KR20060034865A - Thermosetting resin composition - Google Patents
Thermosetting resin composition Download PDFInfo
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- KR20060034865A KR20060034865A KR1020040083878A KR20040083878A KR20060034865A KR 20060034865 A KR20060034865 A KR 20060034865A KR 1020040083878 A KR1020040083878 A KR 1020040083878A KR 20040083878 A KR20040083878 A KR 20040083878A KR 20060034865 A KR20060034865 A KR 20060034865A
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- 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
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C08F220/346—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links and further oxygen
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- 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
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
- C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
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- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
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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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/48—Protective coatings
Abstract
본 발명은 (a1)불포화 카르복시산 및/또는 불포화 카르복시산 무수물, (a2)에폭시기 함유 불포화 화합물, (a3)상기 (a1) 및 (a2) 이외의 올레핀계 불포화 화합물의 공중합체를 포함하는 열경화성 수지 조성물에 관한 것으로서, 다음 화학식 1 내지 6으로 표시되는 화합물들로부터 선택된 1종 또는 2종 이상의 반응성 우레탄 화합물을 더 포함함으로써 보호막으로서 종래로부터 요구된 특성들을 만족시키는 동시에 가교밀도를 효과적으로 향상시켜 기계적 물성 및 내열성이 우수하고, 고온에서의 황변이 없는 열경화성 수지 조성물 및 이를 사용한 광디바이스(device)의 컬러필터 보호막에 관한 것이다. The present invention relates to a thermosetting resin composition comprising (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, and (a3) copolymers of olefinically unsaturated compounds other than (a1) and (a2). The present invention relates to one or two or more reactive urethane compounds selected from the compounds represented by the following Chemical Formulas 1 to 6, which satisfies the characteristics required in the related art as a protective film and at the same time effectively improves the crosslinking density, thereby improving mechanical properties and heat resistance. The present invention relates to a thermosetting resin composition having excellent yellowing at high temperatures and a color filter protective film of an optical device using the same.
상기 식에서, R1은 -(CH2)6-이다.Wherein R1 is-(CH2) 6-.
상기 식에서, R2는 
상기 식에서, R1은 -(CH2)6-이다.Wherein R1 is-(CH2) 6-.
상기 식에서, R2는 
상기 식에서, R3는 
상기 식에서, R1은 -(CH2)6-이다.
Wherein R1 is-(CH2) 6-.
Description
도 1은 통상적인 광디바이스의 단면도이다.1 is a cross-sectional view of a conventional optical device.
*도면의 주요 부분에 대한 부호의 설명* * Description of the symbols for the main parts of the drawings *
Overcoat - 본 발명에서 개발된 열경화성 수지 조성물을 이용하여 형성한 보호막
Overcoat-A protective film formed using the thermosetting resin composition developed in the present invention.
본 발명은 열경화성 수지 조성물에 관한 것으로서, 특히, 광디바이스(device)용 보호막 형성 재료로서 적합한 열경화성 수지 조성물에 관한 것이다.The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition suitable as a protective film forming material for an optical device.
액정 표시 소자와 같은 광디바이스(device)의 단면은 도 1에 나타낸 바와 같은 바, 이는 제조공정 중에 유기용제, 산, 알칼리 용액 등에 의해 침지 처리되거나, 배선 전극층을 제막할 경우 스퍼터링에 의한 표면의 국부적 고온 가열을 받는 등 가혹한 처리를 받게 된다. 따라서 이들 소자에는 제조시의 변질을 막기 위해 그 표면에 보호막(overcoat)이 설치되는 경우가 있다.The cross-section of an optical device such as a liquid crystal display device is shown in FIG. 1, which is immersed with an organic solvent, an acid, an alkali solution, or the like during the manufacturing process, or locally formed on the surface by sputtering when forming a wiring electrode layer. It is subjected to harsh processing such as high temperature heating. Therefore, these devices may be provided with an overcoat on the surface in order to prevent the deterioration at the time of manufacture.
이 보호막은 상기와 같은 처리에 견디는 동시에 기판 또는 하층과의 밀착성 이 뛰어나고, 평활도, 표면경도가 높고, 투명성이 뛰어나고, 장기에 걸쳐 착색, 황변, 백화 등의 변질이 없이 내열성 및 내광성이 뛰어나고, 내용제성, 내산성, 내알칼리성 등의 내약품성이나 내수성 등이 뛰어난 것이 요구된다. 또한, 이와 같은 보호막을 컬러 액정 표시 소자의 컬러 필터에 적용할 경우에는, 바탕기판으로 일반적인 컬러 필터의 단차를 평탄화할 수 있는 것이 바람직하다.This protective film withstands the above treatments, and has excellent adhesion to the substrate or lower layer, high smoothness and surface hardness, excellent transparency, and excellent heat resistance and light resistance without deterioration such as coloring, yellowing and whitening over a long period of time. What is excellent in chemical-resistance, such as chemical resistance, acid resistance, and alkali resistance, water resistance, etc. is calculated | required. In addition, when applying such a protective film to the color filter of a color liquid crystal display element, it is preferable that the level | step difference of a general color filter can be planarized with a base substrate.
이와 같은 재료는 경화성 수지 조성물의 형태로 제조되며, 크게 열경화성과 광경화성(감광성)으로 분류된다. 보호막의 패턴 형성이 필요할 경우에는 감광성 수지 조성물이 요구되지만 그렇지 않을 경우에는 열경화성 수지 조성물이 사용되는데, 이는 공정상 편리하고 가교 밀도를 높일 수 있어 기계적 물성 및 내열성이 우수하기 때문이다.Such a material is manufactured in the form of curable resin composition, and is largely classified into thermosetting and photocurable (photosensitive). When the patterning of the protective film is required, a photosensitive resin composition is required, but otherwise, a thermosetting resin composition is used, because it is convenient in the process and can increase the crosslinking density, thereby providing excellent mechanical properties and heat resistance.
