KR101220224B1 - Polyvinyl acetal film having improved reflectance and preparation method thereof - Google Patents

Polyvinyl acetal film having improved reflectance and preparation method thereof Download PDF

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KR101220224B1
KR101220224B1 KR1020110114090A KR20110114090A KR101220224B1 KR 101220224 B1 KR101220224 B1 KR 101220224B1 KR 1020110114090 A KR1020110114090 A KR 1020110114090A KR 20110114090 A KR20110114090 A KR 20110114090A KR 101220224 B1 KR101220224 B1 KR 101220224B1
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polyvinyl acetal
film
acetal film
resin
titanium oxide
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김경연
송경수
정성진
김상묵
김혜진
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에스케이씨 주식회사
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    • C08L29/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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Abstract

PURPOSE: A polyvinylacetal film is provided to be used as a sealing film for a solar cell module by having excellent light resistance, penetration resistance, and reflectivity. CONSTITUTION: A polyvinylacetal film comprises a polyvinylacetal resin, and a titanium oxide which is heat-resistant coated and has a diameter of 0.4 micrometers or less. The reflectivity of the polyvinylacetal film to a wavelength of 350-1100 nm is 93% or more and the difference of a yellowness index according to EN 410 between before and after UV irradiation(ΔY.I.) is 2.0 or less. A manufacturing method of the polyvinylacetal film comprises: a step of manufacturing a raw material resin by mixing a plasticizer and the heat-resistant coated titanium oxide; and a step of melt-extruding the raw material resin at a temperature of 100-200 deg. C and cooling the extrudate to obtain a final film.

Description

반사율이 우수한 폴리비닐아세탈 필름 및 이의 제조방법{POLYVINYL ACETAL FILM HAVING IMPROVED REFLECTANCE AND PREPARATION METHOD THEREOF}Polyvinyl acetal film with excellent reflectivity and manufacturing method thereof {POLYVINYL ACETAL FILM HAVING IMPROVED REFLECTANCE AND PREPARATION METHOD THEREOF}

본 발명은 태양광 모듈에 봉지재로서 사용될 수 있는 폴리비닐아세탈 필름 및 이의 제조방법에 관한 것이다.The present invention relates to a polyvinyl acetal film that can be used as an encapsulant in a solar module and a method for producing the same.

태양전지는 태양광 에너지를 직접 전기로 바꾸는 태양광 발전 시스템의 심장부를 구성하는 것으로서, 단결정, 다결정 또는 비결정 실리콘계 반도체를 이용하여 제조된다. 태양전지 셀은 그대로 사용되는 경우는 거의 없고, 일반적으로 수장 내지 수십장의 태양전지 소자를 직렬 또는 병렬로 배선하고, 장기간에 걸쳐 셀을 보호하기 위해 여러 가지 패키징(packaging)하여 유닛화되어 있다. 이 패키지에 편입되는 유닛을 태양전지 모듈이라고 부른다.The solar cell constitutes the heart of a photovoltaic system that directly converts solar energy into electricity, and is manufactured using a single crystal, polycrystalline or amorphous silicon-based semiconductor. Solar cells are rarely used as they are, and generally, several to tens of solar cell elements are wired in series or in parallel, and variously packaged and united to protect the cells over a long period of time. The unit incorporated in this package is called a solar cell module.

최근에 환경문제나 에너지 문제 등으로 인해 태양전지가 주목받고 개발이 진행되고 있다. 태양전지 모듈은 일반적으로 표면측 투명 보호 부재인 유리 기판과 이면측 보호 부재인 이면 보호 필름 사이에 봉지재 시트 2매가 태양전지 모듈용 태양전지 셀을 감싸고 있는 구성으로 되어 있다. 이와 같은 태양전지 모듈은 유리 기판, 봉지재 시트, 태양전지 셀, 봉지재 시트, 이면 보호 필름의 순서로 적층하고, 가열 가압하여 봉지재 시트를 가교 경화시킴으로써 접착 일체화하는 것에 의해 제조된다.Recently, solar cells have been attracting attention due to environmental problems and energy problems, and developments are being made. In general, a solar cell module has a structure in which two sheets of encapsulant surround a solar cell for a solar cell module between a glass substrate that is a front side transparent protective member and a backside protective film that is a back side protective member. Such a solar cell module is manufactured by laminating | stacking in order of a glass substrate, an encapsulating material sheet, a solar cell, an encapsulating material sheet, and a back protective film, heat-pressing, and carrying out an adhesive integration by crosslinking-hardening an encapsulating material sheet.

일반적으로 태양전지 모듈용 봉지재 시트로는 가교제를 포함하는 투명연질수지로 이루어진 시트를 사용하며, 수지의 주성분은 에틸렌비닐아세테이트(EVA) 공중합체가 주로 사용되었다. 그러나, 이러한 EVA 필름은 강도와 내관통성이 불량하여 발전소 모듈 외에도 박막형 태양광 모듈(특히 BIPV 시스템)로 사용하기에 적당하지 않다. 그 결과, 현재 태양광 모듈의 봉지재로서 폴리비닐아세탈 필름을 사용하여 기능을 개선한 필름이 개발되고 있다.In general, the encapsulant sheet for a solar cell module uses a sheet made of a transparent soft resin containing a crosslinking agent, and an ethylene vinyl acetate (EVA) copolymer is mainly used as a main component of the resin. However, these EVA films are not suitable for use as thin film solar modules (particularly BIPV systems) in addition to power plant modules due to poor strength and penetration resistance. As a result, the film which improves the function using the polyvinyl acetal film as a sealing material of a solar module is currently developed.

