KR102460090B1 - (meth)acrylic-based resin composition and (meth)acrylic-based resin film - Google Patents

(meth)acrylic-based resin composition and (meth)acrylic-based resin film Download PDF

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KR102460090B1
KR102460090B1 KR1020220027963A KR20220027963A KR102460090B1 KR 102460090 B1 KR102460090 B1 KR 102460090B1 KR 1020220027963 A KR1020220027963 A KR 1020220027963A KR 20220027963 A KR20220027963 A KR 20220027963A KR 102460090 B1 KR102460090 B1 KR 102460090B1
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meth
acrylic
acrylic resin
film
resin composition
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KR20220034089A (en
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타케시 나가쿠라
마사토 갸쿠노
모에미 히로카미
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후지모리 고교 가부시키가이샤
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Abstract

본 발명은 얇은 막두께의 수지 필름을 얻기 위한 용액 캐스트법에 사용할 수 있고, 내절성, 내파단성(인장 파단 강도), 파단 신도, 내용제성(겔분율)이 우수한 (메타)아크릴계 수지 조성물 및 (메타)아크릴계 수지 필름을 제공한다. (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, (메타)아크릴계 폴리머가 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부와, 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머이다.The present invention can be used in a solution casting method for obtaining a resin film having a thin film thickness, and has excellent fold resistance, fracture resistance (tensile fracture strength), elongation at break, solvent resistance (gel fraction) and (meth)acrylic resin composition and ( Provided is a meth)acrylic resin film. A (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent, wherein the (meth)acrylic polymer is 80 parts by weight or more of methyl methacrylate, and the Tg of the homopolymer other than the methyl methacrylate is 0 ° C. or more, and a total of at least 100 parts by weight of at least one type of alkyl (meth)acrylate having a C1-C14 alkyl group and at least one type of copolymerizable monomer having a functional group capable of reacting with a crosslinking agent in a total of 1.0 to 20.0 It is a (meth)acrylic-type polymer which consists of a copolymer whose weight average molecular weight copolymerized by weight part is more than 100,000 and 1 million or less.

Description

(메타)아크릴계 수지 조성물 및 (메타)아크릴계 수지 필름{(METH)ACRYLIC-BASED RESIN COMPOSITION AND (METH)ACRYLIC-BASED RESIN FILM}(meth)acrylic resin composition and (meth)acrylic resin film {(METH)ACRYLIC-BASED RESIN COMPOSITION AND (METH)ACRYLIC-BASED RESIN FILM}

본 발명은 (메타)아크릴계 수지 필름 등의 형성에 바람직하게 사용되는 (메타)아크릴계 수지 조성물, 및 이를 사용한 (메타)아크릴계 수지 필름에 관한 것이다.The present invention relates to a (meth)acrylic resin composition preferably used for forming a (meth)acrylic resin film and the like, and a (meth)acrylic resin film using the same.

종래부터 고투명성, 가열 가공성, 내후성, 내약품성이 우수한 점에서, 전자 기기, 가전 제품, 자동차 내외장 부품, 건축 부재 등의 각종 기기 부품의 표면 피복에 사용하는 수지 필름으로서, (메타)아크릴계 수지 필름이 사용되고 있다.Conventionally, as a resin film used for surface coating of various device parts such as electronic devices, home appliances, automobile interior and exterior parts, and building members, in terms of high transparency, heat workability, weather resistance, and chemical resistance, (meth)acrylic resins film is being used.

또한, 근래에는 고투명성, 내후성 등이 우수한 점에서, (메타)아크릴계 수지 필름이 광학용 필름으로서 사용되고 있다.Moreover, in recent years, since it is excellent in high transparency, weather resistance, etc., the (meth)acrylic-type resin film is used as an optical film.

종래, 폴리메틸메타크릴레이트(PMMA) 수지로 이루어지는 (메타)아크릴계 수지 필름(PMMA 필름)을 제조하는 방법으로는, 생산성이 높은 점에서, PMMA 수지를 용융 압출법에 의해 제막하는 방법이 채용되고 있었다.Conventionally, as a method for producing a (meth)acrylic resin film (PMMA film) made of polymethyl methacrylate (PMMA) resin, a method of forming a PMMA resin by melt extrusion method is adopted from the viewpoint of high productivity. there was.

예를 들면, 특허문헌 1에는, 아크릴 수지 필름과 성형 수지를 일체화하는 부재에 바람직하게 사용 가능한 아크릴 수지 필름으로서, 특히 표면의 보호층 형성에 바람직한 도장 대체 아크릴 수지 필름이 개시되어 있다. 특허문헌 1에 기재된 발명에 따른 아크릴 수지 필름은 아크릴 수지 필름에 첨가하는 자외선 흡수제와 윤활제를 특정 종류로 조합하고, 추가로 이들 성분을 특정 함유량으로 하고 있다. 이 때문에, 특허문헌 1에서는, 표면의 보호층 형성에 사용하는 도장 대체 아크릴 수지 필름으로서, 바람직하게 사용할 수 있다고 하고 있다.For example, Patent Document 1 discloses a coating replacement acrylic resin film suitable for forming a protective layer on the surface as an acrylic resin film that can be preferably used for a member for integrating an acrylic resin film and a molding resin. The acrylic resin film which concerns on invention described in patent document 1 combines the ultraviolet absorber and lubricant added to an acrylic resin film in a specific kind, and is making these components into specific content further. For this reason, in patent document 1, it is said that it can use suitably as a coating replacement acrylic resin film used for surface protective layer formation.

또한, 특허문헌 2에는, 아크릴계 수지의 장점인 독특하게 아름다운 색조, 및 투명성이 저해되는 원인이 되는 고무 함유 그래프트 공중합체를 함유시키지 않고, 아크릴계 수지의 본질적인 결점인 내충격성을 개선하는 방법이 개시되어 있다. 특허문헌 2에 기재된 발명에 따른 아크릴계 수지 조성물은, 상기 수지 조성물을 용융 압출법에 의해 필름화할 때 용융 압출 온도를 높게 하면, 상기 그래프트 공중합체가 열분해함으로써 발생하는 분해 가스, 또는 블리드 아웃물에 의해, 캐스트 롤 등의 냉각 롤이 오염되어, 생산성이 떨어진다는 문제를 해결할 수 있다고 하고 있다.In addition, Patent Document 2 discloses a method for improving the impact resistance, which is an essential drawback of acrylic resins, without containing a rubber-containing graft copolymer that causes a uniquely beautiful color tone, which is an advantage of acrylic resins, and transparency is impaired. . In the acrylic resin composition according to the invention described in Patent Document 2, when the melt extrusion temperature is increased when the resin composition is filmed by the melt extrusion method, decomposition gas or bleed-out material generated by thermal decomposition of the graft copolymer , it is said that the problem that cooling rolls, such as a cast roll, are contaminated and productivity is inferior can be solved.

일본 공개특허공보 2009-286960호Japanese Patent Laid-Open No. 2009-286960 국제공개 제2016/139927호International Publication No. 2016/139927

그런데, 특허문헌 1에 기재된 발명에 따른 아크릴 수지 필름은, 열가소성 중합체를 포함하는 아크릴 수지 조성물의 혼합물을 탈기식 이축 압출기에서 혼련하여, 아크릴 수지 조성물의 펠릿을 얻은 후, 용융 압출기에서 용융한 수지 조성물을 T 다이에 압출하여 행하는 용융 압출법에 의해, 아크릴 수지 필름을 제막한 것이다. 또한, 특허문헌 1에 기재된 실시예 1∼6에서는, 막두께가 50∼125㎛인 아크릴 수지 필름이 얻어지고 있다. 그러나, 특허문헌 1에 기재된 발명에 따른 아크릴 수지 필름은 용융 압출법에 의해 제막한 수지 필름인 점에서, 막두께가 40㎛ 이하인 얇은 수지 필름을 얻는 것이 곤란하다는 문제를 갖고 있었다.By the way, in the acrylic resin film according to the invention described in Patent Document 1, a mixture of an acrylic resin composition containing a thermoplastic polymer is kneaded in a degassing twin screw extruder to obtain pellets of the acrylic resin composition, and then a resin composition melted in a melt extruder An acrylic resin film was formed into a film by the melt extrusion method performed by extruding a T-die. Moreover, in Examples 1-6 of patent document 1, the acrylic resin film whose film thickness is 50-125 micrometers is obtained. However, since the acrylic resin film which concerns on invention described in patent document 1 is a resin film formed into a film by the melt-extrusion method, it had the problem that it was difficult to obtain the thin resin film whose film thickness is 40 micrometers or less.

또한, 특허문헌 2에 기재된 발명에 따른 아크릴 수지 조성물은, 3∼4단계의 그래프트 중합 반응을 행하여 서서히 그래프트 공중합체를 완성시키기 때문에, 그래프트 공중합체를 얻는 공정에 장시간을 요한다는 문제를 갖고 있었다. 또한, 특허문헌 2의, 용융 압출법에 의해 아크릴 수지 필름을 제조한 실시예 6∼8에서는, 연신하지 않고 얻어진 아크릴 수지 필름의 막두께가 80㎛이며, 연신하지 않고 막두께가 40㎛ 이하인 얇은 수지 필름이 얻어지지 않았다.In addition, the acrylic resin composition according to the invention described in Patent Document 2 has a problem in that the process for obtaining the graft copolymer takes a long time because the graft copolymer is gradually completed by performing the graft polymerization reaction in 3 to 4 steps. Moreover, in Examples 6-8 which manufactured the acrylic resin film by the melt extrusion method of patent document 2, the film thickness of the acrylic resin film obtained without extending|stretching is 80 micrometers, and the film thickness of 40 micrometers or less without extending|stretching is thin. A resin film was not obtained.

