KR101660391B1 - Polyester film for solar cells, solar cell back sheet using same, and solar cell - Google Patents
Polyester film for solar cells, solar cell back sheet using same, and solar cell Download PDFInfo
- Publication number
- KR101660391B1 KR101660391B1 KR1020117023064A KR20117023064A KR101660391B1 KR 101660391 B1 KR101660391 B1 KR 101660391B1 KR 1020117023064 A KR1020117023064 A KR 1020117023064A KR 20117023064 A KR20117023064 A KR 20117023064A KR 101660391 B1 KR101660391 B1 KR 101660391B1
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- KR
- South Korea
- Prior art keywords
- film
- solar cell
- back sheet
- polyester
- polyester film
- Prior art date
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- C08G63/183—Terephthalic acids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
본 발명의 내열성과 내가수 분해성이 우수한 태양 전지용 폴리에스테르 필름, 그것을 사용한 태양전지 백시트를 사용함으로써 고내구성인 태양 전지를 제공하는 것을 과제로 한다. 카르복실 말단기 농도가 13eq/ton이하이고, 시차 주사 열량 측정(DSC)에 의해 구해지는 미소 흡열 피크 온도 Tmeta(℃)가 220℃이하인 태영전지용 폴리에스테르 필름에 관한 것이다.It is an object of the present invention to provide a polyester film for a solar cell excellent in heat resistance and hydrolysis resistance of the present invention and a solar cell back sheet using the same. Wherein the carboxyl end group concentration is 13 eq / ton or less and the minute endothermic peak temperature Tmeta (占 폚) obtained by differential scanning calorimetry (DSC) is 220 占 폚 or less.
Description
본 발명은 내열성과 내가수 분해성이 우수한 태양 전지용 폴리에스테르 필름, 그것을 사용한 태양 전지 백시트 및 그것을 사용한 태양 전지에 관한 것이다.The present invention relates to a polyester film for a solar cell excellent in heat resistance and hydrolysis resistance, a solar cell back sheet using the same, and a solar cell using the same.
최근, 반영구적이고 무공해의 차세대 에너지원으로서 클린 에너지인 태양광 발전이 주목을 받고 있어, 태양 전지는 급속하게 보급되고 있다. 태양 전지 백시트의 필름으로서는 예를 들면, 폴리에틸렌계의 수지나 폴리에스테르계 수지 시트를 사용하거나, 불소계 필름을 사용하거나 하는 것이 알려져 있다(특허문헌 1∼3 참조). 태양 전지는 옥외에 설치되는 경우가 많고, 그 경우에 자연 환경에 대한 내구성(내후성, 내열성, 내UV(자외선)성)이 강하게 요구된다.In recent years, as a next-generation energy source of semi-permanent and pollution-free energy, solar power, which is a clean energy, is attracting attention, and solar cells are rapidly spreading. As the film of the solar cell back sheet, for example, a polyethylene resin or a polyester resin sheet is used, or a fluorine film is used (see Patent Documents 1 to 3). In many cases, the solar cell is installed outdoors, and in this case, durability against the natural environment (weather resistance, heat resistance, UV (ultraviolet) resistance) is strongly required.
(선행기술문헌)(Prior art document)
특허문헌 1: 일본특허공개 평11-261085호 공보Patent Document 1: JP-A-11-261085
특허문헌 2: 일본특허공개 평11-186575호 공보Patent Document 2: JP-A-11-186575
특허문헌 3: 일본특허공개 2006-270025호 공보Patent Document 3: JP-A-2006-270025
그러나, 특허문헌 1∼3에 기재된 필름을 지니더라도 내열성과 내가수 분해성이 불충분해서, 태양 전지를 옥외에서 장기 사용하는 것은 꺼려지고 있었다.However, even with the films described in Patent Documents 1 to 3, heat resistance and hydrolysis resistance are insufficient, and it has been a problem to use the solar cell for a long time outdoors.
그래서, 본 발명은 이러한 과제를 해결하기 위해 내열성과 내가수 분해성을 양립한 태양 전지용 폴리에스테르 필름, 그것을 사용한 태양 전지 백시트, 및 태양 전지를 제공하는 것이다.SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polyester film for a solar cell having both heat resistance and hydrolysis resistance, a solar cell back sheet using the same, and a solar cell.
즉, 본 발명은 카르복실 말단기 농도가 13eq/ton이하이고, 시차 주사 열량 측정(DSC)에 의해 구해지는 미소 흡열 피크 온도 Tmeta(℃)가 220℃이하인 태양 전지용 폴리에스테르 필름 및 그것을 사용하여 이루어지는 태양 전지 백시트, 및 태양 전지이다.That is, the present invention relates to a polyester film for a solar cell having a carboxyl end group concentration of 13 eq / ton or less and a very low endothermic peak temperature Tmeta (° C.) obtained by differential scanning calorimetry (DSC) of 220 ° C. or less, A solar cell back sheet, and a solar cell.
(발명의 효과)(Effects of the Invention)
본 발명에 의하면, 내열성과 내가수 분해성을 양립한 태양 전지용 폴리에스테르 필름, 그것을 사용한 태양 전지 백시트, 및 태양 전지를 제공할 수 있다. 또한, 그것을 사용함으로써 태양 전지 백시트의 종래 이상의 내구성 향상이나 박형화 등이 가능해져서 태양 전지의 내구성 향상, 박형화 등이 가능해진다.According to the present invention, it is possible to provide a polyester film for a solar cell having both heat resistance and hydrolysis resistance, a solar cell back sheet using the same, and a solar cell. Further, by using it, it is possible to improve the durability and thinness of the solar cell back sheet as compared with the prior art, thereby making it possible to improve the durability and thickness of the solar cell.
도 1은 필름의 미소 흡열 피크 온도를 구하기 위한 시차 주사 열량 측정(DSC)의 측정 결과의 일예를 나타낸 도면이다.BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing an example of a result of measurement of differential scanning calorimetry (DSC) for determining the temperature of the micro endothermic peak of a film. Fig.
본 발명의 필름은 폴리에스테르 필름일 필요가 있다. 본 발명에 있어서의 폴리에스테르 필름은 에틸렌테레프탈레이트 성분이 폴리에스테르의 에스테르 성분에 대하여 90mol%이상으로 이루어지는 것이 내열성, 기계 특성의 점에서 바람직하지만, 기타 공중합 성분으로서 각종 디카르복실산 또는 그 에스테르 형성성 유도체와 디올을 공중합해도 좋다. 공중합 가능한 디카르복실산 성분으로서는 예를 들면, 이소프탈산, 프탈산, 1,4-나프탈렌디카르복실산, 1,5-나프탈렌디카르복실산, 2,6-나프탈렌디카르복실산, 4,4'-디페닐디카르복실산, 4,4'-디페닐에테르디카르복실산, 4,4'-디페닐술폰디카르복실산 등을 들 수 있다. 또한, 공중합할 수 있는 지환족 디카르복실산 성분으로서는 1,4-시클로헥산디카르복실산 등을 들 수 있다. 또한, 디올 성분으로서는 에틸렌글리콜, 1,2-프로판디올, 네오펜틸글리콜, 1,3-부탄디올, 1,4-부탄디올, 1,5-펜탄디올, 1,6-헥산디올, 1,2-시클로헥산디메탄올, 1,3-시클로헥산디메탄올, 1,4-시클로헥산디메탄올, 디에틸렌글리콜, 트리에틸렌글리콜, 폴리알킬렌글리콜, 2,2-비스(4'-β-히드록시에톡시페닐)프로판 등의 지방족, 지환족, 방향족 디올 등을 들 수 있다. 이들 성분은 1종만을 사용해도 좋고, 또한 2종 이상 병용해도 좋다. 바람직하게 사용되는 폴리에스테르의 융점은 250℃이상의 것이 내열성의 점에서 바람직하고, 300℃이하의 것이 생산성의 점에서 바람직하다. 이 범위내이면, 다른 성분이 공중합되어도, 블렌드되어 있어도 좋다. 또한, 이 폴리에스테르 중에는 공지의 각종 첨가제, 예를 들면 산화 방지제, 대전 방지제, 결정 핵제, 무기 입자, 유기 입자 등이 첨가되어 있어도 좋다. 특히, 무기 입자나 유기 입자는 필름 표면에 이활성을 부여하여, 필름의 취급성을 높이기 때문에 유효하다.The film of the present invention needs to be a polyester film. In the polyester film of the present invention, it is preferable that the ethylene terephthalate component is at least 90 mol% based on the ester component of the polyester from the viewpoint of heat resistance and mechanical properties, but various dicarboxylic acids or ester formations The derivative may be copolymerized with a diol. Examples of the copolymerizable dicarboxylic acid component include isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and 4,4'-diphenyl sulfone dicarboxylic acid. Examples of the alicyclic dicarboxylic acid component that can be copolymerized include 1,4-cyclohexanedicarboxylic acid and the like. Examples of the diol component include ethylene glycol, 1,2-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis (4'-p-hydroxyethoxy Phenyl) propane; and aliphatic, alicyclic, and aromatic diols. These components may be used alone or in combination of two or more. The melting point of the polyester preferably used is preferably 250 ° C or more from the viewpoint of heat resistance, and preferably 300 ° C or less from the viewpoint of productivity. Within this range, other components may be copolymerized or blended. In addition, various known additives such as an antioxidant, an antistatic agent, a nucleating agent, inorganic particles, organic particles and the like may be added to the polyester. Particularly, the inorganic particles and the organic particles are effective because they impart lubricity to the surface of the film and improve the handleability of the film.
폴리에스테르는 종래 공지의 폴리에스테르의 제조 방법에 따라서 제조할 수 있다. 즉, 산성분으로서 디알킬에스테르를 사용하고, 이것과 디올 성분으로 에스테르 교환 반응시킨 후, 이 반응 생성물을 감압 하에서 가열하고, 잉여의 디올 성분을 제거하면서 중축합시킴으로써 제조할 수 있다. 또한, 산성분으로서 디카르복실산을 이용하여, 종래 공지의 직접 중합법에 의해 제조할 수도 있다. 반응 촉매로서는 종래 공지의 티탄 화합물, 리튬 화합물, 칼슘 화합물, 마그네슘 화합물, 안티몬 화합물, 게르마늄 화합물 등을 사용할 수 있다. 이렇게 해서 얻어진 폴리에스테르는 고상 중합을 실시함으로써, 중합도를 더욱 상승시킬 수 있고, 또한 카르복실 말단기 농도를 저감시킬 수 있다. 고상 중합은 건조기 중 200℃∼250℃ 온도에서 1torr이하의 감압 상태 또는 질소 기류하에서 행해진다.The polyester can be produced according to a conventionally known production method of a polyester. That is, it can be produced by using a dialkyl ester as an acid component, transesterifying the diol component with the dialkyl ester, heating the reaction product under reduced pressure, and polycondensation while removing excess diol component. The dicarboxylic acid may be used as the acidic component and may be produced by a conventionally known direct polymerization method. As the reaction catalyst, conventionally known titanium compounds, lithium compounds, calcium compounds, magnesium compounds, antimony compounds, germanium compounds and the like can be used. The polyester obtained in this way can further increase the degree of polymerization and further reduce the carboxyl end group concentration by carrying out the solid phase polymerization. Solid-state polymerization is carried out in a dryer at a temperature of 200 ° C to 250 ° C under a reduced pressure of 1 torr or less or in a nitrogen stream.
본 발명에 있어서는 내가수 분해성을 만족시키기 위해, 폴리에스테르 필름의 고유 점도가 0.6∼1.2dl/g의 범위에 있는 것이 바람직하다. 보다 바람직하게는 0.65∼0.80dl/g이고, 더욱 바람직하게는 0.70∼0.80dl/g이다. 내가수 분해성을 향상시키기 위해서는 고유 점도를 높이는 것이 바람직하지만, 고유 점도가 1.2dl/g을 초과하는 경우에는 폴리에스테르 수지 제조시에 고상 중합 시간을 길게 할 필요가 있어 코스트가 현저하게 높아지기 때문에 바람직하지 못한 경우가 있다. 또한, 0.6dl/g보다 작은 경우에는 중합도가 낮기 때문에 내열성·내가수 분해성이 현저하게 떨어지므로 바람직하지 않다. 고유 점도를 상기 바람직한 범위로 하기 위해서는 폴리에스테르 수지의 제조시의 중합 조건을 조정함으로써 달성할 수 있다.In the present invention, in order to satisfy the hydrolysis resistance, it is preferable that the intrinsic viscosity of the polyester film is in the range of 0.6 to 1.2 dl / g. More preferably from 0.65 to 0.80 dl / g, and still more preferably from 0.70 to 0.80 dl / g. In order to improve the hydrolysis resistance, it is desirable to increase the intrinsic viscosity. However, when the intrinsic viscosity exceeds 1.2 dl / g, it is necessary to increase the solid phase polymerization time at the time of producing the polyester resin, Sometimes you can not. Further, when it is less than 0.6 dl / g, the polymerization degree is low and heat resistance and hydrolysis resistance are remarkably lowered, which is not preferable. In order to keep the intrinsic viscosity within the above preferable range, it can be achieved by adjusting the polymerization conditions at the time of production of the polyester resin.