국제 공개특허공보 제WO 2009/035081호는 폴리비닐아세탈 수지에 평균 직경 0.4~2.0㎛의 산화티탄 입자를 2.0~7.0 x 105 개/㎠가 되도록 분산시켜 제조한 합판유리용 중간막을 개시하고 있다. 그러나, 이와 같이 폴리비닐아세탈 수지를 태양광 모듈의 봉지재로 사용했을 경우, EVA 필름보다 모듈효율이 높지않은 문제점이 있으며, UV를 장기적으로 조사했을 때 EVA 필름보다 내광성이 떨어져 황변이 발생하는 문제점이 있다. WO 2009/035081 discloses an interlayer film for laminated glass prepared by dispersing titanium oxide particles having an average diameter of 0.4 to 2.0 µm in a polyvinyl acetal resin so as to be 2.0 to 7.0 x 10 5 particles / cm 2. . However, when the polyvinyl acetal resin is used as the encapsulant of the solar module, there is a problem that the module efficiency is not higher than that of the EVA film. There is this.

이에 따라, 반사율이 우수하면서도 종래보다 내황변성 및 내충격성이 개선된 새로운 폴리비닐아세탈 필름의 개발이 요구되고 있다.Accordingly, there is a demand for the development of a new polyvinyl acetal film having excellent reflectance and improved yellowing resistance and impact resistance.

국제 공개특허공보 제WO2009/035081호International Publication No. WO2009 / 035081

따라서, 본 발명의 목적은 다양한 외부환경에서도 내관통성, 반사율 등이 우수한 폴리비닐아세탈 필름 및 이의 제조방법을 제공하는 것이다.Accordingly, it is an object of the present invention to provide a polyvinyl acetal film excellent in penetration resistance, reflectance, and the like, even in various external environments.

상기 목적에 따라, 본 발명은 폴리비닐아세탈 수지 및 직경 0.4㎛ 미만의 내열코팅된 산화티탄을 포함하고, 350 내지 1100 nm 파장에 대한 반사율이 93% 이상이며, EN 410에 따른 황색지수의 UV 조사 전후의 차이값(△Y.I.)이 2.0 이하인, 폴리비닐아세탈 필름을 제공한다.According to the above object, the present invention comprises polyvinyl acetal resin and heat-resistant coated titanium oxide with a diameter of less than 0.4 ㎛, reflectance for wavelengths of 350 to 1100 nm is 93% or more, UV irradiation of the yellow index according to EN 410 The polyvinyl acetal film whose difference before and after (DELTA YI) is 2.0 or less is provided.

상기 다른 목적에 따라, 본 발명은 (a) 폴리비닐아세탈 수지에 가소제 및 내열코팅된 직경 0.4㎛ 미만의 산화티탄을 혼합시켜 원료수지를 제조하는 단계; 및 (b) 상기 원료수지를 용융압출하고 냉각시켜 최종 필름을 얻는 단계를 포함하는, 상기 폴리비닐아세탈 필름의 제조방법을 제공한다. According to the above another object, the present invention comprises the steps of (a) preparing a raw material resin by mixing a polyvinyl acetal resin with a plasticizer and heat-resistant coated titanium oxide less than 0.4㎛ diameter; And (b) melt extruding and cooling the raw material resin to obtain a final film, the method for producing the polyvinyl acetal film .

또한, 본 발명은 폴리비닐아세탈 필름을 포함하는 태양광 모듈 봉지재 필름을 제공한다.The present invention also provides a solar module encapsulant film comprising a polyvinyl acetal film.

이상과 같은 본 발명의 폴리비닐아세탈 필름은, 종래의 EVA 필름에 비하여 내관통성이 향상되고 기능성 첨가제에 의해 내광성 및 반사율이 우수하므로, 태양광 모듈에 봉지재 필름으로 사용되어 우수한 성능을 발휘할 수 있다.
As described above, the polyvinyl acetal film of the present invention has improved light resistance and excellent light resistance and reflectance by a functional additive compared to a conventional EVA film, and thus can be used as an encapsulant film in a solar module to exhibit excellent performance. .

본 발명의 필름은, 폴리비닐아세탈 수지에 직경 0.4㎛ 미만의 내열코팅된 산화티탄을 포함하는 것을 특징으로 한다.The film of the present invention is characterized in that the polyvinyl acetal resin comprises heat-resistant coated titanium oxide having a diameter of less than 0.4 m.

본 발명에서 사용되는 폴리비닐아세탈 수지는 폴리비닐부티랄 수지, 폴리비닐포르말 수지, 글루탈알데히드-가교된 폴리비닐부티랄 수지, 또는 이들의 블렌드 수지일 수 있는데, 그 중에서 폴리비닐부티랄 수지가 가장 바람직하다. The polyvinyl acetal resin used in the present invention may be polyvinyl butyral resin, polyvinyl formal resin, glutaraldehyde-crosslinked polyvinyl butyral resin, or a blend resin thereof, among which polyvinyl butyral resin Most preferred.

