KR20030011431A - Photo-curable urethane acrylate having 2,2,6,6-tetramethylpiperidine derivatives and process for preparing thereof, and photo-curable resin composition containing the same - Google Patents
Photo-curable urethane acrylate having 2,2,6,6-tetramethylpiperidine derivatives and process for preparing thereof, and photo-curable resin composition containing the same Download PDFInfo
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- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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Abstract
Description
본 발명은 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트, 이의 제조방법 및 이를 함유한 광경화형 수지 조성물에 관한 것으로서, 좀 더 상세하게는 환경친화적인 이관능성 반응형으로서 고속 경화가 가능하고, 내후성이 우수한 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트, 이의 제조방법 및 이를 함유한 광경화형 수지 조성물에 관한 것이다.The present invention relates to a reactive urethane acrylate to which a 2,2,6,6-tetramethylpiperidine derivative is introduced, a method for preparing the same, and a photocurable resin composition containing the same, and more particularly to environmentally friendly transfer. The present invention relates to a reactive urethane acrylate in which a 2,2,6,6-tetramethylpiperidine derivative capable of high-speed curing and excellent weather resistance is introduced, a preparation method thereof, and a photocurable resin composition containing the same. .
각종 고분자 재료는 경량성, 내약품성 등이 우수한 특성을 갖고 있으므로 산업체와 일상생활 전반에 널리 이용되고 있다. 그러나, 대부분의 고분자 재료는 자외선에 민감하고, 그 작용에 의해 열화, 변색 또는 기계적 강도 저하 등이 야기되며, 장기 사용에 견디지 못하는 단점을 지니고 있다.Since various polymer materials have excellent properties such as light weight and chemical resistance, they are widely used in industrial and daily life. However, most polymer materials are sensitive to ultraviolet rays, and their action causes deterioration, discoloration, or decrease in mechanical strength, and has a disadvantage of not being able to endure long-term use.
상기와 같은 합성 중합체에 대한 자외선 복사의 악영향을 방지하기 위해, 예를 들어 벤조페논 및 벤조트리아졸의 특정 유도체, 니켈 착화합물, 치환된 벤조산에스테르, 알킬리덴 말로네이트, 시아노아클릴레이트, 반향족 옥사미드 및 입체 장애 아민과 같은 광안정화 특성을 갖는 여러 가지 첨가제의 사용이 제안되어 왔다.In order to prevent the adverse effects of ultraviolet radiation on such synthetic polymers, for example, certain derivatives of benzophenone and benzotriazole, nickel complexes, substituted benzoic acid esters, alkylidene malonates, cyanoacrylates, and aromatics The use of various additives with photostabilizing properties such as oxamides and sterically hindered amines has been proposed.
유럽 특허 공개공보 제107615호는 2,4-비스(2,2,6,6,-테트라메틸-4-피페리딜아미노)-1,3,5-트리아진 및 폴리올레핀에 대한 이들의 광안정화 활성을 개시하고 있다. 또한, 유럽 특허 공개공보 제207127호 및 유럽 특허 등록공보 제82244호는 2-[N,N-비스(2,2,6,6,-테트라메틸-4-피페리딜아미노)]-1,3,5-트리아진 및 합성 중합체에 대한 안정화제로서 이들의 용도를 개시하고 있다. 그러나, 상기 문헌에 따른 광안정화제는 그 제조방법이 복잡하고 이의 효과 또한 뛰어나지 못하다.European Patent Publication No. 107615 discloses their photostabilization of 2,4-bis (2,2,6,6, -tetramethyl-4-piperidylamino) -1,3,5-triazine and polyolefins Activity is initiated. In addition, European Patent Publication No. 207127 and European Patent Registration Publication No. 82442 provide 2- [N, N-bis (2,2,6,6, -tetramethyl-4-piperidylamino)]-1, Their use as stabilizers for 3,5-triazines and synthetic polymers is disclosed. However, the light stabilizer according to the above document is complicated in its manufacturing method and its effect is not excellent.