본 발명에 있어서는 내가수 분해성을 향상시키기 위해서, 폴리에스테르 필름의 카르복실 말단기 농도를 13eq(당량)/ton이하의 범위로 하는 것이 필요하다. 바람직하게는 12eq/ton이하이고, 보다 바람직하게는 8eq/ton이하, 가장 바람직하게는 5eq/ton이하이다. 하한은 특별히 한정되는 것은 아니지만 0eq/ton이 이론상의 하한이 된다.In the present invention, in order to improve the hydrolysis resistance, it is necessary to set the carboxyl end group concentration of the polyester film to 13 eq (equivalent) / ton or less. It is preferably 12 eq / ton or less, more preferably 8 eq / ton or less, and most preferably 5 eq / ton or less. The lower limit is not particularly limited, but 0 eq / ton is the theoretical lower limit.
카르복실 말단기 농도를 상기 바람직한 범위로 하기 위해서는 원료가 되는 폴리에스테르 수지로서, 카르복실 말단기 농도가 작은 폴리에스테르 수지를 사용하는 것이 바람직하다. 폴리에스테르 수지의 카르복실 말단기 농도를 작게 하기 위해서는 폴리에스테르 수지 제조시의 고상 중합 시간을 보다 길게 함으로써 달성할 수 있다.In order to keep the carboxyl end group concentration within the above preferable range, it is preferable to use a polyester resin having a low carboxyl end group concentration as the polyester resin to be a raw material. In order to reduce the carboxyl end group concentration of the polyester resin, the solid phase polymerization time at the time of producing the polyester resin can be made longer.
또한, 카르복실 말단기 농도를 상기 바람직한 범위로 하기 위해서, 말단 봉쇄제를 사용하는 것도 바람직한 실시형태의 하나이다. 말단 봉쇄제로서는 카르보디이미드 화합물, 옥사졸린 화합물, 에폭시 화합물, 카보네이트 화합물 등이 열거된다. 제막 시에 폴리에스테르 수지와 함께 첨가한다면 보다 효과가 높다. 바람직하게는 카르보디이미드 화합물을 사용하고, 함유량을 폴리에스테르 필름 전체에 대하여 0.3∼5중량%로 하면 좋다. 물론 고상 중합과 말단 봉쇄제를 동시에 이용해도 좋다.It is also one of the preferred embodiments to use an end blocker in order to keep the carboxyl end group concentration within the above preferable range. Examples of the terminal blocking agent include a carbodiimide compound, an oxazoline compound, an epoxy compound, and a carbonate compound. It is more effective if it is added together with a polyester resin at the time of film formation. Preferably, a carbodiimide compound is used and the content thereof is set to 0.3 to 5% by weight based on the entire polyester film. Solid phase polymerization and end blocker may be used at the same time.
본 발명의 필름은 충분한 내가수 분해성을 만족시키기 위해서, 시차 주사 열량 측정(DSC)에 의해 구해지는 미소 흡열 피크 온도 Tmeta(℃)가 220℃이하의 범위에 있는 것이 필요하다. 바람직하게는 205℃이하이고, 보다 바람직하게는 195℃이하이다. 하한은 특별히 한정되는 것은 아니지만 150℃미만에서는 현저하게 열수축률이 높게 되기 때문에, 150℃이상으로 하는 것이 바람직하다. 보다 바람직하게는 160℃이상이다.In order to satisfy sufficient hydrolysis resistance, the film of the present invention needs to have a very small endothermic peak temperature Tmeta (占 폚) obtained by differential scanning calorimetry (DSC) of 220 占 폚 or less. Preferably not higher than 205 占 폚, and more preferably not higher than 195 占 폚. The lower limit is not particularly limited, but since the heat shrinkage rate becomes remarkably high at temperatures lower than 150 ° C, the lower limit is preferably 150 ° C or higher. More preferably, it is 160 DEG C or more.
미소 흡열 피크 온도를 상기 바람직한 범위로 하기 위해서는 제막시의 열처리 온도를 변경함으로써 달성할 수 있다. 제막시의 필름 두께나 제막 속도에 따라 다르지만, 열처리 온도를 220℃이하로 하는 것이 바람직하다. 또한, 본 발명의 필름의 제막방법 및 열처리 공정의 상세한 것은 후술한다.In order to set the temperature of the small endothermic peak within the above preferable range, it can be achieved by changing the heat treatment temperature at the time of film formation. Although it depends on the film thickness at the time of film formation and the film forming speed, it is preferable to set the heat treatment temperature to 220 캜 or lower. The film forming method and the heat treatment step of the film of the present invention will be described later in detail.
태양 전지의 제조공정에 있어서 열을 가하는 공정이 많기 때문에, 태양 전지용 폴리에스테르 필름의 열수축률이 크면 태양 전지의 제조 공정 중에 태양 전지용 폴리에스테르 필름 또는 태양 전지 백시트가 수축하고, 태양 전지 유닛 전체에 변형이 생겨 균열되어 버리는 경우가 있다. 그 때문에 본 발명의 필름의 열수축률은 작은 쪽이 바람직하다. 구체적으로는 필름의 길이 방향(MD)과 그 직행 방향(TD)(폭방향이라고 칭하는 경우도 있음)의 150℃ 30분의 열수축률이 모두 0.6%이하인 것이 바람직하다. 보다 바람직하게는 0.4%이하, 더욱 바람직하게는 0.2%이하이다. 또한, 열수축률은 -0.5%이상인 것이 바람직하다.The heat shrinkage rate of the polyester film for the solar cell is large, so that the polyester film for the solar cell or the back sheet of the solar cell is shrunk during the manufacturing process of the solar cell, There is a case where a deformation is caused and cracked. Therefore, the heat shrinkage ratio of the film of the present invention is preferably small. Concretely, it is preferable that the heat shrinkage ratio at 150 ° C for 30 minutes in the longitudinal direction (MD) of the film and the direction TD (sometimes referred to as the width direction) of the film is 0.6% or less. More preferably not more than 0.4%, further preferably not more than 0.2%. The heat shrinkage ratio is preferably -0.5% or more.
또한, 본 발명에서는 내가수 분해성 향상을 위해서 열처리 온도를 낮게 하는 것이 바람직한 바, 열수축률이 커지는 경우가 있다. 그 때문에 열수축률을 상기 바람직한 범위로 하기 위해서, 하기의 (1) 또는 (2) 중 어느 하나의 방법을 채용하는 것이 바람직하다(물론, (1)과 (2)의 방법을 병용해도 좋다).Further, in the present invention, it is preferable to lower the heat treatment temperature in order to improve the hydrolysis resistance, and the heat shrinkage ratio may be increased. Therefore, it is preferable to adopt any one of the following methods (1) and (2) (of course, the methods (1) and (2) may be used in combination) in order to keep the heat shrinkage within the above preferable range.
방법(1): 열처리 공정에 있어서, 필름을 열처리함과 동시에 필름 MD방향, TD방향의 각각의 방향으로 0.5∼10% 수축시키는 방법.Method (1): In the heat treatment process, the film is heat-treated and at the same time shrinks by 0.5 to 10% in each of the directions of the film MD and TD.
방법(2): 제막이 완료된 필름을 별도의 장치(예를 들면 오븐 등)에 도입하고, 오프라인으로 가열 처리를 하는 방법. 본 방법에 있어서, 바람직한 가열 온도는 150∼220℃이고, 바람직한 가열 시간은 10∼60초 사이이다.Method (2): A method in which the film-formed film is introduced into a separate apparatus (for example, an oven) and subjected to a heat treatment in an off-line manner. In the present method, the preferred heating temperature is 150 to 220 占 폚, and the preferred heating time is 10 to 60 seconds.
본 발명에서는 필름의 면배향 계수가 0.130이상인 것이 바람직하다. 보다 바람직하게는 0.165이상, 더욱 바람직하게는 0.168이상, 더욱 더 바람직하게는 0.170이상, 가장 바람직하게는 0.174이상이다. 내가수 분해성을 더욱 향상시킬 수 있기 때문이다. 본 발명에서 말하는 면배향 계수란 아베 굴절계를 사용하고, 하기 (A)식으로 구해지는 것이다.In the present invention, it is preferable that the plane orientation coefficient of the film is 0.130 or more. More preferably 0.165 or more, still more preferably 0.168 or more, even more preferably 0.170 or more, and most preferably 0.174 or more. This is because the hydrolysis resistance can be further improved. The plane orientation coefficient referred to in the present invention is obtained by the following formula (A) using an Abbe's refractometer.
면배향 계수 = (nMD + nTD)/2 - nZD … (A)Plane orientation coefficient = (nMD + nTD) / 2 - nZD ... (A)
상기 식(A)에 있어서의 nMD는 필름의 길이 방향(MD)의 굴절률을 나타내고, nTD는 필름의 직행 방향(TD)의 굴절률을 나타내고, nZD는 필름 두께 방향의 굴절률을 나타내고 있다. In the formula (A), nMD represents the refractive index in the longitudinal direction (MD) of the film, nTD represents the refractive index in the film direct direction (TD), and nZD represents the refractive index in the film thickness direction.
필름의 면배향 계수를 상기 수치 범위내로 하기 위해서는 제막시의 연신 배율을 크게 함으로써 달성할 수 있다. 바람직하게는 필름의 길이 방향(MD), 필름의 직행 방향(TD) 함께 연신 배율을 2.5∼6.0배로 조정하면 좋고, 필름의 면배향 계수를 0.165이상으로 하기 위해서는, MD 및 TD방향의 연신 배율을 각각 3.0∼5.0배로 조정하는 것이 바람직하다. 또한, 필름의 면배향 계수의 상한은 특별히 한정되는 것은 아니지만 면배향 계수를 높이기 위해서 연신 배율을 크게 해 가면 제막 안정성이 악화하기 때문에 생산성의 점으로부터 0.200이하인 것이 바람직하고, 보다 바람직하게는 0.185이하이다.In order to keep the plane orientation coefficient of the film within the above-mentioned numerical range, it can be achieved by increasing the drawing magnification at the time of film formation. Preferably, the stretching magnification in the longitudinal direction (MD) of the film and the film in the straight direction (TD) may be adjusted to 2.5 to 6.0 times. In order to make the film have a plane orientation coefficient of 0.165 or more, It is preferable to adjust them to 3.0 to 5.0 times. The upper limit of the plane orientation coefficient of the film is not particularly limited, but if the drawing magnification is increased in order to increase the plane orientation coefficient, the film formation stability deteriorates. Therefore, from the viewpoint of productivity, it is preferably 0.200 or less, more preferably 0.185 or less .
본 발명의 필름에 있어서는 시차 주사 열량 측정(DSC)에 의해 구해지는 미소 흡열 피크 온도 Tmeta(℃)와 필름의 면배향 계수 B2가 다음 식(B)을 만족하는 것이 바람직하다.In the film of the present invention, it is preferable that the small endothermic peak temperature Tmeta (占 폚) obtained by differential scanning calorimetry (DSC) and the plane orientation coefficient B2 of the film satisfy the following formula (B).
B2 ≥ 0.000886 × Tmeta - 0.00286 식(B)B2? 0.000886 占 Tmeta? 0.00286 (B)
식(B)을 만족하게 함으로써, 내가수 분해성(125℃, 습도 100%의 조건 하, 72시간 방치 후의 평균 신도 유지율 등)을 향상시킬 수 있다.By satisfying the formula (B), it is possible to improve the hydrolysis resistance (the average elongation retention after leaving for 72 hours under conditions of 125 캜 and 100% humidity).
본 발명에서는 필름 중에 가수분해의 분해를 억제하도록 화합물을 첨가하는 것이 바람직하다. 특히, 인 화합물을 함유하게 하는 것이 바람직하다. 그 때문에 본 발명에서는 형광 X선으로 측정했을 경우의 폴리에스테르 필름 중의 인 원자량이 200ppm이상인 것이 바람직하다. 보다 바람직하게는 300ppm이상, 더욱 바람직하게는400ppm이상이다. 인 화합물로서는 인산, 아인산, 포스폰산, 이들의 메틸에스테르, 에틸에스테르, 페닐에스테르, 하프에스테르 및 기타 유도체로 이루어지는 군에서 선택되는 1종 이상의 인 화합물을 사용하는 것이 바람직하다. 본 발명에서는 특히 인산, 아인산, 포스폰산의 메틸에스테르, 에틸에스테르, 페닐에스테르가 바람직하다. 또한, 인 화합물의 함유 방법으로서는 폴리에스테르 원료 칩을 제조할 때에 인 화합물을 첨가하는 것이 바람직하다.In the present invention, it is preferable to add a compound to suppress decomposition of hydrolysis in the film. In particular, it is preferable to contain a phosphorus compound. Therefore, in the present invention, it is preferable that the phosphorus atom content in the polyester film measured by fluorescent X-ray is 200 ppm or more. More preferably 300 ppm or more, and even more preferably 400 ppm or more. As the phosphorus compound, it is preferable to use at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, methyl ester, ethyl ester, phenyl ester, half ester and other derivatives thereof. In the present invention, methyl esters, ethyl esters and phenyl esters of phosphoric acid, phosphorous acid and phosphonic acid are particularly preferable. Further, as a method of containing a phosphorus compound, it is preferable to add a phosphorus compound when preparing a polyester raw material chip.
