WO2015019452A1 - Film comprenant de l'acétal polyvinylique - Google Patents

Film comprenant de l'acétal polyvinylique Download PDF

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Publication number
WO2015019452A1
WO2015019452A1 PCT/JP2013/071418 JP2013071418W WO2015019452A1 WO 2015019452 A1 WO2015019452 A1 WO 2015019452A1 JP 2013071418 W JP2013071418 W JP 2013071418W WO 2015019452 A1 WO2015019452 A1 WO 2015019452A1
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Prior art keywords
film
pvb
pva
molecular weight
peak top
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PCT/JP2013/071418
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English (en)
Japanese (ja)
Inventor
楠藤　健
磯上　宏一郎
浩孝 保田
俊輔 藤岡
辻　嘉久
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2013539834A priority Critical patent/JP5420808B1/ja
Priority to PCT/JP2013/071418 priority patent/WO2015019452A1/fr
Publication of WO2015019452A1 publication Critical patent/WO2015019452A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/28—Condensation with aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10688—Adjustment of the adherence to the glass layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a film containing polyvinyl acetal.
  • the present invention also relates to an interlayer film for laminated glass comprising the film, and a laminated glass using the interlayer film. Furthermore, it is related with the solar cell sealing material which consists of the said film, and the solar cell module using the said sealing material.
  • Polyvinyl acetal is obtained by an acetalization reaction in water under acidic conditions using polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”) and an aldehyde compound.
  • PVA polyvinyl alcohol
  • Polyvinyl acetal films are used in various applications because they are tough and have a unique structure that has both hydrophilic hydroxy groups and hydrophobic acetal groups.
  • Various polyvinyl acetals have been proposed. Yes. Among them, polyvinyl formal produced from PVA and formaldehyde, polyvinyl acetal in a narrow sense produced from PVA and acetaldehyde, and polyvinyl butyral produced from PVA and butyraldehyde occupy commercially important positions.
  • polyvinyl butyral is widely used as an interlayer film for laminated glass of automobiles and buildings, and occupies a particularly important position commercially.
  • polyvinyl acetal has a problem that it is easy to be colored by heating; impurities (undissolved components) are easily generated in the film of polyvinyl acetal.
  • impurities undissolved components
  • Patent Documents 1 and 2 describe a method for suppressing coloring of polyvinyl acetal by acetalization at a specific hydroxide ion concentration under high temperature and high pressure.
  • Patent Document 3 describes a method of suppressing coloring of the obtained polyvinyl acetal by adding a reducing agent after neutralization by acetalization reaction.
  • impurities were likely to be generated in the film prepared using the polyvinyl acetal obtained by the methods described in Patent Documents 1 to 3.
  • Patent Document 4 describes a method of suppressing the generation of coarse particles by adjusting the concentration of the obtained resin particle slurry in the neutralization reaction after the acetalization reaction.
  • Patent Document 5 describes a method for suppressing the generation of coarse particles by defining the relationship between an acid catalyst and a surfactant used in the acetalization reaction.
  • impurities were easily generated in the film produced using the polyvinyl acetal obtained by the methods described in Patent Documents 4 and 5.
  • the film was easily colored by heating. For these reasons, there is a strong demand for polyvinyl acetals in which all the above-mentioned problems are solved.
  • a solar cell module usually has a photoelectric semiconductor layer (hereinafter sometimes referred to as a solar cell) having a transparent cover for protection from external influences.
  • the said photovoltaic cell is normally installed between hard cover plates, such as a glass plate and glass, or between a glass plate and a back sheet, and is fixed with the sealing material which has adhesiveness.
  • the problem of the solar cell module using EVA was that the metal component was corroded by acetic acid generated by hydrolysis or thermal decomposition of EVA. Another problem was that it was necessary to laminate while proceeding with the crosslinking reaction, which was difficult to produce by a roll-to-roll process.
  • curable casting resin When manufacturing a solar cell module using a curable casting resin, it is difficult to control the embedding of the solar cell and the curing of the resin, and it is hardly adopted in practice. In addition, some curable casting resins generate bubbles or peel off after several years.
  • PVB polyvinyl butyral
  • EVA ethylene glycol dimethacrylate copolymer
  • PVB polyvinyl butyral
  • the sealing material using PVB is excellent in the adhesiveness with respect to glass, and penetration resistance. Thus, it is excellent also in dynamics.
  • a crosslinking step is not required, it is possible to manufacture a solar cell module by a roll-to-roll process.
  • Patent Document 10 a method using a polyvinyl acetal with a low plasticizer amount has been proposed (Patent Document 10).
  • Patent Document 10 a method using a polyvinyl acetal with a low plasticizer amount has been proposed (Patent Document 10).
  • JP 2011-219670 A JP 2011-219671 A Japanese Patent Laid-Open No. 05-140211 JP-A-5-155915 JP 2002-069126 A JP 58-23870 A Japanese Patent Application Laid-Open No. 6-177412 JP 2006-13505 A International Publication No. 2009/151952 International Publication No. 2013/002292
  • An object of the present invention is to provide a film that is less colored by heating and has less foreign matter (undissolved content) and a method for producing the same. Moreover, it aims at providing the laminated glass using the said intermediate film for laminated glasses which consists of the said film, and the said intermediate film. Moreover, it aims at providing the solar cell module using the sealing material which can extend the lifetime of a solar cell, and the said sealing material.
  • the above problem is a film containing polyvinyl acetal having an acetalization degree of 50 to 85 mol%, a vinyl ester monomer unit content of 0.1 to 20 mol%, and a viscosity average polymerization degree of 200 to 2000.
  • the content of the plasticizer in the film is less than 12 parts by mass with respect to 100 parts by mass of polyvinyl acetal, and this is solved by providing a film that satisfies the following formulas (1) and (2).
  • Peak top molecular weight a peak top measured by a differential refractive index detector when the film heated at 230 ° C. for 3 hours was measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC).
  • GPC Intensity of signal at x Signal intensity at peak top molecular weight measured by differential refractive index detector when GPC measurement of monodisperse polymethyl methacrylate (hereinafter, polymethyl methacrylate may be abbreviated as PMMA)
  • y Absorbance detection when the monodispersed PMMA is measured by GPC A signal intensity in (wavelength 220 nm) peak top molecular weight measured by.
  • hexafluoroisopropanol may be abbreviated as HFIP.
  • Sample concentration 1.00 mg / ml
  • Sample injection volume 100 ⁇ l
  • Column temperature 40 ° C
  • Flow rate 1.0 ml / min.
  • the film satisfies the following formulas (3) and (4).
  • A a, x, y the same as the above formula (1)
  • C the same as the above formula (2)
  • C absorptiometric detector (measurement wavelength: 320 nm) when the film heated at 230 ° C. for 3 hours is measured by GPC Peak top molecular weight c measured by: Signal intensity at peak top molecular weight (C).
  • the polyvinyl acetal is PVB.
  • the film preferably contains triethylene glycol di-2-ethylhexanoate as a plasticizer.
  • the chloride ion concentration in the film is 100 ppm or less.
  • An interlayer film for laminated glass comprising the film of the present invention is a preferred embodiment of the present invention.
  • a laminated glass formed by bonding a plurality of glass plates using the interlayer film for laminated glass is also a preferred embodiment of the present invention.
  • a solar cell encapsulant comprising the film of the present invention is also a preferred embodiment of the present invention.
  • a solar cell module having the solar cell sealing material is also a preferred embodiment of the present invention.
  • the film of the present invention is less colored by heating and less foreign matter (undissolved part). Further, the moisture permeability is unlikely to increase even when the film is used for a long time. Therefore, the film of the present invention is useful as an intermediate film for laminated glass, and the lifetime of the module for solar cells is extended by using the film as a sealing material for solar cells.
  • the relationship between the molecular weight and the value measured with a differential refractive index detector (RI) and the relationship between the molecular weight and the absorbance measured with an absorptiometric detector (UV) (measurement wavelength 280 nm) are shown. It is an example of a graph. It is a cross-sectional schematic diagram of an example of the solar cell module of this invention.
  • RI differential refractive index detector
  • UV absorptiometric detector
  • the film of the present invention contains a polyvinyl acetal having a degree of acetalization of 50 to 85 mol%, a vinyl ester monomer unit content of 0.1 to 20 mol%, and a viscosity average polymerization degree of 200 to 2000. And the content of the plasticizer in the said film is less than 12 mass parts with respect to 100 mass parts of polyvinyl acetals, and satisfy
  • hexafluoroisopropanol may be abbreviated as HFIP.
  • Sample concentration 1.00 mg / ml
  • Sample injection volume 100 ⁇ l
  • Column temperature 40 ° C
  • Flow rate 1.0 ml / min.
  • a GPC apparatus having a differential refractive index detector and an absorptiometric detector and capable of simultaneously performing measurement by these detectors.
  • the cell of the detection part of the absorptiometric detector preferably has a cell length (optical path length) of 10 mm.
  • the absorptiometric detector may measure the absorption of ultraviolet light having a specific wavelength, or may measure the absorption of ultraviolet light having a specific range of wavelengths.
  • the film subjected to the measurement is separated into each molecular weight component by a GPC column.
  • the signal intensity by the differential refractive index detector is approximately proportional to the concentration (g / l) of the film component.
  • the components detected by the absorptiometric detector are only those having a structure that absorbs a predetermined wavelength.
  • the concentration and absorbance at a predetermined wavelength can be measured for each molecular weight component of the film.
  • HFIP containing sodium trifluoroacetate having a concentration of 20 mmol / l is used as the solvent and mobile phase used for dissolving the film and PMMA measured in the GPC measurement.
  • HFIP can dissolve the film and PMMA of the present invention. Further, by adding sodium trifluoroacetate, adsorption of film components and PMMA to the column filler is prevented.
  • the flow rate in the GPC measurement is usually 1.0 ml / min, and the column temperature is usually 40 ° C.
  • the GPC column used in the GPC measurement is not particularly limited as long as the components in the film of the present invention can be separated for each molecular weight.
  • “GPC HFIP-806M” manufactured by Showa Denko KK is preferably used.
  • standard PMMA is monodispersed PMMA.
  • monodispersed PMMA which is usually used as a standard for preparing a calibration curve for molecular weight measurement by GPC measurement, can be used.
  • Several types of standard PMMA with different molecular weights are measured, and a calibration curve is created from the GPC elution volume and the molecular weight of the standard PMMA.
  • a calibration curve prepared using the detector is used for the measurement with the differential refractive index detector, and a calibration prepared using the detector (measurement wavelength: 220 nm) for the measurement with the absorptiometric detector. Use lines. Using these calibration curves, the GPC elution volume is converted into the molecular weight, and the peak top molecular weight (A) and the peak top molecular weight (B) are determined.
  • the film is heated at 230 ° C. for 3 hours before the GPC measurement.
  • the film is heated by the following method.
  • the film is heated by hot pressing for 3 hours at a pressure of 2 MPa and 230 ° C.
  • the thickness of the film to be heated is 600 to 800 ⁇ m, preferably about 760 ⁇ m, which is the thickness of a normal laminated glass interlayer.
  • a measurement sample is obtained by dissolving the heated film in the above-described solvent (HFIP containing sodium trifluoroacetate).
  • the concentration of the measurement sample is 1.00 mg / ml, and the injection volume is 100 ⁇ l.
  • FIG. 1 shows the relationship between the molecular weight obtained by GPC measurement of the film of the present invention and the signal intensity measured with a differential refractive index detector, and the molecular weight measured with an absorptiometric detector (measurement wavelength 280 nm). It is an example of the graph which showed the relationship with signal intensity
  • the GPC measurement in the present invention will be further described with reference to FIG.
  • the chromatogram indicated by “RI” is a plot of the signal intensity measured by the differential refractive index detector against the molecular weight (horizontal axis) of the film component converted from the elution volume.
  • the molecular weight at the peak position in the chromatogram is defined as peak top molecular weight (A), and the signal intensity at peak top molecular weight (A) is defined as signal intensity (a).
  • the molecular weight at the peak position where the peak height is the highest is the peak top molecular weight (A).
  • the chromatogram indicated by “UV” shows the signal intensity (absorbance) measured with an absorptiometric detector (measurement wavelength 280 nm) with respect to the molecular weight (horizontal axis) of the film component converted from the elution volume. It is a plot.
  • the molecular weight at the peak position in the chromatogram is defined as peak top molecular weight (B)
  • the signal intensity (absorbance) at the peak top molecular weight (B) is defined as signal intensity (b).
  • the molecular weight at the peak position where the peak height is the highest is defined as the peak top molecular weight (B).
  • the film of the present invention has a peak top molecular weight (A) measured by a differential refractive index detector and a peak top molecular weight measured by an absorptiometric detector (measurement wavelength 280 nm) when GPC measurement is performed by the above-described method.
  • (B) satisfies the following formula (1).
  • the signal intensity by the differential refractive index detector is an index of the film component concentration (g / l) in each molecular weight component.
  • the signal intensity (absorbance) by the absorptiometric detector is an index of the content of a component having a structure that absorbs ultraviolet light having a wavelength of 280 nm in each molecular weight component.
  • (AB) / A becomes a positive value.
  • the low molecular weight component contains more components that absorb ultraviolet light having a wavelength of 280 nm. In this case, foreign matter in the film increases. Moreover, the lifetime of the solar cell module manufactured using the film of this invention becomes short. Furthermore, the color resistance of the film, the foreign matters (undissolved content) in the film, and the performance related to the lifetime of the obtained solar cell module cannot be balanced.
  • (AB) / A is preferably less than 0.75, more preferably less than 0.70.
  • the film of the present invention satisfies the following formula (2). 1.00 ⁇ 10 ⁇ 2 ⁇ (b / y) / (a / x) ⁇ 2.00 ⁇ 10 ⁇ 1 (2)
  • a is the signal intensity measured by the differential refractive index detector at the peak top molecular weight (A) in the GPC measurement.