이러한 가운데, 용융 압출법에 비해, 보다 간편한 수지 필름의 제막 방법이며, 박막화할 수 있는 이점이 있는 용액 캐스트법에 의해 PMMA 수지를 제막하는 방법이 요구되고 있었다. 본 발명자들은 용액 캐스트법에 의해 PMMA 수지를 제막하는 방법을 예의 검토했다. 그 결과, 특정 PMMA 수지 조성물을 사용함으로써, 용액 캐스트법에 의해 제막한 경우에도, 용융 압출법에 의해 제막한 것과 동등 이상의 우수한 물성을 갖는 PMMA 수지 필름이 얻어지는 것을 알아내어, 본 발명을 완성시킬 수 있었다.Among these, the method of forming a PMMA resin into a film by the solution casting method which is a more convenient film forming method of a resin film compared with the melt-extrusion method, and has the advantage of being able to thin film was calculated|required. The present inventors earnestly studied the method of forming a PMMA resin into a film by the solution casting method. As a result, it was found that by using a specific PMMA resin composition, a PMMA resin film having excellent physical properties equal to or higher than that produced by the melt extrusion method can be obtained even when a film is formed by the solution casting method, and the present invention can be completed. there was.

종래의 용융 압출법에 의해, (메타)아크릴계 수지 필름을 제막하는 방법의 경우에는, 40㎛ 이하의 두께로 박막화하는 것이 곤란했다. 한편, 용액 캐스트법에 의해, (메타)아크릴계 수지 필름을 제막하는 방법의 경우에는, 40㎛ 이하의 두께로 박막화하는 것이 가능하나, 얻어진 (메타)아크릴계 수지 필름의 물성으로서 내용제성 성능을 향상시키는 것이 어렵다는 문제가 있었다. 또한, 용액 캐스트법에 있어서는, (메타)아크릴계 수지 조성물에 함유하는 미가교된 PMMA 수지의 중량 평균 분자량을 100만 이상의 큰 값으로 할 필요가 있기 때문에, 당해 (메타)아크릴계 수지 조성물의 용액이 고점도여서, 제막 공정에서의 작업성이 양호하지 않다는 문제가 있었다.In the case of the method of forming a (meth)acrylic-type resin film into a film by the conventional melt-extrusion method, it was difficult to thin it to the thickness of 40 micrometers or less. On the other hand, in the case of the method of forming a (meth)acrylic resin film by the solution casting method, it is possible to thin the film to a thickness of 40 μm or less, but as a physical property of the obtained (meth)acrylic resin film, solvent resistance performance is improved. The problem was that it was difficult. In addition, in the solution casting method, since it is necessary to set the weight average molecular weight of the uncrosslinked PMMA resin contained in the (meth)acrylic resin composition to a large value of 1 million or more, the solution of the (meth)acrylic resin composition has a high viscosity. Therefore, there was a problem that the workability in the film forming process was not good.

본 발명은 얇은 막두께의 수지 필름을 얻기 위한 용액 캐스트법에 사용할 수 있는 (메타)아크릴계 수지 조성물로서, 제막한 수지 필름 등의 성형품이 내절성, 내파단성(인장 파단 강도), 파단 신도, 내용제성(겔분율)이 우수한 (메타)아크릴계 수지 조성물, 및 (메타)아크릴계 수지 필름을 제공하는 것을 과제로 한다.The present invention is a (meth)acrylic resin composition that can be used in a solution casting method for obtaining a thin film thickness resin film, wherein a molded article such as a resin film formed into a film has fold resistance, fracture resistance (tensile strength at break), elongation at break, content An object is to provide a (meth)acrylic resin composition excellent in formulation (gel fraction), and a (meth)acrylic resin film.

본 발명자들은 상기 과제를 해결하기 위해 예의 검토한 결과, (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 MMA(메틸메타크릴레이트)와, 상기 MMA 이외의 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트와, 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상을 특정 비율로 공중합시킨 공중합체로 이루어지는 (메타)아크릴계 폴리머로 함으로써, 이러한 (메타)아크릴계 수지 조성물을 사용하여 용액 캐스트법에 의해 얻어진 (메타)아크릴계 수지 필름은, 내절성, 내파단성(인장 파단 강도), 파단 신도, 내용제성(겔분율)이 우수한 것을 알아내어, 본 발명을 완성시킬 수 있었다. 즉, 본 발명은 특정 (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물을 가교시킨 수지층으로 이루어지는 (메타)아크릴계 수지 필름을 얻는 것을 기술 사상으로 하고 있다.As a result of the present inventors earnestly studying to solve the above problems, as a (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent, the (meth)acrylic polymer is MMA (methyl methacrylate) and the A copolymer obtained by copolymerizing at least one copolymerizable monomer having a functional group with an alkyl (meth)acrylate having a Tg of 0° C. or higher and having an alkyl group having C1-C14 carbon atoms in a specific ratio of a homopolymer other than MMA. By setting it as the (meth)acrylic-type polymer formed, the (meth)acrylic-type resin film obtained by the solution casting method using this (meth)acrylic-type resin composition has fold resistance, fracture resistance (tensile breaking strength), breaking elongation, solvent resistance ( Gel fraction) was found to be excellent, and the present invention was completed. That is, this invention is making the technical idea to obtain the (meth)acrylic-type resin film which consists of a resin layer which crosslinked the (meth)acrylic-type resin composition containing a specific (meth)acrylic-type polymer and a crosslinking agent.

상기 과제를 해결하기 위해, 본 발명은 (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부와, 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머인 것을 특징으로 하는 (메타)아크릴계 수지 조성물을 제공한다.In order to solve the above problems, the present invention is a (meth)acrylic polymer and a (meth)acrylic resin composition containing a crosslinking agent, wherein the (meth)acrylic polymer is 80 parts by weight or more of methyl methacrylate, and the methyl methacrylic Other than the rate, the Tg of the homopolymer is 0° C. or higher, and the total of 100 parts by weight of at least one or more alkyl (meth)acrylates having C1-C14 carbon atoms in the alkyl group, and a functional group capable of reacting with the crosslinking agent It provides a (meth)acrylic resin composition, characterized in that it is a (meth)acrylic polymer consisting of a copolymer having a weight average molecular weight of more than 100,000 and 1,000,000 or less by copolymerizing 1.0 to 20.0 parts by weight of at least one type of copolymerizable monomer in total.

상기 (메타)아크릴계 폴리머가 (A) 메틸메타크릴레이트 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 1∼20중량부의 합계 100중량부와, 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로서, (B) 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중에서 선택된 적어도 1종 이상의 모노머의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머인 것이 바람직하다.The (meth)acrylic polymer contains (A) 80 to 99 parts by weight of methyl methacrylate and an alkyl ( As a copolymerizable monomer having a total of 100 parts by weight of at least one or more 1 to 20 parts by weight of meth) acrylate and a functional group capable of reacting with the crosslinking agent, (B) a copolymerizable monomer having a hydroxyl group and a carboxyl group copolymerizable It is preferably a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of greater than 100,000 and not more than 1,000,000 obtained by copolymerizing 1.0 to 20.0 parts by weight of a total of at least one or more monomers selected from the group consisting of monomers.

상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군에서 선택된 1종 이상인 것이 바람직하다.It is preferable that the crosslinking agent is at least one selected from the group consisting of an epoxy compound, an aziridine compound, and an isocyanate compound.

또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 것을 특징으로 하는 (메타)아크릴계 수지 필름을 제공한다.In addition, the present invention provides a (meth)acrylic resin film, characterized in that it is a resin layer formed by crosslinking the (meth)acrylic resin composition.

또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 (메타)아크릴계 수지 필름의 한쪽 면 또는 양면에 점착층을 형성하여 이루어지는 것을 특징으로 하는 점착 시트를 제공한다.In addition, the present invention provides a pressure-sensitive adhesive sheet, characterized in that formed by forming an adhesive layer on one or both surfaces of a (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition.

또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 (메타)아크릴계 수지 필름을, 편광자의 한쪽 면 또는 양면에 형성하여 이루어지는 것을 특징으로 하는 편광 필름을 제공한다.Further, the present invention provides a polarizing film characterized in that the (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition, is formed on one or both surfaces of a polarizer.

본 발명에 의하면, 얇은 막두께의 수지 필름을 얻기 위한 용액 캐스트법에 사용할 수 있는 (메타)아크릴계 수지 조성물로서, 제막한 수지 필름 등의 성형품이 내절성, 내파단성(인장 파단 강도), 파단 신도, 내용제성(겔분율)이 우수한 (메타)아크릴계 수지 조성물, 및 (메타)아크릴계 수지 필름을 제공할 수 있다. According to the present invention, as a (meth)acrylic resin composition that can be used in a solution casting method for obtaining a resin film having a thin film thickness, a molded article such as a resin film formed into a film has fold resistance, fracture resistance (tensile strength at break), and elongation at break. , a (meth)acrylic resin composition having excellent solvent resistance (gel fraction), and a (meth)acrylic resin film can be provided.

한편, 본 발명에서는, 내용제성 시험 방법으로서, (메타)아크릴계 수지 필름의 시험편을 용제의 액 중에 소정 시간에 걸쳐 침지한 후, 상기 용제에 용출하지 않고 불용분(잔사)으로서 남은 (메타)아크릴계 수지 필름의 비율(이른바, 겔분율)을 측정하여, 내용제성을 시험했다. On the other hand, in the present invention, as a solvent resistance test method, after immersing a test piece of a (meth)acrylic resin film in a solution of a solvent for a predetermined time, the (meth)acrylic resin remaining as an insoluble content (residue) without eluting into the solvent The ratio (so-called gel fraction) of the resin film was measured and solvent resistance was tested.