태양 전지의 백시트로서 사용할 경우에 태양광에 의한 열화의 영향을 받기 어려운 쪽이 바람직하다. 그러기 위해 UV(자외선) 흡수제나 UV를 반사하는 특성의 것을 필름 중에 첨가해도 좋다. 또한, 적어도 한쪽의 필름 표면에 있어서의 파장 400∼700nm의 평균 반사율을 80%이상으로 하는 것도 바람직한 실시형태의 하나이다. 더욱 바람직하게는 85%이상이고, 특히 바람직하게는 90%이상이다. 파장 400∼700nm의 평균 반사율을 80%이상으로 함으로써 본 발명의 필름을 사용한 태양 전지를 태양광이 직접 쬐이는 곳에 사용해도 필름의 열화가 적어진다.It is preferable that it is hardly affected by deterioration by sunlight when used as a back sheet of a solar cell. For this purpose, UV (ultraviolet) absorber or UV reflecting property may be added to the film. It is also one of the preferred embodiments that the average reflectance at a wavelength of 400 to 700 nm on at least one film surface is 80% or more. , More preferably 85% or more, and particularly preferably 90% or more. By setting the average reflectance at a wavelength of 400 to 700 nm at 80% or more, the deterioration of the film is reduced even when the solar cell using the film of the present invention is used in a place where sunlight directly shines.
파장 400∼700nm의 평균 반사율을 80%이상으로 하는 방법으로서는 필름에 무기 입자를 함유시키는 방법이나, 폴리에스테르와 비상용 수지를 가함으로써 폴리에스테르 필름 중에 공극을 작성하는 방법 등이 있다. 전자에 있어서 바람직하게 사용되는 무기 입자로서는 예를 들면, 습식 및 건식 실리카, 콜로이달 실리카, 탄산 칼슘, 규산 알루미늄, 인산 칼슘, 알루미나, 탄산 마그네슘, 탄산 아연, 산화 티탄, 산화 아연(아연화), 산화 안티몬, 산화 세륨, 산화 지르코늄, 산화 주석, 산화 란탄, 산화 마그네슘, 탄산 바륨, 탄산 아연, 염기성 탄산연(연백), 황산 바륨, 황산 칼슘, 황산 납, 황화 아연, 마이카, 운모 티탄, 탈크, 클레이, 카올린, 불화 리튬 및 불화 칼슘 등을 사용할 수 있지만, 특히 이산화 티탄, 황산 바륨이 바람직하다.무기 입자의 함유량은 폴리에스테르 필름 전체에 대하여 5∼55중량%이고, 바람직하게는 5∼35중량%이다. 함유량이 상기 범위보다 적을 경우에는 반사율이 열악한 필름이 되고, 반대로 함유량이 상기 범위보다 많을 경우에는 연신시에 필름 파단 등이 발생하기 쉬워져서, 생산성이 저하하는 경우가 있다. 생산성을 중시할 경우, 본 발명의 필름은 2층 이상의 폴리에스테르층을 갖는 것이 바람직하다. 2층 이상의 폴리에스테르층을 가질 경우, 어느 하나의 폴리에스테르층이 상기의 무기 입자를 상기 폴리에스테르층에 대하여 5∼55중량% 함유하면 된다. 보다 바람직하게는 5∼35중량% 함유하는 것이다. 또 하나의 폴리에스테르층에 있어서의 무기 입자의 함유량은 특별히 제한되지 않지만, 함유량을 작게 하면 할수록, 생산성을 향상시킬 수 있다.Examples of the method of making the average reflectance of 80% or more at a wavelength of 400 to 700 nm include a method of containing inorganic particles in a film or a method of forming voids in a polyester film by adding a polyester and a non-resin. Examples of inorganic particles that are preferably used in the former include inorganic particles such as wet and dry silica, colloidal silica, calcium carbonate, aluminum silicate, calcium phosphate, alumina, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide Antimony, cerium oxide, zirconium oxide, tin oxide, lanthanum oxide, magnesium oxide, barium carbonate, zinc carbonate, basic carbonate carbonate, barium sulfate, calcium sulfate, lead sulfate, zinc sulfide, mica, The content of the inorganic particles is preferably 5 to 55% by weight, more preferably 5 to 35% by weight, based on the whole polyester film, to be. When the content is less than the above range, the film becomes poor in reflectance. Conversely, when the content is larger than the above range, film breakage or the like is likely to occur during stretching, and productivity may be lowered. When productivity is emphasized, the film of the present invention preferably has two or more polyester layers. When two or more polyester layers are provided, any one of the polyester layers may contain the inorganic particles in an amount of 5 to 55% by weight based on the polyester layer. More preferably 5 to 35% by weight. The content of the inorganic particles in the other polyester layer is not particularly limited, but the smaller the content is, the more the productivity can be improved.
또한, 후자의 방법에 있어서 사용되는 폴리에스테르란 비상용한 수지로서는 폴리에틸렌, 폴리프로필렌, 폴리부텐, 폴리메틸펜텐과 같은 폴리올레핀 수지, 폴리스티렌 수지, 폴리아크릴레이트 수지, 폴리카보네이트 수지, 폴리아크릴로니트릴 수지, 폴리페닐렌술피드 수지 및 불소계 수지 등이 바람직하게 사용된다. 이들의 비상용 수지는 단독 집합체이어도 공중합체이어도 좋고, 또는 2종 이상의 비상용 수지를 병용해도 좋다. 이들 중에서도 표면장력이 작은 폴리프로필렌이나 폴리메틸펜텐과 같은 폴리올레핀 수지가 바람직하고, 또는 폴리메틸펜텐이 가장 바람직하다. 상기 폴리메틸펜텐은 상대적으로 폴리에스테르와의 표면 장력차가 크고, 또한 융점이 높기 때문에, 첨가량당의 공동 형성의 효과가 크다고 하는 특징이 있고, 비상용 수지로서 특별히 바람직한 것이다. 비상용 수지를 함유하는 경우에는 그 양은 폴리에스테르 필름 전체에 대하여 0.5∼20중량%이고, 바람직하게는 0.5∼10중량%의 범위이다. 함유량이 상기 범위보다 적을 경우에는 반사율이 열악한 필름이 되고, 반대로 함유량이 상기 범위보다 많을 경우에는, 필름 전체의 겉보기 밀도가 지나치게 떨어지기 때문에, 연신시에 필름 파단 등이 생기기 쉬워, 생산성이 저하하는 경우가 있다.Examples of the non-functional resin used in the latter method include polyolefin resins such as polyethylene, polypropylene, polybutene and polymethylpentene, polystyrene resins, polyacrylate resins, polycarbonate resins, polyacrylonitrile resins, A polyphenylene sulfide resin and a fluorine resin are preferably used. These emulsion resins may be a single aggregate or a copolymer, or two or more kinds of non-resisting resins may be used in combination. Of these, a polyolefin resin such as polypropylene or polymethylpentene having a small surface tension is preferable, or polymethylpentene is most preferable. The above-mentioned polymethylpentene has a feature that the difference in surface tension with the polyester is relatively large and the melting point is high, so that the effect of forming cavities per addition amount is large, and it is particularly preferable as the non-resisting resin. When an emulsion resin is contained, the amount thereof is in the range of 0.5 to 20% by weight, preferably 0.5 to 10% by weight based on the entire polyester film. When the content is less than the above range, the film becomes poor in reflectance. On the contrary, when the content is larger than the above range, the film becomes excessively low in the apparent density of the entire film, There is a case.
본 발명에서는 내가수 분해성을 더욱 향상시키기 위해서, 적어도 2개의 폴리에스테르층을 갖는 것이 바람직하다. 특히 바람직하게는 내가수 분해성이 특히 뛰어난 층과 파장 400∼700nm의 평균 반사율이 80%이상의 층을 적층하는 것이 특성 및 코스트의 면으로부터 유리하다.In the present invention, in order to further improve the hydrolysis resistance, it is preferable to have at least two polyester layers. Particularly preferably, it is advantageous from the viewpoints of characteristics and cost to laminate a layer having particularly excellent hydrolysis resistance and a layer having an average reflectance of 80% or more at a wavelength of 400 to 700 nm.
본 발명의 태양 전지용 폴리에스테르 필름은 125℃, 습도 100%의 조건 하, 48시간 방치 후의 평균 신도 유지율이 50%이상인 것이 바람직하다. 보다 바람직하게는 55%이상, 더욱 바람직하게는 60%이상, 특히 바람직하게는 65%이상, 가장 바람직하게는 70%이상이다. 평균 신도 유지율이 50%를 만족하지 않으면, 장기 사용했을 때에 기계적 강도가 저하하고, 그 결과, 이것을 사용한 백시트를 갖는 태양 전지의 사용 중에 외부로부터 어떠한 충격이 태양 전지에 가해졌을 때(예를 들면, 낙석 등이 태양 전지에 부딪칠 경우 등)에 백시트가 파단하는 경우가 있기 때문에 바람직하지 않다. 본 발명의 태양 전지용 폴리에스테르 필름에 있어서, 평균 신도 유지율을 50%이상으로 함으로써, 장기 사용시에 있어서의 백시트의 기계적 강도의 내구성을 높일 수 있다.The polyester film for a solar cell of the present invention preferably has an average elongation retention ratio of 50% or more after being left for 48 hours under conditions of 125 deg. C and a humidity of 100%. , More preferably not less than 55%, more preferably not less than 60%, particularly preferably not less than 65%, and most preferably not less than 70%. If the average elongation retention rate is not 50%, the mechanical strength is lowered when used for a long period of time. As a result, when an external shock is applied to the solar cell during use of the solar cell having the back sheet using the same, , Rockfall or the like is hit by a solar cell, etc.), the back sheet may be broken. In the polyester film for a solar cell of the present invention, when the average elongation retention is 50% or more, the durability of the mechanical strength of the back sheet during long-term use can be increased.
본 발명의 태양 전지용 폴리에스테르 필름은 125℃, 습도 100%의 조건 하, 72시간 방치 후의 평균 신도 유지율이 10%이상인 것이 바람직하다. 125℃, 습도 100%의 조건 하, 72시간 후의 평균 신도 유지율 시험은 48시간 후의 평균 신도 유지율 시험보다도 가혹한 촉진시험이다. 그 때문에 태양 전지용도 등 특별히 장기간의 내구성이 요구되는 용도에서는 72시간 후의 평균 신도 유지율이 평가 지표로서 사용된다. 72시간 후의 평균 신도 유지율은 보다 바람직하게는 20%이상, 더욱 바람직하게는 30%이상, 특히 바람직하게는 40%이상, 가장 바람직하게는 50%이상이다.The polyester film for a solar cell of the present invention preferably has an average elongation retention ratio of 10% or more after being left for 72 hours under the conditions of 125 캜 and a humidity of 100%. The average elongation retention rate test after 72 hours under the conditions of 125 DEG C and 100% humidity is a more severe promotion test than the average elongation retention rate test after 48 hours. Therefore, in applications where long-term durability is particularly required, such as a solar battery, the average elongation retention after 72 hours is used as an evaluation index. The average retention after 72 hours is more preferably 20% or more, still more preferably 30% or more, particularly preferably 40% or more, and most preferably 50% or more.
72시간 후의 평균 신도 유지율이 10%를 만족하지 않으면, 태양 전지용 필름으로서, 장기간 사용하고 있는 동안에 기계적 강도가 현저하게 저하한다. 그 때문에 사용 중에 외부로부터 충격이 태양 전지에 가해졌을 경우(예를 들면, 낙석 등이 태양 전지에 부딪칠 경우 등)에 백시트가 파단되는 경우가 있기 때문에 바람직하지 않다.If the average elongation retention after 72 hours does not satisfy 10%, the mechanical strength of the film for a solar cell is remarkably lowered during long-term use. Therefore, when the impact is applied from the outside to the solar cell during use (for example, when falling rocks hit the solar cell, etc.), the back sheet may break, which is undesirable.
또한, 본 발명의 태양 전지용 폴리에스테르 필름을 1장이상 포함하는 태양 전지 백시트에 있어서도 125℃, 습도 100%의 조건 하 48시간 방치 후의 평균 신도 유지율이 50%이상인 것이 바람직하다. 보다 바람직하게는 상술의 방법으로 구해지는 평균 신도 유지율이 55%이상, 더욱 바람직하게는 60%이상, 특히 바람직하게는 65%이상, 가장 바람직하게는 70%이상이다.In the solar cell backsheet containing at least one polyester film for a solar cell of the present invention, it is also preferable that the average elongation retention after standing for 48 hours under conditions of 125 캜 and 100% humidity is 50% or more. More preferably, the average elongation retention rate obtained by the above-mentioned method is 55% or more, more preferably 60% or more, particularly preferably 65% or more, and most preferably 70% or more.
평균 신도 유지율을 상기 바람직한 범위내로 하기 위해서는 본 발명의 태양 전지용 폴리에스테르 필름의 두께 비율을 백시트 전체의 두께에 대하여 5∼100%로 하는 것이 바람직하다. 즉, 보다 평균 신도 유지율을 높이기 위해서는 본 발명의 태양 전지 폴리에스테르 필름의 두께를 보다 두껍게 하는 것이 바람직하다.In order to keep the average elongation retention rate within the above preferable range, it is preferable that the thickness ratio of the polyester film for solar cell of the present invention is 5 to 100% with respect to the thickness of the entire back sheet. That is, in order to further increase the average elongation retention ratio, it is preferable to make the thickness of the solar cell polyester film of the present invention thicker.