  • b is the signal intensity (absorbance) measured with an absorptiometric detector (measurement wavelength 280 nm) at the peak top molecular weight (B).
  • x is the signal intensity at the peak top molecular weight measured by the differential refractive index detector when monodispersed PMMA is measured by GPC.
  • y is the signal intensity (absorbance) at the peak top molecular weight measured with an absorptiometer (measurement wavelength 220 nm) when the monodispersed PMMA is measured by GPC.
  • the GPC measurement of monodisperse PMMA is the same as the GPC measurement of the film described above except that monodisperse PMMA is used instead of the heated film and the measurement wavelength of the absorptiometer is changed to 220 nm. Do.
  • the signal intensity (x) is obtained in the same manner as the signal intensity (a).
  • the signal intensity (y) is obtained in the same manner as the signal intensity (b).
  • PMMA having a weight average molecular weight of about 85,000 is preferable.
  • (B / y) / (a / x) is an index of the content of a component having a structure that absorbs ultraviolet light having a wavelength of 280 nm in the film component. When this value is large, it means that the content is large.
  • the signal intensity by the differential refractive index detector is approximately proportional to the concentration (g / l) of the film component.
  • what is detected by the absorptiometric detector is only the component having absorption at 280 nm which is the measurement wavelength, and the signal intensity (absorbance) by the absorptiometric detector is proportional to the concentration of the component having absorption at 280 nm. .
  • the signal intensity of the differential refractive index detector is indicated by “millivolt”
  • the signal intensity (absorbance) of the absorptiometric detector is indicated by “absorbance unit (AU)”.
  • the ratio of both is simply compared. It ’s difficult.
  • the ratio of the signal intensity obtained by the differential refractive index detector and the signal intensity obtained by the absorptiometric detector is not different depending on the model of the GPC apparatus and the measurement conditions. Desired.
  • ratio (b / y) / (a / x) of both is calculated
  • the film of the present invention preferably satisfies the following formula (2 ′), and more preferably satisfies the following formula (2 ′′). 1.50 ⁇ 10 ⁇ 2 ⁇ (b / y) / (a / x) ⁇ 1.50 ⁇ 10 ⁇ 1 (2 ′) 2.00 ⁇ 10 ⁇ 2 ⁇ (b / y) / (a / x) ⁇ 1.00 ⁇ 10 ⁇ 1 (2 ′′)
  • the film component When (b / y) / (a / x) is 1.00 ⁇ 10 ⁇ 2 or less, as described above, the film component has few components that absorb ultraviolet light having a wavelength of 280 nm. Therefore, foreign matter (undissolved part) in the film increases. Moreover, the lifetime of the solar cell module manufactured using the film of this invention becomes short. Furthermore, the color resistance of the film, the foreign matters (undissolved content) in the film, and the performance related to the lifetime of the obtained solar cell module cannot be balanced. On the other hand, when (b / y) / (a / x) is 2.00 ⁇ 10 ⁇ 1 or more, the film component contains many components that absorb ultraviolet light having a wavelength of 280 nm. Therefore, the color resistance of the film is deteriorated and the life of the obtained solar cell module is shortened.
  • the peak top molecular weight measured by the differential refractive index detector in the GPC measurement (A) and the peak top molecular weight (C) measured by an absorptiometric detector (measurement wavelength: 320 nm) is represented by the following formula (3) (AC) / A ⁇ 0.80 (3) It is preferable to satisfy.
  • the peak top molecular weight (C) is measured in the same manner as the peak top molecular weight (B) except that the measurement wavelength in the absorptiometric detector is 320 nm.
  • the peak top molecular weight (C) is derived from a component having absorption at 320 nm, which is present in the film component.
  • (AC) / A becomes a positive value.
  • the low molecular weight component contains more components that absorb ultraviolet rays having a wavelength of 320 nm.
  • foreign matter in the film may increase.
  • the lifetime of the solar cell module manufactured using the film of this invention may become short.
  • the performance regarding the color resistance of the film, the foreign matter (undissolved part) in the film and the life of the obtained solar cell module may not be balanced.
  • (AC) / A is more preferably less than 0.75, and even more preferably less than 0.70.
  • the film of the present invention preferably satisfies the following formula (4). 5.00 ⁇ 10 ⁇ 3 ⁇ (c / y) / (a / x) ⁇ 7.00 ⁇ 10 ⁇ 2 (4)
  • a, x and y are the same as the above formula (2).
  • c is the signal intensity (absorbance) measured with an absorptiometric detector (measurement wavelength: 320 nm) at the peak top molecular weight (C).
  • (c / y) / (a / x) is an index of the content of a component having a structure that absorbs ultraviolet light having a wavelength of 320 nm in the film component. When this value is large, it means that the content is large. And it calculates
  • the film of the present invention preferably satisfies the following formula (4 ′), and more preferably satisfies the following formula (4 ′′). 7.00 ⁇ 10 ⁇ 3 ⁇ (c / y) / (a / x) ⁇ 6.00 ⁇ 10 ⁇ 2 (4 ′) 1.00 ⁇ 10 -2 ⁇ (c / y) / (a / x) ⁇ 5.00 ⁇ 10 -2 (4 ")
  • the degree of acetalization of the polyvinyl acetal in the film of the present invention is 50 to 85 mol%, preferably 55 to 82 mol%, more preferably 60 to 78 mol%, still more preferably 65 to 75 mol%.
  • the degree of acetalization is less than 50 mol%, the compatibility of polyvinyl acetal with a plasticizer or the like is lowered. Moreover, the penetration resistance of the obtained film falls.
  • the degree of acetalization exceeds 85 mol%, the efficiency of the acetalization reaction is remarkably lowered, so that a reaction at a high temperature for a long time is required. As a result, the coloring resistance of the resulting film is lowered, and the lifetime of the solar cell module produced using the film of the present invention is shortened.
  • the degree of acetalization represents the ratio of the acetalized vinyl alcohol monomer unit to the total monomer units constituting the polyvinyl acetal.
  • the vinyl alcohol monomer units in the raw material PVA those that are not acetalized remain in the resulting polyvinyl acetal as vinyl alcohol monomer units.
  • the viscosity average polymerization degree of polyvinyl acetal in the film of the present invention is represented by the viscosity average polymerization degree of the raw material PVA measured according to JIS-K6726. That is, after re-saponifying and purifying PVA to a saponification degree of 99.5 mol% or more, it can be obtained from the intrinsic viscosity [ ⁇ ] measured in water at 30 ° C. by the following equation.
  • the viscosity average polymerization degree of PVA and the viscosity average polymerization degree of polyvinyl acetal obtained by acetalizing it are substantially the same.
  • P ([ ⁇ ] ⁇ 10000 / 8.29) (1 / 0.62)
  • the viscosity average polymerization degree of the polyvinyl acetal is 200 to 2000, preferably 250 to 1700, more preferably 300 to less than 1400.
  • the viscosity average degree of polymerization is less than 200, practical strength cannot be obtained.
  • the viscosity average polymerization degree exceeds 2000, the melt viscosity becomes too high, and the polyvinyl acetal is easily colored due to shearing heat generation during film formation, and the effect of the present invention cannot be obtained.
  • the content of the vinyl ester monomer unit of polyvinyl acetal in the film of the present invention is 0.1 to 20 mol%, preferably 0.3 to 18 mol%, more preferably 0.5 to 15 mol%. %, More preferably 0.7 to 13 mol%.
  • the content of the vinyl ester monomer unit is less than 0.1 mol%, the polyvinyl acetal cannot be stably produced and the film cannot be formed.
  • the content of the vinyl ester monomer unit exceeds 20 mol%, the film becomes intensely colored.
  • the content of monomer units other than acetalized monomer units, vinyl ester monomer units and vinyl alcohol monomer units in the polyvinyl acetal is preferably 20 mol% or less, more preferably 10%. It is less than mol%.
  • the plasticizer content in the film of the present invention is less than 12 parts by mass, preferably less than 10 parts by mass, and more preferably less than 9 parts by mass with respect to 100 parts by mass of polyvinyl acetal.
  • the plasticizer content is 12 parts by mass or more, the lifetime of the solar cell module manufactured using the film of the present invention is shortened.
  • the film of the present invention preferably contains substantially no plasticizer. The lifetime of the solar cell module manufactured using such a sealing material made of a film is further improved.
  • the plasticizer is not particularly limited as long as the effects of the present invention are not impaired and there is no problem in compatibility with polyvinyl acetal.
  • a mono- or diester of an oligoalkylene glycol having a hydroxyl group at both ends and a carboxylic acid, a diester of a dicarboxylic acid and a hydroxyl group-containing compound, or the like can be used. These can be used alone or in combination of two or more.
  • oligoalkylene glycols having hydroxyl groups at both ends include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,2-propylene glycol dimer and trimer, 1,3 -Propylene glycol, 1,3-propylene glycol dimer and trimer, 1,2-butylene glycol, 1,2-butylene glycol dimer and trimer, 1,4-butylene glycol, 1, 4-butylene glycol dimer and trimer, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, 1,8-octane Diol, 1,9-nonanediol, 2-methyl-1,8-octanediol, , 2-decanediol, 1,4-cyclohexane diol.
  • carboxylic acid examples include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid and decanoic acid.
  • the combination of oligoalkylene glycol and carboxylic acid is arbitrary. Of these, monoesters and diesters of triethylene glycol and 2-ethylhexanoic acid are preferable from the viewpoint of handleability (volatility during molding).
  • Dicarboxylic acids include alkylene dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and sebacic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. An acid etc. are mentioned.
  • hydroxyl group-containing compound examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, nonaol, decanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, Examples include 2-butoxyethanol.
  • the combination of dicarboxylic acid and a hydroxyl-containing compound is arbitrary.
  • the acid value of the plasticizer used in the present invention is preferably 0.50 KOHmg / g or less, more preferably 0.30 KOHmg / g or less, and further preferably 0.10 KOHmg / g or less. It is preferably 0.06 KOH mg / g or less.
  • the acid value of the plasticizer exceeds 0.50 KOHmg / g, the resulting film may be colored or decomposed gas may be generated. As a result, the lifetime of the solar cell module manufactured using the film may be shortened or the long-term durability of the interlayer film for laminated glass made of the film may be reduced.
  • the acid value of the plasticizer is a value measured according to JIS K6728: 1977.
  • the polyvinyl acetal is usually produced by acetalizing PVA.
  • the saponification degree of the raw material PVA is preferably 80 to 99.9 mol%, more preferably 82 to 99.7 mol%, still more preferably 85 to 99.5 mol%, and still more preferably 87 to 99.3. Mol%.
  • the saponification degree of raw material PVA is less than 80 mol%, there is a possibility that the number of foreign matters (undissolved part) in the film may increase or the coloring resistance of the film may deteriorate. Moreover, there exists a possibility that the lifetime of the solar cell module obtained may become short.
  • the degree of saponification exceeds 99.9 mol%, PVA may not be produced stably.
  • the raw material PVA may contain an alkali metal salt of carboxylic acid, and its content is preferably 0.50% by mass or less, more preferably 0.37% by mass or less, and 0.28% by mass in terms of the mass of the alkali metal. % Or less is more preferable, and 0.23 mass or less is particularly preferable.
  • the content of the alkali metal salt of the carboxylic acid in the raw material PVA exceeds 0.50% by mass, the film may be easily colored.
  • the content of alkali metal salt of carboxylic acid (calculated in terms of alkali metal mass) is obtained from the amount of alkali metal ions obtained by ashing PVA with a platinum crucible and then measuring the resulting ash content by ICP emission analysis. Can do.
  • vinyl ester monomers used for the production of raw material PVA include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and versa.
  • vinyl tick acid examples include vinyl tick acid, and vinyl acetate is particularly preferable.
  • the raw material PVA can also be produced by polymerizing vinyl ester monomers in the presence of thiol compounds such as 2-mercaptoethanol, n-dodecyl mercaptan, mercaptoacetic acid, 3-mercaptopropionic acid, and saponifying the resulting polyvinyl ester. You can also By this method, PVA in which a functional group derived from a thiol compound is introduced at the terminal is obtained.
  • thiol compounds such as 2-mercaptoethanol, n-dodecyl mercaptan, mercaptoacetic acid, 3-mercaptopropionic acid
  • Examples of the method for polymerizing the vinyl ester monomer include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • a bulk polymerization method performed without a solvent or a solution polymerization method performed using a solvent such as alcohol is usually employed.
  • a solution polymerization method in which polymerization is performed together with a lower alcohol is preferable.
  • the lower alcohol is not particularly limited, but an alcohol having 3 or less carbon atoms such as methanol, ethanol, propanol and isopropanol is preferable, and methanol is usually used.
  • the reaction can be carried out by either a batch method or a continuous method.
  • the initiator used in the polymerization reaction include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl-valeronitrile), 2,2′-azobis (4-methoxy).
  • Azo initiators such as -2,4-dimethylvaleronitrile
  • organic peroxide initiators such as benzoyl peroxide, n-propyl peroxycarbonate, peroxydicarbonate, etc., within a range that does not impair the effects of the present invention.
  • a well-known initiator is mentioned.
  • an organic oxide initiator having a half-life of 10 to 110 minutes at 60 ° C. is preferable, and peroxydicarbonate is particularly preferable.
  • the polymerization temperature for carrying out the polymerization reaction but a range of 5 ° C to 200 ° C is suitable.
  • a copolymerizable monomer can be copolymerized as necessary as long as the effects of the present invention are not impaired.