또한, 상기와 같은 단점을 개선하는 방안으로서 주로 저분자량의 광안정제를 고분자 재료에 첨가하는 방법들이 제안되어 왔다. 그러나, 대부분의 광안정제가 저분자량이기 때문에 고분자 재료 가공중에 휘발되거나, 또는 물, 유기용매에 의해 추출되기 쉽다는 등의 결점을 가지고 있었다. 따라서, 일본 특개소 52-73886호 공보, 특개소-58-122487호 공보, 특개소 58-47030호 공보, 특개소 58-194931호 공보, 특개소 59-122487호 공보 및 특개소 61-81441호 공보 등은 고분자량의 화합물을 제안하고 있으며, 또한 일본 특개소 61-176662호 공보는 분자중에 에테르기를 갖는 디아민의 시아누레이트 유도체를 개시하고 있으나, 이들 화합물의 안정화 효과는 아직 불충분하고, 각종 수지에 대한 상용성도 문제되어 산업적 활용도에 어려움이 있다.In addition, a method of mainly adding a low molecular weight light stabilizer to the polymer material has been proposed as a solution to the above disadvantage. However, since most light stabilizers have low molecular weights, they have a drawback that they are easily volatilized during processing of polymer materials, or are easily extracted by water or an organic solvent. Therefore, Japanese Patent Application Laid-Open No. 52-73886, Japanese Patent Laid-Open No. 58-242487, Japanese Patent Laid-Open No. 58-47030, Japanese Patent Laid-Open No. 58-194931, Japanese Patent Laid-Open No. 59-122487 and Japanese Patent Laid-Open 61-81441 Japanese Patent Application Laid-Open No. 61-176662 discloses a cyanurate derivative of diamine having an ether group in a molecule, but the stabilizing effect of these compounds is still insufficient, and various resins have been disclosed. There is also a difficulty in the industrial utilization because of compatibility.
전술한 바와 같은 고분자 재료의 내후성 향상 문제 뿐만 아니라 기타 물성 향상을 위해 현재 고분자 재료에 의해 성형된 플라스틱을 표면처리하는 연구들이많이 진행되고 있는데, 특히 광경화형 코팅제에 관한 연구들이 각광을 받고 있다. 광경화 코팅제는 고분자 재료인 플라스틱 뿐만 아니라 금속 및 목재 등의 표면 보호용 소재로서 도장시 공정속도가 빠르고 환경친화적이어서 최근 많은 연구들이 진행되고 있다.In order to improve the weather resistance of the polymer material as described above as well as to improve other physical properties, a lot of researches are currently being conducted on the surface of the plastic molded by the polymer material, in particular, research on the photo-curable coating agent is in the spotlight. The photocurable coating agent is a surface protection material such as metal and wood as well as a polymer material, and thus, many studies have been conducted because the process speed is fast and environmentally friendly at the time of coating.
상술한 문제점들을 해결하기 위하여, 본 발명자들이 연구를 거듭한 결과, 각종 수지 및 도료와의 상용성이 뛰어나고 고속 경화가 가능하며, 내후성이 우수한 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트를 얻을 수 있었으며, 본 발명은 이에 기초하여 완성되었다.In order to solve the above problems, the present inventors have conducted a lot of research, 2,2,6,6-tetramethylpiperidine derivative excellent in compatibility with various resins and paints, high-speed curing, excellent weatherability The reactive urethane acrylate to which was introduced was obtained, and the present invention was completed based on this.
따라서, 본 발명의 목적은 각종 수지 및 도료와의 상용성이 뛰어나고, 내후성이 우수한 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트를 제공하는데 있다.Accordingly, an object of the present invention is to provide a reactive urethane acrylate in which a 2,2,6,6-tetramethylpiperidine derivative is introduced having excellent compatibility with various resins and paints and excellent weather resistance.
본 발명의 다른 목적은 고속 경화가 가능한 상기 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트를 간단하고 경제적인 공정을 통해 얻을 수 있는 제조 방법을 제공하는데 있다.Another object of the present invention is to provide a method for producing a reactive urethane acrylate to which the above-mentioned 2,2,6,6-tetramethylpiperidine derivative is introduced through a simple and economical process. .
본 발명의 또 다른 목적은 상기 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트를 함유하는 광경화형 수지 조성물을 제공하는데 있다.Still another object of the present invention is to provide a photocurable resin composition containing a reactive urethane acrylate to which the 2,2,6,6-tetramethylpiperidine derivative is introduced.
상기 목적을 달성하기 위한 본 발명에 따른 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트는 하기 화학식 1로 표시된다:Reactive urethane acrylate to which a 2,2,6,6-tetramethylpiperidine derivative is introduced according to the present invention for achieving the above object is represented by the following Chemical Formula 1:
상기 식에서, R1, R4및 R6는 각각 독립적으로 히드록시, 또는 하기 화학식 1a, 1b 또는 1c로 표시되는 화합물이며, R2, R3및 R5는 C2-C18의 알킬렌, 시클로헥실렌, 메틸렌디시클로헥실렌, 시클로헥실디메틸렌, 또는 1∼3의 산소원자 또는 메틸렌을 갖는 C4-C18의 알킬렌이고,Wherein R 1 , R 4 and R 6 are each independently hydroxy, or a compound represented by the following Formula 1a, 1b or 1c, and R 2 , R 3 and R 5 are alkylene of C 2 -C 18 , Cyclohexylene, methylenedicyclohexylene, cyclohexyldimethylene, or C 4 -C 18 alkylene having 1 to 3 oxygen atoms or methylene,
상기 식에서, R7, R8, R9, R10및 R11은 각각 독립적으로 수소 또는 메틸이고, R12는 수소 또는 C1-C18의 알킬렌이며, n은 1∼18의 정수이고, m은 1∼4의 정수이다.Wherein R 7 , R 8 , R 9 , R 10 and R 11 are each independently hydrogen or methyl, R 12 is hydrogen or alkylene of C 1 -C 18 , n is an integer from 1 to 18, m is an integer of 1-4.