다음에 본 발명의 폴리에스테르 필름의 구체적인 제조 방법(일례)에 대해서 기재한다.Next, a concrete production method (one example) of the polyester film of the present invention will be described.
우선, 폴리에틸렌테레프탈레이트(PET) 수지를 필요에 따라, 질소 분위기 또는 진공 분위기에서 건조한다. 그리고, 건조시킨 폴리에스테르 수지를 단축 또는 2축 압출기에 공급하여 용융 압출하고, T다이로부터 냉각 드럼 상에 시트상으로 토출하여 미연신 시트를 얻는다.First, a polyethylene terephthalate (PET) resin is dried in a nitrogen atmosphere or a vacuum atmosphere, if necessary. Then, the dried polyester resin is supplied to a single shaft or twin screw extruder for melt extrusion, and discharged from the T die onto the cooling drum in a sheet form to obtain an unstretched sheet.
이어서, 이 미연신 필름을 길이 방향으로 연신한 후, 폭방향으로 연신하거나 또는 폭방향으로 연신한 후, 길이 방향으로 연신하는 차차 2축 연신 방법에 의해,또는 필름의 길이 방향, 폭방향을 거의 동시에 연신해 가는 동시 2축 연신 방법 등에 의해 연신을 행한다.Subsequently, the unoriented film is stretched in the longitudinal direction, stretched in the width direction or stretched in the width direction, and then stretched in the longitudinal direction, or by the longitudinal biaxial stretching method in which the longitudinal direction and width direction of the film are almost And simultaneously stretching is performed by a simultaneous biaxial stretching method or the like.
연신 후, 필름의 열처리를 행한다. 열처리는 텐터나 가열 오븐 중이나 가열한 롤상 등 종래 공지의 임의의 방법에 의해 행할 수 있다. 이 열처리는 일반적으로 폴리에스테르의 융점 이하의 온도에서 행해지지만, 본 발명에서는 Tmeta(℃)를 220℃이하로 하기 때문에, 열처리 온도를 220℃이하로 하는 것이 바람직하다. 보다 바람직하게는 210℃이하이고, 더욱 바람직하게는 200℃이하이고, 가장 바람직하게는 190℃이하이다. 열처리 온도의 하한은 특별히 한정되는 것은 아니지만, 150℃미만에서는 현저하게 열수축률이 높아지기 때문에, 150℃이상으로 하는 것이 바람직하고, 보다 바람직하게는 160℃이상이다.After stretching, the film is heat-treated. The heat treatment can be carried out by any conventionally known method such as heating in a tenter or a heating oven. This heat treatment is generally carried out at a temperature lower than the melting point of the polyester, but in the present invention, the Tmeta (占 폚) is preferably 220 占 폚 or lower, and therefore the heat treatment temperature is preferably 220 占 폚 or lower. More preferably 210 DEG C or lower, further preferably 200 DEG C or lower, and most preferably 190 DEG C or lower. The lower limit of the heat treatment temperature is not particularly limited, but it is preferably 150 占 폚 or higher, and more preferably 160 占 폚 or higher, because the heat shrinkage rate becomes remarkably high at temperatures lower than 150 占 폚.
또한, 열처리는 필름을 길이 방향 및/또는 폭방향으로 이완시키면서 행해도 된다. 그리고, 이렇게 열처리를 행한 필름을 권취하여, 본 발명의 필름을 얻는다.Further, the heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. Then, the heat-treated film is taken up to obtain the film of the present invention.
또한, 복수의 열처리 공정을 거쳐도 좋지만, 그 경우는 가장 고온이 되는 열처리 공정의 열처리 온도가 220℃이하인 것이 바람직하다. 보다 바람직하게는 210℃이하이고, 더욱 바람직하게는 200℃이하이고, 가장 바람직하게는 190℃이하이다.In addition, in this case, it is preferable that the heat treatment temperature in the heat treatment process which becomes the highest temperature is 220 캜 or less. More preferably 210 DEG C or lower, further preferably 200 DEG C or lower, and most preferably 190 DEG C or lower.
[특성의 평가 방법][Evaluation method of characteristics]
(1) 고유 점도(1) intrinsic viscosity
필름을 오르토클로로페놀에 용해시키고, 25℃에서 측정한 용액 점도로부터 하기 식에 의해 고유 점도를 얻었다.The film was dissolved in o-chlorophenol, and intrinsic viscosity was obtained from the solution viscosity measured at 25 캜 by the following formula.
ηsp/C=[η]+K[η]2 ·C? sp / C = [?] + K [?] 2 ? C
여기서, ηsp=(용액 점도/용매 점도)-1이고, C는 용매 100ml당의 용해 폴리머 중량이고(본 측정에서는 1g/100ml로 한다), K는 허긴스 정수(0.343이라고 함)이고, 또한 용액 점도, 용매 점도는 오스왈드 점도계를 이용하여 측정했다.Here, ηsp = (solution viscosity / solvent viscosity) -1, C is the weight of the dissolved polymer per 100 ml of solvent (1 g / 100 ml in this measurement), K is the Huggins constant (0.343) , And the solvent viscosity was measured using an Oswald viscometer.
(2) 카르복실 말단기 농도(2) Carboxyl end group concentration
필름 0.5g을 o-크레졸에 용해하고, 수산화 칼륨을 이용하여 전위차 적정해서 측정하고, 카르복실 말단기 농도를 구했다.0.5 g of the film was dissolved in o-cresol, and the solution was titrated by potentiometric titration using potassium hydroxide to determine the carboxyl end group concentration.
(3) 시차 주사 열량 측정(DSC)에 의해 구해지는 미소 흡열 피크 온도 Tmeta(℃)(3) the small endothermic peak temperature Tmeta (占 폚) obtained by differential scanning calorimetry (DSC)
미소 흡열 피크 온도 Tmeta(℃)는 JIS K7122-1987(JIS hand book 1999년판을 참조함)에 준하여, SEIKO Electronics industrial Co., Ltd.제작 시차 주사 열량 측정 장치"로봇 DSC-RDC220"을 데이터 해석에는 디스크 세션 "SSC/5200"을 이용하여 측정했다. 샘플판에 필름을 5mg칭량하고, 25℃부터 300℃까지 20℃/분의 승온 속도로 승온을 행하여 측정을 행했다. 얻어진 시차 주사 열량 측정 차트에 있어서의 결정 융해 피크전의 미소 흡열 피크 온도를 취하여 Tmeta(℃)로 했다. 미소한 흡열 피크가 관측되기 어려운 경우에는 데이터 해석부에서 피크 부근을 확대하여 피크를 판독했다.The micro-endothermic peak temperature Tmeta (° C) was measured using a differential scanning calorimeter "Robot DSC-RDC220" manufactured by SEIKO Electronics industrial Co., Ltd., according to JIS K7122-1987 (refer to JIS Handbook 1999 edition) Disk session "SSC / 5200 ". 5 mg of the film was weighed on the sample plate, and the temperature was raised from 25 占 폚 to 300 占 폚 at a temperature raising rate of 20 占 폚 / minute to carry out the measurement. The fine heat absorption peak temperature before the crystal melting peak in the obtained differential scanning calorimetry chart was taken as Tmeta (占 폚). When a small endothermic peak is difficult to be observed, the data analyzing section enlarges the vicinity of the peak and reads the peak.
미소 흡열 피크의 그래프 판독 방법은 JIS에 기재되어 있지 않지만, 이하의 방법에 의거하여 실시했다. 우선, 135℃의 값과 155℃의 값에서 직선을 긋고, 그래프의 곡선과의 흡열측의 면적을 구한다. 마찬가지로 140℃와 160℃, 145℃와 165℃, 150℃와 170℃, 155℃와 175℃, 160℃와 180℃, 165℃와 185℃, 170℃와 190℃, 175℃와 195℃, 180℃와 200℃, 185℃와 205℃, 190℃와 210℃, 195℃와 215℃, 200℃와 220℃, 205℃와 225℃, 210℃와 230℃, 215℃와 235℃, 220℃와 240℃의 17점 관해서도 면적을 구한다. 미소 피크의 흡열량은 통상, 0.2∼5.0J/g인 것으로부터 면적이 0.2J/g이상 5.0J/g이하인 데이터만을 유효 데이터로서 취급하는 것으로 한다. 합계 18개의 면적 데이터 중에서 유효 데이터이고, 또한 가장 큰 면적을 나타내는 데이터의 온도 영역에 있어서의 흡열 피크의 피크 온도를 취하여 Tmeta(℃)라고 한다. 유효 데이터가 없을 경우, Tmeta(℃)는 없다고 한다. 차트예 로서, 도 1에 나타낸다.The method of reading the graph of the micro endothermic peak is not described in JIS, but was carried out in accordance with the following method. First, a straight line is drawn at a value of 135 ° C and a value of 155 ° C, and the area on the heat absorption side with respect to the curve of the graph is obtained. Likewise, it is also possible to use a mixture of 140 ° C. and 160 ° C., 145 ° C. and 165 ° C., 150 ° C. and 170 ° C., 155 ° C. and 175 ° C., 160 ° C. and 180 ° C., 165 ° C. and 185 ° C., 170 ° C. and 190 ° C., 215 ° C and 215 ° C, 200 ° C and 220 ° C, 205 ° C and 225 ° C, 210 ° C and 230 ° C, 215 ° C and 235 ° C, and 220 ° C The area is also obtained for 17 points at 240 ° C. Since the heat absorption amount of the minute peaks is usually 0.2 to 5.0 J / g, only data having an area of 0.2 J / g or more and 5.0 J / g or less is treated as effective data. The peak temperature of the endothermic peak in the temperature region of the data showing the largest area, which is the effective data among the total of 18 area data, is taken as Tmeta (占 폚). If there is no valid data, it is said that there is no Tmeta (° C). An example of a chart is shown in Fig.
(4) 열수축률(4) Heat shrinkage
JIS-C2318(2007)에 준하여 폭 10mm, 표선 간극 약 100mm의 샘플을 온도 150℃, 하중 0.5g에서 30분간 열처리했다. 그 열처리 전후의 표선 간극을 TECHNO NEEDS COMPANY LTD. 제작 열수축률 측정기(AMM-1호기)를 이용하여 측정하고, 다음 식으로부터 열수축률을 산출했다.A sample having a width of 10 mm and a clearance of about 100 mm was heat-treated at a temperature of 150 占 폚 and a load of 0.5 g for 30 minutes in accordance with JIS-C2318 (2007). The clearances before and after the heat treatment were measured by TECHNO NEEDS COMPANY LTD. (AMM-1), and the heat shrinkage ratio was calculated from the following equation.
열수축률(%)={(L0-L)/L0}×100Heat shrinkage percentage (%) = {(L0-L) / L0} x100
L0: 가열 처리 전의 표선 간극L0: Line clearance before heat treatment
L : 가열 처리 후의 표선 간극L: Line clearance after heat treatment
(5) 면배향 계수(5) Face orientation coefficient
ATAGO CO., LTD. 제작 아베 굴절률계 Type 4T를 사용하고, 광원을 나트륨 램프로 하여 필름 굴절률의 측정을 행했다.ATAGO CO., LTD. Manufactured by Abbe's Refractive Index Type 4T, and the light source was a sodium lamp, the film refractive index was measured.
면배향 계수 = (nMD+nTD)/2- nZD …(A)Plane orientation coefficient = (nMD + nTD) / 2- nZD ... (A)
상기 식(A)에 있어서의 nMD는 필름의 길이 방향(MD)의 굴절률을 나타내고, nTD는 필름의 직행 방향(TD)의 굴절률을 나타내고, nZD는 필름 두께 방향의 굴절률을 나타내고 있다.In the formula (A), nMD represents the refractive index in the longitudinal direction (MD) of the film, nTD represents the refractive index in the film direct direction (TD), and nZD represents the refractive index in the film thickness direction.
(6) 형광 X선 측정에서의 인 원자의 함유량(6) Content of phosphorus atom in fluorescent X-ray measurement
형광 X선 법(Rigaku Corporation 제작 ZSX100e)에 의해, 인 원자의 함유량을 측정했다.The content of phosphorus atoms was measured by a fluorescent X-ray method (ZSX100e manufactured by Rigaku Corporation).
(7) 파장 400∼700nm의 평균 반사율(7) Average reflectance at a wavelength of 400 to 700 nm
분광광도계(Shimadzu Corporation UV2450)에 적분구 부속 장치(Shimadzu Corporation 제작 ISR2200)을 장착하고, 황산 바륨을 표준판으로 해서 표준판을 100%로 한 상대 반사율을 측정한 값으로 한다. 파장 400∼700nm에 있어서, 파장 0.5nm마다의 상대 반사율을 측정하고, 그들의 평균값을 평균 반사율로 한다.The integral reflector (Shimadzu Corporation ISR2200 manufactured by Shimadzu Corporation) is mounted on a spectrophotometer (Shimadzu Corporation UV2450), and the relative reflectance of the standard plate made of barium sulfate as the standard plate is taken as 100%. Relative reflectance is measured at a wavelength of 400 to 700 nm every 0.5 nm, and the average value thereof is taken as an average reflectance.