  • a monomer include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene; carboxylic acids such as fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; Derivatives thereof; acrylic acid or a salt thereof, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, etc .; methacrylic acid or a salt thereof, methyl methacrylate, ethyl methacrylate, n methacrylate Methacrylic acid esters such as propyl and isopropyl methacrylate; Acrylamide derivatives such as acrylamide, N-methylacryl
  • the amount of monomers that can be copolymerized with these vinyl ester monomers varies depending on the purpose and application of use, but is usually based on all monomers used for copolymerization.
  • the ratio is 20 mol% or less, preferably 10 mol% or less.
  • PVA is obtained by saponifying the polyvinyl ester obtained by the above method in an alcohol solvent.
  • an alkaline substance is usually used, and examples thereof include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal alkoxides such as sodium methoxide.
  • the amount of the alkaline substance used is preferably in the range of 0.002 to 0.2 in the molar ratio based on the vinyl ester monomer unit of the polyvinyl ester, and in the range of 0.004 to 0.1. It is particularly preferred.
  • the saponification catalyst may be added all at once in the early stage of the saponification reaction, or a part thereof may be added in the early stage of the saponification reaction, and the rest may be added during the saponification reaction.
  • Examples of the solvent that can be used for the saponification reaction include methanol, methyl acetate, dimethyl sulfoxide, diethyl sulfoxide, and dimethylformamide. Of these solvents, methanol is preferably used. In its use, the water content of methanol is preferably adjusted to 0.001 to 1% by weight, more preferably 0.003 to 0.9% by weight, and particularly preferably 0.005 to 0.8% by weight.
  • the saponification reaction is preferably performed at a temperature of 5 to 80 ° C., more preferably 20 to 70 ° C.
  • the time required for the saponification reaction is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours.
  • the saponification reaction can be carried out by either a batch method or a continuous method.
  • the remaining saponification catalyst may be neutralized as necessary.
  • Usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate.
  • the alkaline substance containing an alkali metal added during the saponification reaction is usually neutralized by an ester such as methyl acetate produced by the progress of the saponification reaction, or neutralized by adding a carboxylic acid such as acetic acid. At this time, an alkali metal salt of a carboxylic acid such as sodium acetate is formed.
  • the raw material PVA preferably contains a predetermined amount of an alkali metal salt of carboxylic acid.
  • the PVA may be washed with a washing solution containing a lower alcohol such as methanol after saponification.
  • the cleaning liquid may contain 20 parts by mass or less of water with respect to 100 parts by mass of the lower alcohol.
  • cleaning liquid may contain ester, such as methyl acetate produced
  • the content of the ester at this time is not particularly limited, but is preferably 1000 parts by mass or less with respect to 100 parts by mass of the lower alcohol.
  • the amount of the cleaning solution used for cleaning is preferably 100 parts by weight to 10000 parts by weight, more preferably 150 parts by weight to 5000 parts by weight, with respect to 100 parts by weight of the gel obtained by saponification and PVA swollen with alcohol. More preferably, it is 200 to 1000 parts by mass.
  • the addition amount of the cleaning liquid is less than 100 parts by mass, the alkali metal salt amount of the carboxylic acid may exceed the above range.
  • the addition amount of the cleaning liquid exceeds 10,000 parts by mass, the improvement of the cleaning effect by increasing the addition amount cannot be expected.
  • the washing method is not particularly limited.
  • PVA welled gel
  • a washing solution For example, PVA (swelled gel) and a washing solution are added to a tank, and the solution is stirred or allowed to stand for 5 to 180 minutes at 5 to 100 ° C. to remove the liquid.
  • a batch method in which the process is repeated until the content of the alkali metal salt of the carboxylic acid is within the above range can be mentioned.
  • the alkali metal salt of the carboxylic acid contained in the raw material PVA is obtained by neutralizing the alkali catalyst used in the saponification step, for example, sodium hydroxide, potassium hydroxide, sodium methylate, etc. with carboxylic acid,
  • the carboxylic acid added for the purpose of suppressing alcoholysis of the vinyl ester monomer such as vinyl acetate used in the polymerization process is neutralized in the saponification process, to stop radical polymerization
  • a carboxylic acid having a conjugated double bond is used as an inhibitor to be added to the carboxylic acid, those obtained by neutralizing the carboxylic acid in the saponification step or those intentionally added are included.
  • Specific examples include sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium glycerate, potassium glycerate, sodium malate, potassium malate, sodium citrate, potassium citrate, sodium lactate, potassium lactate, tartaric acid Sodium, potassium tartrate, sodium salicylate, potassium salicylate, sodium malonate, potassium malonate, sodium succinate, potassium succinate, sodium maleate, potassium maleate, sodium phthalate, potassium phthalate, sodium oxalate, potassium oxalate , Sodium glutarate, potassium glutarate, sodium abietic acid, potassium abietic acid, sodium sorbate, potassium sorbate, 2,4,6-octatri Sodium 1,1-carboxylate, potassium 2,4,6-octatriene-1-carboxylate, sodium eleostearate, potassium eleostearate, sodium 2,4,6,8-decatetraene-1-carboxylate 2,4,6,8-decatetraene-1-carboxylate, sodium reti
  • the PVA thus obtained is acetalized to produce polyvinyl acetal used for film production.
  • the method of acetalization is not specifically limited, For example, the following method is mentioned.
  • PVA is dissolved in water by heating to 80 to 100 ° C., and then gradually cooled over 10 to 60 minutes to obtain a 3 to 40% by mass aqueous solution of PVA.
  • an aldehyde and an acid catalyst are added to the aqueous solution, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant.
  • polyvinyl acetal having reached a certain degree of acetalization is precipitated.
  • the temperature of the reaction solution is raised to 25 to 80 ° C.
  • aggregated particles made of polyvinyl acetal are generated in such a reaction or processing step, and coarse particles are easily formed.
  • coarse particles are generated, there is a risk of causing variation between batches.
  • a specific PVA described later is used as a raw material, the generation of coarse particles is suppressed from the conventional product, and as a result, foreign matter (undissolved content) is reduced when the resulting polyvinyl acetal is melt-formed. Film can be obtained.
  • the acid catalyst used in the acetalization reaction is not particularly limited, and any of organic acids and inorganic acids can be used. Examples thereof include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, and hydrochloric acid. Of these, hydrochloric acid, sulfuric acid, and nitric acid are preferably used. In general, when nitric acid is used, the reaction rate of the acetalization reaction is increased, and improvement in productivity can be expected. On the other hand, the obtained polyvinyl acetal particles tend to be coarse and the variation between batches tends to increase.
  • the polyvinyl acetal obtained by the above method is decomposed with an acid in the presence of water to produce an aldehyde. From the viewpoint of preventing such aldehyde formation, it is preferable to adjust the alkali titer value of the polyvinyl acetal after alkali neutralization to a positive value.
  • the alkali titer value of the polyvinyl acetal after alkali neutralization is preferably from 0.1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. There exists a possibility that it may become easy to hydrolyze that an alkali titer value is less than 0.1.
  • the alkali titer value is an amount of 0.01 mol / L hydrochloric acid (mL) required for neutralizing and titrating an alkali component in 100 g of polyvinyl acetal.
  • the acid value of the polyvinyl acetal obtained by the above method is preferably 0.50 KOH mg / g or less, more preferably 0.30 KOH mg / g or less, and 0.10 KOH mg / g or less. More preferably, it is particularly preferably 0.06 KOH mg / g or less.
  • the acid value of polyvinyl acetal exceeds 0.50 KOHmg / g, the resulting solar cell sealing material or the interlayer film for laminated glass may be colored, and the resulting solar cell module electrode is corroded to shorten the life. There is a fear.
  • the acid value of polyvinyl acetal is JIS K6728: A value measured according to 1977.
  • the aldehyde used for the acetalization reaction of polyvinyl acetal is not particularly limited, but a conventionally known aldehyde having 1 to 8 carbon atoms is preferable, an aldehyde having 4 to 6 carbon atoms is more preferable, and n-butyraldehyde is particularly preferable.
  • polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.
  • the antioxidant used in the method 1) is not particularly limited, and examples thereof include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Among these, phenolic antioxidants are used. Preferably, alkyl-substituted phenolic antioxidants are particularly preferred.
  • phenolic antioxidants examples include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl- Acrylate compounds such as 6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t -Butyl-4-ethylphenol, octadecyl-3- (3,5-) di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 4,4′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (6-tert-butyl-m-cresol), 4,4′-thiobi (3-methyl-6-tert-butylphenol
  • phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2-t-butyl).
  • sulfur-based antioxidant examples include dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, pentaerythritol-tetrakis- ( ⁇ -lauryl-thiopropionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane.
  • the blending amount of the antioxidant is not particularly limited, but is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polyvinyl acetal. When the amount of the antioxidant is less than 0.001 part by mass, a sufficient effect may not be exhibited, and when it exceeds 5 parts by mass, the effect cannot be improved by increasing the blending amount.
  • the PVA used in the above method 2) includes a peak top molecular weight (D) measured by a differential refractive index detector when the PVA heated at 120 ° C. for 3 hours is measured by GPC, and an absorptiometric detector
  • the peak top molecular weight (E) measured at (measurement wavelength 280 nm) is the following formula (5) (DE) / D ⁇ 0.75 (5)
  • the absorbance at the peak top molecular weight (E) is preferably 0.25 ⁇ 10 ⁇ 3 to 3.00 ⁇ 10 ⁇ 3 .
  • the GPC measurement at this time is performed in the same manner as the GPC measurement method for a film described above except for the following points.
  • GPC HFIP-806M manufactured by Showa Denko KK is used as the GPC column.
  • the cell length of the absorptiometric detector is 10 mm.
  • the column temperature during measurement is 40 ° C., and the flow rate is 1 ml / min.
  • the PVA heated under the following conditions is measured. After casting an aqueous solution in which the PVA powder is dissolved, the PVA film is obtained by drying at 20 ° C. and 65% RH.
  • the PVA film has a thickness of 30 to 75 ⁇ m, preferably 40 to 60 ⁇ m.
  • the film is heated at 120 ° C. for 3 hours using a hot air dryer. From the viewpoint of suppressing heat treatment errors between samples, a gear oven is preferable as the hot air dryer.
  • the PVA thus heated is subjected to GPC measurement.
  • the peak top molecular weight (D) of the PVA is determined in the same manner as the peak top molecular weight (A) of the film described above, and the peak top molecular weight (E) of the raw material PVA is the same as the peak top molecular weight (B) of the film described above. Ask for it.
  • the PVA has a peak top molecular weight (D) measured by a differential refractive index detector and a peak top molecular weight (E) measured by an absorptiometric detector (measurement wavelength 280 nm) when GPC measurement is performed by the above-described method. ) Preferably satisfies the following formula (5). (DE) / D ⁇ 0.75 (5)
  • the peak top molecular weight (D) is a value serving as an index of the molecular weight of PVA.
  • the peak top molecular weight (E) is derived from a component present in PVA and having absorption at 280 nm.
  • (DE) / D becomes a positive value.
  • the low molecular weight component contains more components that absorb ultraviolet light having a wavelength of 280 nm.
  • foreign matter (undissolved part) in the film increases and the life of the solar cell module manufactured using the film of the present invention may be shortened.
  • performance regarding the coloring resistance of a film, the foreign material (undissolved part) in a film, and the lifetime of the solar cell module obtained may be unbalanced.
  • (DE) / D is more preferably less than 0.70, and still more preferably less than 0.65.
  • the PVA preferably has an absorbance (measurement wavelength: 280 nm) at a peak top molecular weight (E) of 0.25 ⁇ 10 ⁇ 3 to 3.00 ⁇ 10 ⁇ 3 when GPC measurement is performed by the method described above.
  • E peak top molecular weight
  • the absorbance is more preferably 0.50 ⁇ 10 ⁇ 3 to 2.80 ⁇ 10 ⁇ 3 , and further preferably 0.75 ⁇ 10 ⁇ 3 to 2.50 ⁇ 10 ⁇ 3 .
  • the PVA has a peak top molecular weight (D) measured by a differential refractive index detector and a peak top molecular weight (F) measured by an absorptiometric detector (measurement wavelength: 320 nm) when GPC measurement is performed by the method described above. ) More preferably satisfies the following formula (6). (DF) / D ⁇ 0.75 (6)
  • the peak top molecular weight (F) is measured in the same manner as the peak top molecular weight (E) except that the measurement wavelength in the absorptiometric detector is 320 nm.
  • the peak top molecular weight (F) is derived from a component having absorption at 320 nm, which is present in the raw material PVA.
  • (DF) / D becomes a positive value.
  • the low molecular weight component contains more components that absorb ultraviolet light having a wavelength of 320 nm.
  • foreign matter (undissolved part) in the film increases and the life of the solar cell module manufactured using the film of the present invention may be shortened.
  • performance regarding the coloring resistance of a film, the foreign material (undissolved part) in a film, and the lifetime of the solar cell module obtained may be unbalanced.
  • (D ⁇ F) / D is more preferably less than 0.70, and particularly preferably less than 0.65.
  • the PVA has an absorbance (measurement wavelength: 320 nm) at a peak top molecular weight (F) of 0.20 ⁇ 10 ⁇ 3 to 2.90 ⁇ 10 ⁇ 3 when GPC measurement is performed by the method described above.
  • F peak top molecular weight
  • the absorbance is less than 0.20 ⁇ 10 ⁇ 3 , foreign matter (undissolved content) in the film may increase, or the life of the solar cell module manufactured using the film of the present invention may be shortened. is there.
  • the performance regarding the coloring resistance of a film, the foreign material (undissolved part) in a film, and the lifetime of the solar cell module obtained may be unbalanced.
  • the absorbance is more preferably 0.40 ⁇ 10 ⁇ 3 to 2.70 ⁇ 10 ⁇ 3 , and particularly preferably 0.60 ⁇ 10 ⁇ 3 to 2.40 ⁇ 10 ⁇ 3 .