또한, 종래 기술의 용융 압출법에 의해 (메타)아크릴계 수지 필름을 제막하는 경우에는, 수지 필름을 제막한 후, 1축 또는 2축 연신 가공을 실시하지 않는 한 막두께를 40㎛ 이하로 할 수 없었다. 한편, 본 발명의 (메타)아크릴계 수지 조성물을 사용하면, 용액 캐스트법만을 이용하여, 막두께가 40㎛ 이하인 박막의 (메타)아크릴계 수지 필름을 제조할 수 있어, 제조 공정이 보다 간편해짐과 함께, 제조 장치의 비용 저감을 도모할 수 있다.In addition, in the case of forming a (meth)acrylic resin film by the melt extrusion method of the prior art, the film thickness can be 40 μm or less unless uniaxial or biaxial stretching is performed after the resin film is formed. there was no On the other hand, if the (meth)acrylic resin composition of the present invention is used, a thin (meth)acrylic resin film having a film thickness of 40 μm or less can be manufactured using only the solution casting method, and the manufacturing process is simplified and , it is possible to reduce the cost of the manufacturing apparatus.

이하, 바람직한 실시형태에 기초하여 본 발명을 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on preferable embodiment.

본 실시형태의 (메타)아크릴계 수지 조성물은 (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부와, 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머인 것을 특징으로 한다.The (meth)acrylic resin composition of this embodiment is a (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent, wherein the (meth)acrylic polymer is 80 parts by weight or more of methyl methacrylate and the methyl meth A Tg of the homopolymer other than acrylate is 0° C. or higher, and a total of 100 parts by weight of at least one or more alkyl (meth)acrylates having C1-C14 carbon atoms in the alkyl group, and a functional group capable of reacting with the crosslinking agent It is characterized in that it is a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and not more than 1 million by copolymerizing 1.0 to 20.0 parts by weight of at least one type of copolymerizable monomer in total.

본 실시형태의 (메타)아크릴계 수지 조성물에 사용되는 (메타)아크릴계 폴리머는 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트를 주성분으로 하고, 특히 메틸메타크릴레이트(MMA)를 주성분으로 하는 (메타)아크릴계 폴리머인 것이 바람직하다. 상기 알킬(메타)아크릴레이트의 알킬기는 비고리형(직쇄, 분지형), 고리형(단환, 다환) 중 어느 하나여도 된다. 상기 (메타)아크릴계 폴리머는 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 2종 이상을 함유하는 공중합체인 것이 바람직하다. 상기 (메타)아크릴계 폴리머는 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상을 공중합시킨 공중합체인 것이 바람직하다. 여기서, (메타)아크릴계 폴리머의 주성분이란, 1종류로 (메타)아크릴계 폴리머의 50중량％ 이상의 비율을 차지하는 화합물, 또는 2종류 이상의 합계로 (메타)아크릴계 폴리머의 50중량％ 이상의 비율을 차지하는 화합물군을 의미한다. 즉, (메타)아크릴계 폴리머의 100중량부 중, 주성분이 50중량부 이상인 비율을 차지하는 경우이다. 한편, 이하의 설명에 있어서, 모노머에 대해, 단순히 Tg라고 하는 경우에는, 호모폴리머의 Tg를 가리키는 경우가 있다.The (meth)acrylic polymer used in the (meth)acrylic resin composition of this embodiment has an alkyl (meth)acrylate having C1-C14 carbon atoms in the alkyl group as a main component, especially methyl methacrylate (MMA) as a main component It is preferable that it is a (meth)acrylic-type polymer. The alkyl group of the said alkyl (meth)acrylate may be either acyclic (linear, branched) or cyclic (monocyclic, polycyclic). It is preferable that the said (meth)acrylic-type polymer is a copolymer containing at least 2 or more types of C1-C14 alkyl (meth)acrylate of carbon number of an alkyl group. The (meth)acrylic polymer is preferably a copolymer obtained by copolymerizing at least one kind of alkyl (meth)acrylate having a Tg of 0° C. or higher of the homopolymer and C1-C14 alkyl group. Here, the main component of the (meth)acrylic polymer is a compound that accounts for 50% by weight or more of the (meth)acrylic polymer in one type, or a compound group that accounts for 50% by weight or more of the (meth)acrylic polymer in a total of two or more types means That is, it is a case where the main component occupies a ratio of 50 parts by weight or more among 100 parts by weight of the (meth)acrylic polymer. In addition, in the following description, when simply Tg is referred to as a monomer, it may refer to Tg of a homopolymer.

상기 (메타)아크릴계 폴리머에 있어서, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트로는, 메틸(메타)아크릴레이트, 에틸메타크릴레이트, n-프로필메타크릴레이트, 이소프로필메타크릴레이트, n-부틸메타크릴레이트, 이소부틸메타크릴레이트, s-부틸메타크릴레이트, t-부틸(메타)아크릴레이트, n-펜틸메타크릴레이트, 이소펜틸메타크릴레이트, n-헥실메타크릴레이트, 이소헥실메타크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트로 이루어지는 화합물군에서 선택된 1종 이상을 들 수 있다. 여기서, (메타)아크릴레이트는 아크릴레이트 또는 메타크릴레이트의 적어도 한쪽을 의미한다.In the (meth)acrylic polymer, the Tg of the homopolymer is 0°C or higher, and the alkyl (meth)acrylate having C1-C14 carbon atoms in the alkyl group is methyl (meth)acrylate, ethyl methacrylate, n -Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl (meth) acrylate, n-pentyl methacrylate, isopentyl One selected from the group consisting of methacrylate, n-hexyl methacrylate, isohexyl methacrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate more can be mentioned. Here, (meth)acrylate means at least one of an acrylate or a methacrylate.

상기 (메타)아크릴계 폴리머에 있어서, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트로는, 알킬기의 탄소수가 C1∼C6인 알킬(메타)아크릴레이트가 바람직하고, 알킬기의 탄소수가 C1∼C4인 알킬(메타)아크릴레이트가 보다 바람직하다. 또한, 메틸메타크릴레이트 이외의, 알킬기의 탄소수가 C1∼C4인 알킬(메타)아크릴레이트 중에서는, 메틸아크릴레이트, 에틸메타크릴레이트, n-프로필메타크릴레이트, 이소프로필메타크릴레이트, n-부틸메타크릴레이트, 이소부틸메타크릴레이트, s-부틸메타크릴레이트, t-부틸아크릴레이트, t-부틸메타크릴레이트로 이루어지는 화합물군에서 선택된 1종 이상인 것이 특히 바람직하다.In the above (meth)acrylic polymer, the Tg of the homopolymer is 0° C. or higher, and the alkyl (meth)acrylate having C1-C14 carbon atoms in the alkyl group is an alkyl (meth)acryl group having C1-C6 carbon atoms. A rate is preferable, and the alkyl (meth)acrylate whose carbon number of an alkyl group is C1-C4 is more preferable. Moreover, in the C1-C4 alkyl (meth)acrylate of C1-C4 alkyl groups other than methyl methacrylate, methyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n- At least one selected from the group consisting of butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl acrylate and t-butyl methacrylate is particularly preferable.

또한, 상기 (메타)아크릴계 폴리머에 있어서, (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부 중, 메틸메타크릴레이트를 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 20중량부 이하의 비율로 함유하는 것이 바람직하고, 메틸메타크릴레이트를 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 1∼20중량부의 비율로 함유하는 것이 보다 바람직하다.Further, in the (meth)acrylic polymer, (A) methyl methacrylate and a homopolymer other than methyl methacrylate have a Tg of 0° C. or higher, and an alkyl (meth) having C1-C14 carbon atoms in the alkyl group. ) In a total of 100 parts by weight of at least one or more of the acrylates, 80 parts by weight or more of methyl methacrylate and Tg of the homopolymer other than the methyl methacrylate is 0° C. or more, and the number of carbon atoms in the alkyl group is C1 to It is preferable to contain at least one type of C14 alkyl (meth)acrylate in a ratio of 20 parts by weight or less in total, and 80 to 99 parts by weight of methyl methacrylate and a homopolymer other than the methyl methacrylate. It is more preferable to contain in a ratio of 1-20 weight part in total of at least 1 type or more of alkyl (meth)acrylate whose Tg is 0 degreeC or more and C1-C14 carbon number of an alkyl group is C1-C14.

상기 (메타)아크릴계 폴리머가 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부에 대해, 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부의 비율로 함유하는 것이 바람직하고, 1.0∼12.0중량부의 비율로 함유하는 것이 보다 바람직하며, 1.0∼9.0중량부의 비율로 함유하는 것이 특히 바람직하다.The (meth)acrylic polymer is an alkyl (meth)acrylate in which the Tg of the homopolymer other than the (A) methyl methacrylate and the methyl methacrylate is 0° C. or higher, and the carbon number of the alkyl group is C1-C14. It is preferable to contain in a ratio of 1.0 to 20.0 parts by weight in total of at least one copolymerizable monomer having a functional group capable of reacting with the crosslinking agent, and 1.0 to 12.0 parts by weight with respect to 100 parts by weight in total of at least one or more of It is more preferable to contain it, and it is especially preferable to contain it in the ratio of 1.0-9.0 weight part.

상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로는, (B) 수산기를 갖는 공중합 가능한 모노머, 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중에서 선택된 적어도 1종 이상의 모노머를 들 수 있다. 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머는 수산기를 갖는 공중합 가능한 모노머만이어도 되고, 카르복실기를 갖는 공중합 가능한 모노머만이어도 되며, 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머의 양쪽을 병용해도 된다.Examples of the copolymerizable monomer having a functional group capable of reacting with the crosslinking agent include (B) at least one monomer selected from the group consisting of a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group. The copolymerizable monomer having a functional group capable of reacting with the crosslinking agent may be only a copolymerizable monomer having a hydroxyl group, may be only a copolymerizable monomer having a carboxyl group, both a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group You may use it together.

상기 수산기를 갖는 공중합 가능한 모노머로는, 8-히드록시옥틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트 등의 히드록시알킬(메타)아크릴레이트류나, N-히드록시(메타)아크릴아미드, N-히드록시메틸(메타)아크릴아미드, N-히드록시에틸(메타)아크릴아미드 등의 수산기 함유 (메타)아크릴아미드류 등으로 이루어지는 화합물군 중에서 선택된 적어도 1종 이상인 것이 바람직하다.Examples of the copolymerizable monomer having a hydroxyl group include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. ) hydroxyalkyl (meth)acrylates such as acrylates, and hydroxyl groups such as N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide It is preferable that it is at least 1 sort(s) or more selected from the compound group which consists of (meth)acrylamides, etc.

