠로 조사한 기판을, 0.05중량% KOH 수용액을 이용하여 스프레이 현상했을 때 현상에 필요한 시간을 측정하였다.The photoresist composition was applied on a glass substrate using a spin coater (1H-DX2 manufactured by MIKASA) at a thickness of 1.5 μm, baked at 100 ° C. for 3 minutes, and then a photomask was formed to form a predetermined exposure pattern. The time required for image development was measured when the board | substrate which arrange | positioned and irradiated with the ultraviolet-ray at 100 mJ / cm <2> was spray-developed using 0.05 weight% KOH aqueous solution.
(밀착성 평가)(Adhesive evaluation)
상기 현상성 평가방법에서 제작된 기판을 현상한 후, 잔사 또는 단면 잔여물 존재여부를 비교하여 밀착성을 상대평가하였다.After developing the substrate produced in the developability evaluation method, the presence or absence of residues or cross-section residues was compared to evaluate the relative adhesion.
(내용매성 평가)(Contents Rating)
각각의 포토레지스트 조성물에 적색 조색제 (KCC사 SY903-SR2)를 3중량% 추가한 다음 Dispermat을 이용하여 균일하게 혼합하여 각각의 착색 조성물로 제조하였다.3% by weight of a red colorant (KCC SY903-SR2) was added to each photoresist composition, and then uniformly mixed using Dispermat to prepare each colorant composition.
유리 기판상에 스핀코터(MIKASA제 1H-DX2)를 사용하여 상기 착색 조성물을 1.5㎛ 두께로 도포하고 100℃에서 3분간 베이킹한 다음 소정의 노광 패턴을 형성할 수 있도록 포토마스크를 배치하고 자외선을 100 mJ/㎠로 조사한 기판을, 25℃의 N-메틸 피롤리돈(NMP)에 60분간 침지한 다음 기판의 에칭상태를 육안관찰하여 상대평가하였다.Using a spin coater (1H-DX2 manufactured by MIKASA) on a glass substrate, the coloring composition was applied to a thickness of 1.5 μm, baked at 100 ° C. for 3 minutes, and then a photomask was placed to form a predetermined exposure pattern and UV light was emitted. The board | substrate irradiated at 100 mJ / cm <2> was immersed in 25 degreeC N-methyl pyrrolidone (NMP) for 60 minutes, and the relative etching of the board | substrate was observed visually.
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