  • the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the PVA, which is obtained by the differential refractive index detector in the GPC measurement of PVA described above, is preferably 2.2 to 6.0.
  • Mw and Mn are obtained from a chromatogram obtained by plotting the value measured by the differential refractive index detector with respect to the molecular weight of PVA used when obtaining the above-described peak top molecular weight (D). Therefore, Mw and Mn calculated
  • Mw / Mn When Mw / Mn is less than 2.2, it indicates that the proportion of low molecular weight components is small in PVA. When Mw / Mn is less than 2.2, the number of foreign matters (undissolved parts) in the film may increase or the life of the solar cell module manufactured using the film of the present invention may be shortened. It is more preferable that Mw / Mn is 2.3 or more. On the other hand, when Mw / Mn exceeds 6.0, it shows that the ratio of a low molecular weight component is large in PVA. When Mw / Mn exceeds 6.0, the film may be easily colored or the life of the obtained solar cell module may be shortened. Mw / Mn is more preferably 4.5 or less, and further preferably 3.0 or less.
  • Examples of the adjustment method include the following methods.
  • a vinyl ester monomer from which a radical polymerization inhibitor contained in the raw material vinyl ester monomer has been removed in advance is used for polymerization.
  • Impurities include aldehydes such as acetaldehyde, crotonaldehyde, and acrolein; acetals such as acetaldehyde dimethyl acetal, crotonaldehyde dimethyl acetal, and acrolein dimethyl acetal obtained by acetalizing the aldehyde with a solvent alcohol; ketones such as acetone; methyl acetate and ethyl acetate And esters.
  • Organic acids specifically hydroxycarboxylic acids such as glycolic acid, glyceric acid, malic acid, citric acid, lactic acid, tartaric acid, salicylic acid; malonic acid, succinic acid, maleic acid, phthalic acid, oxalic acid, glutaric acid, etc.
  • a carboxylic acid or the like is added to suppress the generation of aldehydes such as acetaldehyde generated by decomposition as much as possible.
  • the addition amount of the organic acid is preferably 1 to 500 ppm, more preferably 3 to 300 ppm, and still more preferably 5 to 100 ppm with respect to the raw material vinyl ester monomer.
  • the impurities contained in the solvent include those described above as the impurities contained in the raw material vinyl ester monomer.
  • Organic peroxide is used as a radical polymerization initiator used for radical polymerization of a vinyl ester monomer.
  • Organic peroxides include acetyl peroxide, isobutyl peroxide, di-isopropyl peroxycarbonate, di-allyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-myristyl peroxydicarbonate, di ( 2-ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (methoxyisopropyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, etc.
  • Peroxydicarbonate having a half-life of 10 to 110 minutes at 60 ° C. is preferably used.
  • an inhibitor When an inhibitor is added after radical polymerization of the vinyl ester monomer in order to suppress the polymerization, an inhibitor of 5 molar equivalents or less is added to the remaining undecomposed radical polymerization initiator.
  • the inhibitor include a compound having a conjugated double bond having a molecular weight of 1000 or less and a compound that stabilizes a radical and inhibits a polymerization reaction.
  • isoprene 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 1,3-pentadiene, , 3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, 2-methyl-1 , 3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4-hexadiene, , 3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene, 1-
  • Polyenes such as conjugated polyene consisting Motoni double bond of four or more conjugated structure. Any one having a plurality of stereoisomers such as 1,3-pentadiene, myrcene, and farnesene may be used.
  • a polyvinyl ester alcohol solution from which the remaining vinyl ester monomer is removed as much as possible is used for the saponification reaction.
  • the residual monomer removal rate is 99% or more, more preferably 99.5% or more, still more preferably 99.8% or more.
  • the desired PVA can be obtained by appropriately combining A) to H).
  • the polyvinyl acetal obtained by acetalizing the PVA thus obtained is preferably used as a raw material for the film.
  • the peak top molecular weight (G) measured by a differential refractive index detector and the light absorption is the following formula (7) (GH) / G ⁇ 0.60 (7)
  • the absorbance at the peak top molecular weight (H) is 0.50 ⁇ 10 ⁇ 3 to 1.00 ⁇ 10 ⁇ 2 .
  • the GPC measurement at this time is performed in the same manner as the GPC measurement method for a film described above except for the following points.
  • GPC HFIP-806M manufactured by Showa Denko KK is used as the GPC column.
  • the cell length of the absorptiometric detector is 10 mm.
  • the column temperature during measurement is 40 ° C., and the flow rate is 1.0 ml / min.
  • polyvinyl acetal heated under the following conditions is measured.
  • the thickness of the film at this time is 600 to 800 ⁇ m, and is preferably about 760 ⁇ m, which is the thickness of a normal laminated glass interlayer film.
  • the polyvinyl acetal thus heated is subjected to GPC measurement.
  • the peak top molecular weight (G) of the polyvinyl acetal is determined in the same manner as the peak top molecular weight (A) of the film described above, and the peak top molecular weight (H) of the polyvinyl acetal is determined as the peak top molecular weight (B) of the film described above. Find in the same way as
  • the polyvinyl acetal has a peak top molecular weight (G) measured by a differential refractive index detector and a peak top molecular weight measured by an absorptiometric detector (measurement wavelength 280 nm) when GPC measurement is performed by the method described above. It is preferable that H) satisfy
  • the peak top molecular weight (G) is a value serving as an index of the molecular weight of polyvinyl acetal.
  • the peak top molecular weight (H) is derived from a component present in polyvinyl acetal and having absorption at 280 nm.
  • (GH) / G becomes a positive value.
  • the low molecular weight component contains more components that absorb ultraviolet light having a wavelength of 280 nm.
  • foreign matter (undissolved part) in the film increases and the life of the solar cell module manufactured using the film of the present invention may be shortened.
  • performance regarding the coloring resistance of a film, the foreign material (undissolved part) in a film, and the lifetime of the solar cell module obtained may be unbalanced.
  • (GH) / G is more preferably less than 0.55, and still more preferably less than 0.50.
  • the polyvinyl acetal preferably has an absorbance (measurement wavelength: 280 nm) at a peak top molecular weight (H) of 0.50 ⁇ 10 ⁇ 3 to 1.00 ⁇ 10 ⁇ 2 when GPC measurement is performed by the method described above. .
  • H peak top molecular weight
  • the absorbance is less than 0.50 ⁇ 10 ⁇ 3 , foreign matter (undissolved content) in the film may increase, or the life of the solar cell module manufactured using the film of the present invention may be shortened. is there.
  • the performance regarding the color resistance of the film, the foreign matter (undissolved part) in the film and the life of the obtained solar cell module may not be balanced, while the absorbance exceeds 1.00 ⁇ 10 ⁇ 2
  • a component that absorbs an ultraviolet ray having a wavelength of 280 nm is increased in the film, the film is likely to be colored, and the life of the obtained solar cell module may be shortened.
  • the absorbance is more preferably 1.50 ⁇ 10 ⁇ 3 to 1.00 ⁇ 10 ⁇ 2 , further preferably 1.55 ⁇ 10 ⁇ 3 to 8.50 ⁇ 10 ⁇ 3 , and 1.60 ⁇ 10 ⁇ 3 to 7. Particularly preferred is 0.000 ⁇ 10 ⁇ 3 .
  • the polyvinyl acetal has a peak top molecular weight (G) measured by a differential refractive index detector and a peak top molecular weight measured by an absorptiometric detector (measurement wavelength: 320 nm) when GPC measurement is performed by the method described above ( More preferably, I) satisfies the following formula (8). (GI) / G ⁇ 0.65 (8)
  • the peak top molecular weight (I) is measured in the same manner as the peak top molecular weight (H) except that the measurement wavelength in the absorptiometric detector is 320 nm.
  • the peak top molecular weight (I) is derived from a component having absorption at 320 nm, which is present in the raw material PVA.
  • (GI) / G becomes a positive value.
  • the low molecular weight component contains more components that absorb ultraviolet light having a wavelength of 320 nm.
  • foreign matter (undissolved part) in the film increases and the life of the solar cell module manufactured using the film of the present invention may be shortened.
  • performance regarding the coloring resistance of a film, the foreign material (undissolved part) in a film, and the lifetime of the solar cell module obtained may be unbalanced.
  • (GI) / G is more preferably less than 0.60, and particularly preferably less than 0.55.
  • the polyvinyl acetal has an absorbance (measurement wavelength of 320 nm) at a peak top molecular weight (I) of 0.35 ⁇ 10 ⁇ 3 to 4.50 ⁇ 10 ⁇ 3 when GPC measurement is performed by the above-described method. preferable.
  • the absorbance is less than 0.35 ⁇ 10 ⁇ 3 , foreign matter (undissolved content) in the film may increase or the life of the solar cell module manufactured using the film of the present invention may be shortened. is there.
  • the performance regarding the coloring resistance of a film, the foreign material (undissolved part) in a film, and the lifetime of the solar cell module obtained may be unbalanced.
  • the absorbance exceeds 4.50 ⁇ 10 ⁇ 3 , there may be an increase in the absorption component of 320 nm ultraviolet visible light in the film, which may cause the film to be easily colored and the life of the obtained solar cell module. May be shortened.
  • the absorbance is more preferably 0.75 ⁇ 10 ⁇ 3 to 4.50 ⁇ 10 ⁇ 3 , particularly preferably 0.80 ⁇ 10 ⁇ 3 to 3.50 ⁇ 10 ⁇ 3 , and 0.85 ⁇ 10 ⁇ 3 to 2. .50 ⁇ 10 ⁇ 3 is most preferred.
  • the content of chloride ions in the film of the present invention is preferably 100 ppm or less, and more preferably 50 ppm or less.
  • the content of chloride ions exceeds 100 ppm, discoloration due to corrosion of the metal component of the obtained solar cell module may easily occur under high temperature and high humidity. As a result, the output of the solar cell module may be reduced.
  • the lower limit value of the chloride ion content is not particularly limited, but is 0.1 ppm for reasons of the production method.
  • the method for measuring the chloride ion content can be measured by potentiometric titration.
  • the chloride ion concentration in the film can be determined from the change in electrical conductivity when the solution is dropped.
  • the chloride ion content is preferably in the above range.
  • a method of reducing the content of chloride ions in the polyvinyl acetal used can be mentioned.
  • a method using a non-chlorine catalyst is exemplified as a catalyst used when acetalizing PVA with aldehyde.
  • the above-mentioned thing is used as a non-chlorine type catalyst.
  • Sulfuric acid or nitric acid is preferable from the viewpoint of having a sufficient reaction rate and easy washing after the reaction, and nitric acid is more preferable from the viewpoint of easy handling.
  • the polyvinyl acetal obtained by acetalization is filtered and / or neutralized, and then repeatedly washed with water or the like to contain chloride ions. It is also possible to reduce the amount.
  • the film of the present invention may contain an ultraviolet absorber, a light stabilizer, a pH adjusting buffer, rubber, an adhesion adjusting agent, a pigment, a dye, and other conventionally known additives unless contrary to the gist of the present invention. good. This is explained below.
  • Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3,5-bis ( ⁇ , ⁇ '-dimethylbenzyl) phenyl) -2H-benzotriazole. 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 , 5-di-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′- Benzotriazole ultraviolet absorbers such as hydroxy-5′-t-octylphenyl) benzotriazole; 2,2,6,6-tetramethyl-4-pipe Lysylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl)
  • the content of the ultraviolet absorber in the film is not particularly limited, but is preferably 10 to 50,000 ppm, and more preferably 100 to 10,000 ppm. If the content is less than 10 ppm, sufficient effects may not be exhibited, and even if the content is more than 50,000 ppm, the effect cannot be improved by increasing the content.
  • ADEKA STAB LA-57 manufactured by ADEKA Co., Ltd. may be mentioned.
  • pH adjusting buffers can be used, such as citric acid-citrate buffer (citric acid and sodium citrate, etc.), acetic acid-acetate buffer (acetic acid and sodium acetate, potassium acetate, Magnesium acetate, etc.), butyric acid-acetate buffer (butyric acid and sodium acetate, potassium acetate, magnesium acetate, etc.), citric acid-phosphate buffer (citric acid, disodium hydrogen phosphate, etc.), phosphate-phosphorus Acid salt buffers (sodium dihydrogen phosphate and disodium hydrogen phosphate, etc.), tris (hydroxymethyl) aminomethane-hydrochloric acid buffer, glycine-sodium hydroxide buffer, carbonate-bicarbonate buffer (sodium carbonate And sodium bicarbonate).
  • citric acid-citrate buffer citric acid and sodium citrate, etc.
  • acetic acid-acetate buffer acetic acid and sodium acetate, potassium acetate, Magne
  • buffering agent may be appropriately selected according to the corrosion resistance of the metal or metal oxide that comes into contact with the film of the present invention.
  • a buffering agent having a pH in the range of 5 to 9 is preferable, and particularly acetic acid-acetic acid. Salt buffers, butyric acid-acetate buffers, and phosphate-phosphate buffers are preferred from the viewpoints of pH value, handleability and cost.
  • the addition amount of the pH adjusting buffer is not particularly limited, but is preferably 1 to 50,000 ppm, more preferably 5 to 10,000 ppm, and more preferably 10 to 5,000 ppm with respect to polyvinyl acetal. More preferred is 15 to 2,000 ppm.
  • the film of the present invention is used as an interlayer film for laminated glass or a sealing material for solar cells, it is preferable to mix rubber from the viewpoint of improving impact resistance.
  • the rubber used is not particularly limited.
  • silicone / acrylic composite rubber acrylic rubber, silicone rubber, butadiene rubber (MBS, NBR, ABS, SBR, etc.), urethane rubber, natural rubber, chloroprene rubber, butyl rubber Ethylene-propylene rubber, fluororubber, ethylene-vinyl acetate copolymer (EVA), polyester-based thermoplastic elastomer (TPEE), styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, thermosetting elastomer, and the like.