상기 카르복실기를 갖는 공중합 가능한 모노머로는, (메타)아크릴산, 카르복시에틸(메타)아크릴레이트, 카르복시펜틸(메타)아크릴레이트, 2-(메타)아크릴로일옥시에틸헥사히드로프탈산, 2-(메타)아크릴로일옥시프로필헥사히드로프탈산, 2-(메타)아크릴로일옥시에틸프탈산, 2-(메타)아크릴로일옥시에틸숙신산, 2-(메타)아크릴로일옥시에틸말레산, 카르복시폴리카프로락톤모노(메타)아크릴레이트, 2-(메타)아크릴로일옥시에틸테트라히드로프탈산 등으로 이루어지는 화합물군 중에서 선택된 적어도 1종 이상인 것이 바람직하다.As the copolymerizable monomer having a carboxyl group, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) Acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl maleic acid, carboxypolycaprolactone It is preferable that it is at least 1 sort(s) or more selected from the compound group which consists of mono(meth)acrylate, 2-(meth)acryloyloxyethyl tetrahydrophthalic acid, etc.

상기 아크릴계 폴리머는 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부에 대해, 상기 (B) 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중에서 선택된 적어도 1종 이상의 모노머의 합계 1.0∼20.0중량부의 비율로 함유하는 것이 바람직하다.In the acrylic polymer, at least one of (A) methyl methacrylate and an alkyl (meth) acrylate having a Tg of 0° C. or higher and a C1-C14 alkyl group other than the methyl methacrylate. It is preferable to contain in a ratio of 1.0 to 20.0 parts by weight of a total of at least one or more monomers selected from the group consisting of (B) a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group with respect to a total of 100 parts by weight of the above species. do.

상기 아크릴계 폴리머의 제조 방법은 특별히 한정되는 것이 아니며, 용액 중합법, 유화 중합법 등, 적절히 공지의 중합 방법이 사용 가능하다. 상기 아크릴계 폴리머는 중량 평균 분자량이 10만 초과 100만 이하인 공중합체인 것이 바람직하고, 중량 평균 분자량이 10만 초과 95만 이하인 공중합체인 것이 보다 바람직하며, 중량 평균 분자량이 10만 초과 90만 이하인 공중합체인 것이 특히 바람직하다. 상기 아크릴계 폴리머의 중량 평균 분자량이 10만 이하이면, (메타)아크릴계 수지 조성물을 가교해도 우수한 물성을 갖는 (메타)아크릴계 수지 필름 등의 성형품이 얻어지기 어려워진다. 상기 아크릴계 폴리머의 중량 평균 분자량이 100만보다 크면, (메타)아크릴계 수지 조성물의 용액이 고점도가 되어, 제막 공정의 작업성이 양호하지 않다.The manufacturing method of the said acrylic polymer is not specifically limited, Well-known polymerization methods, such as a solution polymerization method and an emulsion polymerization method, can be used suitably. The acrylic polymer is preferably a copolymer having a weight average molecular weight of more than 100,000 and 1 million or less, more preferably a copolymer having a weight average molecular weight of more than 100,000 and 950,000 or less, and a copolymer having a weight average molecular weight of more than 100,000 and 900,000 or less Especially preferred. When the weight average molecular weight of the acrylic polymer is 100,000 or less, it becomes difficult to obtain a molded article such as a (meth)acrylic resin film having excellent physical properties even if the (meth)acrylic resin composition is crosslinked. When the weight average molecular weight of the said acrylic polymer is larger than 1 million, the solution of a (meth)acrylic-type resin composition will become high viscosity, and workability|operativity of a film forming process is not favorable.

상기 가교제로는, 상기 (메타)아크릴계 폴리머가 갖는 관능기와, 가교 반응할 수 있는 가교성 관능기를 갖는 화합물을 들 수 있다. 상기 가교제는 상기 (메타)아크릴계 수지 조성물의 보존 안정성 등의 관점에서, 상온(일반적으로는 5∼35℃)에서는 가교 반응이 일어나기 어렵고, 소정 온도 이상으로 가열하면 가교 반응이 개시되는 화합물인 것이 바람직하다.As said crosslinking agent, the compound which has the functional group which the said (meth)acrylic-type polymer has, and the crosslinkable functional group which can crosslinking-react is mentioned. The crosslinking agent is preferably a compound in which the crosslinking reaction hardly occurs at room temperature (generally 5 to 35° C.) from the viewpoint of storage stability of the (meth)acrylic resin composition, and the crosslinking reaction is initiated when heated to a predetermined temperature or higher. do.

상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군에서 선택된 1종 이상인 것이 바람직하다. 본 실시형태의 (메타)아크릴계 수지 조성물은 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부에 대해, 상기 가교제를 0.01∼10중량부의 비율로 함유하는 것이 바람직하다.It is preferable that the crosslinking agent is at least one selected from the group consisting of an epoxy compound, an aziridine compound, and an isocyanate compound. In the (meth)acrylic resin composition of the present embodiment, the Tg of the homopolymer other than the (A) methyl methacrylate and the methyl methacrylate is 0° C. or higher, and the alkyl group having C1-C14 carbon atoms ( It is preferable to contain the said crosslinking agent in the ratio of 0.01-10 weight part with respect to a total of 100 weight part of at least 1 or more types of meth)acrylate.

상기 에폭시 화합물로 이루어지는 가교제(에폭시계 가교제)로는, 2관능 이상의 에폭시 화합물이면 특별히 한정되지 않으나, 예를 들면, 폴리올류(디올류, 글리콜류, 비스페놀류를 포함한다)의 폴리글리시딜에테르, 디카르복실산의 디글리시딜에스테르, 디글리시딜 치환 아민류, 테트라글리시딜 치환 디아민류 등으로 이루어지는 화합물군으로부터 선택되는 적어도 1종 이상을 들 수 있다.The crosslinking agent (epoxy-based crosslinking agent) made of the above epoxy compound is not particularly limited as long as it is a bifunctional or more epoxy compound, for example, polyglycidyl ether of polyols (including diols, glycols, and bisphenols); At least 1 sort(s) or more chosen from the compound group which consists of diglycidyl ester of dicarboxylic acid, diglycidyl-substituted amines, tetraglycidyl-substituted diamines, etc. are mentioned.

상기 에폭시계 가교제 중, 폴리올류 폴리글리시딜에테르로는 예를 들면, 에틸렌글리콜디글리시딜에테르, 프로필렌글리콜디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 레조르신디글리시딜에테르, 글리세롤폴리글리시딜에테르, 트리메틸올프로판폴리글리시딜에테르, 펜타에리트리톨폴리글리시딜에테르, 소르비톨폴리글리시딜에테르 등을 들 수 있다.Among the epoxy-based crosslinking agents, polyol polyglycidyl ethers include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol. Diglycidyl ether, polyethylene glycol diglycidyl ether, resorcinol diglycidyl ether, glycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether Cidyl ether etc. are mentioned.

또한, 디카르복실산의 디글리시딜에스테르로는 예를 들면, 아디프산디글리시딜에스테르, 프탈산디글리시딜에스테르 등을 들 수 있다.Moreover, as diglycidyl ester of dicarboxylic acid, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, etc. are mentioned, for example.

또한, 디글리시딜 치환 아민류로는 예를 들면, N,N-디글리시딜아닐린, N,N-디글리시딜톨루이딘 등을 들 수 있다.Moreover, as diglycidyl-substituted amines, N,N- diglycidyl aniline, N,N- diglycidyl toluidine, etc. are mentioned, for example.

또한, 테트라글리시딜 치환 디아민류로는, 1,3-비스(N,N-디글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일렌디아민 등을 들 수 있다.Examples of tetraglycidyl-substituted diamines include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m-xyl rendiamine and the like.

상기 아지리딘 화합물로 이루어지는 가교제(아지리딘계 가교제)로는, 2관능 이상의 아지리딘 화합물, 1분자 중에 2개 이상의 아지리딘계 관능기를 갖는 화합물 등이면 특별히 한정되지 않는다. 아지리딘계 관능기로는, 1-아지리디닐기[-N(CH2)2], 2-아지리디닐기, 메틸기 등의 치환기를 갖는 치환 아지리디닐기 등을 들 수 있다. 아지리딘계 가교제의 구체예로는 예를 들면, 다음의 (1)∼(2)와 같은, 폴리이소시아네이트 화합물과 아지리딘의 부가 생성물, 다음의 (3)∼(4)와 같은, 폴리올폴리아크릴레이트 화합물과 아지리딘의 부가 생성물, 다음의 (5)∼(7)과 같은. 그 외의 폴리아크리딘 화합물을 들 수 있다.The crosslinking agent (aziridine-based crosslinking agent) comprising the aziridine compound is not particularly limited as long as it is a bifunctional or more functional aziridine compound, a compound having two or more aziridine-based functional groups in one molecule, or the like. Examples of the aziridine-based functional group include a substituted aziridinyl group having a substituent such as a 1-aziridinyl group [-N(CH 2 ) 2 ], a 2-aziridinyl group, and a methyl group. Specific examples of the aziridine-based crosslinking agent include, for example, an addition product of a polyisocyanate compound and aziridine as shown in (1) to (2) below, and polyol polyacrylate as shown in (3) to (4) below. Adducts of compounds and aziridine, as in the following (5) to (7). Other polyacridine compounds are mentioned.