이와 같은 폴리비닐아세탈 수지는 필름의 총 중량을 30 내지 90 중량%, 더욱 바람직하게는 50 내지 75 중량%로 함유되는 것이 유리와 접합시 내충격성, 기계적 특성, 내열성이 양호하여 좋다.
Such polyvinyl acetal resin may contain 30 to 90% by weight, more preferably 50 to 75% by weight of the total weight of the film is good in impact resistance, mechanical properties, heat resistance when bonding with glass.

본 발명의 필름에는 트리에틸렌글리콜 비스 2-에틸헥사노에이트 (3G8), 테트라에틸렌글리콜 디헵타노에이트 (4G7), 트리에틸렌글리콜 비스 2-에틸부티레이트 (3GH), 트리에틸렌글리콜 비스 2-헵타노에이트 (3G7), 디부톡시에톡시에틸 아디페이트 (DBEA), 디부틸 세바케이트 (DBS), 비스 2-헥실 아디페이트 (DHA), 및 이들의 혼합물 중에서 선택되는 가소제가 함유될 수 있다. 이러한 가소제는 필름의 총중량을 기준으로 8 내지 68 중량%, 더욱 바람직하게는 20 내지 45 중량%로 각 수지층에 함유되는 것이 필름의 내열성, 기계적특성, 내충격성, 및 내수성 면에서 우수하여 좋다.The film of the present invention contains triethylene glycol bis 2-ethylhexanoate (3G8), tetraethylene glycol diheptanoate (4G7), triethylene glycol bis 2-ethylbutyrate (3GH), triethylene glycol bis 2-heptanoate (3G7), dibutoxyethoxyethyl adipate (DBEA), dibutyl sebacate (DBS), bis 2-hexyl adipate (DHA), and mixtures thereof may be contained. Such a plasticizer may be contained in each resin layer at 8 to 68% by weight, more preferably 20 to 45% by weight based on the total weight of the film, and may be excellent in terms of heat resistance, mechanical properties, impact resistance, and water resistance of the film.

상기 내열코팅된 산화티탄은, 알루미나 또는 알루미나-실리카 코팅된 산화티탄인 것이 바람직하고, 입자의 직경은 0.4㎛ 미만인 것이 바람직하다. 직경이 0.4㎛ 이상일 경우, 필름내 무기물 분산이 어려워져 무기물간의 응집이 발생하여 반사율이 높지 않고, 균일성이 떨어지는 문제점이 있다. 더욱 바람직하게는 입자의 직경이 0.05 내지 0.3 ㎛인 것이 좋다. The heat-resistant coated titanium oxide is preferably alumina or alumina-silica coated titanium oxide, and the diameter of the particles is preferably less than 0.4 mu m. When the diameter is 0.4 μm or more, dispersion of the inorganic material in the film becomes difficult, so that aggregation between the inorganic materials occurs, the reflectance is not high, and there is a problem that the uniformity is inferior. More preferably, the diameter of the particles is 0.05 to 0.3 ㎛.

상기 내열코팅된 산화티탄의 함량은 필름의 중량을 기준으로 1 내지 30 중량%인 것이 바람직하며, 3 내지 20 중량%인 것이 더욱 바람직하다. 상기 범위 내일 때 반사율과 내관통성이 우수한 장점이 있다.The heat-resistant coated titanium oxide is preferably 1 to 30% by weight, more preferably 3 to 20% by weight based on the weight of the film. Within the above range, there is an advantage of excellent reflectance and penetration resistance.

또한, 본 발명의 필름에는 산화방지제, UV 안정제, UV 흡수제, 유리부착력 조절제 및 이들의 혼합물 중에서 선택되는 첨가제가 함유될 수 있다.In addition, the film of the present invention, antioxidants, UV Stabilizer, UV Absorbent, Glass Adhesion Additives selected from modulators and mixtures thereof may be contained.

구체적으로, 산화방지제로서는 Basf사의 Irganox, 부틸하이드록시톨루엔(BHT) 등이 사용될 수 있고; UV 안정제로서는 Basf사의 Tinuvin 등이 사용될 수 있고; UV 흡수제로서는 케미프로화성사의 Chemisorb 12, Chemisorb 79, Chemisorb 74, Chemisorb 102, Basf사의 Tinuvin 328, Tinuvin 329, Tinuvin 326 등이 사용될 수 있고; 유리부착력 조절제로서는 Mg, K, Na, 에폭시계 변성 Si오일, 또는 이들의 혼합물이 사용될 수 있다.Specifically, as the antioxidant, Irganox, butylhydroxytoluene (BHT) and the like of Basf may be used; As the UV stabilizer, Tinuvin or the like of Basf may be used; Examples of UV absorbers include Chemisorb 12, Chemisorb 79, Chemisorb 74, Chemisorb 102, and Tinuvin from Basf. 328, Tinuvin 329, Tinuvin 326 and the like can be used; As the glass adhesion modifier, Mg, K, Na, epoxy-modified Si oil, or a mixture thereof may be used.

이러한 첨가제는 필름의 중량을 기준으로 0.01 내지 1.0 중량%, 더욱 바람직하게는 0.2 내지 0.5 중량%로 함유되는 것이 열적안전성, 내광성, 및 유리접합력 면에서 우수하여 좋다.Such additives may be contained in an amount of 0.01 to 1.0% by weight, more preferably 0.2 to 0.5% by weight based on the weight of the film, in terms of thermal safety, light resistance, and glass bonding strength.