  • TPEE polyester-based thermoplastic elastomer
  • styrene-based thermoplastic elastomer styrene-based thermoplastic elastomer
  • olefin-based thermoplastic elastomer thermosetting elastomer, and the like.
  • silicone / acrylic composite rubber, acrylic rubber, and butadiene rubber are preferable, and silicone / acrylic composite rubber and acrylic rubber are more preferable.
  • a rubber that is incompatible with polyvinyl acetal is also preferable, and as such a rubber, a thermosetting elastomer is more preferable.
  • only 1 type of rubber may be used independently and 2 or more types may be used together.
  • the glass transition temperature of the rubber is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 20 ° C. or lower, and further preferably ⁇ 30 ° C. or lower.
  • the lower limit of the glass transition temperature of the rubber is not particularly limited, but the glass transition temperature of the rubber is preferably ⁇ 200 ° C. or higher, more preferably ⁇ 150 ° C. or higher.
  • the average particle size of the rubber is preferably 50 to 400 nm.
  • the average particle diameter of rubber can be determined by, for example, a turbidity method.
  • the rubber content is preferably 1 to 100 parts by weight, more preferably 3 to 80 parts by weight, and more preferably 5 to 5 parts by weight with respect to 100 parts by weight of polyvinyl acetal. More preferably, it is 60 parts by mass. If the rubber content is less than 1 part by mass, the impact resistance improving effect may be insufficient. On the other hand, when the rubber content exceeds 100 parts by mass, the storage modulus at room temperature (about 25 ° C.) and 50 ° C. and the adhesive strength with glass may be reduced, so that the breaking strength may be insufficient. . In addition, the fluidity of the interlayer film for laminated glass and the encapsulant for solar cells to be obtained may be lowered, making lamination difficult.
  • the amount of rubber added may be appropriately selected depending on the composition of the polyvinyl acetal, the degree of viscosity average polymerization, and the like.
  • the transparency of the interlayer film is also important.
  • the difference in refractive index between the rubber and polyvinyl acetal is preferably 0.04 or less, more preferably 0.02 or less, and 0.01 or less. Particularly preferred.
  • acrylic rubber is preferable to use.
  • the film of the present invention may contain an adhesion adjusting agent in order to appropriately adjust the adhesion with glass.
  • an adhesive control agent for example, sodium salts, potassium salts, magnesium salts of organic acids such as acetic acid, propionic acid, butanoic acid, hexanoic acid, 2-ethylbutanoic acid and 2-ethylhexanoic acid are used. These can be used alone or in combination of two or more.
  • the preferred content of the adhesion modifier varies depending on the type, but the adhesive strength of the resulting film to glass is generally 3 in the Pummel test (Pummel test; described in International Publication No. 03/033583 etc.).
  • the content is preferably adjusted to 3 to 6, and when high glass scattering prevention property is required, the content is adjusted to 7 to 10. It is preferable.
  • high glass scattering prevention property it is also a useful method not to add an adhesion modifier.
  • the content of the adhesion adjusting agent in the film is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.1% by mass, and 0.001 to 0.03% by mass. Is more preferable.
  • silane coupling agent is mentioned as another additive for adjusting the said adhesiveness.
  • the content of the silane coupling agent in the film is preferably 0.01 to 5% by mass.
  • the glass transition temperature thereof is not particularly limited and can be appropriately selected according to the purpose, but is in the range of 20 to 100 ° C. It is preferably 25 to 95 ° C, more preferably 30 to 90 ° C.
  • the method for producing the film of the present invention is not particularly limited, but it is preferable to obtain a polyvinyl acetal by acetalizing PVA and then melt-mold the resin composition containing the polyvinyl acetal.
  • the melt molding method using an extruder, the obtained polyvinyl acetal, if necessary, a plasticizer and other components are melt-kneaded to obtain a resin composition, and then the resin composition is formed into a film.
  • the method is preferred.
  • the resin temperature at the time of extrusion is preferably 150 to 250 ° C, more preferably 170 to 230 ° C. When the resin temperature becomes too high, polyvinyl acetal is decomposed, and the content of volatile substances in the intermediate film after film formation increases.
  • the film of the present invention can also be produced by a method in which a film obtained by dissolving or dispersing polyvinyl acetal, a plasticizer and other components in an organic solvent is formed, and then the organic solvent is distilled off.
  • the film may be formed using only a virgin resin (not containing recycled polyvinyl acetal), but the trim and off-spec products described later are reused.
  • a film may be formed.
  • a film forming apparatus provided with a weighing machine such as a gear pump and a die such as a T die in an extruder is used.
  • a weighing machine such as a gear pump
  • a die such as a T die in an extruder
  • both ends (trims) of the film are cut off. It is very important to collect and reuse such trims from the viewpoints of energy saving, effective utilization of resources and improvement of yield.
  • an off-spec product produced during the production of a film having irregularities on the surface is useful because it can be reused in the same manner as the trim.
  • the film of the present invention has few foreign matters (undissolved content) generated when it is melt-formed.
  • the recovered film can be effectively reused.
  • a method of feeding the recovered film into the extruder again a method in which a trim or off-spec film is wound on a roll is unwound and then fed back into the extruder; the trim or off-spec film is put on a roll Examples include a method of cutting a wound product into a certain size and then re-feeding it into an extruder.
  • the ratio of the virgin resin to the recovered film (virgin resin: recovered film) in the raw material can be arbitrarily changed between 0: 100 and 100: 0.
  • the contents of the plasticizer and other components can be adjusted by the following method.
  • a desired film is obtained by adjusting the addition amount of each component to an extruder, analyzing the component of the obtained film.
  • An interlayer film for laminated glass made of the film and a solar cell sealing material made of the film are preferred embodiments of the present invention. Since the film of this invention is excellent in transparency and a softness
  • the thickness of the film in this case is not particularly limited, but is preferably 0.05 to 5.0 mm, more preferably 0.1 to 2.0 mm, and 0.1 to 1.2 mm. Is more preferable.
  • pigments, dyes, and the like may be added to the interlayer film for laminated glass and the sealing material for solar cells.
  • the shape of the surface of the interlayer film for laminated glass is not particularly limited. However, in consideration of the handleability (foaming property) when laminating with glass, the melt fracture and embossing are performed on the surface in contact with the glass by a conventionally known method. It is preferable that a concavo-convex structure such as is formed.
  • the emboss height is not particularly limited, but is preferably 5 ⁇ m to 500 ⁇ m, more preferably 7 ⁇ m to 300 ⁇ m, and still more preferably 10 ⁇ m to 200 ⁇ m.
  • emboss height is less than 5 ⁇ m
  • bubbles formed between the glass and the intermediate film may not be efficiently removed during lamination, and when it exceeds 500 ⁇ m, it is difficult to form the emboss.
  • Embossing may be performed on one side of the intermediate film or on both sides, but it is usually preferable to apply on both sides.
  • the emboss pattern may be regular or irregular.
  • embossing roll method In order to form such embossing, a conventionally known embossing roll method, profile extrusion method, extrusion lip embossing method using melt fracture, or the like is employed.
  • the embossing roll method is suitable for stably obtaining an embossed film on which uniform and fine irregularities are formed.
  • the embossing roll used in the embossing roll method can be produced by, for example, using an engraving mill (mother mill) having a desired concavo-convex pattern and transferring the concavo-convex pattern onto the surface of the metal roll.
  • an embossing roll can also be produced using laser etching.
  • blasting is performed on the surface using an abrasive such as aluminum oxide, silicon oxide, glass beads, etc. to form a finer concavo-convex pattern. It can also be formed.
  • a mold release treatment on the embossing roll used in the embossing roll method.
  • a known method such as silicon treatment, Teflon (registered trademark) treatment, plasma treatment or the like can be used.
  • a laminated glass obtained by bonding a plurality of glass plates using the interlayer film for laminated glass is a preferred embodiment of the present invention.
  • the laminated glass can be produced by sandwiching the intermediate film between at least two glass plates and heating and bonding the intermediate film.
  • the glass used for the laminated glass is not particularly limited.
  • inorganic glass such as float plate glass, tempered plate glass, polished plate glass, mold plate glass, netted plate glass, heat ray absorbing plate glass, conventionally known polymethyl methacrylate, polycarbonate and the like.
  • Organic glass or the like can be used. These may be either colorless or colored. These may be either transparent or non-transparent.
  • the same type of glass may be laminated, or different types of glass may be laminated. Although the thickness of glass is not specifically limited, It is preferable that it is 100 mm or less.
  • the laminated glass can be produced by a conventionally known method, and examples thereof include a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. Further, there is a method in which the obtained laminate is put into an autoclave after being temporarily pressed using these methods.
  • the glass and the interlayer film are laminated at 100 to 200 ° C., particularly 130 to 160 ° C. under a reduced pressure of 1 ⁇ 10 ⁇ 6 to 3 ⁇ 10 ⁇ 2 MPa.
  • a method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683, and is laminated at 130 to 145 ° C. under a pressure of about 2 ⁇ 10 ⁇ 2 MPa.
  • a production method using a nip roll there is a method in which after degassing with a roll at a temperature equal to or lower than the flow start temperature of the film, pressure bonding is performed at a temperature close to the flow start temperature. Specifically, for example, there is a method of heating to 30 to 70 ° C. with an infrared heater or the like, then degassing with a roll, further heating to 50 to 120 ° C., and then pressing with a roll.
  • the operating conditions of the autoclave process are appropriately selected depending on the thickness and configuration of the laminated glass. For example, 1.0 to 1.5 MPa The treatment is preferably carried out at 130 to 145 ° C. for 0.5 to 3 hours under pressure.
  • a solar cell module having the solar cell sealing material is also a preferred embodiment of the present invention.
  • the said sealing material can be used in order to seal between a photovoltaic cell and a surface side transparent protection member and / or a back surface side protection member.
  • Various types of solar cell modules are exemplified. For example, a structure in which a solar battery cell is sandwiched between sealing materials from both sides, such as a front surface side transparent protective member / front surface sealing material / solar battery cell / back surface sealing material / back surface side protective member; Solar cell / encapsulant / back surface protection member (super straight structure), front side transparent protection member / encapsulant / solar cell / back surface protection member (sub) Straight structure).
  • Solar cells constituting the solar cell module include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and periodic tables III-V and II-VI such as gallium / arsenic, CIGS, cadmium / tellurium, etc.
  • silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon
  • periodic tables III-V and II-VI such as gallium / arsenic, CIGS, cadmium / tellurium, etc.
  • Various types of solar cells such as compound semiconductors, dye sensitizers, and organic thin films such as organic thin films can be mentioned.
  • FIG. 2 is a schematic cross-sectional view of an example of the solar cell module of the present invention.
  • FIG. 2 shows a solar cell module using thin film silicon (silicon power generation element or the like) as a solar cell.
  • a solar cell module using thin film silicon is between a glass substrate 11 that is a front surface side transparent protective member and a glass substrate 16 that is a back surface side protective member (back cover).
  • a super straight configuration in which solar cells are sealed via the sealing material 15 of the present invention may be used.
  • the solar cell refers to a portion composed of the transparent electrode layer 12, the photoelectric conversion unit 13, and the back electrode 14.
  • the photoelectric conversion unit 13 includes, for example, a p-layer amorphous Si film as the p-type layer 13a, an i-layer amorphous Si film as the i-type layer 13b, and an n-layer amorphous Si film as the n-type layer 13c.
  • the sealing material 15 of the present invention is excellent in corrosion resistance. Therefore, the corrosion of the metal component is further reduced as compared with the case where the back electrode 14 in contact with the sealing material 15 is a metal layer such as silver, aluminum, titanium, or molybdenum. That is, the effect that the corrosion of the metal component is further reduced when at least a part of the sealing material is in contact with the metal layer is useful.
  • corrosion of metal components can be cited as one factor in reducing the power generation efficiency of the solar cell module.
  • the sealing material of the present invention for a solar cell module in which the sealing material and the metal layer are in contact with each other, it is possible to greatly suppress a decrease in power generation efficiency.
  • the sealing material is also useful, for example, for a solar cell module in which the sealing material and a wiring containing a metal component are in contact with each other.
  • the surface-side transparent protective member constituting the solar cell module examples include glass, acrylic resin, polycarbonate, polyester, and fluorine-containing resin. Among these, glass is preferable in terms of moisture barrier properties and cost.
  • glass is preferable in terms of moisture barrier properties and cost.
  • a back surface side protection member single layer or multilayer sheets, such as a metal and various thermoplastic resin films, can be mentioned, Specifically, metals, such as tin, aluminum, stainless steel, inorganic materials, such as glass And single layer or multilayer sheets of polyester, inorganic vapor-deposited polyester, fluorine-containing resin, polyolefin and the like. Among these, glass is preferable in terms of moisture barrier properties and cost.
  • the end portion of the solar cell module in order to further suppress discoloration due to metal corrosion, can be subjected to a water-resistant seal treatment with silicone rubber, butyl rubber or the like.
  • a frameless configuration that does not perform such processing is preferable. Since the sealing material is excellent in corrosion resistance, it is particularly useful when used in such a frameless module.
  • a conventionally known method in which a film (sealing material) prepared in advance is pressure-bonded at a temperature at which the film melts can be employed.
  • a method of laminating at 100 to 200 ° C., particularly preferably 130 to 170 ° C. under a reduced pressure of 1 to 30,000 Pa can be mentioned.
  • a vacuum bag or a vacuum ring it is preferable to laminate at 130 to 170 ° C. under a pressure of about 20,000 Pa as described in, for example, European Patent No. 1235683.