(1) 4,4'-비스[(1-아지리디닐)카르보닐아미노]디페닐메탄(1) 4,4'-bis[(1-aziridinyl)carbonylamino]diphenylmethane

(CH2)2NCONH-C6H4CH2C6H4-NHCON(CH2)2 (CH 2 ) 2 NCONH-C 6 H 4 CH 2 C 6 H 4 -NHCON(CH 2 ) 2

(2) 1,6-비스[(1-아지리디닐)카르보닐아미노]헥산(2) 1,6-bis[(1-aziridinyl)carbonylamino]hexane

(CH2)2NCONH-(CH2)6-NHCON(CH2)2 (CH 2 ) 2 NCONH-(CH 2 ) 6 -NHCON(CH 2 ) 2

(3) 트리메틸올프로판-트리스[2-(1-아지리디닐)프로피오네이트](3) trimethylolpropane-tris[2-(1-aziridinyl)propionate]

CH3CH2C[CH2O-COCH2CH2N(CH2)2]3 CH 3 CH 2 C[CH 2 O-COCH 2 CH 2 N(CH 2 ) 2 ] 3

(4) 테트라메틸올메탄-트리스[2-(1-아지리디닐)프로피오네이트](4) tetramethylolmethane-tris[2-(1-aziridinyl)propionate]

HOCH2C[CH2O-COCH2CH2N(CH2)2]3 HOCH 2 C[CH 2 O-COCH 2 CH 2 N(CH 2 ) 2 ] 3

(5) 트리스(1-아지리디닐)포스핀옥사이드(5) tris (1-aziridinyl) phosphine oxide

O=P[N(CH2)2]3 O=P[N(CH 2 ) 2 ] 3

(6) 트리스(1-아지리디닐)포스핀설피드(6) tris(1-aziridinyl)phosphinesulfide

S=P[N(CH2)2]3 S=P[N(CH 2 ) 2 ] 3

(7) 2,4,6-트리스(1-아지리디닐)-1,3,5-트리아진(7) 2,4,6-tris(1-aziridinyl)-1,3,5-triazine

(C3N3)[N(CH2)2]3 (C 3 N 3 )[N(CH 2 ) 2 ] 3

상기 이소시아네이트 화합물로 이루어지는 가교제(이소시아네이트계 가교제)로는, 헥사메틸렌디이소시아네이트(HDI), 이소포론디이소시아네이트(IPDI), 디페닐메탄디이소시아네이트(MDI), 톨릴렌디이소시아네이트(TDI), 자일릴렌디이소시아네이트(XDI) 등의 2관능 이소시아네이트(디이소시아네이트 화합물)나, 이들의 뷰렛 변성체, 이소시아누레이트 변성체, 어덕트체 등의 3관능 이상의 폴리이소시아네이트 화합물로 이루어지는 화합물군으로부터 선택되는 적어도 1종 이상을 들 수 있다. 여기서, 3관능 이상의 어덕트체는 디이소시아네이트 화합물과, 트리메틸올프로판, 글리세린 등의 3가 이상의 폴리올의 어덕트체를 들 수 있다.Examples of the crosslinking agent (isocyanate-based crosslinking agent) comprising the isocyanate compound include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate ( At least one or more selected from the group consisting of difunctional isocyanates (diisocyanate compounds) such as XDI), trifunctional or more than trifunctional polyisocyanate compounds such as burette-modified products, isocyanurate-modified products and adducts thereof can be heard Here, the adduct body of trivalent or more trivalent or more trivalent polyols, such as a diisocyanate compound and trimethylol propane and glycerol, is mentioned as an adduct body more than trifunctional.

상기 (메타)아크릴계 수지 조성물은 상술한 첨가제에 한정하지 않고, 계면 활성제, 경화 촉진제, 경화 지연제, 가소제, 충전제, 윤활제, 가공 보조제, 노화 방지제, 열안정제, 광안정제, 산화 방지제, 대전 방지제, 착색제, 자외선 흡수제, 적외선 흡수제 등의 공지의 첨가제가 적절히 배합되어도 된다. 이들 첨가제는 단독으로, 또는 2종 이상을 병용할 수 있다.The (meth)acrylic resin composition is not limited to the above additives, but a surfactant, a curing accelerator, a curing retardant, a plasticizer, a filler, a lubricant, a processing aid, an anti-aging agent, a heat stabilizer, a light stabilizer, an antioxidant, an antistatic agent, Well-known additives, such as a coloring agent, a ultraviolet absorber, and an infrared absorber, may be mix|blended suitably. These additives are independent or can use 2 or more types together.

상기 (메타)아크릴계 수지 조성물은 소정 형상으로 성형 또는 도포한 후, 상기 (메타)아크릴계 폴리머와 상기 가교제를 반응시킴으로써 경화시킬 수 있다. 상기 (메타)아크릴계 수지 조성물로부터 얻어지는 성형품으로는, 특별히 한정되지 않으나, 필름, 판(시트), 봉(로드), 섬유(파이버) 등을 들 수 있다. 상기 성형품의 성형 방법은 특별히 한정되지 않으나, 캐스트 성형, 적층 성형, 압출 성형 등을 들 수 있다. 상기 (메타)아크릴계 수지 조성물을 기재 상에 도포하는 경우에는 예를 들면, 용액 코팅에 의해 당해 기재 상에 수지막을 형성할 수 있다. 당해 기재로는, 특별히 한정되지 않으나, 수지 필름, 이형 필름, 종이 기재, 금속박, 적층체 등을 들 수 있다.The (meth)acrylic resin composition may be molded or coated in a predetermined shape, and then cured by reacting the (meth)acrylic polymer with the crosslinking agent. Although it does not specifically limit as a molded article obtained from the said (meth)acrylic-type resin composition, A film, a board (sheet), a rod (rod), a fiber (fiber), etc. are mentioned. Although the molding method of the said molded article is not specifically limited, Cast molding, lamination molding, extrusion molding, etc. are mentioned. When the (meth)acrylic resin composition is applied on a substrate, a resin film may be formed on the substrate by, for example, solution coating. Although it does not specifically limit as said base material, A resin film, a release film, a paper base material, metal foil, a laminated body, etc. are mentioned.

상기 (메타)아크릴계 수지 조성물에 함유되어 있는 상기 가교제가 가열에 의해 가교 반응을 개시하는 열 가교제인 경우, 상기 성형품의 성형시에 있어서 상기 아크릴계 폴리머를 가열 용융시켜 유동화시키는 것이 아니라, 상기 (메타)아크릴계 수지 조성물의 용액으로서 유동화시키는 것이 바람직하다. 상기 (메타)아크릴계 수지 조성물의 용액을 얻기 위한 용제로는, 상기 아크릴계 폴리머의 관능기 및 상기 가교제의 반응성을 저해하지 않고, 상기 아크릴계 폴리머를 용해시킬 수 있으면 특별히 한정되지 않는다. 상기 용제로는 톨루엔 등의 탄화수소계 용제, 에탄올이나 이소프로필알코올 등의 알코올계 용제, 디에틸에테르나 테트라히드로푸란 등의 에테르계 용제, 아세톤이나 메틸에틸케톤(MEK) 등의 케톤계 용제, 초산에틸 등의 에스테르계 용제 등을 들 수 있다. 상기 아크릴계 폴리머를 용액 중합법에 의해 제조한 경우, 중합에 사용한 용제의 적어도 일부가 상기 (메타)아크릴계 수지 조성물의 용제의 적어도 일부가 되어도 된다.When the crosslinking agent contained in the (meth)acrylic resin composition is a thermal crosslinking agent that initiates a crosslinking reaction by heating, the (meth) It is preferable to make it fluidize as a solution of an acrylic resin composition. The solvent for obtaining a solution of the (meth)acrylic resin composition is not particularly limited as long as it can dissolve the acrylic polymer without inhibiting the reactivity of the functional group of the acrylic polymer and the crosslinking agent. Examples of the solvent include hydrocarbon solvents such as toluene, alcohol solvents such as ethanol and isopropyl alcohol, ether solvents such as diethyl ether and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone (MEK), and acetic acid Ester solvents, such as ethyl, etc. are mentioned. When the said acrylic polymer is manufactured by the solution polymerization method, at least a part of the solvent used for superposition|polymerization may become at least a part of the solvent of the said (meth)acrylic-type resin composition.

본 실시형태의 (메타)아크릴계 수지 필름은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 것을 특징으로 한다. 상기 (메타)아크릴계 수지 필름은 예를 들면, 용액 캐스트법을 사용함으로써, 상기 (메타)아크릴계 수지 조성물의 용액을 소정의 기재 상에 도포하여 박막을 형성한 후, 가열 건조시켜 상기 박막으로부터 용제를 휘발시킴과 함께 가교시킴으로써 제조할 수 있다. 상기 기재로는, 고정된 평면에 한정하지 않고, 수지 필름의 롤체로부터 되감긴 수지 필름, 가동 벨트, 드럼 등을 들 수 있다. 상기 기재의 표면 성상은 평활면이 바람직하나, 기재에 소정의 요철을 형성함으로써, 얻어지는 상기 (메타)아크릴계 수지 필름의 표면에 요철을 전사하는 것도 가능하다.The (meth)acrylic resin film of this embodiment is a resin layer formed by bridge|crosslinking the said (meth)acrylic resin composition, It is characterized by the above-mentioned. The (meth)acrylic resin film is, for example, by using a solution casting method, by applying a solution of the (meth)acrylic resin composition on a predetermined substrate to form a thin film, then heat-drying to remove the solvent from the thin film It can manufacture by crosslinking with volatilization. As said base material, it is not limited to a fixed plane, A resin film rewound from the roll body of a resin film, a movable belt, a drum, etc. are mentioned. The surface property of the substrate is preferably a smooth surface, but it is also possible to transfer the unevenness to the surface of the (meth)acrylic resin film obtained by forming predetermined unevenness on the substrate.