이러한 열경화성 수지 조성물로 제조된 보호막과 관련된 기술로는 일본 특허공개 제2000-103937호, 제2000-119472호, 제2000-143772호에서 제안된 바 있다.Techniques related to a protective film made of such a thermosetting resin composition have been proposed in Japanese Patent Laid-Open Nos. 2000-103937, 2000-119472, and 2000-143772.
이러한 보호막에 적용되는 재료로는 카르복실기나 에폭시기를 함유하고 있는 아크릴 수지, 가교제의 역할을 하는 에틸렌성 불포화기를 함유하는 다관능성 모노머(중합성 화합물) 및 열중합개시제로 구성된 조성물이 많이 사용되고 있다. As a material to be applied to such a protective film, a composition composed of an acrylic resin containing a carboxyl group or an epoxy group, a polyfunctional monomer (polymerizable compound) containing an ethylenically unsaturated group serving as a crosslinking agent, and a thermal polymerization initiator are used.
이러한 종래의 열경화성 수지 조성물의 경우, 기계적 물성이 우수하지 못하고, 특히 고온에서 내열성이 좋지 않아서 황변 현상을 나타내는 경우가 많았다. 따라서 이러한 현상을 방지하기 위하여 에틸렌성 불포화기를 함유하는 다관능성 모노머(중합성 화합물)를 과다하게 사용하게 되는데, 이러한 과다 사용은 고온에서의 황변 현상을 심화시키는 단점이 있다.In the case of such a conventional thermosetting resin composition, mechanical properties are not excellent, and in particular, yellowing phenomenon is often exhibited due to poor heat resistance at high temperatures. Therefore, in order to prevent such a phenomenon, the polyfunctional monomer (polymerizable compound) containing an ethylenically unsaturated group is excessively used, and such excessive use has a disadvantage of intensifying yellowing at a high temperature.
본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위한 것으로, 반응성 우레탄 화합물을 가교제로서 사용함으로써, 보호막으로서 종래로부터 요구된 특성들을 만족시키는 동시에, 가교밀도를 효과적으로 향상시켜 기계적 물성 및 내열성이 우수하고, 광 디바이스용 보호막 형성 재료로서 매우 적합한 열경화성 수지 조성물을 제공하는 것을 목적으로 한다. The present invention is to solve the problems of the prior art as described above, by using a reactive urethane compound as a crosslinking agent, while satisfying the characteristics conventionally required as a protective film, while effectively improving the crosslinking density and excellent mechanical properties and heat resistance It is an object to provide a thermosetting resin composition which is very suitable as a protective film forming material for an optical device.
본 발명의 다른 목적은 고온에서의 황변 현상이 없는 열경화성 수지 조성물을 제공하는 것이다.Another object of the present invention is to provide a thermosetting resin composition free from yellowing at high temperatures.
상기와 같은 목적을 달성하기 위한 본 발명은 [A] (a1)불포화 카르복시산 및/또는 불포화 카르복시산 무수물, (a2)에폭시기 함유 불포화 화합물, (a3)상기 (a1) 및 (a2) 이외의 올레핀계 불포화 화합물의 공중합체를 포함하는 열경화성 수지 조성물로서, The present invention for achieving the above object is [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (a3) olefinic unsaturated other than (a1) and (a2) As a thermosetting resin composition containing the copolymer of a compound,
[B]다음 화학식 1 내지 6으로 표시되는 화합물들로부터 선택된 1종 또는 2종 이상의 반응성 우레탄 화합물을 포함하는 것임을 그 특징으로 한다. [B] is characterized in that it comprises one or two or more reactive urethane compounds selected from the compounds represented by the following formulas (1) to (6).
화학식 1Formula 1
상기 식에서, R1은 -(CH2)6-이다. Wherein R1 is-(CH2) 6-.
화학식 2Formula 2
상기 식에서, R2는 
화학식 3Formula 3
상기 식에서, R1은 -(CH2)6-이다.Wherein R1 is-(CH2) 6-.
화학식 4Formula 4
상기 식에서, R2는 
화학식 5Formula 5
상기 식에서, R3는 
화학식 6Formula 6
상기 식에서, R1은 -(CH2)6-이다.
Wherein R1 is-(CH2) 6-.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
공중합체 [A]는 종래부터 공지되어 있는 중합 방법에 의해서 얻어지는데, 즉 화합물 (a1), 화합물(a2), 화합물(a3)을 용매 중에서 중합개시제의 존재 하에 래디칼 중합하여 합성한다.Copolymer [A] is obtained by a conventionally known polymerization method, that is, compound (a1), compound (a2) and compound (a3) are synthesized by radical polymerization in the presence of a polymerization initiator in a solvent.
본 발명에서 사용된 공중합체 [A]는 화합물 (a1)으로부터 유도된 구성단위를 5∼40 중량%, 바람직한 것은 10∼30중량%로 함유하고 있다. 이 구성단위가 5중량% 미만인 공중합체는 내열성, 내약품성, 표면경도가 저하된 경향에 있고, 40중량%를 초과한 공중합체는 보존안전성이 저하된다. 화합물 (a1)으로서는, 예를 들면 아크 릴산, 메타크릴산, 크로톤산 등의 모노카르복시산; 말레산, 푸마르산, 시트라콘산, 메사콘산, 이타콘산 등의 디카르복시산; 및 이들 디카르복시산의 무수물을 들 수 있다. 이 중, 아크릴산, 메타크릴산, 무수 말레산 등이 공중합 반응성, 내열성 및 입수가 용이한 점에서 바람직하게 사용된다. 이러한 화합물 (a1)은 단독으로 또는 조합해서 사용된다.Copolymer [A] used in the present invention contains 5 to 40% by weight of a structural unit derived from compound (a1), preferably 10 to 30% by weight. Copolymers having a structural unit of less than 5% by weight tend to have low heat resistance, chemical resistance and surface hardness, and copolymers of more than 40% by weight have poor storage safety. Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability. These compounds (a1) are used individually or in combination.