  • said vacuum laminator apparatus the well-known apparatus used for manufacture of a solar cell module is mentioned.
  • a production method using a nip roll there is a method in which after degassing with a roll at a temperature equal to or lower than the flow start temperature of the film, pressure bonding is performed at a temperature close to the flow start temperature.
  • a method of heating to 30 to 100 ° C. with an infrared heater or the like, then degassing with a roll, further heating to 50 to 150 ° C. and then pressing with a roll can be mentioned.
  • the treatment conditions for the case where the above-described method is used for pressure bonding and then the pressure is applied to the autoclave for further pressure bonding are appropriately adjusted depending on the thickness and configuration of the solar cell module. For example, it is preferable to perform the treatment at 130 to 155 ° C. for about 2 hours under a pressure of about 1 to 1.5 MPa.
  • a solar cell module using a sealing material made of the film of the present invention includes a window, a wall, a roof, a solarium, a soundproof wall, a show window, a balcony, a handrail member, a partition glass member such as a conference room, and a home appliance. It can also be used as a product member. It can also be used at solar power plants.
  • GPC measurement (measuring device) GPC measurement was performed using “GPCmax” manufactured by VISCOTECH. As a differential refractive index detector, “TDA305” manufactured by VISCOTECH was used. “UV Detector 2600” manufactured by VISCOTECH was used as an ultraviolet-visible absorption detector. The optical path length of the detection cell of the absorptiometric detector is 10 mm. As the GPC column, “GPC HFIP-806M” manufactured by Showa Denko KK was used. Moreover, OmniSEC (Version 4.7.0.406) attached to the apparatus was used as analysis software.
  • the mobile phase 20 mmol / l sodium trifluoroacetate-containing HFIP was used.
  • the mobile phase flow rate was 1.0 ml / min.
  • the sample injection amount was 100 ⁇ l, and measurement was performed at a GPC column temperature of 40 ° C.
  • the sample in which the PVA viscosity average polymerization degree in a sample exceeded 2400 performed GPC measurement using the sample (100 microliters) diluted suitably.
  • the absorbance at a sample concentration of 1.00 mg / ml was calculated from the measured value according to the following formula. ⁇ (mg / ml) is the concentration of the diluted sample.
  • Absorbance at a sample concentration of 1.00 mg / ml (1.00 / ⁇ ) ⁇ measured value of absorbance
  • the signal intensity obtained from the differential refractive index detector is expressed in millivolts
  • the signal intensity obtained from the absorptiometric detector is expressed in absorbance (abs unit: Absorbance unit).
  • the polymerization degree was measured using a part of the methanol solution of PVAc-1 obtained.
  • a 10% methanol solution of sodium hydroxide was added to the methanol solution of PVAc-1 so that the molar ratio of sodium hydroxide to vinyl acetate units in polyvinyl acetate was 0.1.
  • the gelled product was formed, the gel was pulverized, Soxhlet extraction was performed with methanol for 3 days, the obtained PVA was dried, and the viscosity average degree of polymerization was measured.
  • the degree of polymerization was 1000.
  • Polyvinyl acetate (PVAc-2 to 22) was obtained by the same method as PVAc-1, except that the conditions described in Table 1 were changed.
  • “ND” means less than 1 ppm.
  • the degree of polymerization of each polyvinyl acetate obtained was determined in the same manner as PVAc-1. The results are shown in Table 1.
  • the polymerization degree and saponification degree of PVA-1 were determined by the method described in JIS-K6726.
  • the degree of polymerization of the obtained PVA was 1000, and the degree of saponification was 98.4 mol%.
  • These physical property data are also shown in Table 2.
  • the sodium acetate content of PVA-1 was determined by measuring the amount of sodium in the obtained ash using an ICP emission analyzer “IRIS AP” manufactured by Jarrel Ash. .
  • the sodium acetate content was 0.7% (0.20% in terms of sodium).
  • a sample for GPC measurement of PVA-1 was prepared by the following method. After heating at 95 ° C. for 1 hour to dissolve PVA-1 in water, it was cooled to room temperature to obtain a 2% aqueous solution of PVA-1. The obtained aqueous solution was cast on a polyethylene terephthalate film (20 cm ⁇ 20 cm) and dried for 1 week under the conditions of 20 ° C. and 65% RH to obtain a PVA film having a thickness of 50 ⁇ m. The obtained film was fixed with a clip to a stainless steel metal frame (20 cm ⁇ 20 cm, 1 cm wide metal frame) and heat-treated at 120 ° C. for 3 hours in a gear oven. A sample was collected from around the center of the PVA film after the heat treatment.
  • the obtained sample was subjected to GPC measurement by the above method.
  • the chromatogram which plotted the signal intensity measured with the differential refractive index detector with respect to the molecular weight (PMMA conversion molecular weight) converted from the elution capacity at this time was created, and the peak top molecular weight (D) was calculated
  • a chromatogram in which the signal intensity (absorbance) measured with an absorptiometric detector (measurement wavelength 280 nm) was plotted against the molecular weight (PMMA equivalent molecular weight) was created to determine the peak top molecular weight (E).
  • the obtained value is expressed by the following formula (DE) / D
  • the value obtained by substituting for was 0.39.
  • the absorbance (280 nm) at the peak top molecular weight (E) was 1.41 ⁇ 10 ⁇ 3 .
  • the peak top molecular weight (F) measured with an absorptiometric detector (320 nm) obtained in the same manner as the method for obtaining the peak top molecular weight (E) was obtained.
  • the peak top molecular weight (D) and the peak top molecular weight (F) are expressed by the following formula (DF) / D
  • the value obtained by substituting for was 0.45.
  • the absorbance (320 nm) at the peak top molecular weight (F) was 1.13 ⁇ 10 ⁇ 3 .
  • PVA-2 to PVA-8 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 2 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 2.
  • PVA-9, comparative PVA-6 and comparative PVA-7 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 3 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 3.
  • PVA-10, and comparative PVA-8 to comparative PVA-10 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 4 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 4.
  • PVA-11, comparative PVA-11 and comparative PVA-12 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 5 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 5.
  • PVA-12, comparative PVA-13 and comparative PVA-14 Each PVA was synthesized in the same manner as PVA-1 except that the conditions were changed to those shown in Table 6.
  • the polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1.
  • GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 6.
  • Comparative PVA-15 to Comparative PVA-17 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 7 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 7.
  • PVA-13 to PVA-19 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 8 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 8.
  • PVA-20, comparative PVA-22 and comparative PVA-23 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 9 were changed.
  • the polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1.
  • GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 9.
  • PVA-21, comparative PVA-24 and comparative PVA-25 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 10 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 10.
  • Comparative PVA-26 The molar ratio of sodium hydroxide to methanol and the vinyl acetate unit of the polyvinyl acetate polymer is 0.1 so that the total solid concentration (saponification concentration) is 40% by mass with respect to a 55% by mass methanol solution of PVAc-3.
  • a saponification reaction was started at 40 ° C. by adding an 8% methanol solution of sodium hydroxide under stirring so that 005 was obtained. Note that saponification reaction was performed by adding distilled water so that the water content in the system was 3.0%.
  • Comparative PVA-26 The resulting solution was transferred to a dryer, dried at 65 ° C. for 12 hours, and then dried at 100 ° C. for 2 hours to obtain Comparative PVA-26.
  • the polymerization degree of the obtained PVA was 300, the saponification degree was 45.3 mol%, and the sodium acetate content was 1.2% (0.34% in terms of sodium).
  • the results are also shown in Table 10.
  • the film preparation for GPC measurement was not able to be performed, but GPC measurement was not able to be performed.
  • Comparative PVA-27 The molar ratio of sodium hydroxide to vinyl acetate units of methanol and polyvinyl acetate polymer is 0 so that the total solid concentration (saponification concentration) is 40% by mass with respect to a 55% by mass methanol solution of PVAc-3. An 8% methanol solution of sodium hydroxide was added under stirring so as to obtain 0.005, and the saponification reaction was started at 40 ° C. Note that saponification reaction was performed by adding distilled water so that the water content in the system was 1.2%. One hour after adding the methanol solution of sodium hydroxide, 0.8 mol equivalent of 1% aqueous acetic acid and a large amount of distilled water were added to stop the saponification reaction.
  • Comparative PVA-27 The polymerization degree of the obtained PVA was 300, the saponification degree was 60.2 mol%, and the sodium acetate content was 1.3% (0.36% in terms of sodium). GPC measurement was performed in the same manner as PVA-1. These results are shown in Table 10.
  • PVA-22, comparative PVA-28 and comparative PVA-29 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 11 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 11.
  • PVA-23, comparative PVA-30 and comparative PVA-31 Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 12 were changed. The polymerization degree, saponification degree, and sodium acetate content (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. GPC measurement was performed in the same manner as PVA-1. The results are shown in Table 12.
  • PVB-1 A 10 L (liter) glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-1 (PVA concentration 7.5%), and the content was adjusted to 95 ° C. The temperature was raised and completely dissolved. Next, the contents were gradually cooled to 8 ° C. over about 30 minutes while stirring at 120 rpm, and 384 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to the vessel, and a butyralization reaction was performed for 150 minutes. . Thereafter, the temperature was raised to 60 ° C.
  • the resulting polyvinyl butyral had a butyralization degree (acetalization degree) of 68.5 mol%, a vinyl acetate monomer unit content of 1.6 mol%, and a vinyl alcohol monomer unit content of 29 It was 9 mol%.
  • the degree of butyralization of the obtained polyvinyl butyral, the content of vinyl acetate monomer units, and the content of vinyl alcohol monomer units were measured according to JIS K6728. The results are also shown in Table 14.
  • PVB-1 GPC measurement sample was prepared by the following method. PVB-1 powder was hot-pressed at a pressure of 2 MPa at 230 ° C. for 3 hours and cooled to obtain a polyvinyl acetal film having a size of 30 cm ⁇ 30 cm and a thickness of 760 ⁇ m. A sample was taken from near the center of the heat-treated film.
  • the obtained sample was subjected to GPC measurement by the above method.
  • a chromatogram in which the signal intensity measured by the differential refractive index detector was plotted with respect to the molecular weight converted from the elution volume (PMMA converted molecular weight) was prepared, and the peak top molecular weight (G) was obtained.
  • the obtained value is expressed by the following formula (GH) / G
  • the value obtained by substituting for was 0.22.
  • the absorbance (280 nm) at the peak top molecular weight (H) was 2.40 ⁇ 10 ⁇ 3 .
  • the peak top molecular weight (I) measured by the spectrophotometric detector (320 nm) obtained in the same manner as the method for obtaining the peak top molecular weight (H) was obtained.
  • the peak top molecular weight (G) and the peak top molecular weight (I) are expressed by the following formula (GI) / G The value obtained by substituting for was 0.33.
  • the absorbance (320 nm) at the peak top molecular weight (I) was 1.36 ⁇ 10 ⁇ 3 .
  • PVB-2 to PVB-8 PVB was synthesized and evaluated in the same manner as PVB-1, except that the raw material PVA was changed to that shown in Table 14. The results are shown in Table 14.
  • PVB-9 PVB was synthesized and evaluated in the same manner as PVB-1, except that the amount of n-butyraldehyde added was changed to 320 g. The results are shown in Table 14.
  • PVB-10 PVB was synthesized and evaluated in the same manner as PVB-1, except that the amount of n-butyraldehyde added was changed to 365 g. The results are shown in Table 14.
  • PVB-11 PVB was synthesized and evaluated in the same manner as PVB-1, except that the amount of n-butyraldehyde added was changed to 449 g. The results are shown in Table 14.
  • PVB-12 After washing with 6 times the amount of ion-exchanged water of the resin deposited after the butyralization reaction, an excess amount of aqueous sodium hydroxide solution was added, neutralized sufficiently, and then again with 6 times the amount of ion-exchanged water of polyvinyl butyral. PVB was synthesized and evaluated in the same manner as PVB-1, except that it was washed. The results are shown in Table 14.
  • PVB-13 After washing with 4 times the amount of ion-exchanged water of the resin deposited after the butyralization reaction, an excess amount of aqueous sodium hydroxide solution was added, neutralized sufficiently, and then again with 4 times the amount of ion-exchanged water of polyvinyl butyral. PVB was synthesized and evaluated in the same manner as PVB-1, except that it was washed. The results are shown in Table 14.
  • PVB-14 In the butyralization reaction, 20% nitric acid was added instead of 20% hydrochloric acid, and after washing with ion-exchanged water 3 times the amount of the resin deposited after the butyralization reaction, an excess amount of sodium hydroxide aqueous solution was added and neutralized sufficiently, and then PVB was synthesized and evaluated in the same manner as PVB-1, except that it was washed again with ion-exchanged water 3 times the amount of polyvinyl butyral. The results are shown in Table 14.
  • PVB-15 In the butyralization reaction, 20% nitric acid was added instead of 20% hydrochloric acid, and after washing with twice the amount of ion-exchanged water of the resin deposited after the butyralization reaction, an excess amount of sodium hydroxide aqueous solution was added and neutralized sufficiently, and then PVB was synthesized and evaluated in the same manner as PVB-1, except that it was washed again with ion-exchanged water twice the amount of polyvinyl butyral. The results are shown in Table 14.
  • Comparative PVB-1 to Comparative PVB-5 PVB was synthesized and evaluated in the same manner as PVB-1, except that the raw material PVA was changed to that shown in Table 15. The results are shown in Table 15.
  • Comparative PVB-6 PVB was synthesized and evaluated in the same manner as PVB-1, except that comparative PVA-1 was used as the raw material PVA, and the amount of n-butyraldehyde added was changed to 271 g. The results are shown in Table 15.
  • Comparative PVB-7 PVB was synthesized and evaluated in the same manner as PVB-9, except that comparative PVA-1 was used as the raw material PVA. The results are shown in Table 15.