(8) 125℃, 습도 100%의 조건 하 48시간 방치 후의 신도 유지율(8) Elongation retention after standing for 48 hours under conditions of 125 DEG C and 100% humidity
파단 신도의 측정은 ASTM-D882-97(1999년판 ANNUAL BOOK OF ASTM STANDARDS를 참조함)에 준하고, 샘플을 1cm×20cm의 크기로 자르고, 척간 5cm, 인장 속도300mm/min로 인장했을 때의 파단 신도(초기)를 측정했다. 또한, 측정은 5샘플에 대해서 측정을 실시하고, 그 평균값을 취하여 파단 신도(초기)(A0)로 했다.The breaking elongation was measured according to ASTM-D882-97 (refer to ANNUAL BOOK OF ASTM STANDARDS, 1999). The sample was cut into a size of 1 cm x 20 cm, and the tensile elongation at break of 5 cm at a chuck and a tensile speed of 300 mm / (Initial) was measured. Further, the measurement was carried out for five samples, and the average value was taken to obtain the elongation at break (initial) (A0).
이어서, 샘플을 1cm×20cm의 크기로 자르고, ESPEC CORP.제작 고도 가속 수명 시험 장치 EHS-221MD를 이용하여, 125℃, 습도 100%의 조건 하 48시간 처리를 행한 후, 처리 후의 샘플의 파단 신도를 ASTM-D882-97(1999년판 ANNUAL BOOK OF ASTM STANDARDS를 참조함)에 준하고, 척간 5cm, 인장 속도 300mm/min으로 인장했을 때의 파단 신도(처리 후)를 측정했다. 또한, 측정은 5샘플에 대해서 측정을 실시해 그 평균값을 취하여 파단 신도(처리 후)(A1)로 했다.Subsequently, the sample was cut into a size of 1 cm x 20 cm and processed for 48 hours under the conditions of 125 DEG C and 100% humidity using EHS-221MD manufactured by ESPEC CORP. (After treatment) was measured in accordance with ASTM-D882-97 (refer to ANNUAL BOOK OF ASTM STANDARDS, 1999), and the tensile elongation (after treatment) when stretched at 5 cm in the chuck and at a tensile speed of 300 mm / min. In addition, the measurement was carried out for five samples, and the average value was taken to determine the elongation at break (after treatment) (A1).
얻어진 파단 신도(A0, A1)를 이용하여, 하기 식(1)에 의해 신도 유지율을 산출했다.Using the obtained elongation at break (A0, A1), elongation retention was calculated by the following equation (1).
신도 유지율(%)=A1/A0×100 (1)Elongation Retention Rate (%) = A1 / A0 x 100 (1)
또한, 하기 식(2)에 의해 평균 신도 유지율을 산출했다.The average elongation retention ratio was calculated by the following formula (2).
평균 신도 유지율(%) = (MD방향의 신도 유지율 + TD방향의 신도 유지율)/2 (2)Average elongation retention ratio (%) = (elongation retention in MD direction + elongation retention in TD direction) / 2 (2)
또한, HIRAYAMA MANUFACTURING CORP.제작 고가속 수명 시험 장치(HAST 장치) PC-304R8D을 이용하여 측정해도, ESPEC CORP.제작 고도 가속 수명 시험 장치 EHS-221MD을 이용하여 측정되는 값과 동일한 값이 되므로, HIRAYAMA MANUFACTURING CORP.제작 고가속 수명 시험 장치(HAST 장치) PC-304R8D을 이용하여 측정해도 좋다.Also, even when measured using HIRAYAMA MANUFACTURING CORP. High-speed life test equipment (HAST device) PC-304R8D, it becomes the same value measured by EHS-221MD manufactured by ESPEC CORP. Manufactured by MANUFACTURING CORP. High-speed lifetime tester (HAST device) PC-304R8D may be used.
(9) 125℃, 습도 100%의 조건 하 72시간 방치 후의 신도 유지율(9) Elongation retention rate after leaving for 72 hours under conditions of 125 DEG C and 100% humidity
파단 신도의 측정은 ASTM-D882-97(1999년판 ANNUAL BOOK OF ASTM STANDARDS를 참조함)에 준하여 샘플을 1cm×20cm의 크기로 자르고, 척간 5cm, 인장 속도300mm/min으로 인장했을 때의 파단 신도(초기)를 측정했다. 또한, 측정은 5샘플에 대해서 측정을 실시하고, 그 평균값을 취하여 파단 신도(초기)(A2)로 했다.The breaking elongation was measured according to ASTM-D882-97 (refer to ANNUAL BOOK OF ASTM STANDARDS, 1999). The sample was cut into a size of 1 cm x 20 cm and stretched at a stretch rate of 5 cm at a chuck and a tensile speed of 300 mm / min Initial) was measured. Further, the measurement was carried out for five samples, and the average value was taken to obtain the elongation at break (initial) (A2).
이어서, 샘플을 1cm×20cm의 크기로 자르고, (주)HIRAYAMA MANUFACTURING CORP.제작 고가속 수명 시험 장치(HAST 장치) PC-304R8D를 이용하여, 125℃, 습도 100%의 조건 하 72시간 처리를 행한 후, 처리 후의 샘플의 파단 신도를 ASTM-D882(1999)-97(1999년판 ANNUAL BOOK OF ASTM STANDARDS를 참조함)에 준하여 척간 5cm, 인장 속도 300mm/min으로 인장했을 때의 파단 신도(처리 후)를 측정했다. 또한, 측정은 5샘플에 대해서 측정을 실시하고 그 평균값을 취하여 파단 신도(처리 후)(A3)로 했다.Subsequently, the sample was cut into a size of 1 cm x 20 cm and treated for 72 hours under conditions of 125 ° C and 100% humidity using a high-speed life test apparatus (HAST apparatus) PC-304R8D manufactured by HIRAYAMA MANUFACTURING CORPORATION (After treatment) when the elongation at break of the sample after the treatment was 5 cm and the tensile rate was 300 mm / min in accordance with ASTM-D882 (1999) -97 (refer to ANNUAL BOOK OF ASTM STANDARD, 1999) . In addition, the measurement was carried out for five samples, and the average value thereof was taken as the breaking extension (after processing) (A3).
얻어진 파단 신도(A2, A3)를 이용하여, 하기 식(3)에 의해 신도 유지율을 산출했다.Using the obtained elongation at break (A2, A3), elongation retention was calculated by the following equation (3).
신도 유지율(%) = A3/A2×100 (3)Elongation Retention Rate (%) = A3 / A2 x 100 (3)
또한, 하기(4)에 의해 평균 신도 유지율을 산출했다.The average elongation retention ratio was calculated by the following (4).
평균 신도 유지율(%) = (MD방향의 신도 유지율 + TD방향의 신도 유지율)/2 (4)Average elongation retention ratio (%) = (elongation retention in MD direction + elongation retention in TD direction) / 2 (4)
(( 실시예Example ))
이하, 본 발명에 대해서 실시예를 들어서 설명하지만, 본 발명은 반드시 이들에 한정되는 것은 아니다.Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.
실시예 1Example 1
(원료 PET-1)(Raw PET-1)
디메틸테레프탈레이트 100중량부 및 에틸렌글리콜 60중량부의 혼합물을, 아세트산 칼슘 0.08중량부, 3산화안티몬 0.03중량부를 첨가하고, 통상의 방법에 의해 가열 승온해서 에스테르교환 반응을 행했다. 이어서, 상기 에스테르 교환 반응 생성물을 아세트산 리튬 0.16중량부, 인산 트리메틸 0.11중량부를 첨가한 후, 중합 반응조로 이행한다. 다음에, 가열 승온하면서 반응계를 서서히 감압하여 1mmHg의 감압 하, 290℃에서 통상의 방법에 의해 중합하고, 고유 점도[η] 0.52의 폴리에스테르(폴리에틸렌테레프탈레이트)를 얻었다. 상기 폴리에스테르는 각 변 2mm×4mm×4mm의 직방체로 절단하고, 회전형 진공 중합 장치를 이용하여, 0.5mmHg의 감압 하, 230℃에서 20시간 가열 처리하고, 고유 점도[η] 0.79, 카르복실 말단기 농도 10.5eq/ton의 폴리에스테르를 얻었다.0.08 part by weight of calcium acetate and 0.03 part by weight of antimony trioxide were added to a mixture of 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol. Subsequently, 0.16 part by weight of lithium acetate and 0.11 part by weight of trimethyl phosphate are added to the transesterification reaction product, and then the polymerization is carried out. Next, while the temperature was raised by heating, the reaction system was gradually decompressed and polymerized by a usual method at 290 占 폚 under a reduced pressure of 1 mmHg to obtain a polyester (polyethylene terephthalate) having an intrinsic viscosity [?] Of 0.52. The polyester was cut into rectangular parallelepipeds of 2 mm x 4 mm x 4 mm on each side and subjected to heat treatment at 230 DEG C for 20 hours under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus to obtain a polyester having an intrinsic viscosity [ A polyester having a terminal end concentration of 10.5 eq / ton was obtained.
상기에서 얻어진 원료 PET-1을 온도 180℃, 진공도 0.5mmHg의 조건 하, 2시간의 감압 건조를 행하고, 295℃에서 가열한 압출기에 공급하고, 50㎛ 커트 필터에 의해 이물 여과를 행한 후에 T 다이 구금에 도입했다. 이어서, T다이 구금내로부터 시트상으로 압출해서 용융 단층 시트로 하고, 상기 용융 단층 시트를 표면 온도 20℃로 유지된 드럼 상에 정전 인가법으로 밀착 냉각 고화시켜서 미연신 단층 필름을 얻었다. 이어서, 상기 미연신 단층 필름을 85℃ 온도로 가열한 롤군에서 예열한 후, 90℃온도의 가열롤을 이용하여 길이 방향(MD)으로 3.3배의 연신 배율로 연신을 행하고, 25℃온도의 롤군에서 냉각해서 1축 연신 필름(1축 배향 필름)을 얻었다. 얻어진 1축 연신 필름의 양단을 클립으로 파지하면서 텐터내의 95℃온도의 예열 존으로 안내하고, 계속해서 연속적으로 105℃온도의 가열 존에서 길이 방향으로 직각인 방향(TD)으로 3.6배의 연신 배율로 연신했다. 또한, 이어서, 텐터내의 열처리 존에서 185℃의 열처리 온도(제 1 열처리 온도)에서 20초간의 열처리를 실시하고, 180℃ 온도에서 3%의 이완율로 폭방향(TD)으로 이완 처리를 더 행했다. 이어서, 25℃까지 균일하게 냉각 후, 권취, 두께 125㎛의 필름을 얻었다. 평가한 결과를 표 1에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.The raw material PET-1 obtained above was subjected to vacuum drying for 2 hours under the conditions of a temperature of 180 캜 and a degree of vacuum of 0.5 mmHg, fed to an extruder heated at 295 캜, subjected to foreign-matter filtration with a 50 탆 cut filter, Introduced into detention. Then, the sheet was extruded from the inside of the T-die into a sheet to form a molten single-layer sheet, and the molten single-layer sheet was tightly cooled and solidified on a drum maintained at a surface temperature of 20 占 폚 by electrostatic application to obtain an unstretched single-layer film. Then, the unstretched single-layer film was preheated in a roll group heated to 85 DEG C, stretched at a draw ratio of 3.3 times in the machine direction (MD) using a heating roll at 90 DEG C temperature, To obtain a monoaxially stretched film (uniaxially oriented film). The obtained uniaxially stretched film was guided to a preheating zone at a temperature of 95 DEG C in the tenter while gripping both ends of the uniaxially stretched film with a clip and subsequently stretched continuously in a heating zone at a temperature of 105 DEG C in a direction perpendicular to the longitudinal direction . Then, heat treatment was performed at a heat treatment temperature (first heat treatment temperature) of 185 캜 for 20 seconds in a heat treatment zone in the tenter, and further relaxed in the width direction (TD) at a temperature of 180 캜 at a relaxation rate of 3% . Subsequently, the film was uniformly cooled to 25 占 폚, and then wound to obtain a film having a thickness of 125 占 퐉. The evaluation results are shown in Table 1. The hydrolysis resistance of this film was evaluated as good.
또한, 이하의 방법으로 태양 전지 백시트를 작성했다.In addition, a solar cell back sheet was prepared by the following method.