상기 다른 목적을 달성하기 위한 상기 화학식 1로 표시되는 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트의 제조방법은 3관능 이소시아누레이트 0.005몰∼0.2몰을 유기용매에 넣고 상온 내지 90℃의 온도로 유지시키면서 여기에 산화방지제, 촉매 및 중합금지제를 투입하고 2,2,6,6-테트라메틸피페리딘 화합물 0.005몰∼0.1몰을 30분 내지 4시간 동안 적가한 후, 40∼100℃의 온도에서 30분 내지 5시간 동안 교반 반응시킨 다음 히드록시기를 함유한 아크릴레이트 화합물 0.005몰∼0.3몰을 적가하여 1∼8시간 동안 반응시킨다.Method for producing a reactive urethane acrylate in which the 2,2,6,6-tetramethylpiperidine derivative represented by Formula 1 to achieve the above another object is trifunctional isocyanurate 0.005 mol to 0.2 mol Was added to an organic solvent and kept at a temperature of from room temperature to 90 ° C., and an antioxidant, a catalyst, and a polymerization inhibitor were added thereto. After dropping for 4 hours, the mixture was stirred for 30 minutes to 5 hours at a temperature of 40 to 100 ° C, and then 0.005 to 0.3 mol of an acrylate compound containing a hydroxyl group was added dropwise to react for 1 to 8 hours.
본 발명의 또 다른 목적을 달성하기 위한 광경화형 수지조성물은 적어도 하나 이상의 아크릴기를 갖는 아크릴계 프리폴리머 30∼70중량%; 1관능성 내지 다관능성인 아크릴계 모노머 또는 비닐 에테르계 모노머 20∼60중량%; 광개시제 2∼7중량%; 및 상기 화학식 1로 표시되는 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트 0.1∼10중량%를 포함한다.Photocurable resin composition for achieving another object of the present invention is 30 to 70% by weight acrylic prepolymer having at least one acrylic group; 20 to 60% by weight of a monofunctional to polyfunctional acrylic monomer or vinyl ether monomer; 2-7 wt% of photoinitiator; And 0.1 to 10% by weight of urethane acrylate having 2,2,6,6-tetramethylpiperidine derivative represented by Chemical Formula 1 introduced therein.
이하, 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Hereinafter, the present invention will be described in more detail.
전술한 바와 같이, 본 발명은 내후성이 우수한 2,2,6,6-테트라메틸피페리딘이 도입된 우레탄 아크릴레이트, 이의 제조방법 및 이를 함유한 광경화형 수지 조성물에 관한 것으로서, 좀 더 상세하게는 환경친화적인 이관능성 반응형으로서 고속 경화가 가능하고, 내후성이 우수한 2,2,6,6-테트라메틸피페리딘이 도입된 우레탄 아크릴레이트, 이의 제조방법 및 이를 함유한 광경화형 수지 조성물에 관한 것이다.As described above, the present invention relates to a urethane acrylate in which 2,2,6,6-tetramethylpiperidine is introduced, a preparation method thereof, and a photocurable resin composition containing the same, in more detail. Is an environmentally-friendly bifunctional reaction type, which is capable of high-speed curing and has excellent weather resistance to urethane acrylate having a 2,2,6,6-tetramethylpiperidine introduced thereto, a method for preparing the same, and a photocurable resin composition containing the same. It is about.
본 발명에 따르면 내후성이 우수한 입체장애 (HALS)를 포함하는 신규한 광경화형 광안정제는 일단 경화되면 수세나 마모에도 용이하게 탈락하지 않고, 영구적으로 내후성을 부여할 수 있을 뿐만 아니라 올리고머 및 모노머의 상용성이 우수하기 때문에 수지 본래의 다양한 물성을 저하시키지 않고 내후성을 향상시킬 수 있다.According to the present invention, a novel photocurable light stabilizer including HALS, which is excellent in weatherability, does not easily fall off in water washing or abrasion once cured, and can impart weather resistance permanently, and also commercially available oligomers and monomers. Because of its excellent properties, weather resistance can be improved without lowering various physical properties of the resin.