상기 용액 캐스트법에 의해 얻어진 상기 (메타)아크릴계 수지 필름은 길이 방향, 폭 방향 등의 소정 방향으로 연신해도 되고, 무연신인 상태로 해도 된다. 광학용 필름의 용도에 있어서, 이방성을 저감할 필요가 있는 경우에는 상기 (메타)아크릴계 수지 필름을 무연신 필름으로 하는 것이 바람직하다. 상기 (메타)아크릴계 수지 필름의 길이 방향 및 폭 방향으로 연신하는 조작을 추가하여, 이축 연신 필름으로 가공해도 된다. 한편, 필름의 이방성으로는, 「파단 신도」 등의 기계적 특성의 이방성에 한정하지 않고, 「복굴절률」 등의 광학 이방성도 들 수 있다.The said (meth)acrylic-type resin film obtained by the said solution casting method may be extended|stretched in predetermined directions, such as a longitudinal direction and a width direction, and it is good also as a non-stretched state. The use of the optical film WHEREIN: When it is necessary to reduce anisotropy, it is preferable to use the said (meth)acrylic-type resin film as a non-stretched film. You may process into a biaxially stretched film by adding operation of extending|stretching in the longitudinal direction and the width direction of the said (meth)acrylic-type resin film. In addition, as anisotropy of a film, not only the anisotropy of mechanical properties, such as "elongation at break", but optical anisotropy, such as a "birefringence," is also mentioned.

상기 (메타)아크릴계 수지 필름의 기계적 특성은 용도에도 의존하나, 점착 시트, 광학용 필름, 표면 보호 필름, 공정 필름 등에 사용하는 경우나, 길이 방향의 반송, 롤로부터 풀어내기, 롤에 권취하기 등을 행하는 경우에는, 내절성 및 내파단성(인장 파단 강도)이 높은 것에 추가로, 피착체 등에 대한 추종성이 얻어지도록, 적절한 파단 신도를 갖는 것이 바람직하다.The mechanical properties of the (meth)acrylic resin film also depend on the use, but when used in an adhesive sheet, an optical film, a surface protection film, a process film, etc. In addition to high bending resistance and breaking resistance (tensile breaking strength), it is preferable to have an appropriate breaking elongation so that followability to an adherend or the like can be obtained.

상기 (메타)아크릴계 수지 필름을 구성하는, 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층의 겔분율은 50％ 이상인 것이 바람직하고, 70％ 이상인 것이 보다 바람직하며, 90∼100％인 것이 더욱 바람직하고, 93∼100％인 것이 특히 바람직하다. 이와 같이 상기 수지층의 겔분율이 높음으로써, 상기 (메타)아크릴계 수지 필름의 필요한 물성인 내용제성을 개선할 수 있다.The gel fraction of the resin layer formed by crosslinking the (meth)acrylic resin composition constituting the (meth)acrylic resin film is preferably 50% or more, more preferably 70% or more, and furthermore is 90 to 100%. It is preferable, and it is especially preferable that it is 93-100 %. As described above, when the gel fraction of the resin layer is high, solvent resistance, which is a necessary physical property of the (meth)acrylic resin film, can be improved.

상기 (메타)아크릴계 수지 필름의 두께는 특별히 한정되지 않으나, 예를 들면, 광학용 필름의 경우에는 10∼200㎛ 정도의 두께가 바람직하고, 두께가 10∼50㎛인 것이 보다 바람직하며, 두께가 10∼40㎛인 것이 특히 바람직하고, 두께를 40㎛ 이하의 박막으로 할 수도 있다. 상기 (메타)아크릴계 수지 필름의 한쪽 면 또는 양면에 다른 재료를 적층하는 경우에는 필요에 따라, 코로나 방전에 의한 표면 개질, 앵커 코트제 도포 등의 이(易)접착 처리를 실시해도 된다.The thickness of the (meth)acrylic resin film is not particularly limited, but for example, in the case of an optical film, a thickness of about 10-200 μm is preferable, and a thickness of 10-50 μm is more preferable, and the thickness is It is especially preferable that it is 10-40 micrometers, and thickness can also be made into the thin film of 40 micrometers or less. When laminating another material on one side or both surfaces of the (meth)acrylic resin film, if necessary, an easy-adhesive treatment such as surface modification by corona discharge or application of an anchor coat agent may be performed.

상기 (메타)아크릴계 수지 필름은 광학용 필름의 기재에 사용해도 된다. 광학용 필름으로는, 편광 필름, 위상차 필름, 반사 방지 필름, 방현(안티 글레어) 필름, 자외선 흡수 필름, 적외선 흡수 필름, 광학 보상 필름, 휘도 향상 필름 등을 들 수 있다. 광학용 부재가 적용되는 기기로는, 액정 패널, 유기 EL 패널, 터치 패널 등을 들 수 있다. 상기 (메타)아크릴계 수지 필름을 광학용 필름으로 사용하는 경우에는 무색 투명인 것이 바람직하다.You may use the said (meth)acrylic-type resin film for the base material of the optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an anti-glare (anti-glare) film, an ultraviolet absorption film, an infrared absorption film, an optical compensation film, and a brightness improving film. As an apparatus to which the member for optics is applied, a liquid crystal panel, organic electroluminescent panel, a touch panel, etc. are mentioned. When the (meth)acrylic resin film is used as an optical film, it is preferably colorless and transparent.

상기 (메타)아크릴계 수지 필름의 한쪽 면 또는 양면에는, 하드 코트층, 대전 방지층, 반사 방지층, 방오층, 방현층, 저굴절률층, 점착층, 이형층 등의 1종 또는 2종 이상을 적층해도 된다. 저굴절률층 형성용 조성물에 사용되는 불소 화합물로는, 불소화 올레핀류, 불소화 비닐에테르류, 불소화 알킬(메타)아크릴레이트 등의 1종 또는 2종 이상의 중합물인 함불소 공중합체, 불소화 알킬기 함유 실란 화합물 등의 축합물을 들 수 있다. 함불소 공중합체는 불소화된 모노머에 추가로, 올레핀류, 비닐에테르류, (메타)아크릴레이트 등의 불소화되어 있지 않은 모노머가 공중합되어도 된다. 저굴절률층은 고굴절률층 등과 조합하여 반사 방지층을 구성해도 된다.On one or both sides of the (meth)acrylic resin film, one or two or more of a hard coat layer, an antistatic layer, an antireflection layer, an antifouling layer, an antiglare layer, a low refractive index layer, an adhesive layer, a release layer, etc. may be laminated do. Examples of the fluorine compound used in the composition for forming a low refractive index layer include a fluorinated copolymer that is one or more polymers such as fluorinated olefins, fluorinated vinyl ethers, and fluorinated alkyl (meth) acrylates, and fluorinated alkyl group-containing silane compounds. Condensates, such as these are mentioned. The fluorinated copolymer may be copolymerized with non-fluorinated monomers such as olefins, vinyl ethers and (meth)acrylates in addition to the fluorinated monomers. The low-refractive-index layer may be combined with a high-refractive-index layer or the like to constitute an antireflection layer.

본 실시형태의 점착 시트는, 상기 (메타)아크릴계 수지 조성물을 가교해서 이루어지는 수지층인 상기 (메타)아크릴계 수지 필름의 한쪽 면 또는 양면에 점착층을 형성하여 이루어지는 것을 특징으로 한다. 상기 점착층으로는, (메타)아크릴계 점착제로 이루어지는 점착제층이 바람직하다. 상기 (메타)아크릴계 수지 필름에 점착층을 형성하는 방법은 공지의 방법으로 행하면 된다. 구체적으로는, 리버스 코팅, 콤마 코팅, 그라비아 코팅, 슬롯 다이 코팅, 메이어 바 코팅, 에어 나이프 코팅 등의 공지의 도공 방법을 사용할 수 있다.The pressure-sensitive adhesive sheet of the present embodiment is characterized in that the pressure-sensitive adhesive layer is formed on one or both surfaces of the (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition. As said adhesive layer, the adhesive layer which consists of a (meth)acrylic-type adhesive is preferable. What is necessary is just to perform the method of forming an adhesion layer in the said (meth)acrylic-type resin film by a well-known method. Specifically, known coating methods such as reverse coating, comma coating, gravure coating, slot die coating, Mayer bar coating, and air knife coating can be used.

상기 점착 시트는 상기 (메타)아크릴계 수지 필름을 기재로 하여 이루어지는 광학용 필름의 적어도 한쪽 면에 점착층이 적층되어 이루어지는 점착층 형성 광학용 필름으로 해도 된다. 점착층 형성 광학용 필름은 액정 표시 장치, 터치 패널, 전자 종이, 유기 EL 등의 각종 표시 장치에 있어서의 광학용 필름의 첩합에 사용할 수 있다. 광학용 필름의 첩합에 사용되는 점착층의 점착면은 이형 필름을 사용하여 보호해도 된다. 이형 필름에는, 점착층의 점착면과 합쳐지는 측의 면에 실리콘계, 불소계 이형제 등에 의해 이형 처리가 실시되어도 된다.The said adhesive sheet is good also as an adhesive layer formation optical film in which the adhesive layer is laminated|stacked on at least one surface of the optical film which uses the said (meth)acrylic-type resin film as a base material. The film for adhesion layer formation optics can be used for bonding of the film for optics in various display apparatuses, such as a liquid crystal display device, a touchscreen, electronic paper, and organic electroluminescent. You may protect the adhesion surface of the adhesion layer used for bonding of the film for optics using a release film. The release film may be subjected to a mold release treatment with a silicone-based, fluorine-based mold release agent, or the like, to the surface on the side that is combined with the adhesive surface of the pressure-sensitive adhesive layer.

상기 점착 시트는 유리, 광학용 필름, 광학용 부재 등의 피착체의 표면을 보호하기 위해, 상기 점착층을 개재하여 첩합되는 표면 보호 필름을 구성해도 된다. 표면 보호 필름을 피착체에 첩합한 상태에서 피착체의 광학 특성, 이물질의 유무 등을 광학적으로 검사할 수 있다. 또한, 피착체를 제품에 탑재하는 단계에서는, 표면 보호 필름을 피착체로부터 박리하여 제거할 수 있다.The said adhesive sheet may comprise the surface protection film bonded together through the said adhesive layer in order to protect the surface of to-be-adhered objects, such as glass, an optical film, and an optics member. In a state in which the surface protection film is bonded to the adherend, the optical properties of the adherend, the presence or absence of foreign substances, and the like can be optically inspected. In addition, in the step of mounting the adherend on the product, the surface protection film can be peeled off from the adherend to be removed.