본 발명의 폴리비닐아세탈 필름은 총 두께가 0.2 내지 2.0 mm 인 것이 바람직한데, 상기 범위 내일 때 내충격성 및 내관통성을 양호하게 하는 장점이 있다.Polyvinyl acetal film of the present invention preferably has a total thickness of 0.2 to 2.0 mm, there is an advantage to improve the impact resistance and penetration resistance within the above range.

본 발명의 필름은 양면의 표면조도(Rz)가 모두 20㎛ 이상인 것이 바람직하며, 예를 들어 20 내지 70 ㎛일 수 있다. 표면조도가 상기 범위일 때 공정 중에 필름을 적재시 블로킹(blocking) 현상이 발생하는 것이 최소화될 수 있으며 유리 접합 공정시에 탈기(deairing)가 보다 효과적으로 이루어질 수 있다.
It is preferable that both of the surface roughness Rz of the film of this invention are 20 micrometers or more, for example, it may be 20-70 micrometers. When the surface roughness is in the above range, a blocking phenomenon may occur when the film is loaded during the process, and deairing may be more effectively performed during the glass bonding process.

이와 같은 본 발명의 폴리비닐아세탈 필름은, Such polyvinyl acetal film of the present invention,

(a) 폴리비닐아세탈 수지에 가소제 및 내열코팅된 직경 0.4㎛ 미만의 산화티탄을 포함하는 첨가제를 혼합시켜 원료수지를 제조하는 단계; 및(a) preparing a raw material resin by mixing a polyvinyl acetal resin with an additive including a plasticizer and a heat-resistant coated titanium oxide having a diameter of less than 0.4 µm; And

(b) 상기 원료수지를 용융압출하고 냉각시켜 최종 필름을 얻는 단계를 포함하여 제조될 수 있다.(b) melt-extruding the raw material resin and cooling to obtain a final film.

상기 제조방법에 있어서, 재료성분인 폴리비닐아세탈 수지, 가소제, 첨가제 등은 앞에서 설명한 바와 같은 본 발명의 필름의 조성을 갖도록 각각의 성분 및 함량범위로 혼합할 수 있다. In the above production method, polyvinyl acetal resin, plasticizer, additives, etc., which are the material components, may be mixed in each component and content range to have the composition of the film of the present invention as described above.

상기 용융압출 온도는 100 내지 200 ℃의 온도인 것이 바람직한데, 만약 200℃ 초과일 경우에는 열에너지에 의해 가장 결합에너지가 낮은 아세테이트 결합이 깨지면서 열분해가 발생할 수 있고, 분해에 의한 점도가 낮아질 수 있으며, 가소제 휘발로 인해 가공성이 떨어질 수 있다.The melt extrusion temperature is preferably a temperature of 100 to 200 ℃, if it exceeds 200 ℃ thermal decomposition may occur as the thermal bond breaks the acetate bond of the lowest binding energy, the viscosity may be lowered by decomposition, Due to the volatilization of the plasticizer, workability may be degraded.

상기 단계 (b) 이후에 필름의 양면에 표면패턴 처리하여 양면의 표면조도(Rz)가 모두 20㎛ 이상이 되도록 하는 단계를 추가로 포함할 수 있는데, 구체적으로 Rz 20㎛ 이상으로 표면가공한 매트 롤을 이용하여 가열 및 표면압착하는 공정을 통해 수행할 수 있으며, 이 경우 내블로킹성 및 탈기성이 향상될 수 있다.
After the step (b) it may further include the step of the surface pattern treatment on both sides of the film so that both the surface roughness (Rz) of both sides to 20㎛ or more, specifically, the surface of the mat Rz 20㎛ or more It can be carried out through a process of heating and surface pressing using a roll, in which case blocking resistance and degassing resistance can be improved.

이상과 같은 본 발명의 폴리비닐아세탈 필름은, 폴리비닐아세탈 수지를 주성분으로 하여 종래의 EVA 필름 대비 내관통성을 향상시키고, 내열코팅된 직경 0.4㎛ 미만의 산화티탄을 이용하여 내광성과 반사율을 동시에 높일 수 있다.Polyvinyl acetal film of the present invention as described above, the polyvinyl acetal resin as a main component to improve the penetration resistance compared to conventional EVA film, and simultaneously improve the light resistance and reflectance by using titanium oxide having a diameter of less than 0.4㎛ coated heat-resistant Can be.

바람직하게는, 본 발명의 필름의 EN 410에 의거한 반사율이 350 내지 1100 nm 범위의 파장에 대해 93% 초과를 나타낸다. 상기 범위 내일 때 반사율이 보다 우수하므로 태양광 모듈 적용시 태양광 효율이 상승가는 장점이 있다.Preferably, the reflectance according to EN 410 of the film of the invention exhibits greater than 93% for wavelengths in the range from 350 to 1100 nm. Since the reflectance is more excellent when in the above range, there is an advantage that the solar efficiency increases when the solar module is applied.

또한, 본 발명의 필름에 대해 ASTM E313에 의거하여 황색지수(Y.I.)를 측정하였을 때, 400~1100nm의 조건에서 초기 값과 UV 조사 후의 값의 차이(△Y.I.)가 2.0 미만을 나타낼 수 있다. 상기 범위 내일 때 가시광선 영역 투과율 높일 수 있으므로, 태양광 모듈 적용시에 태양광 효율이 올라가고, 유리와 접합시 내충격성과 기계적 특성, 투명성, 시인성, 및 품질이 상승하는 장점이 있다.In addition, when the yellow index (Y.I.) was measured based on ASTM E313 for the film of the present invention, the difference between the initial value and the value after UV irradiation (ΔY.I.) may be less than 2.0 under conditions of 400 to 1100 nm. Since it is possible to increase the visible light region transmittance within the above range, the solar efficiency is increased when the solar module is applied, and impact and mechanical properties, transparency, visibility, and quality are increased when bonding with glass.