  • Comparative PVB-8 PVB was synthesized and evaluated in the same manner as PVB-11 except that comparative PVA-1 was used as the raw material PVA. The results are shown in Table 15.
  • Comparative PVB-9 PVB was synthesized and evaluated in the same manner as Comparative PVB-6 except that Comparative PVA-2 was used as the raw material PVA. The results are shown in Table 15.
  • Comparative PVB-10 PVB was synthesized and evaluated in the same manner as Comparative PVB-7, except that Comparative PVA-2 was used as the raw material PVA. The results are shown in Table 15.
  • Comparison PVB-11 PVB was synthesized and evaluated in the same manner as Comparative PVB-8 except that Comparative PVA-2 was used as the raw material PVA. The results are shown in Table 15.
  • Comparative PVB-12 PVB was synthesized and evaluated in the same manner as Comparative PVB-6 except that PVA-1 was used as the raw material PVA. The results are shown in Table 15.
  • Comparative PVB-13 A butyralization reaction was performed in the same manner as PVB-1, except that the addition amount of n-butyraldehyde was changed to 740 g and the addition amount of 20% hydrochloric acid was changed to 810 mL. Thereafter, the temperature was raised to 80 ° C. over 90 minutes, kept at 80 ° C. for 16 hours, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 15.
  • PVB-16, comparative PVB-14 and comparative PVB-15 PVB was synthesized and evaluated in the same manner as PVB-1, except that the raw material PVA was changed to that shown in Table 16. The results are shown in Table 16.
  • PVB-17 A 10 L (liter) glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-10 (PVA concentration 7.5%), and the content was adjusted to 95 ° C. The temperature was raised and completely dissolved. Next, the contents were gradually cooled to 1 ° C. over about 30 minutes while stirring at 120 rpm, and then 422 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to carry out a butyralization reaction for 120 minutes. Thereafter, the temperature was raised to 45 ° C. over 60 minutes, held at 45 ° C. for 120 minutes, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 17.
  • Comparative PVB-16 to Comparative PVB-18 PVB was synthesized and evaluated in the same manner as PVB-17 except that the raw material PVA was changed to that shown in Table 17. The results are shown in Table 17.
  • PVB-18 A 10 L glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion exchange water and 660 g of PVA-11 (PVA concentration 7.5%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents were gradually cooled to 5 ° C. over about 30 minutes while stirring at 120 rpm, and then 402 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to carry out a butyralization reaction for 120 minutes. Thereafter, the temperature was raised to 50 ° C. over 60 minutes, held at 50 ° C. for 120 minutes, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 18.
  • Comparative PVB-19 and Comparative PVB-20 PVB was synthesized and evaluated in the same manner as PVB-18 except that the raw material PVA was changed to that shown in Table 18. The results are shown in Table 18.
  • PVB-19 A 10 L glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-12 (PVA concentration 7.5%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents were gradually cooled to 10 ° C. over about 30 minutes while stirring at 120 rpm, 384 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 150 minutes. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 19.
  • Comparative PVB-21 and Comparative PVB-22 PVB was synthesized and evaluated in the same manner as PVB-19 except that the raw material PVA was changed to that shown in Table 19. The results are shown in Table 19.
  • Comparative PVB-23 A 10L glass vessel equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8234g of ion-exchanged water and 526g of comparative PVA-15 (PVA concentration 6.0%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents were gradually cooled to 15 ° C. over about 30 minutes while stirring at 120 rpm, and then 307 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to carry out a butyralization reaction for 120 minutes. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 20.
  • Comparative PVB-24 and Comparative PVB-25 PVB was synthesized and evaluated in the same manner as Comparative PVB-23 except that the raw material PVA was changed to that shown in Table 20. The results are shown in Table 20.
  • PVB-20 A 10 L glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-13 (PVA concentration 7.5%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents were gradually cooled to 10 ° C. over about 60 minutes while stirring at 120 rpm, 450 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 90 minutes. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 21.
  • PVB-21 to PVB-26 PVB was synthesized and evaluated in the same manner as PVB-20 except that the raw material PVA was changed to that shown in Table 21. The results are shown in Table 21.
  • PVB-27 PVB was synthesized and evaluated in the same manner as PVB-20 except that the amount of n-butyraldehyde added was changed to 269 g. The results are shown in Table 21.
  • PVB-28 PVB was synthesized and evaluated in the same manner as PVB-20 except that the amount of n-butyraldehyde added was changed to 307 g. The results are shown in Table 21.
  • PVB-29 PVB was synthesized and evaluated in the same manner as PVB-20 except that the amount of n-butyraldehyde added was changed to 458 g. The results are shown in Table 21.
  • PVB-30 After washing with 6 times the amount of ion-exchanged water of the resin deposited after the butyralization reaction, an excess amount of aqueous sodium hydroxide solution was added, neutralized sufficiently, and then again with 6 times the amount of ion-exchanged water of polyvinyl butyral. PVB was synthesized and evaluated in the same manner as PVB-20 except that it was washed. The results are shown in Table 21.
  • PVB-31 After washing with 4 times the amount of ion-exchanged water of the resin deposited after the butyralization reaction, an excess amount of aqueous sodium hydroxide solution was added, neutralized sufficiently, and then again with 4 times the amount of ion-exchanged water of polyvinyl butyral. PVB was synthesized and evaluated in the same manner as PVB-20 except that it was washed. The results are shown in Table 21.
  • PVB-32 In the butyralization reaction, 20% nitric acid was added instead of 20% hydrochloric acid, and after washing with ion-exchanged water 3 times the amount of the resin deposited after the butyralization reaction, an excess amount of sodium hydroxide aqueous solution was added and neutralized sufficiently, and then PVB was synthesized and evaluated in the same manner as PVB-20 except that it was further washed again with ion-exchanged water 3 times the amount of polyvinyl butyral. The results are shown in Table 21.
  • PVB-33 In the butyralization reaction, 20% nitric acid was added instead of 20% hydrochloric acid, and after washing with twice the amount of ion-exchanged water of the resin deposited after the butyralization reaction, an excess amount of sodium hydroxide aqueous solution was added and neutralized sufficiently, and then PVB was synthesized and evaluated in the same manner as PVB-20 except that it was washed again with ion-exchanged water twice the amount of polyvinyl butyral. The results are shown in Table 21.
  • Comparative PVB-26 to Comparative PVB-29 PVB was synthesized and evaluated in the same manner as PVB-20 except that the raw material PVA was changed to that shown in Table 22. The results are shown in Table 22.
  • Comparative PVB-30 PVB was synthesized and evaluated in the same manner as PVB-20, except that comparative PVA-18 was used as the raw material PVA, and the amount of n-butyraldehyde added was changed to 225 g. The results are shown in Table 22.
  • Comparative PVB-31 PVB was synthesized and evaluated in the same manner as PVB-27 except that comparative PVA-18 was used as the raw material PVA. The results are shown in Table 22.
  • Comparative PVB-32 PVB was synthesized and evaluated in the same manner as PVB-29 except that comparative PVA-18 was used as the raw material PVA. The results are shown in Table 22.
  • Comparative PVB-33 PVB was synthesized and evaluated in the same manner as Comparative PVB-30, except that Comparative PVA-19 was used as the raw material PVA. The results are shown in Table 22.
  • Comparative PVB-34 PVB was synthesized and evaluated in the same manner as PVB-27 except that comparative PVA-19 was used as the raw material PVA. The results are shown in Table 22.
  • Comparative PVB-35 PVB was synthesized and evaluated in the same manner as PVB-29 except that comparative PVA-19 was used as the raw material PVA. The results are shown in Table 22.
  • Comparative PVB-36 PVB was synthesized and evaluated in the same manner as Comparative PVB-30 except that PVA-13 was used as the raw material PVA. The results are shown in Table 22.
  • Comparative PVB-37 A butyralization reaction was performed in the same manner as PVB-20, except that the amount of n-butyraldehyde added was changed to 837 g and the amount of 20% hydrochloric acid added was changed to 810 mL. Then, it heated up to 60 degreeC over 60 minutes, and hold
  • PVB-34, comparative PVB-38 and comparative PVB-39 PVB was synthesized and evaluated in the same manner as PVB-20 except that the raw material PVA was changed to that shown in Table 23. The results are shown in Table 23.
  • PVB-35 A 10 L glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion exchange water and 660 g of PVA-21 (PVA concentration 7.5%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents were gradually cooled to 1 ° C. over about 60 minutes while stirring at 120 rpm, and then 468 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 90 minutes. Thereafter, the temperature was raised to 25 ° C. over 30 minutes, held at 25 ° C. for 180 minutes, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 24.
  • Comparative PVB-40 to Comparative PVB-43 PVB was synthesized and evaluated in the same manner as PVB-35 except that the raw material PVA was changed to that shown in Table 24. The results are shown in Table 24.
  • Comparative PVB-42 the raw material Comparative PVA-26 was insufficient in water solubility, and an aqueous solution could not be obtained. Therefore, synthesis was stopped.
  • PVB-36 A 10 L glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-22 (PVA concentration 7.5%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents were gradually cooled to 5 ° C. over about 60 minutes while stirring at 120 rpm, 450 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 90 minutes. Thereafter, the temperature was raised to 30 ° C. over 30 minutes, held at 30 ° C. for 180 minutes, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 25.
  • Comparative PVB-44 and Comparative PVB-45 PVB was synthesized and evaluated in the same manner as PVB-36 except that the raw material PVA was changed to that shown in Table 25. The results are shown in Table 25.
  • PVB-37 A 10 L glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion exchange water and 660 g of PVA-23 (PVA concentration 7.5%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents were gradually cooled to 15 ° C. over about 30 minutes while stirring at 120 rpm, 432 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 90 minutes. Thereafter, the temperature was raised to 45 ° C. over 30 minutes, held at 45 ° C. for 180 minutes, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 26.
  • Comparative PVB-46 and Comparative PVB-47 PVB was synthesized and evaluated in the same manner as PVB-37 except that the raw material PVA was changed to that shown in Table 26. The results are shown in Table 26.
  • Comparative PVB-48 A 10L glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8234 g of ion-exchanged water and 526 g of PVA-18 (PVA concentration 6.0%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents were gradually cooled to 15 ° C. over about 60 minutes while stirring the contents at 120 rpm, 344 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 90 minutes. Thereafter, the temperature was raised to 45 ° C. over 30 minutes, held at 45 ° C. for 180 minutes, and then cooled to room temperature. The steps after washing of the precipitated resin were performed in the same manner as PVB-1 to obtain PVB. The obtained PVB was evaluated in the same manner as PVB-1. The results are shown in Table 27.
  • Comparative PVB-49 and Comparative PVB-50 PVB was synthesized and evaluated in the same manner as Comparative PVB-48 except that the raw material PVA was changed to that shown in Table 27. The results are shown in Table 27.
  • Example 1 70 parts by mass of PVB-1 powder and 0.014 parts by mass of magnesium acetate were melt-kneaded for 5 minutes at 190 ° C. and 50 rpm using a lab plast mill “C model” manufactured by Toyo Seiki Co., Ltd. During melt kneading, nitrogen (100 mL / min) was continuously blown into the container. The obtained kneaded product was hot-pressed at 170 ° C. and 5 MPa for 30 minutes to prepare a film of 30 cm ⁇ 30 cm and a thickness of 760 ⁇ m. The obtained film was subjected to GPC measurement, chloride ion content measurement and evaluation of foreign matter (undissolved content) as follows. Moreover, the obtained film was used for preparation of a solar cell module.
  • the signal intensity (absorbance, y) at the peak top molecular weight measured with an absorptiometric detector (220 nm) obtained in the same manner as the method for determining the peak top molecular weight (B) was 269.28 mV (0.26928 absorber). Unit).
  • Signal intensity (a), signal intensity (b), signal intensity (x), and signal intensity (y) are expressed by the following formula (b / y) / (a / x) The value obtained by substituting for was 4.00 ⁇ 10 ⁇ 2 . The results are also shown in Table 28.
  • Signal intensity (a), signal intensity (c), signal intensity (x), and signal intensity (y) are expressed by the following formula (c / y) / (a / x) The value obtained by substituting for was 2.14 ⁇ 10 ⁇ 2 . The results are also shown in Table 28.
  • FIG. 1 The manufacturing method of a thin film photovoltaic cell and a solar cell module is demonstrated using FIG.
  • An SnO 2 film having a thickness of about 700 nm was formed as a transparent electrode layer 12 on a glass substrate 11 having a size of 100 mm ⁇ 100 mm and a thickness of 4 mm by a CVD method.
  • an amorphous silicon thin film was formed as a photoelectric conversion unit 13 on the entire surface of the substrate on the transparent electrode layer 12 using a plasma CVD apparatus.
  • the p-type layer 13a is a p-layer amorphous Si film (film thickness of about 15 nm)
  • the i-type layer 13b is an i-layer amorphous Si film (film thickness of about 500 nm)
  • the n-type layer 13c is an n-layer amorphous Si film. (Film thickness is about 3 nm).
  • a ZnO film film thickness of about 80 nm
  • an Ag film film thickness of about 200 nm
  • the glass substrate 11 on which the solar cells were formed was placed on a hot plate of a vacuum laminator (“1522N” manufactured by Nisshinbo Mechatronics Inc.) so that the glass substrate 11 was in contact with the hot plate.
  • a vacuum laminator 1522N manufactured by Nisshinbo Mechatronics Inc.
  • the film containing PVB-1 cut to 100 mm ⁇ 100 mm as the sealing material 15, and a glass substrate 16 having a thickness of 100 mm ⁇ 100 mm and a thickness of 4 mm were laminated on the film, and then the following The solar cell was sealed under conditions to produce a solar cell module.