우선, 상기에서 얻은 두께 125㎛의 본 발명의 필름을 제 1 층으로서 사용한다. 이어서, 접착층으로서 "타케랙(등록상표)" A310(Mitsui Chemicals, Inc.제작) 90중량부, "타케네이트(등록상표)" A3(Mitsui Chemicals, Inc.제작)을 제 1 층의 표면에 도포하고, 또한 그 접착층 상에 제 2 층으로서 두께 12㎛ 배리어록스 "HGTS"(Toray Advanced Film Co., Ltd.제작 알루미나 증착 PET 필름)을 증착층이 제 1 층과 반대측이 되도록 접합했다. 다음에 제 2 층상에 상술의 접착층과 마찬가지로 접착층을 도포하고, 또한 해당 접착층 상에, 두께 50㎛의 이축 배향 폴리에스테르 필름 "루미러(등록상표)" E20(Toray Industries, Inc.제작)을 접합시켜 총두께 187㎛의 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.First, the above-obtained film of the present invention having a thickness of 125 mu m is used as the first layer. Subsequently, 90 parts by weight of "Takeake (registered trademark)" A310 (manufactured by Mitsui Chemicals, Inc.) and "Takenate (registered trademark)" A3 (manufactured by Mitsui Chemicals, Inc.) And 12 占 퐉 thick barrier locks "HGTS" (alumina-deposited PET film produced by Toray Advanced Film Co., Ltd.) as a second layer were bonded on the adhesive layer so that the vapor deposition layer was opposite to the first layer. Next, an adhesive layer was coated on the second layer in the same manner as the above-mentioned adhesive layer, and a biaxially oriented polyester film "LMILLER (registered trademark)" E20 (manufactured by Toray Industries, Inc.) To prepare a back sheet having a total thickness of 187 탆. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 2-4Examples 2-4
표에 나타내는 제막 조건으로 한 것 이외는, 실시예 1과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다.이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained by film formation in the same manner as in Example 1 except that the film forming conditions shown in the table were used. The results of evaluation of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated, which was good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 5Example 5
(원료 PET-2)(Raw material PET-2)
회전형 진공중합장치를 이용하여, 0.5mmHg의 감압 하, 230℃에서 40시간 가열 처리한 것 이외는 원료 PET-1와 동일한 제법으로 고유 점도[η] 0.82, 카르복실 말단기 농도 8.5eq/ton의 폴리에스테르(폴리에틸렌테레프탈레이트)를 얻었다.The intrinsic viscosity [?] Of 0.82, the carboxyl end group concentration of 8.5 eq / ton, and the intrinsic viscosity [?] Of 0.88 were measured by the same method as that of the raw material PET-1 except that the resultant was heated at 230 deg. C for 40 hours under reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus. Of polyester (polyethylene terephthalate) was obtained.
원료로서 상기 원료 PET-2를 사용한 것 이외는, 실시예 1과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained in the same manner as in Example 1 except that the raw material PET-2 was used as a raw material. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 6-8Examples 6-8
표에 나타내는 제막 조건으로 한 것 이외는, 실시예 5와 동일한 방법으로 제막하고, 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A film was formed in the same manner as in Example 5 except that the film forming conditions shown in the table were used, to obtain a polyester film. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 9Example 9
(원료 PET-3)(Raw material PET-3)
원료 PET-1 90중량부에 대하여, RheinChemie사 제작 스타박솔 P100」(폴리 카르보디이미드)을 10중량부 가해서 컴파운딩했다. 이 컴파운딩품을 원료 PET-3으로 한다.10 parts by weight of "Starboksol P100" (polycarbodiimide manufactured by Rhein Chemie) was compounded to 90 parts by weight of the raw material PET-1. This compounding is used as the raw material PET-3.
원료로서, 원료 PET-1을 90중량부와 원료 PET-3을 10중량부(폴리카르보디이미드 1중량부 상당)를 혼합한 것을 사용하는 것 이외는, 실시예 1과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.Except that 90 parts by weight of raw material PET-1 and 10 parts by weight of raw material PET-3 (corresponding to 1 part by weight of polycarbodiimide) were used as raw materials, An ester film was obtained. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 10-12Examples 10-12
표에 나타내는 제막조건으로 한 것 이외는, 실시예 9와 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained by film formation in the same manner as in Example 9 except that the film forming conditions shown in the table were used. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 13-14Examples 13-14
표에 나타내는 제막조건으로 한 것 이외는, 실시예 6과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained by film formation in the same manner as in Example 6 except that the film forming conditions shown in the table were used. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 15Example 15
(원료 PET-4)(Raw material PET-4)
인산 트리메틸의 첨가량을 0.13중량부로 하고 회전형 진공중합장치를 이용하여, 0.5mmHg의 감압 하, 230℃에서 40시간 가열 처리한 것 이외는 원료 PET-1와 동일한 제법으로 고유 점도[η] 0.82, 카르복실 말단기 농도 8.5eq/ton의 폴리에스테르(폴리에틸렌테레프탈레이트)를 얻었다.The intrinsic viscosity [?] Of 0.82, the intrinsic viscosity [?] Of 0.82, the intrinsic viscosity [?] Of 0.82, and the intrinsic viscosity [?] Of 0.82 were determined by the same method as that of the raw PET- A polyester (polyethylene terephthalate) having a carboxyl end group concentration of 8.5 eq / ton was obtained.
원료로서, 상기한 PET-4를 사용한 것 이외는, 실시예 13과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained in the same manner as in Example 13 except that the above-mentioned PET-4 was used as the raw material. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 16Example 16
(원료 PET-5)(Raw PET-5)
인산 트리메틸의 첨가량을 0.25중량부로 하고 회전형 진공중합장치를 이용하여, 0.5mmHg의 감압 하, 230℃에서 40시간 가열 처리한 것 이외는 원료 PET-1와 동일한 제법으로, 고유 점도[η] 0.82, 카르복실 말단기 농도 8.5eq/ton의 폴리에스테르(폴리에틸렌테레프탈레이트)를 얻었다.The intrinsic viscosity [?] Of 0.82 was measured in the same manner as in the production of PET-1 except that the addition amount of trimethyl phosphate was changed to 0.25 parts by weight and heat treatment was performed at 230 占 폚 under reduced pressure of 0.5 mmHg for 40 hours using a rotary vacuum polymerization apparatus. , And a polyester (polyethylene terephthalate) having a carboxyl end group concentration of 8.5 eq / ton was obtained.
원료로서, 상기한 PET-5를 사용한 것 이외는, 실시예 13과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained in the same manner as in Example 13 except that the above-mentioned PET-5 was used as the raw material. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 17Example 17
원료 PET-5를 온도 180℃, 진공도 0.5mmHg의 조건 하에서 2시간의 감압 건조를 행하고, 295℃에서 가열한 압출기에 공급하고, 50㎛ 컷필터에 의해 이물 여과를 행한 후 T다이 구금에 도입했다. 이어서, T다이 구금내에서, 시트상으로 압출해서 용융 단층 시트로 하고, 상기 용융 단층 시트를 표면 온도 20℃로 유지된 드럼 상에 정전 인가법으로 밀착 냉각 고화시켜서 미연신 단층 필름을 얻었다. 이어서, 상기미연신 단층 필름을 85℃ 온도로 가열한 롤군에서 예열한 후, 90℃ 온도의 가열 롤을 이용하여 길이 방향(MD)으로 3.5배 연신을 행하고, 25℃ 온도의 롤군에서 냉각해서 1축 연신 필름을 얻었다. 얻어진 1축 연신 필름의 양단을 클립으로 파지하면서 텐터내의 95℃ 온도의 예열 존으로 안내하고, 이어서 연속적으로 105℃ 온도의 가열 존에서 길이 방향으로 직각인 방향(TD)으로 4.0배 연신했다. 또한, 이어서 텐터내의 열처리 존에서 205℃ 온도(제 1 열처리 온도)에서 20초간의 열처리를 실시했다. 이어서, 180℃ 온도 하에 있어서, 필름을 폭방향(TD)으로 3%의 이완율로 이완시키고, 또한 텐터의 클립 간격을 단축함으로써, 길이 방향(MD)으로 1.5%의 이완율로 이완시켰다. 이어서, 25℃까지 균일하게 냉각 후 권취하여, 폴리에스테르 필름을 얻었다. 평가한 결과를 표에 나타냈다. 이 필름에서 내가수 분해성을 평가한 결과, 양호했다.The raw material PET-5 was dried under reduced pressure for 2 hours under the conditions of a temperature of 180 캜 and a degree of vacuum of 0.5 mmHg, fed to an extruder heated at 295 캜, subjected to foreign-matter filtration through a 50 탆 cut filter, . Subsequently, the sheet was extruded into a sheet in a T-die compartment to form a molten single-layer sheet, and the molten single-layer sheet was closely cooled and solidified on a drum maintained at a surface temperature of 20 占 폚 by electrostatic application to obtain an unstretched single-layer film. Then, the unstretched single-layer film was preheated in a roll group heated to 85 DEG C, stretched 3.5 times in the longitudinal direction (MD) using a heating roll at 90 DEG C, cooled in a roll group at 25 DEG C to obtain 1 Axis stretched film was obtained. Both ends of the obtained monoaxially stretched film were held in a clip while being guided to a preheating zone at a temperature of 95 DEG C in the tenter, and then continuously stretched 4.0 times in the direction TD perpendicular to the longitudinal direction in a heating zone at a temperature of 105 DEG C successively. Then, a heat treatment was performed at a temperature of 205 占 폚 (first heat treatment temperature) for 20 seconds in a heat treatment zone in the tenter. The film was then relaxed at a relaxation rate of 1.5% in the longitudinal direction (MD) by relaxing the film at a relaxation rate of 3% in the transverse direction (TD) and shortening the clip interval of the tenter under the temperature of 180 占 폚. Subsequently, the film was uniformly cooled to 25 DEG C and then wound to obtain a polyester film. The evaluation results are shown in the table. As a result of evaluating the hydrolysis resistance in this film, it was good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 18Example 18
텐터의 클립 간격을 단축함으로써, 길이 방향(MD)의 이완율을 2.0%로 한 것 이외는, 실시예 17과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained in the same manner as in Example 17 except that the clip interval of the tenter was shortened to set the relaxation ratio in the longitudinal direction (MD) to 2.0%. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 19Example 19
압출기(a), 압출기(b)를 갖는 복합 제막장치를 사용했다.A composite film-forming apparatus having an extruder (a) and an extruder (b) was used.
평균 입자 지름 0.2㎛의 산화 티탄(표면 미처리, 루틸형)을 5중량부, 형광증백제 "OB-1"(Eastman Kodak Company 제작)을 0.15중량부 및 원료 PET-5를 94.85중량부의 비율로 혼합한 것을 온도 180℃, 진공도 0.5mmHg의 조건 하에서 2시간의 감압 건조를 행한 후, 압출기(a)측에 공급하고, 280℃에서 용융 압출 후, 50㎛ 컷 필터에 의해 이물 여과를 행한 후, T다이 복합 구금에 도입했다.5 parts by weight of titanium oxide having an average particle diameter of 0.2 占 퐉 (surface untreated rutile type), 0.15 parts by weight of a fluorescent whitening agent "OB-1" (manufactured by Eastman Kodak Company) and 94.85 parts by weight of a raw PET- The mixture was extruded at 280 ° C. and vacuum-dried under the conditions of a vacuum of 0.5 mmHg for 2 hours and then fed to the extruder (a). The extruded product was melt-extruded at 280 ° C., Die composite detention was introduced.
또한, 원료 PET-5를 온도 180℃, 진공도 0.5mmHg의 조건 하에서 2시간의 감압 건조를 행한 것을 준비하고, 이것을 295℃에서 가열한 압출기(b)에 공급하고, 50 ㎛ 컷필터에 의해 이물여과를 행한 후에 T다이 복합 구금에 도입했다.The raw PET-5 was dried under reduced pressure for 2 hours under the conditions of a temperature of 180 占 폚 and a vacuum degree of 0.5 mmHg. The PET-5 was fed to an extruder (b) heated at 295 占 폚, And then introduced into a T-die composite detachment.
이어서, T다이 복합 구금내에서, 압출기(a)로부터의 폴리머와 압출기(b)로부터의 폴리머가 2층으로 적층되도록 합류시킨 후, 시트상으로 공압출해서 용융 적층 시트로 했다. 또한, 양 압출기의 압출량을 컨트롤하여 상기 복합비[압출기(a)층/([압출기(a)층+[압출기(b)층]]을 12%로 했다.Then, in the T-die composite separator, the polymer from the extruder (a) and the polymer from the extruder (b) were combined so as to be laminated in two layers, and then co-extruded into a sheet to obtain a melt-laminated sheet. Further, the extruded amount of the extruder was controlled so that the mixed ratio [extruder (a) layer / ([extruder (a) layer + [extruder (b)]] was adjusted to 12%.