본 발명에서 사용된 공중합체 [A]는 화합물 (a2)로부터 유도된 구성단위를 10∼70중량%, 바람직한 것은 20∼60중량%로 함유하고 있다. 이 구성단위가 10중량% 미만인 공중합체는 얻어지는 보호막의 내열성, 표면경도가 저하되는 경향이 있고, 70중량%를 초과하는 경우에는 공중합체의 보존안전성이 저하되는 경향이 있다. 화합물 (a2)로서는, 예를 들면 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸 아크릴산 글리시딜, α-n-프로필 아크릴산 글리시딜, α-n-부틸 아크릴산 글리시딜, 아크릴산-3,4-에폭시 부틸, 메타크릴산-3,4-에폭시 부틸, 아크릴산-6,7-에폭시 헵틸, 메타크릴산-6,7-에폭시 헵틸, α-에틸 아크릴산-6,7-에폭시 헵틸, o-비닐 벤질 글리시딜 에테르, m-비닐 벤질 글리시딜 에테르, p-비닐 벤질 글리시딜 에테르 등이 공중합 반응성 및 얻어지는 보호막의 내열성, 경도를 높인다는 점에서 바람직하게 사용된다. 이러한 화합물 (a2)는 단독으로 또는 조합해서 사용된다.The copolymer [A] used in the present invention contains 10 to 70% by weight of the structural unit derived from the compound (a2), preferably 20 to 60% by weight. The copolymer of which the structural unit is less than 10% by weight tends to lower the heat resistance and surface hardness of the protective film obtained, and when it exceeds 70% by weight, the storage safety of the copolymer tends to be lowered. As the compound (a2), for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid -3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7-epoxy heptyl , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferably used in view of increasing copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds (a2) are used individually or in combination.
본 발명에서 사용된 공중합체 [A]는 화합물 (a3)로부터 유도된 구성단위를 10∼70중량%, 바람직한 것은 20∼50중량%를 함유하고 있다. 이 구성단위가 10중량% 미만인 경우는 공중합체 [A]의 보존안전성이 저하되는 경향이 있고, 70중량%를 초과하는 경우에는 공중합체 [A]의 내열성, 표면경도가 저하되는 경향이 있다. 화합 물 (a3)으로서는, 예를 들면 메틸 메타크릴레이트, 에틸 메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, t-부틸 메타크릴레이트 등의 메타크릴산 알킬 에스테르; 메틸 아크릴레이트, 이소프로필 아크릴레이트 등의 아크릴산 알킬 에스테르; 시클로헥실 메타크릴레이트, 2-메틸 시클로헥실 메타크릴레이트, 디시클로펜테닐 메타크릴레이트, 디시클로펜테닐옥시에틸 메타크릴레이트, 이소보로닐 메타크릴레이트 등의 메타크릴산 시클로알킬 에스테르; 시클로헥실 아크릴레이트, 2-메틸 시클로헥실 아크릴레이트, 디시클로펜테닐 아크릴레이트, 디시클로펜테닐옥시에틸 아크릴레이트, 이소보로닐 아크릴레이트 등의 아크릴산 시클로알킬 에스테르; 페틸 메타크릴레이트, 벤질 메타크릴레이트 등의 메타크릴산 아릴 에스테르; 페닐 아크릴레이트, 벤질 아크릴레이트 등의 아크릴산 아릴 에스테르; 말레산 디에틸, 푸마르산 디에틸, 이타콘산 디에틸 등의 디카르복시산 디에스테르; 2-히드록시 에틸 메타크릴레이트, 2-히드록시 프로필 메타크릴레이트 등의 히드록시알킬 에스테르; 및 스티렌, o-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐 톨루엔, p-메톡시 스티렌, 아크릴로니트릴, 메타크릴로니트릴, 염화 비닐, 염화 비닐리덴, 아크릴 아미드, 메타크릴 아미드, 초산 비닐, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔 등을 들 수 있다. 이 중 스티렌, t-부틸 메타크릴레이트, 디시클로펜테닐 메타크릴레이트, p-메톡시 스티렌, 2-메틸 시클로헥실 아크릴레이트, 1,3-부타디엔 등이 공중합 반응성 및 내열성의 관점에서 바람직하다. 이러한 화합물 (a3)는 단독으로 또는 조합하여 사용된다.Copolymer [A] used in the present invention contains 10 to 70% by weight of the structural unit derived from compound (a3), and preferably 20 to 50% by weight. When this structural unit is less than 10 weight%, there exists a tendency for the storage stability of copolymer [A] to fall, and when it exceeds 70 weight%, there exists a tendency for the heat resistance and surface hardness of copolymer [A] to fall. Examples of the compound (a3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isoboroyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate and isoboroyl acrylate; Methacrylic acid aryl esters such as petyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; Hydroxyalkyl esters such as 2-hydroxy ethyl methacrylate and 2-hydroxy propyl methacrylate; And styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene, and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance. These compounds (a3) are used alone or in combination.
본 발명에서 사용된 상기와 같은 공중합체 [A]는 카르복실기 및/또는 카르복 시산 무수물기 및 에폭시기를 갖고 있으며, 특별한 경화제를 병용하지 않더라도 가열에 의하여 용이하게 경화시키는 것이 가능하다.The copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating even without using a special curing agent.
공중합체 [A]의 합성에 사용된 용매로는 메탄올, 에탄올 등의 알코올류; 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류; 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로펠렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르 아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류 등이 바람직하다.As a solvent used for the synthesis | combination of copolymer [A], Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate, etc. are preferable.