본 실시형태의 편광 필름은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 상기 (메타)아크릴계 수지 필름을, 편광자의 한쪽 면 또는 양면에 형성하여 이루어지는 것을 특징으로 한다. 상기 편광자의 보호층의 표면에 실시되어 있는 표면 처리가, 미처리, AG 처리, LR 처리, AR 처리, AG-LR 처리, AG-AR 처리로 이루어지는 군으로부터 선택되는 적어도 1종 이상이어도 된다. 여기서, AG는 안티 글레어(Anti Glare), LR은 로우 리플렉션(Low Reflection), AR은 안티 리플렉션(Anti Reflection)이다.The polarizing film of this embodiment is formed by forming the said (meth)acrylic-type resin film which is a resin layer formed by bridge|crosslinking the said (meth)acrylic-type resin composition on one side or both surfaces of a polarizer, It is characterized by the above-mentioned. The surface treatment applied to the surface of the protective layer of the polarizer may be at least one selected from the group consisting of untreated, AG treatment, LR treatment, AR treatment, AG-LR treatment, and AG-AR treatment. Here, AG is anti-glare, LR is low reflection, and AR is anti-reflection.

실시예Example

이하, 실시예에 의해 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be specifically described by way of Examples.

＜(메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물의 제조＞<Production of (meth)acrylic polymer and (meth)acrylic resin composition>

[실시예 1][Example 1]

교반기, 온도계, 환류 냉각기, 및 질소 도입관을 구비한 반응 장치에 질소 가스를 도입하여, 반응 장치 내의 공기를 질소 가스로 치환했다. 그 후, 반응 장치에 메틸메타크릴레이트 95중량부, 메틸아크릴레이트 5중량부, 8-히드록시옥틸아크릴레이트 3.0중량부와 함께 용제(초산에틸)를 첨가했다. 그 후, 중합 개시제로서 아조비스이소부티로니트릴 0.1중량부를 적하시키고, 65℃로 가열하여 소정 시간 반응시켜, 실시예 1의 (메타)아크릴계 폴리머 용액을 얻었다. 이 (메타)아크릴계 폴리머 용액에 포함되는 (메타)아크릴계 폴리머의 중량 평균 분자량(Mw)을 측정한 결과, 20만이었다. 실시예 1의 (메타)아크릴계 폴리머 용액에 대해, 코로네이트 HX(헥사메틸렌디이소시아네이트 화합물의 이소시아누레이트체) 3.0중량부를 첨가하고 교반 혼합하여, 실시예 1의 (메타)아크릴계 수지 조성물을 얻었다.Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Then, the solvent (ethyl acetate) was added to the reaction apparatus with 95 weight part of methyl methacrylate, 5 weight part of methyl acrylates, and 3.0 weight part of 8-hydroxy octyl acrylate. Then, 0.1 weight part of azobisisobutyronitrile was dripped as a polymerization initiator, it heated at 65 degreeC, and it was made to react for predetermined time, and the (meth)acrylic-type polymer solution of Example 1 was obtained. It was 200,000 as a result of measuring the weight average molecular weight (Mw) of the (meth)acrylic-type polymer contained in this (meth)acrylic-type polymer solution. To the (meth)acrylic polymer solution of Example 1, 3.0 parts by weight of coronate HX (isocyanurate of hexamethylene diisocyanate compound) was added and stirred and mixed to obtain a (meth)acrylic resin composition of Example 1 .

[실시예 2∼5 및 비교예 1∼2][Examples 2-5 and Comparative Examples 1-2]

실시예 1의 (메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물의 조성을 각각, 표 1의 기재와 같게 한 것 이외에는, 실시예 1과 동일하게 하여, 실시예 2∼5 및 비교예 1∼2의 (메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물을 얻었다. 실시예 2∼5 및 비교예 1∼2의 (메타)아크릴계 폴리머의 중량 평균 분자량(Mw)은 표 1에 나타내는 바와 같다.Except that the composition of the (meth)acrylic polymer and the (meth)acrylic resin composition of Example 1 were the same as those of Table 1, respectively, in the same manner as in Example 1, Examples 2 to 5 and Comparative Examples 1 to 2 A (meth)acrylic polymer and a (meth)acrylic resin composition were obtained. The weight average molecular weight (Mw) of the (meth)acrylic polymers of Examples 2-5 and Comparative Examples 1-2 is as showing in Table 1.

[비교예 3][Comparative Example 3]

용융 압출법에 의해 제조된 시판의 PMMA 필름(두께: 80㎛)을 용제로서 메틸에틸케톤(MEK)에 용해하고, PMMA 필름에 포함되는 폴리머의 중량 평균 분자량(Mw)을 측정한 결과, 30만이었다.A commercially available PMMA film (thickness: 80 μm) prepared by melt extrusion was dissolved in methyl ethyl ketone (MEK) as a solvent, and the weight average molecular weight (Mw) of the polymer contained in the PMMA film was measured. As a result, 300,000 It was.

Figure 112022024093770-pat00001
Figure 112022024093770-pat00001

또한, 표 1에 사용한 (A)∼(C)의 각 성분의 약기호 화합물명을 표 2에 나타낸다. 한편, (C)군의 가교제에 있어서, 코로네이트(등록상표) HX 및 동 HL은 토소 주식회사의 상품명이고, 타케네이트(등록상표) D-140N은 미츠이 화학 주식회사의 상품명이며, TETRAD(등록상표)-X는 미츠비시 가스 화학 주식회사의 상품명이다.In addition, the abbreviation compound name of each component of (A)-(C) used in Table 1 is shown in Table 2. On the other hand, in the crosslinking agent of group (C), Coronate (registered trademark) HX and HL are trade names of Toso Corporation, Takenate (registered trademark) D-140N is a trade name of Mitsui Chemicals, Ltd., TETRAD (registered trademark) -X is a trade name of Mitsubishi Gas Chemical Co., Ltd.

Figure 112022024093770-pat00002
Figure 112022024093770-pat00002

＜(메타)아크릴계 수지 필름의 제작＞<Production of (meth)acrylic resin film>

실시예 1∼5 및 비교예 1∼2의 (메타)아크릴계 수지 조성물을 용액 캐스트법에 따라 수지 필름상으로 제막하고, 용제의 건조 및 가교제의 경화에 적합한 온도 조건으로 하여 가열 건조 및 가교시켜, 실시예 1∼5 및 비교예 1∼2의 (메타)아크릴계 수지 필름을 얻었다. 각 필름의 두께를 표 3에 나타낸다.The (meth)acrylic resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were formed into a resin film according to the solution casting method, dried by heat and crosslinked under temperature conditions suitable for drying the solvent and curing the crosslinking agent, The (meth)acrylic-type resin film of Examples 1-5 and Comparative Examples 1-2 was obtained. Table 3 shows the thickness of each film.

또한, 비교예 3의 (메타)아크릴계 수지 필름으로는, 상기와 같이, 용융 압출법에 의해 제조된 시판의 PMMA 필름(두께: 80㎛)을 사용했다.In addition, as the (meth)acrylic resin film of Comparative Example 3, a commercially available PMMA film (thickness: 80 µm) produced by the melt extrusion method as described above was used.

＜(메타)아크릴계 수지 필름의 시험 방법 및 평가＞<Test method and evaluation of (meth)acrylic resin film>

실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름을 이하의 시험 방법에 따라 평가했다.The (meth)acrylic resin films of Examples 1-5 and Comparative Examples 1-3 were evaluated according to the following test methods.

＜내절성＞＜Flexibility＞

실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름으로부터 시험편을 제작한 후, JIS P8115(종이 및 판지-내절 강도 시험 방법-MIT 시험기법)에 준거하고, 내절도 시험 장치(제조사: 테스터 산업 주식회사, 형식: MIT 내절도 시험 장치 BE-201)를 이용하여 내절성 시험을 행하고, 시험편이 파단될 때까지의 왕복 절곡 횟수(내절 횟수)를 측정했다.After preparing a test piece from the (meth)acrylic resin film of Examples 1 to 5 and Comparative Examples 1 to 3, in accordance with JIS P8115 (paper and paperboard-Bending strength test method-MIT test method), a cut-resistance test apparatus ( Manufacturer: Tester Industry Co., Ltd., Model: MIT The bending resistance test was done using the cut-resistance testing apparatus BE-201), and the number of reciprocating bending (number of bending resistance) until the test piece fracture|ruptures was measured.

＜내용제성(겔분율)＞<Solvent resistance (gel fraction)>

내용제성 시험 방법으로서, 하기와 같이 (메타)아크릴계 수지 필름의 시험편을 용제의 액 중에 소정 시간에 걸쳐 침지한 후, 상기 용제에 용출하지 않고 불용분(잔사)으로서 남은 (메타)아크릴계 수지 필름의 비율(이른바, 겔분율)을 측정하여, 내용제성을 시험했다.As a solvent resistance test method, after immersing a test piece of a (meth)acrylic resin film in a solution of a solvent for a predetermined time as follows, the (meth)acrylic resin film remaining as an insoluble content (residue) without eluting into the solvent The ratio (so-called gel fraction) was measured and solvent resistance was tested.

실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름으로부터 시험편을 제작하고, 시험편의 질량을 정확하게 측정하고, 메틸에틸케톤(MEK) 중에 24hr 침지한 후, 200메시의 철망으로 여과했다. 그 후, 여과물을 온도 100℃에서 1hr 건조하여 얻어지는 잔사의 질량을 정확하게 측정하고, 이하의 식으로부터 내용제성 시험 방법으로서, 용제에 대한 침지에 의한 겔분율(％)을 측정했다.A test piece was prepared from the (meth)acrylic resin film of Examples 1 to 5 and Comparative Examples 1 to 3, the mass of the test piece was accurately measured, immersed in methyl ethyl ketone (MEK) for 24 hours, and then filtered through a 200 mesh wire mesh. did. Then, the mass of the residue obtained by drying a filtrate at the temperature of 100 degreeC for 1 hr was measured accurately, and the gel fraction (%) by immersion in a solvent was measured as a solvent resistance test method from the following formula.