또한, KS L 2007 규격 기준에 따른 폴리비닐아세탈 필름 접합 유리의 내관통성 시험의 관통 높이가 4m 초과인 내관통성을 가질 수 있다. 상기 범위 내일 때 충격흡수, 유리보호, 및 안전성 면에서 우수한 장점이 있다.In addition, the penetration height of the penetration resistance test of the polyvinyl acetal film laminated glass according to the KS L 2007 standard may have a penetration resistance of more than 4m. Within this range there are excellent advantages in terms of shock absorption, glass protection, and safety.

또한, 펌멜(pummel) 접합력 평가로서, 2.1T 유리-폴리비닐아세탈 필름-2.1 T유리 적층체를 -18℃로 냉각하여 해머를 이용하여 연달아 친 후에 필름에 남아있는 유리의 양이 30~80% 수준을 나타낼 수 있는데, 만약 30% 미만인 경우 유리와 필름간의 접합력이 불량하고 반대로 90% 이상인 경우 접합력이 너무 높아 필름이 찢어질 수 있어 바람직하지 않다.In addition, as evaluation of the pummel bonding force, the amount of glass remaining in the film after cooling the 2.1T glass-polyvinyl acetal film-2.1T glass laminate to -18 ° C and successively using a hammer is 30 to 80%. If it is less than 30%, the bonding strength between the glass and the film is poor, and if it is more than 90%, the bonding strength is too high and the film may be torn, which is undesirable.

또한, 백화거리 평가로서 2.1T 유리-폴리비닐아세탈 필름-2.1T 유리 적층체를 100℃의 물에 6시간 침지한 뒤, 상기 적층체의 가장자리 부위로부터 측정한 백화거리가 7mm 미만일 수 있다. 상기 범위 내일 때 내수성이 우수하여 태양 모듈 전극이 산화되는 것을 방지하고 모듈을 보호하여 장기 내구성을 갖는 장점이 있다.
In addition, after immersing the 2.1T glass-polyvinyl acetal film-2.1T glass laminate in water at 100 ° C. for 6 hours as an evaluation of the whitening distance, the whitening distance measured from the edge portion of the laminate may be less than 7 mm. Within the above range, it is excellent in water resistance to prevent oxidation of the solar module electrode and protects the module, which has the advantage of having long-term durability.

이에 따라, 본 발명의 필름은 태양광 모듈에 봉지재 필름으로 사용될 경우, 태양광 모듈의 효율을 높일 수 있다.
Accordingly, when the film of the present invention is used as an encapsulant film in the solar module, it is possible to increase the efficiency of the solar module.

이하, 본 발명을 실시예에 의해 보다 상세히 설명한다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

하기 실시예 및 비교예에서 사용한 성분은 다음과 같다:The components used in the following examples and comparative examples are as follows:

- 폴리비닐부티랄(PVB) 수지: 부틸화도 70mol%, 수평균분자량 14.0만, Tg 72℃, GH, Xingwei사, 중국-Polyvinyl butyral (PVB) resin: 70 mol% butylation degree, number average molecular weight 140,000, Tg 72 ℃, GH, Xingwei China

- 에틸렌비닐아세테이트(EVA) : VA 28%, 1626-EVA, 한화석유화학사, 한국-Ethylene vinyl acetate (EVA): VA 28%, 1626-EVA, Hanwha Petrochemical, Korea

- 트리에틸렌글리콜 비스 2-에틸렌헥사노에이트: 순도 97.0%이상, WVC3800, Celanese사, 독일 -Triethylene glycol bis 2-ethylenehexanoate: purity of at least 97.0%, WVC3800, Celanese, Germany

- Chemisorb 12: 벤조페논계열, 케미프로화성사, 일본-Chemisorb 12: Benzophenone series, Chemipro Chemicals, Japan

- Chemisorb 79: 벤조트리아졸계열, 케미프로화성사, 일본-Chemisorb 79: Benzotriazole series, Chemiprosseong Co., Japan

- Irganox: 입체장애적(hindered) 페놀계, Basf사, 독일Irganox: hindered phenolic, Basf, Germany

- 부틸하이드록시톨루엔(BHT): Lanxess, Vulkanox사, 독일Butylhydroxytoluene (BHT): Lanxess, Vulkanox, Germany

- Mg, K, 및 Na: Mg 아세테이트, K 아세테이트, Na 아세테이트, OCI사, 한국Mg, K, and Na: Mg acetate, K acetate, Na acetate, OCI Corporation, Korea

- 알루미나-실리카 코팅된 직경 0.3㎛ 산화티탄 입자: R105, Dupont사, 미국Alumina-silica coated titanium oxide particles 0.3 탆 in diameter: R105, Dupont, USA

- 알루미나 코팅된 직경 0.2㎛ 산화티탄 입자: R104, Dupont사, 미국Alumina coated 0.2 μm diameter titanium oxide particles: R104, Dupont, USA

- 직경 0.5㎛ 산화티탄 입자: COTIOX KA-100, 코스모화학사, 한국-0.5㎛ titanium oxide particles: COTIOX KA-100, Cosmo Chemical, Korea