공중합체 [A]의 합성에 사용된 중합개시제로는, 일반적으로 래디칼 중합개시제로서 알려져 있는 것을 사용할 수 있다. 예를 들면 2,2'-아조비스 이소부티로니트릴, 2,2'-아조비스-(2,4-디메틸발레로니트릴), 2,2'-아조비스-(4-메톡시-2,4-디메틸발레로니트릴) 등의 아조 화합물; 벤조일 퍼옥시드, t-부틸 퍼옥시 피바레이트, 1,1'-비스-(t-부틸 퍼옥시) 시클로 헥산 등의 유기 과산화물; 및 과산화수소를 들 수 있다. 래디칼 중합개시제로서 과산화물을 이용한 경우에는 과산화물을 환원제와 함께 이용하여 산화-환원 개시제로 사용해도 좋다.As a polymerization initiator used for the synthesis | combination of copolymer [A], what is generally known as a radical polymerization initiator can be used. For example 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, t-butyl peroxy pibarate, 1,1'-bis- (t-butyl peroxy) cyclohexane; And hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, you may use it as an oxidation-reduction initiator by using a peroxide together with a reducing agent.
본 발명에서는 상기와 같은 공중합체 A와 더불어서, [B]경화성 화합물을 사용하는 바, 이는 [A]에 대하여 경화제로서 작용한다. 반응성 우레탄 화합물은 상기 화학식 1 내지 6으로 표시되는 화합물들로부터 선택된다. In the present invention, in addition to the copolymer A as described above, a curable compound [B] is used, which acts as a curing agent for [A]. The reactive urethane compound is selected from the compounds represented by Chemical Formulas 1 to 6.
본 발명의 열경화성 수지 조성물은, 공중합체 [A] 100 중량부에 대하여 경화성 화합물[B]를 1∼10중량부, 바람직한 것은 3∼10중량부의 비율로 포함한다. 경화 성 화합물 [B]가 공중합체 [A] 100중량부에 대해 1중량부 미만인 경우에는 충분히 높은 가교밀도를 갖는 보호막을 얻기 어렵고, 보호막의 각종 내성이 저하되는 경우가 있다. 경화성 화합물 [B]가 공중합체 [A] 100중량부에 대해 10중량부를 초과하는 경우에는 얻어지는 보호막의 막 내부에 미반응 경화성 화합물 [B]가 다량 잔존하기 쉽고, 그 결과 보호막의 성질이 불안정해지거나 밀착성이 저하되기 쉽다.The thermosetting resin composition of this invention contains 1-10 weight part of curable compounds [B] with respect to 100 weight part of copolymers [A], and preferably 3-10 weight part. When curable compound [B] is less than 1 weight part with respect to 100 weight part of copolymers [A], it is difficult to obtain the protective film which has a sufficiently high crosslink density, and the various tolerances of a protective film may fall. When the curable compound [B] exceeds 10 parts by weight with respect to 100 parts by weight of the copolymer [A], a large amount of unreacted curable compound [B] is likely to remain in the film of the resulting protective film, resulting in unstable properties of the protective film. It is easy to lose or adhesiveness.
한편, 공중합체 [A], 경화성 화합물 [B] 이외에 [C] 에틸렌성 불포화 결합을 갖는 중합성 화합물이나, [D] 열 래디칼 중합개시제을 함유하여도 좋다. On the other hand, in addition to copolymer [A] and curable compound [B], you may contain the polymeric compound which has [C] ethylenically unsaturated bond, and the [D] thermal radical polymerization initiator.
본 발명에서 사용된 중합성 화합물 [C]로는 단관능, 2관능, 또는 3관능 이상의 (메타)아크릴레이트가 중합성이 양호하고, 얻어지는 보호막의 내열성, 표면경도가 향상된다는 관점에서 바람직하다.As the polymerizable compound [C] used in the present invention, monofunctional, bifunctional, or trifunctional or higher (meth) acrylates are preferred from the viewpoint of good polymerizability and improved heat resistance and surface hardness of the resulting protective film.
단관능 (메타)아크릴레이트로는, 예를 들면 2-히드록시 에틸 (메타)아크릴레이트, 카비톨 (메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 3-메톡시 부틸 (메타)아크릴레이트, 2-(메타)아크릴로일 옥시 에틸 2-히드록시 프로필 프탈레이트 등을 들 수 있다.As monofunctional (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl (meth) acrylate, for example , 2- (meth) acryloyl oxyethyl 2-hydroxy propyl phthalate, and the like.
2관능 (메타)아크릴레이트로는, 예를 들면 에텔렌글리콜 (메타)아크릴레이트, 1,6-헥산디올 (메타)아크릴레이트, 1,9-노난디올 (메타)아크릴레이트, 프로필렌글리콜 (메타)아크릴레이트, 테트라에틸렌글리콜 (메타)아크릴레이트, 비스페녹시 에틸알콜 플루오렌 디아크릴레이트 등을 들 수 있다.As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) acrylate, propylene glycol (meth) ) Acrylate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, etc. are mentioned.
3관능 이상의 (메타)아크릴레이트로는, 예를 들면 트리스히드록시에틸이소시아누레이트 트리(메타)아크릴레이트, 트리메틸프로판 트리(메타)아크릴레이트, 펜 타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트 등을 들 수 있다.As (meth) acrylate more than trifunctional, for example, tris hydroxyethyl isocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
이러한 단관능, 2관능 또는 3관능 이상의 (메타)아크릴레이트는 단독으로 또는 조합하여 사용된다.Such mono-, bi-, or tri- or more (meth) acrylates are used alone or in combination.