이어서, T다이 구금내로부터, 시트상으로 압출된 용융 적층 시트를 표면 온도 20℃로 유지된 드럼 상에 정전 인가법으로 밀착 냉각 고화시켜서 미연신 적층 필름을 얻었다. 이어서, 상기 미연신 필름을 85℃ 온도로 가열한 롤군에서 예열한 후, 90℃ 온도의 가열롤을 이용하여 길이 방향(MD)으로 3.5배 연신을 행하고, 25℃ 온도의 롤군에서 냉각해서 1축 연신 필름을 얻었다. 얻어진 1축 연신 필름의 양단을 클립에서 파지하면서 텐터내의 95℃ 온도의 예열 존으로 안내하고, 이어서, 연속적으로 105℃ 온도의 가열 존에서 길이 방향으로 직각인 방향(TD)으로 4.0배 연신했다. 또한, 이어서 텐터내의 열처리 존에서 205℃ 온도(제 1 열처리 온도)에서 20초간의 열처리를 실시했다. 이어서, 180℃ 온도 하에 있어서, 필름을 폭방향(TD)으로 3%의 이완율로 이완시키고, 또한 텐터의 클립 간격을 단축함으로써 길이 방향(MD)으로 1.5%의 이완율로 이완시켰다.Subsequently, a melt-laminated sheet extruded into a sheet form was tightly cooled and solidified on a drum maintained at a surface temperature of 20 占 폚 by electrostatic application to obtain an unstretched laminated film. Then, the unstretched film was preheated in a roll group heated to 85 DEG C, stretched 3.5 times in the longitudinal direction (MD) using a heating roll at 90 DEG C, cooled in a roll group at 25 DEG C, A stretched film was obtained. Both ends of the obtained monoaxially stretched film were held in a clip while being guided to a preheating zone at a temperature of 95 DEG C in the tenter, and subsequently stretched 4.0 times in a direction TD perpendicular to the longitudinal direction in a heating zone at 105 DEG C temperature successively. Then, a heat treatment was performed at a temperature of 205 占 폚 (first heat treatment temperature) for 20 seconds in a heat treatment zone in the tenter. The film was then relaxed at a relaxation rate of 3% in the transverse direction (TD) and at a relaxation rate of 1.5% in the longitudinal direction (MD) by shortening the clip interval of the tenter under a temperature of 180 占 폚.
이어서, 25℃까지 균일하게 냉각 후, 권취하여, 두께 125㎛의 폴리에스테르 필름을 얻었다. 얻어진 필름은 (a)층의 두께가 15㎛, (b)층의 두께가 110㎛이었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.Subsequently, the film was uniformly cooled to 25 占 폚 and then taken up to obtain a polyester film having a thickness of 125 占 퐉. The obtained film had a thickness of the layer (a) of 15 mu m and a thickness of the layer (b) of 110 mu m. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
또한, 이하의 방법으로 태양 전지 백시트를 작성했다.In addition, a solar cell back sheet was prepared by the following method.
우선, 상기에서 얻어진 2층 적층 필름을 제 1 층으로서 사용한다. 접착층으로서 "타케랙(등록 상표)" A310(Mitsui Chemicals, Inc. 제작) 90중량부, "타케네이트(등록상표)" A3(Mitsui Chemicals, Inc.제작)을 (b)층의 표면에 도포하고, 그 상에 제 2 층으로서 두께 12㎛ 배리어록스 "HGTS"(Toray Advanced Film Co., Ltd. 제작 알루미나 증착 PET 필름)을 증착층이 제 1 층과 반대측이 되도록 접합시켰다.First, the above-obtained two-layer laminated film is used as the first layer. 90 parts by weight of "Takeake (registered trademark)" A310 (manufactured by Mitsui Chemicals, Inc.) and "Takenate (registered trademark)" A3 (manufactured by Mitsui Chemicals, Inc.) were applied to the surface of the layer (b) And 12 占 퐉 thick barrier locks "HGTS" (alumina-deposited PET film produced by Toray Advanced Film Co., Ltd.) as a second layer were adhered thereon so that the vapor deposition layer was opposite to the first layer.
다음에 제 2 층 상에 상술의 접착층과 동일한 접착층을 도포하고, 그 접착층 상에 두께 50㎛의 이축 배향 폴리에스테르 필름 "루미러(등록상표)" E20(Toray Industries, Inc.제작)을 접합시켜 총두께 187㎛의 백시트를 작성했다. 평가한 결과를 표 1에 나타냈다. 이 백시트의 내가수 분해성을 평가한 결과, 양호했다. 또한, (a)층이 최표층에 위치하고 있기 때문에, 내UV성에 우수한 것이 되었다.Next, the same adhesive layer as the above-mentioned adhesive layer was applied on the second layer, and a biaxially oriented polyester film "Lumirror (registered trademark)" E20 (manufactured by Toray Industries, Inc.) having a thickness of 50 mu m was bonded to the adhesive layer Thereby forming a back sheet having a total thickness of 187 탆. The evaluation results are shown in Table 1. As a result of evaluating the hydrolysis resistance of this back sheet, it was good. Further, since the layer (a) is located at the outermost layer, it has excellent UV resistance.
실시예 20Example 20
평균 입자 지름 0.2㎛의 산화티탄(표면 미처리, 루틸형)을 30중량부, 형광증백제 "OB-1"(Eastman Kodak Company 제작)을 0.15중량부, 원료 PET-5를 69.85중량부의 비율로 혼합한 것을 온도 180℃, 진공도 0.5mmHg의 조건 하에서, 2시간의 감압 건조를 행한 후, 압출기(a)측에 공급한 것 이외는, 실시예 19와 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.30 parts by weight of titanium oxide having an average particle diameter of 0.2 占 퐉 (surface untreated rutile type), 0.15 parts by weight of a fluorescent whitening agent "OB-1" (manufactured by Eastman Kodak Company) and 69.85 parts by weight of a raw PET- Was fed to the extruder (a) side under the conditions of a temperature of 180 캜 and a degree of vacuum of 0.5 mmHg for 2 hours under reduced pressure, and then a film was formed in the same manner as in Example 19 to obtain a polyester film. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 21Example 21
(원료 PET-6)(Raw material PET-6)
회전형 진공중합장치를 이용하여, 0.5mmHg의 감압 하, 230℃에서 5시간 가열 처리한 것 이외는 원료 PET-1와 동일한 제법으로 고유 점도[η] 0.65, 카르복실 말단기 농도 18eq/ton의 폴리에스테르(폴리에틸렌테레프탈레이트)를 얻었다.The intrinsic viscosity [] of 0.65 and the carboxyl end group concentration of 18 eq / ton were measured in the same manner as in the case of the raw PET-1 except that the rotary vacuum polymerization equipment was used and the heat treatment was carried out at 230 DEG C under reduced pressure of 0.5 mmHg for 5 hours. To obtain a polyester (polyethylene terephthalate).
(원료 PET-7)(Raw PET-7)
원료 PET-6 90중량부에, RheinChemie사 제작 스타박솔 P100」(폴리 카르보디이미드)를 10중량부가해서 컴파운딩했다. 이 컴파운딩품을 원료 PET-7로 한다.10 parts by weight of "Starboksol P100" (manufactured by Rhein Chemie Co., Ltd.) (polycarbodiimide) was added to 90 parts by weight of the raw material PET-6. This compounding product is used as the raw material PET-7.
원료로서, 원료 PET-6 90중량부와 원료 PET-710중량부(폴리카르보디이미드 1중량부 상당)를 혼합한 것을 사용한 것 이외는, 실시예 6과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained in the same manner as in Example 6 except that 90 parts by weight of raw material PET-6 and 710 parts by weight of raw PET-7 (corresponding to 1 part by weight of polycarbodiimide) were used as raw materials . The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 22Example 22
(원료 PET-8)(Raw material PET-8)
회전형 진공중합장치를 이용하여, 0.5mmHg의 감압 하, 230℃에서 100시간 가열 처리한 것 이외는 원료 PET-1와 동일한 제법으로 고유 점도[η] 1.2, 카르복실 말단기 농도 8.0eq/ton의 폴리에스테르를 얻었다.The intrinsic viscosity [?] Of 1.2, the carboxyl end group concentration of 8.0 eq / ton [?] Were obtained by the same method as that of the raw PET-1 except that the resultant was subjected to heat treatment at 230 deg. C for 100 hours under reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus. Of polyester was obtained.
원료로서, 원료 PET-8을 사용한 것 이외는, 실시예 6과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A polyester film was obtained in the same manner as in Example 6 except that the raw material PET-8 was used as the raw material. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
실시예 23Example 23
실시예 6과 동일한 방법으로 행하여 두께 125㎛의 필름을 얻었다. 평가한 결과를 표에 나타냈다.Was carried out in the same manner as in Example 6 to obtain a film having a thickness of 125 탆. The evaluation results are shown in the table.
또한 이하의 방법으로 태양 전지 백시트를 작성했다.In addition, a solar cell back sheet was prepared by the following method.
상기에서 얻어진 두께 125㎛의 필름을 제 1 층으로서 사용한다. 이어서, 접착층으로서 "타케 랙(등록상표)" A310(Mitsui Chemicals, Inc.제작) 90중량부, "타케네이트(등록상표)" A3(Mitsui Chemicals, Inc.제작)을 제 1 층의 표면에 도포하고, 그 접착층 상에 제 2 층으로서 두께 12㎛ 배리어락스 "HGTS"(Toray Advanced Film Co., Ltd.제작 알루미나 증착 PET 필름)을 증착층이 제 1 층과 반대측이 되도록 접합시키고, 다음에 제 2 층 상에 상술의 접착층과 동일한 접착층을 도포하고, 상기 접착층 상에 제 3 층으로서 두께 250㎛의 이축 배향 폴리에스테르 필름 "루미러(등록상표)" S10(Toray Industries, Inc.제작)을 접합시켰다. 또한, 제 3 층 상에 상술의 접착층과 동일한 접착층을 도포하고, 해당 접착층 상에 두께 50㎛의 이축 배향 폴리에스테르 필름 "루미러(등록상표)" E20(Toray Industries, Inc.제작)을 접합시켜, 총두께 437㎛의 백시트를 형성했다. 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 결과, 양호했다.The thus obtained film having a thickness of 125 mu m is used as the first layer. Subsequently, 90 parts by weight of "Takeake (registered trademark)" A310 (manufactured by Mitsui Chemicals, Inc.) and "Takenate (registered trademark)" A3 (manufactured by Mitsui Chemicals, Inc.) , And a barrier layer "HGTS" (Alumina-deposited PET film produced by Toray Advanced Film Co., Ltd.) having a thickness of 12 μm was adhered as a second layer on the adhesive layer so that the vapor deposition layer was on the opposite side of the first layer, The same adhesive layer as the above-mentioned adhesive layer was applied on the two layers, and a biaxially oriented polyester film "LMILLER (registered trademark)" S10 (manufactured by Toray Industries, Inc.) having a thickness of 250 mu m was bonded . Further, the same adhesive layer as the above-mentioned adhesive layer was applied on the third layer, and a biaxially oriented polyester film "Lumirror (registered trademark)" E20 (manufactured by Toray Industries, Inc.) having a thickness of 50 mu m was bonded to the adhesive layer To form a back sheet having a total thickness of 437 mu m. The evaluation results are shown in the table. As a result of evaluating the hydrolysis resistance of this back sheet, it was good.
실시예 24Example 24
폴리에스테르 필름의 두께를 50㎛로 하는 것 이외는, 실시예 6과 동일한 제조 방법으로 폴리에스테르 필름을 얻었다. 필름을 평가한 결과를 표에 나타냈다.A polyester film was obtained in the same manner as in Example 6 except that the thickness of the polyester film was 50 탆. The evaluation results of the film are shown in the table.
또한, 이하의 방법으로 태양 전지 백시트를 작성했다. In addition, a solar cell back sheet was prepared by the following method.
상기에서 얻어진 두께 50㎛의 필름을 제1층으로서 사용한다.The thus obtained film having a thickness of 50 mu m is used as the first layer.
이어서, 접착층으로서 "타케랙(등록상표)" A310(Mitsui Chemicals, Inc. 제작) 90중량부, "타케네이트(등록상표)" A3(Mitsui Chemicals, Inc. 제작)을 제 1 층에 도포하고, 상기 접착층 상에 제 2 층으로서 두께 12㎛ 배리어락스 "HGTS"(Toray Advanced Film Co., Ltd.제작 알루미나 증착 PET 필름)를 증착층이 제 1 층과 반대측이 되도록 접합시키고, 이어서 제 2 층 상에 상기의 접착층과 동일한 접착층을 도포하고, 상기 접착층 상에 제 3 층으로서 두께 250㎛의 이축 배향 폴리에스테르 필름 "루미러(등록상표)" S10(Toray Industries, Inc.제작)을 접합시켰다. 또한, 제 3 층 상에 상술의 접착층과 동일한 접착층을 도포하고, 상기 접착층 상에 두께 188㎛의 이축 배향 폴리에스테르 필름 "루미러(등록상표)" E20(Toray Industries, Inc. 제작)을 접합시켜, 총두께 500㎛의 백시트를 형성했다. 평가한 결과를 표 1에 나타냈다. 이 백시트의 내가수 분해성을 평가한 결과, 양호했다.Subsequently, 90 parts by weight of "Takeake (registered trademark)" A310 (manufactured by Mitsui Chemicals, Inc.) and "Takenate (registered trademark)" A3 (manufactured by Mitsui Chemicals, Inc.) A 12 占 퐉 thick barrier lock "HGTS" (an alumina-deposited PET film produced by Toray Advanced Film Co., Ltd.) as a second layer was bonded on the adhesive layer so that the vapor deposition layer was on the opposite side of the first layer, , And a biaxially oriented polyester film "Loumir (registered trademark)" S10 (manufactured by Toray Industries, Inc.) having a thickness of 250 mu m was bonded as a third layer onto the adhesive layer. Further, the same adhesive layer as the above-mentioned adhesive layer was applied on the third layer, and a biaxially oriented polyester film "LMILLAR (registered trademark)" E20 (manufactured by Toray Industries, Inc.) having a thickness of 188 mu m was bonded to the adhesive layer To form a back sheet having a total thickness of 500 mu m. The evaluation results are shown in Table 1. As a result of evaluating the hydrolysis resistance of this back sheet, it was good.