겔분율(％)＝불용분(잔사)질량(g)／필름(시험편)질량(g)×100 Gel fraction (%) = insoluble content (residue) mass (g) / film (test piece) mass (g) x 100

＜내파단성(인장 파단 강도), 파단 신장률＞<Fracture resistance (tensile strength at break), elongation at break>

실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름으로부터 시험편을 제작하고, 인장 시험 장치(제조사: 주식회사 시마즈 제작소, 형식: AGS-X)를 이용하여 측정하고, 시험편이 파단될 때까지의 내파단성(인장 파단 강도(MPa)) 및 파단 신장률(％)의 값을 구했다.A test piece was prepared from the (meth)acrylic resin film of Examples 1 to 5 and Comparative Examples 1 to 3, measured using a tensile tester (manufacturer: Shimadzu Corporation, model: AGS-X), and the test piece was torn The values of fracture resistance (tensile strength at break (MPa)) and elongation at break (%) were calculated.

＜위상차＞<Phase difference>

실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름의 면내 위상차(Re) 값(㎚)을, 위상차 측정 장치(제조사: 오지 계측 기기 주식회사, 형식: KOBRA-HBPR/SPC)를 이용하여 측정했다. 위상차의 측정 파장은 예를 들면, 450∼550㎚ 등의 가시 영역에서 적절히 선택할 수 있다. Re값은 면내의 굴절률이 최대가 되는 방향을 x축(지상축), 이와 직교하는 방향을 y축(진상축)으로 할 때, x축 방향의 굴절률 nx와, y축 방향의 굴절률 ny와, 필름의 막두께 d로부터, 다음의 식에 의해 산출된다.The in-plane retardation (Re) values (nm) of the (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3 were measured using a retardation measuring device (manufacturer: Oji Instruments Co., Ltd., model: KOBRA-HBPR/SPC). was measured using The measurement wavelength of the phase difference can be appropriately selected in a visible region of, for example, 450 to 550 nm. The Re value is the refractive index n x in the x-axis direction and the refractive index n y in the y-axis direction when the direction in which the in-plane refractive index is maximum is the x-axis (slow axis) and the direction orthogonal thereto is the y-axis (fast axis). and from the film thickness d of the film, it is computed by the following formula.

면내 위상차 Re＝(nx－ny)×d In-plane phase difference Re=(n x- n y )×d

여기서, 필름의 막두께 d는 면내 위상차 Re와 동일하게 ㎚ 단위인 점에서, 필름 두께(㎛)의 1000배이다.Here, the film thickness d of the film is 1000 times as large as the in-plane retardation Re, in terms of the nm unit, the film thickness (µm).

표 3에 실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름에 대한 평가 결과를 나타낸다.In Table 3, the evaluation result about the (meth)acrylic-type resin film of Examples 1-5 and Comparative Examples 1-3 is shown.

Figure 112022024093770-pat00003
Figure 112022024093770-pat00003

실시예 1∼5의 (메타)아크릴계 수지 필름은 두께가 40㎛ 이하인 박막으로 제막된 것이며, 내절성이 50회 이상, 내파단성(인장 파단 강도)이 50MPa 이상, 파단 신장률이 9∼12％, 내용제성(겔분율)이 93％ 이상이며, 어느 특성도 우수한 것이었다.The (meth)acrylic resin film of Examples 1 to 5 was formed as a thin film having a thickness of 40 µm or less, and had a bending resistance of 50 or more, a breaking resistance (tensile breaking strength) of 50 MPa or more, and a breaking elongation of 9 to 12%, Solvent resistance (gel fraction) was 93% or more, and both properties were excellent.

이와 같이, 실시예 1∼5의 (메타)아크릴계 수지 필름에서는, 본 발명의 과제를 해결할 수 있음이 실증되었다.Thus, in the (meth)acrylic-type resin film of Examples 1-5, it was demonstrated that the subject of this invention could be solved.

비교예 1의 (메타)아크릴계 수지 필름은 (메타)아크릴계 폴리머가 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트로서 MMA만을 공중합한 것이며, MMA 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트를 공중합하지 않기 때문인지, 내절성이 매우 낮고, 파단 신장률이 낮았다.The (meth)acrylic resin film of Comparative Example 1 is an alkyl (meth)acrylate in which the (meth)acrylic polymer has C1-C14 carbon atoms in the alkyl group, and only MMA is copolymerized, and the Tg of the homopolymer other than MMA is 0 ° C. or higher and the C1-C14 alkyl (meth)acrylate was not copolymerized, and the bending resistance was very low, and the breaking elongation was low.

비교예 2의 (메타)아크릴계 수지 필름은 (메타)아크릴계 수지 조성물이 가교제를 함유하지 않기 때문인지, 내절성 및 내용제성(겔분율)이 매우 낮았다.The (meth)acrylic resin film of Comparative Example 2 had very low folding resistance and solvent resistance (gel fraction), possibly because the (meth)acrylic resin composition did not contain a crosslinking agent.

비교예 3의 (메타)아크릴계 수지 필름은 용융 압출법에 의해 제조된 수지 필름이나, 내절성 및 내용제성(겔분율)이 실시예 1∼5에 의한 (메타)아크릴계 수지 필름에 비해 매우 낮은 것이 판명되었다. 한편, 비교예 3의 (메타)아크릴계 수지 필름의 두께가 20㎛라고 가정하면, Re의 값은 두께의 비율(20/80)에 따라, 1/4의 값이 되나, 그럼에도 Re값이 큰 점에서, 복굴절률(nx－ny)의 값 자체가 큰 것으로 생각된다.The (meth)acrylic resin film of Comparative Example 3 is a resin film prepared by melt extrusion, but the fold resistance and solvent resistance (gel fraction) are very low compared to the (meth)acrylic resin film according to Examples 1 to 5. It turned out On the other hand, assuming that the thickness of the (meth)acrylic resin film of Comparative Example 3 is 20 μm, the value of Re becomes 1/4 according to the ratio of thickness (20/80), but the Re value is still large , the value of the birefringence (n x - n y ) is considered to be large.

이상과 같이, 비교예 1∼3의 (메타)아크릴계 수지 필름에서는, 본 발명의 과제인 내절성, 내파단성(인장 파단 강도), 파단 신장률, 내용제성(겔분율)이 우수한 (메타)아크릴계 수지 필름을 제공하는 것을 해결할 수 없었다.As described above, in the (meth)acrylic resin film of Comparative Examples 1 to 3, the (meth)acrylic resin excellent in fold resistance, fracture resistance (tensile fracture strength), elongation at break, and solvent resistance (gel fraction), which is the subject of the present invention Couldn't solve providing the film.

본 발명의 (메타)아크릴계 수지 조성물 및 이를 사용한 (메타)아크릴계 수지 필름은 종래의 용융 압출법에 의해 얻어진 (메타)아크릴계 수지 필름과 비교하면, 특히, 박막화, 내절성, 내용제성(겔분율)의 점에 있어서 우수한 특성을 갖는 점에서, 디스플레이 등 각종 광학 기기의 박형화 및 내구성 향상에 효과를 발휘하는 것을 기대할 수 있기 때문에, 산업상의 이용 가치가 크다.The (meth)acrylic resin composition of the present invention and the (meth)acrylic resin film using the same are compared with the (meth)acrylic resin film obtained by the conventional melt extrusion method, in particular, thinning, folding resistance, solvent resistance (gel fraction) Since it can be expected to exert an effect on the thickness reduction and durability improvement of various optical devices such as displays, since it has excellent characteristics in terms of the value of industrial use.

Claims (5)

(메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서,
상기 (메타)아크릴계 폴리머가
메틸메타크릴레이트 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상 1∼20중량부의 합계 100중량부와,
상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머이고,
막두께가 40㎛ 이하인 박막의 (메타)아크릴계 수지 필름의 제조에 사용되는 것을 특징으로 하는 (메타)아크릴계 수지 조성물.As a (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent,
The (meth)acrylic polymer is
80 to 99 parts by weight of methyl methacrylate and at least one or more of an alkyl (meth) acrylate having a Tg of 0° C. or higher and C1-C14 of the homopolymer other than the above methyl methacrylate 1 A total of 100 parts by weight of ∼20 parts by weight,
A (meth)acrylic polymer consisting of a copolymer having a weight average molecular weight of more than 100,000 and 1 million or less obtained by copolymerizing 1.0 to 20.0 parts by weight of at least one copolymerizable monomer having a functional group capable of reacting with the crosslinking agent,
A (meth)acrylic resin composition for use in the production of a thin (meth)acrylic resin film having a film thickness of 40 μm or less. 제 1 항에 있어서,
상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머가 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중에서 선택된 적어도 1종 이상인 것을 특징으로 하는 (메타)아크릴계 수지 조성물.The method of claim 1,
(meth)acrylic resin composition, characterized in that the copolymerizable monomer having a functional group capable of reacting with the crosslinking agent is at least one selected from the group consisting of a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group. 제 1 항 또는 제 2 항에 있어서,
상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군에서 선택된 1종 이상인 것을 특징으로 하는 (메타)아크릴계 수지 조성물.3. The method according to claim 1 or 2,
The (meth)acrylic resin composition, characterized in that the crosslinking agent is at least one selected from the group consisting of an epoxy compound, an aziridine compound, and an isocyanate compound. 제 1 항 또는 제 2 항에 있어서,
상기 (메타)아크릴계 수지 필름이 용액 캐스트법에 의해 제조되는 것을 특징으로 하는 (메타)아크릴계 수지 조성물.3. The method according to claim 1 or 2,
A (meth)acrylic resin composition, characterized in that the (meth)acrylic resin film is prepared by a solution casting method. 제 1 항 또는 제 2 항의 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 것을 특징으로 하는 (메타)아크릴계 수지 필름.A (meth)acrylic resin film comprising a resin layer formed by crosslinking the (meth)acrylic resin composition according to claim 1 or 2.
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