본 발명에서 사용된 열 래디칼 중합개시제 [D]로는 2,2'-아조비스 이소부티로니트릴, 2,2'-아조비스-(2,4-디메틸발레로니트릴), 2,2'-아조비스-(4-메톡시-2,4-디메틸발레로니트릴), 1,1'-아조비스-1-시클로헥실니트릴 등의 아조 화합물; 벤조일 퍼옥시드, t-부틸 퍼옥시드, 1,1'-비스-(t-부틸 퍼옥시) 시클로 헥산 등의 유기 과산화물 등을 들 수 있다.The thermal radical polymerization initiator [D] used in the present invention is 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azo Azo compounds such as bis- (4-methoxy-2,4-dimethylvaleronitrile) and 1,1'-azobis-1-cyclohexylnitrile; Organic peroxides such as benzoyl peroxide, t-butyl peroxide, 1,1'-bis- (t-butyl peroxy) cyclohexane, and the like.
본 발명의 열경화성 수지 조성물은 상기의 공중합체 [A], 경화성 화합물 [B], 중합성 화합물 [C], 열 래디칼 중합개시제 [D]의 각 성분을 균일하게 혼합하여 제조된다. 보통, 본 발명의 열경화성 수지 조성물은 적당한 용매에 용해되어 용액 상태로 사용된다. 즉, 공중합체 [A], 경화성 화합물 [B], 중합성 화합물 [C], 열 래디칼 중합개시제 [D] 및 그 밖의 첨가제를 소정의 비율로 혼합하여 용액 상태로 열경화성 수지 조성물을 조제하게 된다. 본 발명의 조성물은 공중합체 [A]와 경화성 화합물 [B]는 반드시 포함하고 있어야 한다.The thermosetting resin composition of this invention is manufactured by uniformly mixing each component of said copolymer [A], curable compound [B], polymeric compound [C], and thermal radical polymerization initiator [D]. Usually, the thermosetting resin composition of this invention is melt | dissolved in a suitable solvent, and is used in a solution state. That is, a copolymer [A], a curable compound [B], a polymerizable compound [C], a thermal radical polymerization initiator [D], and other additives are mixed at a predetermined ratio to prepare a thermosetting resin composition in a solution state. The composition of this invention must contain copolymer [A] and curable compound [B].
본 발명의 열경화성 수지 조성물은, 공중합체 [A] 100중량부에 대하여 중합성 화합물 [C]를 150중량부 이하, 보다 바람직한 것은 120중량부 이하의 비율로 포함할 수 있다. 중합성 화합물 [C]의 사용시 그 함량이 공중합체 [A] 100중량부에 대해 150중량부를 초과하는 경우에는 얻어지는 보호막의 밀착성이 저하되기 쉽다. The thermosetting resin composition of this invention can contain 150 weight part or less of polymerizable compounds [C] with respect to 100 weight part of copolymers [A], and more preferably 120 weight part or less. When the content of the polymerizable compound [C] exceeds 150 parts by weight relative to 100 parts by weight of the copolymer [A], the adhesion of the protective film obtained is likely to be lowered.
본 발명의 열경화성 수지 조성물은, 공중합체 [A] 100중량부에 대하여 열 래디칼 중합개시제 [D]를 20중량부 이하, 바람직한 것은 15중량부 이하의 비율로 포함할 수 있다. 열 래디칼 중합개시제 [D]가 공중하베 [A] 100중량부에 대해 20중량부를 초과하는 경우에는 보호막의 내열성, 평탄화성 등이 저하되기 쉽다.The thermosetting resin composition of this invention can contain a thermal radical polymerization initiator [D] 20 weight part or less with respect to 100 weight part of copolymers [A], and a preferable thing may be contained in the ratio of 15 weight part or less. When the thermal radical polymerization initiator [D] exceeds 20 parts by weight with respect to 100 parts by weight of the aerial herb [A], the heat resistance, the flattening property, and the like of the protective film tend to be lowered.
본 발명의 열경화성 수지 조성물의 조제에 사용된 용매로는 공중합체 [A], 경화성 화합물 [B], 중합성 화합물 [C], 열 래디칼 중합개시제 [D]의 각 성분을 균일하게 용해할 수 있으며, 어느 한 성분과도 반응하지 않는 것이 사용된다. 구체적으로 예를 들면, 메탄올, 에탄올 등의 알코올류; 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류; 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로필렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르 아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류 등을 들 수 있다. 이러한 용매 가운데에서 용해성, 각 성분과의 반응성 및 도막 형성의 편리성의 관점에서 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 프로펠렌 글리콜 메틸 에테르 아세테이트가 바람직하게 사용된다.As a solvent used for preparation of the thermosetting resin composition of this invention, each component of a copolymer [A], a curable compound [B], a polymerizable compound [C], and a thermal radical polymerization initiator [D] can be melt | dissolved uniformly. It is used that does not react with either component. Specifically, For example, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate are preferably used in view of solubility, reactivity with each component, and convenience of coating film formation.
또한 상기 용매와 함께 고비등점 용매를 병용한 것도 가능하다. 병용할 수 있는 고비등점 용매로서는, 예를 들면 N-메틸 포름아미드, N,N-디메틸 포름아미드, N-메틸 아세트아미드, N,N-디메틸 아세트아미드, N-메틸 피롤리돈, 디메틸 설폭시드, 벤질 에틸 에테르 등을 들 수 있다.Moreover, it is also possible to use a high boiling point solvent together with the said solvent. As a high boiling point solvent which can be used together, it is N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, for example. And benzyl ethyl ether.
본 발명의 열경화성 수지 조성물은 본 발명의 목적을 손상시키지 않는 범위 에서 필요에 의해 상기 이외의 다른 성분을 함유하고 있어도 좋다.The thermosetting resin composition of this invention may contain other components of that excepting the above as needed in the range which does not impair the objective of this invention.