실시예 25 - 42Examples 25 to 42
표에 나타내는 제막 조건으로 한 것 이외는, 실시예 5와 동일한 방법으로 제막하고, 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 이 필름의 내가수 분해성을 평가한 바, 양호했다.A film was formed in the same manner as in Example 5 except that the film forming conditions shown in the table were used, to obtain a polyester film. The evaluation results of the obtained film are shown in the table. The hydrolysis resistance of this film was evaluated as good.
이어서, 얻어진 폴리에스테르 필름을 이용하여, 실시예 1과 동일한 방법으로 백시트를 작성했다. 상기 백시트를 평가한 결과를 표에 나타냈다. 이 백시트의 내가수 분해성을 평가한 바, 양호했다.Subsequently, a back sheet was prepared in the same manner as in Example 1, using the obtained polyester film. The results of evaluating the back sheet are shown in the table. The hydrolysis resistance of this back sheet was evaluated as good.
비교예 1Comparative Example 1
(원료 PET-9)(Raw material PET-9)
디메틸테레프탈레이트 100부 및 에틸렌글리콜 60부의 혼합물을 아세트산 칼슘 0.08부, 3산화 안티몬 0.03부를 첨가하고, 통상의 방법에 의해 가열 승온해서 에스테르 교환 반응을 행했다. 이어서, 상기 에스테르 교환 반응 생성물을 아세트산 리튬 0.16부, 인산 트리메틸 0.11부를 첨가한 후, 중합 반응조로 이행한다. 다음에, 가열 승온하면서 반응계를 서서히 감압하여 1mmHg의 감압 하, 290℃에서 통상의 방법에 의해 중합하고, 고유 점도[η] 0.52의 폴리에스테르를 얻었다. 상기 폴리에스테르는 각 변 2mm×4mm×4mm의 직방체로 절단하고, 회전형 진공중합장치를 이용하여, 0.5mmHg의 감압 하, 230℃에서 8시간 가열 처리하고, 고유 점도[η] 0.74, 카르복실 말단기 농도 13eq/ton의 폴리에스테르를 얻었다.0.08 part of calcium acetate and 0.03 part of antimony trioxide were added to a mixture of 100 parts of dimethyl terephthalate and 60 parts of ethylene glycol, and the temperature was elevated by heating in a conventional manner to effect transesterification reaction. Subsequently, 0.16 part of lithium acetate and 0.11 part of trimethyl phosphate are added to the transesterification reaction product, and then transition to the polymerization reaction tank is carried out. Next, while the temperature was raised by heating, the reaction system was gradually decompressed and polymerized at 290 占 폚 under a reduced pressure of 1 mmHg by a conventional method to obtain a polyester having an intrinsic viscosity [?] Of 0.52. The polyester was cut into rectangular parallelepipeds of 2 mm x 4 mm x 4 mm on each side and heat-treated at 230 deg. C for 8 hours under a reduced pressure of 0.5 mmHg using a rotary vacuum polymerization apparatus to give an intrinsic viscosity [?] Of 0.74, And a polyester having a terminal group concentration of 13 eq / ton was obtained.
원료로서 상기 원료 PET-9를 사용한 것 이외는, 실시예 1과 동일한 방법으로, 두께 125㎛의 필름을 얻었다. 평가한 결과를 표에 나타냈다. 이 필름을 평가한 바, 내가수 분해성이 열악한 것이 판명되었다.A film having a thickness of 125 탆 was obtained in the same manner as in Example 1 except that the raw material PET-9 was used as a raw material. The evaluation results are shown in the table. Evaluation of this film revealed that the hydrolysis resistance was poor.
또한, 실시예 1과 동일한 방법으로, 두께 187㎛의 백시트를 형성했다. 평가한 결과를 표에 나타냈다. 이 백시트를 평가한 바, 내가수 분해성이 열악한 것이 판명되었다.Further, a back sheet having a thickness of 187 탆 was formed in the same manner as in Example 1. The evaluation results are shown in the table. Evaluation of this back sheet revealed that the hydrolysis resistance was poor.
비교예 2Comparative Example 2
표에 나타내는 제막조건으로 한 것 이외는, 비교예 1과 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 특히, 내가수 분해성이 열악한 결과가 되었다.A polyester film was obtained by film formation in the same manner as in Comparative Example 1 except that the film forming conditions shown in the table were used. The evaluation results of the obtained film are shown in the table. Particularly, the hydrolysis resistance was poor.
또한, 백시트도 실시예 1의 방법으로 작성, 두께 187㎛의 백시트를 얻었다. 평가한 결과를 표 1에 나타냈다. 특히, 내가수 분해성이 열악한 결과가 되었다.A back sheet having a thickness of 187 占 퐉 was also obtained by the method of Example 1. The evaluation results are shown in Table 1. Particularly, the hydrolysis resistance was poor.
비교예 3Comparative Example 3
표에 나타내는 제막조건으로 한 것 이외는, 실시예 1과 동일한 방법으로 제막하고, 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 특히, 내가수 분해성이 열악한 결과가 되었다.A film was formed in the same manner as in Example 1 except that the film forming conditions shown in the table were used, to obtain a polyester film. The evaluation results of the obtained film are shown in the table. Particularly, the hydrolysis resistance was poor.
또한 백시트도 실시예 1의 방법으로 작성, 두께 187㎛의 백시트를 얻었다. 평가한 결과를 표 1에 나타냈다. 특히, 내가수 분해성이 열악한 결과가 되었다.A back sheet having a thickness of 187 占 퐉 was also obtained by the method of Example 1. The evaluation results are shown in Table 1. Particularly, the hydrolysis resistance was poor.
비교예 4Comparative Example 4
표에 나타내는 제막조건으로 한 것 이외는, 실시예 9와 동일한 방법으로 제막하고, 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 특히 내가수 분해성이 열악한 결과가 되었다.A film was formed in the same manner as in Example 9 except that the film forming conditions shown in the table were used, to obtain a polyester film. The evaluation results of the obtained film are shown in the table. In particular, the hydrolysis resistance was poor.
또한 백시트도 실시예 1의 방법으로 작성하여, 두께 187㎛의 백시트를 얻었다.The back sheet was also formed by the method of Example 1 to obtain a back sheet having a thickness of 187 占 퐉.
평가한 결과를 표 1에 나타냈다. 특히, 내가수 분해성이 열악한 결과가 되었다.The evaluation results are shown in Table 1. Particularly, the hydrolysis resistance was poor.
비교예 5Comparative Example 5
표에 나타내는 제막조건으로 한 것 이외는, 실시예 5와 동일한 방법으로 제막하여 폴리에스테르 필름을 얻었다. 얻어진 필름을 평가한 결과를 표에 나타냈다. 특히 내가수 분해성이 열악한 결과가 되었다.A polyester film was obtained by film formation in the same manner as in Example 5 except that the film forming conditions shown in the table were used. The evaluation results of the obtained film are shown in the table. In particular, the hydrolysis resistance was poor.
또한, 백시트도 실시예 1의 방법으로 작성하여, 두께 187㎛의 백시트를 얻었다. 평가한 결과를 표 1에 나타냈다. 특히 내가수 분해성이 열악한 결과가 되었다.The back sheet was also formed by the method of Example 1 to obtain a back sheet having a thickness of 187 占 퐉. The evaluation results are shown in Table 1. In particular, the hydrolysis resistance was poor.
또한, 표 중의 「시트」란 「백시트」를 나타낸다.The " sheet " in the table indicates " back sheet ".
(산업상의 이용 가능성)(Industrial availability)
본 발명의 필름은 백시트를 사용하는 태양 전지에 적합하게 사용할 수 있다.The film of the present invention can be suitably used for a solar cell using a back sheet.
Claims (19)
시차 주사 열량 측정(DSC)에 의해 구해지는 미소 흡열 피크 온도 Tmeta(℃)는 220℃이하이고,
125℃, 습도 100%의 조건 하에서 72시간 방치 후의 평균 신도 유지율이 10%이상이고,
상기 Tmeta(℃)와 면배향 계수(B2)는 하기 식(B)을 만족하는 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.
B2 ≥ 0.000886 × Tmeta - 0.00286 식(B)The carboxyl end group concentration is 13 eq / ton or less,
The small endothermic peak temperature Tmeta (占 폚) obtained by differential scanning calorimetry (DSC) is 220 占 폚 or less,
The average elongation retention after standing for 72 hours under the conditions of 125 DEG C and 100% humidity is 10% or more,
Wherein the Tmeta (占 폚) and the plane orientation coefficient (B2) satisfy the following formula (B).
B2? 0.000886 占 Tmeta? 0.00286 (B)
에틸렌테레프탈레이트 성분이 폴리에스테르의 에스테르 성분에 대하여 90mol%이상인 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.The method according to claim 1,
Wherein the ethylene terephthalate component is at least 90 mol% based on the ester component of the polyester.
면배향 계수(B2)는 0.165이상인 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.The method according to claim 1,
And a planar orientation coefficient (B2) of 0.165 or more.
형광 X선 측정에 의해 구해지는 인 원자의 함유량은 200ppm이상인 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.3. The method according to claim 1 or 2,
Wherein the content of phosphorus atoms determined by fluorescent X-ray measurement is 200 ppm or more.
상기 미소 흡열 피크 온도 Tmeta(℃)는 150℃이상 205℃이하인 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.3. The method according to claim 1 or 2,
Wherein the small endothermic peak temperature Tmeta (占 폚) is 150 占 폚 or higher and 205 占 폚 or lower.
고유 점도는 0.6∼1.2dl/g의 범위인 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.3. The method according to claim 1 or 2,
Wherein the intrinsic viscosity is in the range of 0.6 to 1.2 dl / g.
상기 카르복실 말단기 농도는 12eq/ton이하인 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.3. The method according to claim 1 or 2,
Wherein the carboxyl end group concentration is 12 eq / ton or less.
폴리에스테르층을 적어도 2층 갖는 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.3. The method according to claim 1 or 2,
A polyester film for a solar cell, comprising at least two polyester layers.
125℃, 습도 100%의 조건 하 48시간 방치 후의 평균 신도 유지율은 50%이상인 것을 특징으로 하는 태양 전지용 폴리에스테르 필름.3. The method according to claim 1 or 2,
And the average elongation retention after standing for 48 hours under conditions of 125 DEG C and 100% humidity is 50% or more.
미연신 폴리에스테르 필름을 적어도 1축으로 연신한 후, 155℃이상 220℃이하의 온도에서 열처리하는 것을 특징으로 하는 태양 전지용 폴리에스테르 필름의 제조 방법.A process for producing a polyester film for a solar cell according to any one of claims 1 to 3,
Wherein the unstretched polyester film is stretched at least in one axis, and then heat-treated at a temperature of from 155 캜 to 220 캜.
125℃, 습도 100%의 조건 하 48시간 방치 후의 평균 신도 유지율은 50%이상인 것을 특징으로 하는 태양 전지 백시트.15. The method of claim 14,
And the average elongation retention after standing for 48 hours under the conditions of 125 DEG C and 100% humidity is 50% or more.
하기 방법 (1) 및 방법 (2) 중 적어도 하나의 방법을 포함하는 것을 특징으로 하는 태양 전지용 폴리에스테르 필름의 제조방법.
방법 (1) : 상기 열처리 공정에 있어서, 필름을 열처리함과 동시에 필름 MD 방향, TD 방향의 각각의 방향으로 0.5~10% 수축시키는 방법.
방법 (2) : 제막이 완료된 필름을 별도의 장치에 도입하고, 가열 온도 150~220℃, 가열 시간 10~60초 사이의 가열 처리를 하는 방법.14. The method of claim 13,
A method for producing a polyester film for a solar cell, which comprises at least one of the following methods (1) and (2).
Method (1): In the heat treatment step, the film is heat-treated and at the same time shrinks by 0.5 to 10% in the directions of the MD and TD directions.
Method (2): A method in which a formed film is introduced into a separate apparatus and a heat treatment is performed at a heating temperature of 150 to 220 캜 and a heating time of 10 to 60 seconds.
에틸렌테레프탈레이트 성분이 폴리에스테르의 에스테르 성분에 대하여 90mol%이상이고, 폴리에스테르 필름의 카르복실 말단기 농도가 12eq/ton이하인 것을 특징으로 하는 태양 전지용 폴리에스테르 필름의 제조방법.
14. The method of claim 13,
Wherein the ethylene terephthalate component is at least 90 mol% based on the ester component of the polyester, and the carboxyl end group concentration of the polyester film is 12 eq / ton or less.
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| JPJP-P-2009-075884 | 2009-03-26 | ||
| JP2009075884 | 2009-03-26 | ||
| PCT/JP2010/054424 WO2010110119A1 (en) | 2009-03-26 | 2010-03-16 | Polyester film for solar cells, solar cell back sheet using same, and solar cell |
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| JP (1) | JP5728944B2 (en) |
| KR (1) | KR101660391B1 (en) |
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| JPWO2010110119A1 (en) | 2012-09-27 |
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