본 발명에 따른 2,2,6,6-테트라메틸피페리딘이 도입된 우레탄 아크릴레이트는 하기 화학식 1로 표시된다:Urethane acrylate incorporating 2,2,6,6-tetramethylpiperidine according to the present invention is represented by the following general formula (1):
화학식 1Formula 1
상기 식에서, R1, R4및 R6는 각각 독립적으로 히드록시, 또는 하기 화학식 1a, 1b 또는 1c로 표시되는 화합물이며, R2, R3및 R5는 C2-C18의 알킬렌, 시클로헥실렌, 메틸렌디시클로헥실렌, 시클로헥실디메틸렌, 또는 1∼3의 산소원자 또는 메틸렌을 갖는 C4-C18의 알킬렌이고,Wherein R 1 , R 4 and R 6 are each independently hydroxy, or a compound represented by the following Formula 1a, 1b or 1c, and R 2 , R 3 and R 5 are alkylene of C 2 -C 18 , Cyclohexylene, methylenedicyclohexylene, cyclohexyldimethylene, or C 4 -C 18 alkylene having 1 to 3 oxygen atoms or methylene,
화학식 1aFormula 1a
화학식 1bFormula 1b
화학식 1cFormula 1c
상기 식에서, R7, R8, R9, R10및 R11은 각각 독립적으로 수소 또는 메틸이고, R12는 수소 또는 C1-C18의 알킬렌이며, n은 1∼18의 정수이고, m은 1∼4의 정수이다.Wherein R 7 , R 8 , R 9 , R 10 and R 11 are each independently hydrogen or methyl, R 12 is hydrogen or alkylene of C 1 -C 18 , n is an integer from 1 to 18, m is an integer of 1-4.
상기 화학식 1로 표시되는 신규한 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 반응형 우레탄 아크릴레이트의 제조방법은 3관능 이소시아누레이트 0.005몰∼0.2몰을 유기용매에 넣고 상온 내지 90℃의 온도로 유지시키면서 여기에 산화방지제, 촉매 및 중합금지제를 투입하고 2,2,6,6-테트라메틸피페리딘 화합물 0.005몰∼0.1몰을 30분 내지 4시간 동안 적가한 후, 40∼100℃의 온도에서 30분 내지 5시간 동안 교반 반응시킨 다음 히드록시기를 함유한 아크릴레이트 화합물 0.005몰∼0.3몰을 적가하여 1∼8시간 동안 반응시킨다.Method for preparing a reactive urethane acrylate in which the novel 2,2,6,6-tetramethylpiperidine derivative represented by Chemical Formula 1 is introduced is added 0.005 mol to 0.2 mol of trifunctional isocyanurate in an organic solvent. An antioxidant, a catalyst, and a polymerization inhibitor were added thereto while maintaining the temperature at room temperature to 90 ° C, and 0.005 to 0.1 mol of 2,2,6,6-tetramethylpiperidine compound was added dropwise for 30 minutes to 4 hours. Thereafter, the mixture was stirred for 30 minutes to 5 hours at a temperature of 40 to 100 ° C, and then 0.005 to 0.3 mol of an acrylate compound containing a hydroxyl group was added dropwise to react for 1 to 8 hours.
본 발명에 따른 반응용매는 테트라하이드로퓨란, 무수에테르, 디에틸 에테르, 헥산, 톨루엔 및 벤젠 등을 비롯한 통상의 유기 용매를 사용하는 것이 바람직하며, 이에 대한 특별한 제한은 없다.As the reaction solvent according to the present invention, it is preferable to use a conventional organic solvent including tetrahydrofuran, anhydrous ether, diethyl ether, hexane, toluene, benzene and the like, without particular limitation.
본 발명에 따른 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트는 각종 수지 및 도료와의 상용성이 우수하기 때문에 광경화형 수지에 함유되어 우수한 광안정제로서 사용될 수 있다. 본 발명에 따른 광경화형 수지 조성물은 적어도 하나 이상의 아크릴기를 갖는 아크릴계 프리폴리머 30∼70중량%; 1관능성 내지 다관능성인 아크릴계 모노머 또는 비닐 에테르계 모노머 20∼60중량%; 광개시제 2∼7중량%; 및 상기 화학식 1로 표시되는 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트를 포함한다.The urethane acrylate in which the 2,2,6,6-tetramethylpiperidine derivative is introduced according to the present invention can be used as an excellent light stabilizer because it is contained in a photocurable resin because of excellent compatibility with various resins and paints. . The photocurable resin composition according to the present invention comprises 30 to 70% by weight of an acrylic prepolymer having at least one acrylic group; 20 to 60% by weight of a monofunctional to polyfunctional acrylic monomer or vinyl ether monomer; 2-7 wt% of photoinitiator; And urethane acrylate to which 2,2,6,6-tetramethylpiperidine derivative represented by Chemical Formula 1 is introduced.