여기에서 다른 성분으로는 도포성을 향상하기 위한 계면활성제를 들 수 있다. 계면활성제로는 불소 및 실리콘계 계면활성제를 들 수 있는데, 예를 들면 3M사의 FC-129, FC-170C, FC-430, 신에츠실리콘사의 KP322, KP323, KP340, KP341 등을 들 수 있다. 이러한 계면활성제는 공중합체 [A] 100 중량부에 대하여 5중량부 이하, 바람직한 것은 2중량부 이하의 양으로 사용할 수 있다. 계면활성제의 양이 공중합체 [A] 100중량부에 대해 5중량부를 초과한 경우에는 도포시 거품이 발생하기 쉬워진다.Here, as another component, surfactant for improving applicability | paintability is mentioned. Examples of the surfactant include fluorine and silicone-based surfactants, and examples thereof include FC-129, FC-170C, FC-430, KP322, KP323, KP340, and KP341 manufactured by Shin-Etsu Silicone. Such surfactant can be used in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant exceeds 5 parts by weight with respect to 100 parts by weight of the copolymer [A], bubbles are likely to occur during application.
상기와 같이 조제된 조성물 용액은 구멍지름 0.1∼5㎛ 정도의 필터 등을 이용하여 여과한 후 사용된다.The composition solution prepared as described above is used after filtration using a filter having a pore diameter of about 0.1 to 5 μm.
본 발명의 열경화성 수지 조성물을 바탕기판에 도포하고, 오븐에서 150∼300℃로 10∼100분간 처리한 것에 의하여 목적으로 하는 보호막을 얻을 수 있다.
The target protective film can be obtained by apply | coating the thermosetting resin composition of this invention to a base substrate, and processing it for 10 to 100 minutes at 150-300 degreeC in oven.
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.
<실시예 1><Example 1>
냉각관과 교반기가 구비된 반응 용기에 2,2'-아조비스 이소부티로니트릴 5중량부를 디에틸렌글리콜디메틸에테르 200중량부에 녹였다. 계속해서 스티렌 20중량부, 메타크릴산 30중량부, 메타크릴산 글리시딜 40중량부 및 디시클로펜테닐옥시에 틸 메타크릴레이트 10중량부를 투입하고 질소 치환한 후 부드럽게 교반을 시작했다. 용액의 온도를 80℃로 상승시키고 이 온도를 4시간 동안 유지하여 공중합체 [A-1]을 포함한 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 농도는 33중량%이었다. 5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxy ethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%.
얻어진 공중합체 [A-1] 100중량부(고형분 함량 기준)), 경화성 화합물 [B]로서 교에이사社 AH-600(화학식 1 화합물) 5중량부 및 계면활성제로서 FC-430(3M사 제품) 0.1중량부를 혼합하여 디에틸렌글리콜디메틸에테르와 N-메틸 피롤리돈에 용해시킨 후 고형분농도가 25중량%가 되도록 하였다. 그 후, 구멍지름 0.45㎛의 필터로 여과하여 열경화성 수지 조성물 용액(S-1)을 조제했다.100 parts by weight of the obtained copolymer [A-1] (based on the solid content)), 5 parts by weight of Kyowa Corporation AH-600 (Compound 1) as the curable compound [B], and FC-430 (manufactured by 3M Corporation) as a surfactant. ) 0.1 parts by weight was mixed and dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone so that the solid content concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-1).
<실시예 2><Example 2>
냉각관과 교반기가 구비된 반응 용기에 2,2'-아조비스 이소부티로니트릴 5중량부를 디에틸렌글리콜 디메틸 에테르 200중량부에 녹였다. 계속해서 스티렌 20중량부, 메타크릴산 30중량부, 메타크릴산 글리시딜 40중량부 및 디시클로펜테닐옥시에틸 메타크릴레이트 10중량부를 투입하고 질소 치환한 후 부드럽게 교반을 시작했다. 용액의 온도를 80℃로 상승시키고 이 온도를 4시간 동안 유지하여 공중합체 [A-1]을 포함한 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 농도는 33중량%이었다. 5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%.
얻어진 공중합체 [A-1] 100중량부(고형분 함량 기준), 경화성 화합물 [B]로서 교에이사社 AT-600(화학식 2 화합물) 5중량부, 계면활성제로서 KP341(신에츠실리콘사 제품) 0.1중량부를 혼합하여 디에틸렌글리콜디메틸에테르와 N-메틸 피롤리 돈에 용해시킨 후 고형분농도가 25중량%가 되도록 하였다. 그 후, 구멍지름 0.45㎛의 필터로 여과하여 열경화성 수지 조성물 용액(S-2)을 조제했다.100 parts by weight of the obtained copolymer [A-1] (based on the solid content), 5 parts by weight of Kyoe Corporation AT-600 (Compound 2) as the curable compound [B], and 0.1 KP341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as the surfactant. By weight, the mixture was dissolved in diethylene glycol dimethyl ether and N-methyl pyrrolidone, and the solid content concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-2).
<실시예 3><Example 3>
냉각관과 교반기가 구비된 반응 용기에 2,2'-아조비스 이소부티로니트릴 5중량부를 디에틸렌글리콜 디메틸 에테르 200중량부에 녹였다. 계속해서 스티렌 20중량부, 메타크릴산 30중량부, 메타크릴산 글리시딜 40중량부 및 디시클로펜테닐옥시에틸 메타크릴레이트 10중량부를 투입하고 질소 치환한 후 부드럽게 교반을 시작했다. 용액의 온도를 80℃로 상승시키고 이 온도를 4시간 동안 유지하여 공중합체 [A-1]을 포함한 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 농도는 33중량%이었다. 5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%.