- 직경 2.0㎛ 산화티탄 입자: COTIOX KA-300, 코스모화학사, 한국
-Titanium oxide particles with diameter 2.0㎛: COTIOX KA-300, Cosmo Chemical, Korea

실시예 1Example 1

원료수지 100중량% 기준으로, 폴리비닐부티랄(PVB) 수지 59.69중량%, 가소제로서 트리에틸렌글리콜 비스 2-에틸렌헥사노에이트 30중량%, UV 흡수제로서 Chemisorb 79 0.2중량%, 산화방지제로서 Irganox 0.1중량%, 유리부착력 조절제로서 Mg+K+Na 0.01중량%, 및 알루미나-실리카 코팅된 직경 0.3㎛ 산화티탄 10중량%를 첨가하여, 원료수지 조성물을 제조하였다.Based on 100% by weight of the raw material resin, 59.69% by weight of polyvinyl butyral (PVB) resin, 30% by weight of triethylene glycol bis 2-ethylenehexanoate as a plasticizer, 0.2% by weight of Chemisorb 79 as a UV absorber, Irganox 0.1 as an antioxidant A raw material resin composition was prepared by adding% by weight, 0.01% by weight of Mg + K + Na as a glass adhesion modifier, and 10% by weight of alumina-silica coated diameter 0.3 μm titanium oxide.

상기 원료수지 조성물을 150℃의 용융온도에서 1개의 반죽기(kneader)가 구비된 트윈 스크류 압출기를 통하여 용융 압출하고, 160℃의 캐스팅롤에서 냉각시켜 필름을 얻었다. The raw resin composition was melt extruded through a twin screw extruder equipped with one kneader at a melting temperature of 150 ° C., and cooled on a casting roll at 160 ° C. to obtain a film.

캐스팅롤에서 냉각한 필름을 Rz 70㎛ 거칠기를 가지는 매트롤에서 100℃의 온도로 가열 압착하여, 표면거칠기 Rz 25㎛이고 총 두께가 0.76mm인 필름을 최종 완성하였다.
The film cooled by the casting roll was heat-pressed at a temperature of 100 ° C. in a matrol having a Rz 70 μm roughness to finally complete a film having a surface roughness Rz of 25 μm and a total thickness of 0.76 mm.

실시예 2 및 비교예 1 및 2Example 2 and Comparative Examples 1 and 2

원료수지 조성물로서 하기 표 1에 기재된 바와 같은 조성의 수지 조성물을 사용한 것을 제외하고는, 상기 실시예 1과 동일한 절차를 수행하여 폴리비닐아세탈 필름을 제조하였다.
A polyvinyl acetal film was prepared in the same manner as in Example 1, except that a resin composition having a composition as shown in Table 1 was used as the raw material resin composition.

시험예Test Example

상기 실시예 및 비교예에서 제조된 폴리비닐아세탈 필름에 대하여 다음과 같이 물성을 평가하여, 그 결과를 하기 표 1에 나타내었다.
The physical properties of the polyvinyl acetal films prepared in Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 1 below.

* 반사율* Reflectance

EN 410 에 의거하여 폴리비닐아세탈 필름의 350 내지 1100 nm 파장에 대한 반사율을 측정하였다. 구체적으로, 유리-폴리비닐아세탈 필름-백시트(PVDF/PET)의 적층구조로 라미네이터에서 150℃의 온도로 15분간 가열가압을 통해 접합하여 시편을 제작하고, 헌터랩사의 측정기를 이용하여 반사모드의 조건으로 측정하였다.
In accordance with EN 410 the reflectance of the polyvinyl acetal film for the wavelength of 350 to 1100 nm was measured. Specifically, a glass-polyvinyl acetal film-back sheet (PVDF / PET) laminated structure laminated by laminating at 150 ° C. for 15 minutes by heating and pressure to prepare a specimen, and using a Hunter Lab's measuring device, a reflection mode It measured on condition of.

* △Y.I(황색지수변화량) 측정* △ Y.I (Yellow index change) measurement

EN 410에 의거하여 폴리비닐아세탈 필름의 황색지수변화를 평가하였다. 구체적으로, 유리-폴리비닐아세탈 필름-유리의 적층구조로 라미네이터에서 150℃의 온도로 15분간 가열가압을 통해 접합하여 시편을 제작하고, 헌터랩사의 측정기를 이용하여 400~1100nm의 조건으로 초기 값과 UV 조사후의 값의 차이값(△Y.I.)을 계산하였다.
The yellowness index of the polyvinyl acetal film was evaluated according to EN 410. Specifically, the lamination structure of glass-polyvinyl acetal film-glass was laminated in a laminator at a temperature of 150 ° C. for 15 minutes by heating and pressing to prepare a specimen, and the initial value under the conditions of 400-1100 nm using Hunter Lab's measuring device. And the difference value (ΔYI) between the values after UV irradiation were calculated.