상기 화학식 1로 표시되는 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트의 첨가량은 0.1∼10중량%이 바람직하며, 더욱 바람직하게는 0.25∼5중량%이 좋다. 이 때, 상기 첨가량이 0.1 중량% 미만이면 양호한 광안정성을 부여할 수 없으며, 10중량%를 초과하면 도막의 종합 물성이 크게 저하되어 바람직하지 않다.The amount of the urethane acrylate to which the 2,2,6,6-tetramethylpiperidine derivative represented by Formula 1 is introduced is preferably 0.1 to 10% by weight, more preferably 0.25 to 5% by weight. At this time, if the addition amount is less than 0.1% by weight, good light stability cannot be imparted, and if it exceeds 10% by weight, the overall physical properties of the coating film are greatly reduced, which is not preferable.
본 발명에 따른 프리폴리머는 적어도 하나 이상의 아크릴 그룹을 갖는 1관능성 내지 다관능성의 아크릴계 수지로서 예를 들면, 폴리에스터 아크릴레이트, 우레탄 아크릴레이트 및 에폭시 아크릴레이트 등으로 이루어진 군으로부터 선택된 것이 바람직하다.The prepolymer according to the present invention is preferably a monofunctional to polyfunctional acrylic resin having at least one acrylic group, for example, selected from the group consisting of polyester acrylate, urethane acrylate, epoxy acrylate and the like.
또한, 본 발명에 따른 모노머는 1관능성 내지 다관능성인 아크릴계 모노머또는 비닐 에테르계 모노머가 바람직하며, 상기 아크릴계 모노머는 히드록시에틸 아크릴레이트(HEA), 히드록시에틸 메타아크릴레이트(HEMA), 1,6-헥산디올아크릴레이트(HDDA), 트리프로필렌 글리콜디아크릴레이트(TPGDA) 및 트리메틸올 프로판 트리아크릴레이트(TMPTA) 등으로 이루어진 군으로부터 선택된 것이 바람직하며, 상기 비닐 에테르계 모노머는 부탄디올 모노비닐에테르, 1,4-시클로헥산 디메탄올 모노비닐에테르 및 트리에틸렌글리콜 디비닐에테르 등으로 이루어진 군으로부터 선택된 것이 바람직하다.In addition, the monomer according to the present invention is preferably a mono- or polyfunctional acrylic monomer or a vinyl ether monomer, the acrylic monomer is hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), 1 , 6-hexanediol acrylate (HDDA), tripropylene glycol diacrylate (TPGDA) and trimethylol propane triacrylate (TMPTA) and the like are preferably selected from the group, the vinyl ether monomer is butanediol monovinyl ether , 1,4-cyclohexane dimethanol monovinyl ether, triethylene glycol divinyl ether and the like are preferable.
본 발명에 사용 가능한 광개시제는 자유라디칼계 광개시제로서는 1-히드록시 시클로헥실페닐케톤 또는 α,α-디메톡시-α'-히드록시 아세토 페논 등이 바람직하며, 현재 시판되는 스위스 시바가이사의 이가큐어(Irgacure) 184, 다로커(Darocur) 1173 또는 코오롱 유화의 UVICURE 204 등의 상품 등이 있다. 여기서, 상기 광개시제의 사용량은 최종생성물을 기준으로 약 2∼7중량%가 바람직한데, 이때 2중량% 미만이면 미반응 물질이 발생되어 물성이 저하되고, 7중량%를 초과하면 미반응 개시제가 잔류하여 내후성이 저하된다. 또한 선택적으로, 양이온계 광개시제와 기타 첨가제가 사용될 수도 있으며, 상기 광개시제를 사용하지 않고 전자선에 의해 본 발명의 수지 조성물을 가교화시켜도 무방하다.The photoinitiator usable in the present invention is preferably 1-hydroxy cyclohexylphenyl ketone or α, α-dimethoxy-α'-hydroxy acetophenone as a free radical type photoinitiator. Products such as Irgacure 184, Darocur 1173, or UVICURE 204 of Kolon Oil. Here, the amount of the photoinitiator is preferably about 2 to 7% by weight based on the final product, if less than 2% by weight unreacted substances are generated, the physical properties are lowered, if more than 7% by weight unreacted initiator is left The weather resistance is lowered. Also optionally, a cationic photoinitiator and other additives may be used, and the resin composition of the present invention may be crosslinked by an electron beam without using the photoinitiator.
또한, 본 발명에 따르면 상기 화학식 1로 표시되는 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트와 함께 통상적으로 사용되어온 광안정제로서 예를 들면, 히드록시벤조페논, 히드록시페닐 벤조트리아졸, 살리실레이트, 옥사닐라이드, 디케톤 또는 힌더드 아민계를 5.0중량% 미만의 범위내에서 혼용하여사용할 수 있다.In addition, according to the present invention, for example, hydroxybenzophenone, as a light stabilizer that has been commonly used with the urethane acrylate to which the 2,2,6,6-tetramethylpiperidine derivative represented by Formula 1 is introduced Hydroxyphenyl benzotriazoles, salicylates, oxanilides, diketones or hindered amines can be used interchangeably within the range of less than 5.0% by weight.