얻어진 공중합체 [A-1] 100중량부(고형분 함량 기준), 경화성 화합물 [B]로서 교에이사社 UA-306H(화학식 3 화합물) 5중량부, 중합성 화합물 [C]로서 트리메틸프로판 트리메타아크릴레이트 100중량부, 열 래디칼 중합개시제 [D]로서 벤조일 퍼옥시드 5 중량부 및 계면활성제로서 FC-430(3M사 제품) 0.1중량부를 혼합하여 디에틸렌글리콜디메틸에테르와 N-메틸 피롤리돈에 용해시킨 후 고형분농도가 25중량%가 되도록 하였다. 그 후, 구멍지름 0.45㎛의 필터로 여과하여 열경화성 수지 조성물 용액(S-3)을 조제했다.100 parts by weight of the obtained copolymer [A-1] (based on the solid content), 5 parts by weight of Kyowa Corporation UA-306H (Compound 3) as the curable compound [B], and a trimethylpropane trimeta as the polymerizable compound [C]. 100 parts by weight of acrylate, 5 parts by weight of benzoyl peroxide as thermal radical polymerization initiator [D] and 0.1 parts by weight of FC-430 (manufactured by 3M) as a surfactant were mixed with diethylene glycol dimethyl ether and N-methyl pyrrolidone. After dissolution, the solid content concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-3).
<실시예 4><Example 4>
냉각관과 교반기가 구비된 반응 용기에 2,2'-아조비스 이소부티로니트릴 5중량부를 디에틸렌글리콜 디메틸 에테르 200중량부에 녹였다. 계속해서 스티렌 20중 량부, 메타크릴산 30중량부, 메타크릴산 글리시딜 40중량부 및 디시클로펜테닐옥시에틸 메타크릴레이트 10중량부를 투입하고 질소 치환한 후 부드럽게 교반을 시작했다. 용액의 온도를 80℃로 상승시키고 이 온도를 4시간 동안 유지하여 공중합체 [A-1]을 포함한 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 농도는 33중량%이었다. 5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%.
얻어진 공중합체 [A-1] 100중량부(고형분 함량 기준), 경화성 화합물 [B]로서 교에이사社 UA-306T(화학식 4 화합물) 5중량부, 중합성 화합물 [C]로서 펜타에리스리톨 테트라메타아크릴레이트 100중량부, 열 래디칼 중합개시제 [D]로서 1,1'-아조비스-1-시클로헥실니트릴 5 중량부, 계면활성제로서 KP341(신에츠실리콘사 제품) 0.1중량부를 혼합하여 디에틸렌글리콜디메틸에테르와 N-메틸 피롤리돈에 용해시킨 후 고형분농도가 25중량%가 되도록 하였다. 그 후, 구멍지름 0.45㎛의 필터로 여과하여 열경화성 수지 조성물 용액(S-4)을 조제했다.100 parts by weight (based on the solid content) of the obtained copolymer [A-1], 5 parts by weight of Kyowa Corporation UA-306T (compound 4) as the curable compound [B], and pentaerythritol tetrametha as the polymerizable compound [C]. 100 parts by weight of acrylate, 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as thermal radical polymerization initiator [D], 0.1 part by weight of KP341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a surfactant, and diethylene glycol dimethyl After dissolving in ether and N-methyl pyrrolidone, the solid concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-4).
<실시예 5><Example 5>
냉각관과 교반기가 구비된 반응 용기에 2,2'-아조비스 이소부티로니트릴 5중량부를 디에틸렌글리콜 디메틸 에테르 200중량부에 녹였다. 계속해서 스티렌 20중량부, 메타크릴산 30중량부, 메타크릴산 글리시딜 40중량부 및 디시클로펜테닐옥시에틸 메타크릴레이트 10중량부를 투입하고 질소 치환한 후 부드럽게 교반을 시작했다. 용액의 온도를 80℃로 상승시키고 이 온도를 4시간 동안 유지하여 공중합체 [A-1]을 포함한 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 농도는 33중량%이었다. 5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33 weight%.
얻어진 공중합체 [A-1] 100중량부(고형분 함량 기준), 경화성 화합물 [B]로서 교에이사社 UA-510H(화학식 6 화합물) 5중량부, 중합성 화합물 [C]로서 디펜타에리스리톨 펜타메타아크릴레이트 100중량부, 열 래디칼 중합개시제 [D]로서 1,1'-아조비스-1-시클로헥실니트릴 5중량부, 계면활성제로서 KP341(신에츠실리콘사 제품) 0.1중량부를 혼합하여 디에틸렌글리콜디메틸에테르와 N-메틸 피롤리돈에 용해시킨 후 고형분농도가 25중량%가 되도록 하였다. 그 후, 구멍지름 0.45㎛의 필터로 여과하여 열경화성 수지 조성물 용액(S-5)을 조제했다.100 parts by weight (based on solids content) of the obtained copolymer [A-1], 5 parts by weight of Kyowa Corporation UA-510H (Compound 6) as the curable compound [B], and dipentaerythritol penta as the polymerizable compound [C]. 100 parts by weight of methacrylate, 5 parts by weight of 1,1'-azobis-1-cyclohexylnitrile as thermal radical polymerization initiator [D], and 0.1 parts by weight of KP341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a surfactant were mixed with diethylene glycol. After dissolving in dimethyl ether and N-methyl pyrrolidone, the solid content concentration was 25% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the thermosetting resin composition solution (S-5).
<비교예1>Comparative Example 1
상기 실시예 1과 동일한 방법으로 열경화성 수지조성물 용액을 조제하되, 다만 경화성 화합물 [B]를 사용하지 않았다.A thermosetting resin composition solution was prepared in the same manner as in Example 1, except that the curable compound [B] was not used.
<비교예2>Comparative Example 2
상기 실시예 3과 동일한 방법으로 열경화성 수지조성물 용액을 조제하되, 다만 경화성 화합물 [B]를 사용하지 않았다.A thermosetting resin composition solution was prepared in the same manner as in Example 3, except that the curable compound [B] was not used.
<보호막의 형성><Formation of protective film>
스핀코터를 이용하여 유리기판 위에 상기의 열경화성 수지 조성물을 막 두께 2㎛ 되도록 도포하고, 이를 클린 오븐에서 220℃로 30분 동안 소성하여 유리기판 위에 보호막을 형성하였다.Using a spin coater, the thermosetting resin composition was coated on the glass substrate to have a thickness of 2 μm, and then fired at 220 ° C. for 30 minutes in a clean oven to form a protective film on the glass substrate.