* 낙하높이 * Drop height

KS L 2007에 의거하여 폴리비닐아세탈 필름이 접합된 유리의 내관통성을 평가하였다. 구체적으로, 300mm x 300mm의 2.1T유리-폴리비닐아세탈 필름-2.1T유리의 적층구조로 라미네이터에서 150℃의 온도로 15분간 가열가압을 통해 접합하여 시편을 제작한 뒤, 2.26kg의 강구를 시편에 낙구시켜, 시편이 관통이 되는 높이(MBH)를 측정하였다.
Based on KS L 2007, the penetration resistance of the glass by which the polyvinyl acetal film was laminated was evaluated. Specifically, the laminated structure of 2.1T glass-polyvinyl acetal film-2.1T glass of 300mm x 300mm was laminated in a laminator at 150 ° C. for 15 minutes by heating and pressing to prepare a specimen, and then, a steel ball of 2.26 kg was prepared. The height (MBH) through which the specimen penetrated was measured.

* 유리접착력 평가* Glass adhesion evaluation

유리-폴리비닐아세탈 필름-백시트(PVDF/PET)의 적층구조로 라미네이터에서 150℃의 온도로 15분간 가열가압을 통해 접합하여 시편을 제작하고, 만능시험기(UTM, QM100, 큐머시스)를 이용하여 인장속도 50mm/min로 180도 잡아당겨 유리에서 필름이 탈락될 때 걸리는 힘을 측정하였다.
Laminated structure of glass-polyvinyl acetal film-backsheet (PVDF / PET) was laminated by laminating in a laminator at 150 ℃ for 15 minutes by heating and pressing to make a specimen, and using a universal testing machine (UTM, QM100, Cumulsis) By pulling 180 degrees at a tensile rate of 50mm / min was measured the force taken when the film is removed from the glass.

* 펌멜접합력 평가* Fummel Bonding Force Evaluation

펌멜(pummel) 접합력 평가를 통해 폴리비닐아세탈 필름과 유리간의 접합력을 평가하였다. 구체적으로, 300mm x 300mm의 2.1T유리-폴리비닐아세탈필름-2.1T유리의 적층구조로 라미네이터에서 150℃의 온도로 15분간 가열가압을 통해 접합하여 시편을 제작하고, 상기 시편을 -18℃로 냉각하여 해머로 같은 힘으로 연달아친 후에, 폴리비닐아세탈 필름에 남아있는 유리의 양의 정도를 측정한 뒤, 필름에 남아있는 유리가 없는 경우를 0으로 하고, 필름에 유리가 모두 남아있는 경우를 10으로 하여, 0 부터 10까지의 값을 매겼다.
The adhesive force between the polyvinyl acetal film and the glass was evaluated through the evaluation of the pummel bonding force. Specifically, a laminated structure of 2.1T glass-polyvinyl acetal film-2.1T glass of 300 mm x 300 mm was laminated in a laminator at 150 ° C. for 15 minutes by heating and pressing to prepare a specimen, and the specimen was −18 ° C. After cooling and continuous with the same force with a hammer, the amount of glass remaining in the polyvinyl acetal film is measured, and the case where there is no glass remaining on the film is set to 0, and all the glass remains on the film. A value of 0 to 10 was assigned as 10.

Figure 112011086761105-pat00001
Figure 112011086761105-pat00001

(상기 표에서 괄호안의 숫자는 각 성분의 중량%이다)
(The numbers in parentheses in the table above represent the weight percentage of each component.)

상기 표 1에서 보듯이, 본 발명에 따른 실시예의 폴리비닐아세탈 필름은 반사율, 내황변성, 내충격성 등에서 종래기술에 따른 비교예의 폴리비닐아세탈 필름에 비해 우수한 성능을 발휘하였다.
As shown in Table 1, the polyvinyl acetal film of the embodiment according to the present invention exhibited excellent performance compared to the polyvinyl acetal film of the comparative example according to the prior art in reflectance, yellowing resistance, impact resistance and the like.

이상, 본 발명을 상기 실시예를 중심으로 하여 설명하였으나 이는 예시에 지나지 아니하며, 본 발명은 본 발명의 기술분야에서 통상의 지식을 가진 자에게 자명한 다양한 변형 및 균등한 기타의 실시예를 이하에 첨부한 청구범위 내에서 수행할 수 있다는 사실을 이해하여야 한다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, It is to be understood that the invention may be practiced within the scope of the appended claims.

Claims (9)