이하 실시예 및 비교예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples.
제조예 1Preparation Example 1
오일배스, 온도계, 환류냉각기, 적가펀넬 및 마그네틱 스터링바가 설치된 100㎖ 3구 플라스크네 3관능 이소시아누레이트 0.01몰과 톨루엔 30㎖를 넣고 교반하면서 온도를 50℃로 상승시킨 후 여기에 디부틸틴디라우레이트 0.03g 및 이가녹스 1076(시바가이기 상품명) 0.009g, 및 4-메톡시페놀 0.03g을 투입하였다. 상기 온도에서 4-히드록시-2,2,6,6-테트라메틸피페리딘 0.02 몰을 적가 후, 온도를 70℃로 승온하여 2시간 동안 반응시켰다. 여기에 펜타에리트리톨 트리아크릴레이트 0.01몰을 적가하여 4시간 동안 반응시켜 반응을 종료하였다.100 ml three-necked flask equipped with oil bath, thermometer, reflux cooler, dropping funnel and magnetic sterling bar. 0.03 g of laurate, 0.009 g of Iganox 1076 (Shibagai trade name), and 0.03 g of 4-methoxyphenol were added thereto. At this temperature, 0.02 mol of 4-hydroxy-2,2,6,6-tetramethylpiperidine was added dropwise, and the temperature was raised to 70 ° C. for 2 hours. 0.01 mol of pentaerythritol triacrylate was added dropwise thereto to react for 4 hours to complete the reaction.
제조예 2Preparation Example 2
펜타에리트리톨 트리아크릴레이트 대신 트리메틸올 프로판 다이아릴 아크릴레이트를 사용한 것을 제외하고는 상기 제조예 1과 동일한 방법으로 실시하였다.The same procedure as in Preparation Example 1 was conducted except that trimethylol propane diaryl acrylate was used instead of pentaerythritol triacrylate.
제조예 3Preparation Example 3
펜타에리트리톨 트리아크릴레이트 대신 다이펜타에릴트리톨 펜타아크릴레이트를 사용한 것을 제외하고는 상기 제조예 1과 동일한 방법으로 실시하였다.The same procedure as in Preparation Example 1 was conducted except that dipentaerythritol pentaacrylate was used instead of pentaerythritol triacrylate.
제조비교예 1Comparative Example 1
피페리딘 0.9g(0.01몰)과 빙초산 0.6g(0.01몰)을 무수 톨루엔 100㎖ 중의 α-메틸-신남알데히드 14.6g(0.01몰)과 디(2,2,6,6-테트라메틸-피페리딜)말로네이트 38.2g (0.1몰)의 용액에 가한다. 반응 혼합물을 3시간 동안 환류시킨 후 분리된 반응수를 반응 혼합물로부터 연속하여 제거하였다. 이를 냉각시킨 후, 상기 반응 혼합물을 매번 50㎖의 물로 3회 추출하여 유기상을 분리하고 황산나트륨으로 건조시킨 다음 여과 후 증류를 통해 농축시켰다. 이소프로판올로부터 잔류하는 잔사를 결정화하여 백색분말의 목적생성물을 얻었다.0.9 g (0.01 mole) of piperidine and 0.6 g (0.01 mole) of glacial acetic acid were added to 14.6 g (0.01 mole) of α-methyl-cinnaaldehyde in 100 ml of anhydrous toluene and di (2,2,6,6-tetramethyl-pi Ferridyl) malonate is added to a solution of 38.2 g (0.1 mol). The reaction mixture was refluxed for 3 hours and then the separated reaction water was continuously removed from the reaction mixture. After cooling, the reaction mixture was extracted three times with 50 ml each time to separate the organic phase, dried over sodium sulfate, filtered and concentrated by distillation. The residue remaining from isopropanol was crystallized to obtain the target product of the white powder.
실시예 1∼6 및 비교예 1∼3Examples 1-6 and Comparative Examples 1-3
하기 표 1에 나타낸 바와 같이, 상기 제조예 1∼3 및 제조 비교예에서 합성한 각각의 화합물을 광경화형 수지 조성물에 함유시켜 시험편을 다음과 같이 제작하였다.As shown in Table 1 below, each of the compounds synthesized in Preparation Examples 1 to 3 and Comparative Comparative Example was contained in the photocurable resin composition to prepare a test piece as follows.