앞에서 언급한 실시예 및 비교실시예에 대한 평가 방법은 하기와 같다.Evaluation methods for the aforementioned examples and comparative examples are as follows.
(1)밀착성(1) adhesion
바둑판 무늬 테이프 법에 따라 보호막에 100개의 바둑판 무늬를 커터 나이프 로 형성하고 밀착성 시험을 행하여, 박리된 바둑판 무늬의 수를 측정하고 다음 기준에 의하여 보호막의 밀착성을 평가하였다.According to the checkered tape method, 100 checkers were formed on the protective film with a cutter knife, and the adhesion test was carried out to measure the number of peeled checkered patterns and to evaluate the adhesion of the protective film according to the following criteria.
○ : 박리된 바둑판 무늬의 수 5개 이하(Circle): The number of the peeled checkerboard patterns 5 or less
△ : 박리된 바둑판 무늬의 수 6∼49개(Triangle | delta): The number of the peeled checkerboard patterns 6-49 pieces
× : 박리된 바둑판 무늬의 수 50개 이상×: 50 or more pieces of checkered patterns
(2)표면경도(2) surface hardness
연필경도법에 따라 보호막에 대하여 연필경도 시험법을 행하여 보호막의 표면경도를 평가하였다.The surface hardness of the protective film was evaluated by performing a pencil hardness test method on the protective film according to the pencil hardness method.
(3)투명성(3) transparency
분광 광도계를 이용하여 400∼700nm에서 보호막의 투과율을 측정하고 다음 기준에 의하여 보호막의 투명성을 평가하였다.The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer, and the transparency of the protective film was evaluated according to the following criteria.
○ : 최저 투과율 95% 초과○: 95% minimum transmittance
△ : 최저 투과율 90∼95% 초과(Triangle | delta): More than 90 to 95% of minimum transmittance | permeability
× : 최저 투과율 90% 미만X: less than 90% of the lowest transmittance
(4)평탄화성(4) leveling
보호막의 표면 요철을 α스텝을 이용하여 조사하고 기판의 단차를 측정하였다.The surface irregularities of the protective film were irradiated using the α step, and the step difference of the substrate was measured.
(5)내UV성(5) UV resistance
보호막에 UV를 조사하였다. UV조사 전후에 보호막의 투과 스펙트럼을 측정하고 다음 기준에 의하여 보호막의 내UV성을 평가하였다. The protective film was irradiated with UV. The transmission spectrum of the protective film was measured before and after UV irradiation, and the UV resistance of the protective film was evaluated according to the following criteria.
○ : 투과 스펙트럼의 변화가 1% 이내(Circle): The change of a transmission spectrum is within 1%.
× : 투과 스펙트럼의 변화가 1% 이상X: 1% or more of change in transmission spectrum
(6)내열성(황변정도)(6) heat resistance (degree of yellowing)
보호막을 클린 오븐 240℃, 60분 동안 가열하고, 가열 전후에 투과 스펙트럼을 측정하고 다음 기준에 의하여 보호막의 내열성을 평가하였다.The protective film was heated in a clean oven at 240 ° C. for 60 minutes, and the transmission spectrum was measured before and after heating, and the heat resistance of the protective film was evaluated according to the following criteria.
○ : 투과 스펙트럼의 변화가 1% 이내(Circle): The change of a transmission spectrum is within 1%.
× : 투과 스펙트럼의 변화가 1% 이상X: 1% or more of change in transmission spectrum
(7)내산성(7) acid resistance
보호막이 형성된 유리기판을 25중량% 염산 수용액 중에 30℃, 20분간 침지한 후, 보호막의 외관 변화를 관찰하여 보호막의 내산성을 평가하였다.After the glass substrate on which the protective film was formed was immersed in a 25 wt% aqueous hydrochloric acid solution for 30 minutes at 30 ° C., the appearance change of the protective film was observed to evaluate the acid resistance of the protective film.
(8)내알칼리성(8) alkali resistance
보호막이 형성된 유리기판을 10중량% 수산화나트륨 수용액 중에 30℃, 60분간 침지한 후, 보호막의 외관 변화를 관찰하여 보호막의 내알칼리성을 평가하였다.After the glass substrate on which the protective film was formed was immersed in a 10 wt% sodium hydroxide aqueous solution for 30 ° C. for 60 minutes, the appearance change of the protective film was observed to evaluate the alkali resistance of the protective film.
상기 실시예 및 비교실시예의 평가 물성은 다음 표 1과 같다.Evaluation properties of the Examples and Comparative Examples are shown in Table 1 below.
(표 1)Table 1
이상에서 설명한 바와 같이, 본 발명에 따라 카르복실기나 에폭시기를 함유하고 있는 아크릴 수지에 가교제의 역할을 하는 반응성 우레탄 화합물을 배합하는 경우 보호막으로서 종래로부터 요구된 특성들을 만족시키는 동시에 가교밀도를 효과적으로 향상시켜 기계적 물성 및 내열성이 우수하고, 고온에서의 황변이 없는 열경화성 수지 조성물 및 이를 사용한 광디바이스(device)의 컬러필터 보호막을 제공할 수 있다.As described above, when the reactive urethane compound acting as a crosslinking agent is blended with an acrylic resin containing a carboxyl group or an epoxy group according to the present invention, the protective film satisfies the characteristics required in the related art and at the same time effectively improves the crosslinking density by mechanically It is possible to provide a thermosetting resin composition excellent in physical properties and heat resistance and free from yellowing at a high temperature, and a color filter protective film of an optical device using the same.
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| KR101485607B1 (en) * | 2008-09-17 | 2015-01-26 | 코오롱인더스트리 주식회사 | Thermosetting resin composition |
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