폴리비닐아세탈 수지 및 직경 0.4㎛ 미만의 내열코팅된 산화티탄을 포함하고,
350 내지 1100 nm 파장에 대한 반사율이 93% 이상이며, EN 410에 따른 황색지수의 UV 조사 전후의 차이값(△Y.I.)이 2.0 이하인, 폴리비닐아세탈 필름.
Polyvinyl acetal resin and heat-resistant coated titanium oxide having a diameter of less than 0.4 μm,
The polyvinyl acetal film whose reflectance with respect to the wavelength of 350-1100 nm is 93% or more, and the difference value ((DELTA) YI) before and after UV irradiation of the yellow index according to EN 410 is 2.0 or less.
제1항에 있어서,
상기 내열코팅된 산화티탄은, 알루미나 또는 알루미나-실리카가 코팅된 산화티탄이며, 1 내지 30 중량%의 함량으로 폴리비닐아세탈 필름에 함유되는 것을 특징으로 하는, 폴리비닐아세탈 필름.
The method of claim 1,
The heat-resistant coated titanium oxide, alumina or alumina-silica coated titanium oxide, characterized in that contained in the polyvinyl acetal film in an amount of 1 to 30% by weight, polyvinyl acetal film.
제1항에 있어서,
상기 폴리비닐아세탈 수지는 폴리비닐부티랄(PVB) 수지이며, 30 내지 90 중량%의 함량으로 함유되는 것을 특징으로 하는, 폴리비닐아세탈 필름.
The method of claim 1,
The polyvinyl acetal resin is a polyvinyl butyral (PVB) resin, characterized in that contained in an amount of 30 to 90% by weight, polyvinyl acetal film.
제1항에 있어서,
상기 폴리비닐아세탈 필름의 양면의 표면조도(Rz)는 모두 20㎛ 이상인 것을 특징으로 하는, 폴리비닐아세탈 필름.
The method of claim 1,
The surface roughness (Rz) of both surfaces of the said polyvinyl acetal film is 20 micrometers or more, The polyvinyl acetal film characterized by the above-mentioned.
제1항에 있어서,
상기 폴리비닐아세탈 필름은, 트리에틸렌글리콜 비스 2-에틸헥사노에이트 (3G8), 테트라에틸렌글리콜 디헵타노에이트 (4G7), 트리에틸렌글리콜 비스 2-에틸부티레이트 (3GH), 트리에틸렌글리콜 비스 2-헵타노에이트 (3G7), 디부톡시에톡시에틸 아디페이트 (DBEA), 디부틸 세바케이트 (DBS), 비스 2-헥실 아디페이트 (DHA), 및 이들의 혼합물 중에서 선택되는 가소제를 8 내지 68 중량% 함량으로 함유하는 것을 특징으로 하는, 폴리비닐아세탈 필름.
The method of claim 1,
The polyvinyl acetal film is triethylene glycol bis 2-ethylhexanoate (3G8), tetraethylene glycol diheptanoate (4G7), triethylene glycol bis 2-ethylbutyrate (3GH), triethylene glycol bis 2-hep 8 to 68% by weight of a plasticizer selected from tanoate (3G7), dibutoxyethoxyethyl adipate (DBEA), dibutyl sebacate (DBS), bis 2-hexyl adipate (DHA), and mixtures thereof Polyvinyl acetal film, characterized in that it contains.
제1항에 있어서,
상기 폴리비닐아세탈 필름은, 산화방지제, UV 안정제, UV 흡수제, 유리부착력 조절제 및 이들의 혼합물 중에서 선택되는 첨가제를 필름의 중량을 기준으로 0.01 내지 1 중량%로 함유하는 것을 특징으로 하는, 폴리비닐아세탈 필름.
The method of claim 1,
The polyvinyl acetal film, polyvinyl acetal, characterized in that it contains an additive selected from antioxidants, UV stabilizers, UV absorbers, glass adhesion control agents and mixtures thereof in an amount of 0.01 to 1% by weight based on the weight of the film. film.
제1항에 있어서,
상기 폴리비닐아세탈 필름은, KS L 2007 규격 기준에 따른 폴리비닐아세탈 필름 접합 유리의 내관통성 시험 결과 관통 높이가 4m 초과인 것을 특징으로 하는, 폴리비닐아세탈 필름.
The method of claim 1,
The polyvinyl acetal film is a polyvinyl acetal film, characterized in that the penetration height is greater than 4m as a result of the penetration resistance test of polyvinyl acetal film laminated glass according to KS L 2007 standard.
(a) 폴리비닐아세탈 수지에 가소제 및 내열코팅된 직경 0.4㎛ 미만의 산화티탄을 혼합시켜 원료수지를 제조하는 단계; 및
(b) 상기 원료수지를 100 내지 200 ℃의 온도에서 용융 압출하고 냉각시켜 최종 필름을 얻는 단계를 포함하는, 제1항의 폴리비닐아세탈 필름의 제조방법.
(a) preparing a raw material resin by mixing a polyvinyl acetal resin with a plasticizer and heat-resistant coated titanium oxide having a diameter of less than 0.4 µm; And
(b) Melt-extrusion and cooling the raw material resin at a temperature of 100 to 200 ℃ to obtain a final film, the method of producing a polyvinyl acetal film of claim 1.
제1항 내지 제7항 중 어느 한 항의 폴리비닐아세탈 필름을 포함하는 태양광 모듈 봉지재 필름. A solar module encapsulant film comprising the polyvinyl acetal film of any one of claims 1 to 7.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08259279A (en) * 1995-01-23 1996-10-08 Central Glass Co Ltd Laminated glass and its production
WO2009035081A1 (en) 2007-09-12 2009-03-19 Sekisui Chemical Co., Ltd. Interliner for laminated glass
JP2010019720A (en) 2008-07-11 2010-01-28 Toshiba Electron Tubes & Devices Co Ltd Composition for reflective film, reflective film and x-ray detector
JP2011138009A (en) 2009-12-28 2011-07-14 Sharp Corp Coating liquid for intermediate layer of electrophotographic photoreceptor having organic photosensitive layer, electrophotographic photoreceptor, image forming apparatus and image forming method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08259279A (en) * 1995-01-23 1996-10-08 Central Glass Co Ltd Laminated glass and its production
WO2009035081A1 (en) 2007-09-12 2009-03-19 Sekisui Chemical Co., Ltd. Interliner for laminated glass
JP2010019720A (en) 2008-07-11 2010-01-28 Toshiba Electron Tubes & Devices Co Ltd Composition for reflective film, reflective film and x-ray detector
JP2011138009A (en) 2009-12-28 2011-07-14 Sharp Corp Coating liquid for intermediate layer of electrophotographic photoreceptor having organic photosensitive layer, electrophotographic photoreceptor, image forming apparatus and image forming method

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