광경화성수지 기본 조성물: 우레탄 아크릴레이트 50중량부, 하이드록시 에틸 아크릴레이트 15중량부, 트리메틸프로판 트리아크릴레이트 30중량부, 시바가이기사의 광개시제 5중량부로 구성된 광경화형 수지 98중량%에 광안정제를 하기 표 1에 나타낸 바와 같이 첨가하고, 혼합물을 폴리카보네이트 시트상에 약 20㎛ 두께로 코팅한후 자외선 경화시켜 시험편을 제작하였다.Photocurable resin base composition: Light stabilizer was added to 98% by weight of a photocurable resin composed of 50 parts by weight of urethane acrylate, 15 parts by weight of hydroxy ethyl acrylate, 30 parts by weight of trimethylpropane triacrylate, and 5 parts by weight of a photoinitiator of Ciba-Geigy Corporation. As shown in Table 1 below, the mixture was coated with a thickness of about 20 μm on a polycarbonate sheet, and then cured by UV to prepare a test piece.
1)힌더드아민 광안정제 : Tinnuvin 292, 시바가이기사 1) Hindered Amine Light Stabilizer: Tinnuvin 292
2)트리아졸계 광안정제 : Tinnuvin 1130, 시바가이기사 2) Triazole light stabilizer: Tinnuvin 1130
또한, 각각의 시험편에 대해서는 하기 항목 및 방법으로 측정한 후, 그 결과를 하기 표 2에 나타내었다.In addition, about each test piece, it measured by the following item and method, and the result is shown in following Table 2.
[측정항목 및 측정방법][Measurement Items and Methods]
(1) 내후성: 촉진내후성 시험기에서 50℃의 온도에서 313㎚의 파장을 방출하는 UV-B 램프를 사용하여 자외선을 조사한 후 기계적 강도 및 표면외관을 평가하였다.(1) Weather resistance: In the accelerated weather resistance tester, mechanical strength and surface appearance were evaluated after irradiating ultraviolet rays using a UV-B lamp emitting a wavelength of 313 nm at a temperature of 50 ° C.
(2) 인장강도: 시험편의 인장강도를 내후성 시험기의 광으로 조사하기 전과 소정기간 동안 조사한 후를 통상방법(ASTM-D638)에 따라 측정하였다.(2) Tensile strength: The tensile strength of the test piece was measured according to the conventional method (ASTM-D638) before and after irradiating with the light of the weather resistance tester for a predetermined period.
(3) 균열형성시간: 촉진내후성 시험기로 자외선이 조사된 시험편의 표면을10배 확대렌즈로 관찰하여 균열형성을 확인하였다. 균열형성시간은 균열형성이 시작되는 시간이다.(3) Crack formation time: The crack formation was confirmed by observing the surface of the test piece irradiated with the ultraviolet-ray with the 10 times magnification lens by the accelerated weather resistance tester. The crack formation time is the time at which crack formation begins.
(4) 색조: 촉진내후성 시험기에서 처리한 후 표면색상을 미놀타사의 칼라측정기를 사용하여 하기의 △E 값으로 나타내었다.(4) Color tone: The surface color after treatment in the accelerated weathering tester is represented by the following ΔE value using a color analyzer of Minolta.
여기서, ΔL: 밝기 변화폭, Δa: 적색 변화폭, Δb : 황색 변화폭Where ΔL: brightness change, Δa: red change, Δb: yellow change
(5) 광택도 : 입사각과 수광각이 각각 20。일 때의 반사율을 측정하여, 기준면의 광택도를 100으로 하였을 때의 백분율로 나타내었다.(5) Glossiness: The reflectance was measured when the incident angle and the received angle were 20 °, respectively, and were expressed as a percentage when the glossiness of the reference plane was 100.
(6) 연필경도 : JIS D0202로 측정하였다(UNI-PENCIL 사용).(6) Pencil hardness: It measured by JIS D0202 (using UNI-PENCIL).
상기 표 2로부터 알 수 있는 바와 같이, 본 발명에 따른 신규한 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트 및 이를 함유한 광경화형수지의 광안정성을 기존 제품과 비교 평가한 결과, 상기 화학식 1로 표시되는 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트를 함유한 수지가 종래의 광안정제를 함유한 수지에 비하여 내후성이 매우 우수하게 나타났다.As can be seen from Table 2, the urethane acrylate to which the novel 2,2,6,6-tetramethylpiperidine derivative according to the present invention is introduced and the light stability of the photocurable resin containing the same are compared with the existing products. As a result of the comparative evaluation, the resin containing the urethane acrylate to which the 2,2,6,6-tetramethylpiperidine derivative represented by the formula (1) was introduced was much better in weatherability than the resin containing the conventional light stabilizer. Appeared.
전술한 바와 같이, 본 발명은 환경친화적인 광경화형 광안정제로서 내후성 및 광안정성이 우수한 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트를 제공한다. 특히, 본 발명에 따른 2,2,6,6-테트라메틸피페리딘 유도체가 도입된 우레탄 아크릴레이트는 이관능성 반응형이므로 경화과정에서 고속 경화가 가능하고, 단관능 및 다관능성 모노머와의 조성비를 조절하므로써 내후성이 우수한 코팅도막을 얻을 수 있을 뿐만 아니라 제조공정이 단순하여 생산성을 향상시키고, 산업적인 활용도를 높힐 수 있다.As described above, the present invention provides a urethane acrylate in which a 2,2,6,6-tetramethylpiperidine derivative having excellent weather resistance and light stability is introduced as an environmentally friendly photocurable light stabilizer. In particular, the urethane acrylate in which the 2,2,6,6-tetramethylpiperidine derivative is introduced according to the present invention is a bifunctional reaction type, so that it is possible to cure at high speed during the curing process, and the composition ratio with the monofunctional and polyfunctional monomers. By controlling the not only can obtain a coating film excellent weather resistance, but also the manufacturing process is simple, it can improve the productivity, and increase the industrial utilization.
Claims (9)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010046847A KR20030011431A (en) | 2001-08-02 | 2001-08-02 | Photo-curable urethane acrylate having 2,2,6,6-tetramethylpiperidine derivatives and process for preparing thereof, and photo-curable resin composition containing the same |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020010046847A KR20030011431A (en) | 2001-08-02 | 2001-08-02 | Photo-curable urethane acrylate having 2,2,6,6-tetramethylpiperidine derivatives and process for preparing thereof, and photo-curable resin composition containing the same |
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| KR20030011431A true KR20030011431A (en) | 2003-02-11 |
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| KR1020010046847A KR20030011431A (en) | 2001-08-02 | 2001-08-02 | Photo-curable urethane acrylate having 2,2,6,6-tetramethylpiperidine derivatives and process for preparing thereof, and photo-curable resin composition containing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180002285A1 (en) * | 2014-12-22 | 2018-01-04 | 3M Innovative Properties Company | Sterically hindered alkyl and oxyalkyl amine light stabilizers |
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|---|---|---|---|---|
| US4317911A (en) * | 1976-07-08 | 1982-03-02 | Ciba-Geigy Corporation | Piperidine containing cyanuric acid derivatives |
| KR900004902A (en) * | 1988-09-08 | 1990-04-13 | 도날드 밀러 셀 | Binder for Coating Abrasives |
| US5182390A (en) * | 1990-10-29 | 1993-01-26 | Kyodo Chemical Company Limited | Isocyanuric acid derivative useful as a light stabilizer |
| JPH06293754A (en) * | 1993-04-06 | 1994-10-21 | Asahi Denka Kogyo Kk | New isocyanuric acid derivative |
| KR950032521A (en) * | 1994-02-22 | 1995-12-22 | 후지이 히로시 | Curing agent and cationic electrodeposition paint composition containing same |
| KR960010757A (en) * | 1994-09-27 | 1996-04-20 | 박원배 | Photocurable resin composition with excellent stain resistance and its products |
| KR970074891A (en) * | 1996-05-16 | 1997-12-10 | 김용구 | Polymerizable hydroxyalkyl quaternary ammonium salt and photocurable resin composition containing the same |
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2001
- 2001-08-02 KR KR1020010046847A patent/KR20030011431A/en not_active Application Discontinuation
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4317911A (en) * | 1976-07-08 | 1982-03-02 | Ciba-Geigy Corporation | Piperidine containing cyanuric acid derivatives |
| KR900004902A (en) * | 1988-09-08 | 1990-04-13 | 도날드 밀러 셀 | Binder for Coating Abrasives |
| US5182390A (en) * | 1990-10-29 | 1993-01-26 | Kyodo Chemical Company Limited | Isocyanuric acid derivative useful as a light stabilizer |
| JPH06293754A (en) * | 1993-04-06 | 1994-10-21 | Asahi Denka Kogyo Kk | New isocyanuric acid derivative |
| KR950032521A (en) * | 1994-02-22 | 1995-12-22 | 후지이 히로시 | Curing agent and cationic electrodeposition paint composition containing same |
| KR960010757A (en) * | 1994-09-27 | 1996-04-20 | 박원배 | Photocurable resin composition with excellent stain resistance and its products |
| KR970074891A (en) * | 1996-05-16 | 1997-12-10 | 김용구 | Polymerizable hydroxyalkyl quaternary ammonium salt and photocurable resin composition containing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180002285A1 (en) * | 2014-12-22 | 2018-01-04 | 3M Innovative Properties Company | Sterically hindered alkyl and oxyalkyl amine light stabilizers |
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