  • Hot plate temperature 165 ° C
  • Vacuuming time 12 minutes
  • Pressing pressure 50 kPa Press time: 17 minutes
  • the solar cell module thus obtained was measured for changes in appearance and reduction rate of conversion efficiency after holding for 5000 hours under conditions of 85 ° C. and 85% RH.
  • a solar cell module was produced by the same method as described above except that wiring was performed so that the electrical characteristics of the solar cell could be measured.
  • the solar cell module was irradiated with AM1.5 and 1000 W / m 2 reference sunlight to measure the conversion efficiency.
  • a solar simulator manufactured by Nisshinbo Mechatronics Inc. was used to measure the conversion efficiency.
  • the conversion efficiency was measured by the above method. When the conversion efficiency before exposure was 100% (standard), the reduction rate (%) of the conversion efficiency after exposure was calculated. As a result, the rate of decrease in conversion efficiency was less than 1%.
  • the results are also shown in Table 28.
  • Examples 2 to 11 and Examples 13 to 16 A film was prepared and evaluated in the same manner as in Example 1 except that PVB shown in Table 28 was used instead of PVB-1. The results are shown in Table 28.
  • Example 12 PVB-1 powder 64.4 parts by mass, triethylene glycol di-2-ethylhexanoate 5.6 parts by mass and magnesium acetate 0.014 parts by mass were manufactured by Toyo Seiki Seisakusho Co., Ltd. The model was melt kneaded at 190 ° C. and 50 rpm for 5 minutes. During melt kneading, nitrogen (100 mL / min) was continuously blown into the container. The obtained kneaded product was hot-pressed at 170 ° C. and 5 MPa for 30 minutes to prepare a film of 30 cm ⁇ 30 cm and a thickness of 760 ⁇ m. The GPC measurement and chloride ion content measurement of the obtained film were performed in the same manner as in Example 1. Further, a solar cell module was produced and evaluated in the same manner as in Example 1 except that the obtained film was used. These results are shown in Table 28. Furthermore, the undissolved content in the film was evaluated as follows.
  • Comparative Examples 1 to 13 A film was prepared and evaluated in the same manner as in Example 1 except that PVB shown in Table 29 was used instead of PVB-1. The results are shown in Table 29.
  • Comparative Example 14 61.5 parts by mass of PVB-1 powder, 8.5 parts by mass of triethylene glycol di-2-ethylhexanoate and 0.014 parts by mass of magnesium acetate were added to a laboratory plast mill “C The model was melt kneaded at 190 ° C. and 50 rpm for 5 minutes. During melt kneading, nitrogen (100 mL / min) was continuously blown into the container. The obtained kneaded product was hot-pressed at 170 ° C. and 5 MPa for 30 minutes to prepare a film of 30 cm ⁇ 30 cm and a thickness of 760 ⁇ m. The GPC measurement and chloride ion content measurement of the obtained film were performed in the same manner as in Example 1. Further, a solar cell module was produced and evaluated in the same manner as in Example 1 except that the obtained film was used. These results are shown in Table 29. Furthermore, the undissolved content in the film was evaluated as follows.
  • Example 17 Comparative Example 15 and Comparative Example 16 A film was prepared and evaluated in the same manner as in Example 1 except that PVB shown in Table 30 was used instead of PVB-1. The results are shown in Table 30.
  • Example 18 A film was prepared and evaluated in the same manner as in Example 12 except that PVB-16 was used instead of PVB-1. The results are shown in Table 30.
  • Comparative Example 17 A film was prepared and evaluated in the same manner as in Comparative Example 14 except that PVB-16 was used instead of PVB-1. The results are shown in Table 30.
  • Example 19 and Comparative Examples 18 to 20 A film was prepared and evaluated in the same manner as in Example 1 except that PVB shown in Table 31 was used instead of PVB-1. The results are shown in Table 31.
  • Comparative Example 21 A film was prepared and evaluated in the same manner as in Comparative Example 14 except that PVB-17 was used instead of PVB-1. The results are shown in Table 31.
  • Example 20 Comparative Example 22 and Comparative Example 23 A film was prepared and evaluated in the same manner as in Example 1 except that PVB shown in Table 32 was used instead of PVB-1. The results are shown in Table 32.
  • Comparative Example 24 A film was prepared and evaluated in the same manner as Comparative Example 14 except that PVB-18 was used instead of PVB-1. The results are shown in Table 32.
  • Example 21 Comparative Example 25 and Comparative Example 26 A film was prepared and evaluated in the same manner as in Example 12 except that PVB shown in Table 33 was used instead of PVB-1. The results are shown in Table 33.
  • Comparative Example 27 A film was prepared and evaluated in the same manner as in Comparative Example 14 except that PVB-19 was used instead of PVB-1. The results are shown in Table 33.
  • Comparative Example 28 to Comparative Example 30 A film was prepared and evaluated in the same manner as in Example 12 except that PVB shown in Table 34 was used instead of PVB-1. The results are shown in Table 34.
  • Comparative Example 31 A film was prepared and evaluated in the same manner as Comparative Example 14 except that Comparative PVB-23 was used instead of PVB-1. The results are shown in Table 34.
  • Examples 22 to 31 and Examples 33 to 36 A film was prepared and evaluated in the same manner as in Example 1 except that PVB shown in Table 35 was used instead of PVB-1. However, the evaluation of the color resistance of the film was changed to the following method. The results are shown in Table 35.
  • Example 32 A film was prepared and evaluated in the same manner as in Example 12 except that PVB-20 was used instead of PVB-1. However, the evaluation of the color resistance of the film was changed to the following method. The results are shown in Table 35.
  • Example 12 is the same as Example 12 except that the PVB powder, triethylene glycol-di-2-ethylhexanoate and magnesium acetate were newly added to the kneaded material, and then the melt-kneading step was performed only once. Evaluation was performed in the same manner.
  • Comparative Example 32 to Comparative Example 43 A film was prepared and evaluated in the same manner as in Example 22 except that PVB shown in Table 36 was used instead of PVB-20. The results are shown in Table 36.
  • Comparative Example 44 A film was prepared and evaluated in the same manner as in Comparative Example 14 except that PVB-16 was used instead of PVB-1. However, the evaluation of the color resistance of the film was changed to the following method. The results are shown in Table 36.
  • Example 37 Comparative Example 45 and Comparative Example 46 A film was prepared and evaluated in the same manner as in Example 22 except that PVB shown in Table 37 was used instead of PVB-20. The results are shown in Table 37.
  • Example 38 A film was prepared and evaluated in the same manner as in Example 32 except that PVB-34 was used instead of PVB-20. The results are shown in Table 37.
  • Comparative Example 47 A film was prepared and evaluated in the same manner as in Comparative Example 44, except that PVB-34 was used instead of PVB-16. The results are shown in Table 37.
  • Example 39 Comparative Examples 48 to 51 A film was prepared and evaluated in the same manner as in Example 22 except that PVB shown in Table 38 was used instead of PVB-20. The results are shown in Table 38.
  • Comparative Example 52 A film was prepared and evaluated in the same manner as in Comparative Example 44, except that PVB-35 was used instead of PVB-16. The results are shown in Table 38.
  • Example 40 Comparative Example 53 and Comparative Example 54 A film was prepared and evaluated in the same manner as in Example 22 except that PVB shown in Table 39 was used instead of PVB-20. The results are shown in Table 39.
  • Comparative Example 55 A film was prepared and evaluated in the same manner as in Comparative Example 44 except that PVB-36 was used instead of PVB-16. The results are shown in Table 39.
  • Example 41 Comparative Example 56 and Comparative Example 57 A film was prepared and evaluated in the same manner as in Example 32 except that PVB shown in Table 40 was used instead of PVB-20. The results are shown in Table 40.
  • Comparative Example 58 A film was produced and evaluated in the same manner as in Comparative Example 44, except that PVB-37 was used instead of PVB-16. The results are shown in Table 40.
  • Comparative Example 59 to Comparative Example 61 A film was prepared and evaluated in the same manner as in Example 32 except that PVB shown in Table 41 was used instead of PVB-20. The results are shown in Table 41.
  • Comparative Example 62 A film was prepared and evaluated in the same manner as Comparative Example 44, except that Comparative PVB-48 was used instead of PVB-16. The results are shown in Table 41.
  • the films of the present invention had little undissolved content in the film and were excellent in coloration resistance of the film. Further, in the solar cell module of the present invention (Examples 1 to 41), no foaming was observed after exposure, and the decrease in conversion efficiency was small. Thus, the film of the present invention showed a well-balanced performance. On the other hand, any of the films (Comparative Examples 1 to 62) that did not satisfy the conditions defined in the present invention deteriorated.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un film comprenant de l'acétal polyvinylique qui présente un degré d'acétalisation de 50 à 85 % en moles, une teneur en motif monomère d'ester vinylique de 0,1 à 20 % en moles et un degré de polymérisation moyen viscosimétrique de 200 à 2000, le film présentant une teneur en plastifiant inférieure à 10 parties en masse par rapport à 100 parties en masse d'acétal polyvinylique et satisfaisant aux formules (1) et (2). (A-B)/A<0,80 (1) 1,00x10-2<(b/y)/(a/x)<2,00×10-1 (2) Par conséquent, l'invention concerne un film qui est moins coloré en raison de la chaleur, renferme moins de matières étrangères (fractions non dissoutes), et dans lequel la perméabilité de la vapeur d'eau n'a pas tendance à augmenter, même en cas d'utilisation prolongée.
PCT/JP2013/071418 2013-08-07 2013-08-07 Film comprenant de l'acétal polyvinylique Ceased WO2015019452A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
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WO2015125690A1 (fr) * 2014-02-18 2015-08-27 株式会社クラレ Couche intermédiaire pour verre feuilleté
WO2020067162A1 (fr) * 2018-09-26 2020-04-02 株式会社クラレ Film de résine d'acétal polyvinylique et stratifié comprenant celui-ci
WO2020067184A1 (fr) * 2018-09-26 2020-04-02 株式会社クラレ Film de résine d'acétal polyvinylique et son rouleau de film, et produit en couches
WO2020067176A1 (fr) * 2018-09-26 2020-04-02 株式会社クラレ Film de résine d'acétal de polyvinyle et corps multicouche le contenant
CN113527755A (zh) * 2021-07-08 2021-10-22 暨南大学 一种pva衍生物辐射制冷膜材料及其制备方法与应用
CN115266966A (zh) * 2022-07-07 2022-11-01 重庆光谱新材料科技有限公司 一种检测聚乙烯醇薄膜溶出物含量的方法
WO2023171710A1 (fr) * 2022-03-09 2023-09-14 株式会社クラレ Film d'alcool polyvinylique et procédé pour la production d'un film d'alcool polyvinylique
CN118085342A (zh) * 2024-04-23 2024-05-28 广东工业大学 一种自适应环境温度的水凝胶的制备方法

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JP5799192B1 (ja) * 2014-02-18 2015-10-21 株式会社クラレ 高接着性樹脂組成物及びそれからなる成形体並びに積層体
JP6529496B2 (ja) * 2014-06-17 2019-06-12 三菱ケミカル株式会社 ゴム含有グラフト重合体粉体、並びにそれを含有する太陽電池用封止材及び合わせガラス用中間膜

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0931124A (ja) * 1994-11-24 1997-02-04 Sekisui Chem Co Ltd ポリビニルアセタールの製造方法、ポリビニルアセタール、合わせガラス用中間膜及び合わせガラス
JPH09316110A (ja) * 1996-03-29 1997-12-09 Kuraray Co Ltd 酢酸ビニル系重合体の製造方法
JPH1180272A (ja) * 1997-09-10 1999-03-26 Nof Corp エチレン−酢酸ビニル共重合体けん化物の製造方法
JP2005029764A (ja) * 2003-07-11 2005-02-03 Kuraray Co Ltd ビニルアセタール系重合体およびその製造法
JP2008214435A (ja) * 2007-03-01 2008-09-18 Denki Kagaku Kogyo Kk ポリビニルアセタール樹脂及びその製造方法
JP2011508802A (ja) * 2007-12-21 2011-03-17 セキスイ・スペシャルティ・ケミカルズ・アメリカ・エルエルシー 低色ポリビニルアルコールの作成方法
WO2011108152A1 (fr) * 2010-03-03 2011-09-09 電気化学工業株式会社 Procédé d'obtention de résine d'alcool polyvinylique
JP2011241234A (ja) * 2009-04-28 2011-12-01 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系樹脂組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0931124A (ja) * 1994-11-24 1997-02-04 Sekisui Chem Co Ltd ポリビニルアセタールの製造方法、ポリビニルアセタール、合わせガラス用中間膜及び合わせガラス
JPH09316110A (ja) * 1996-03-29 1997-12-09 Kuraray Co Ltd 酢酸ビニル系重合体の製造方法
JPH1180272A (ja) * 1997-09-10 1999-03-26 Nof Corp エチレン−酢酸ビニル共重合体けん化物の製造方法
JP2005029764A (ja) * 2003-07-11 2005-02-03 Kuraray Co Ltd ビニルアセタール系重合体およびその製造法
JP2008214435A (ja) * 2007-03-01 2008-09-18 Denki Kagaku Kogyo Kk ポリビニルアセタール樹脂及びその製造方法
JP2011508802A (ja) * 2007-12-21 2011-03-17 セキスイ・スペシャルティ・ケミカルズ・アメリカ・エルエルシー 低色ポリビニルアルコールの作成方法
JP2011241234A (ja) * 2009-04-28 2011-12-01 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系樹脂組成物
WO2011108152A1 (fr) * 2010-03-03 2011-09-09 電気化学工業株式会社 Procédé d'obtention de résine d'alcool polyvinylique

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WO2015125690A1 (fr) * 2014-02-18 2015-08-27 株式会社クラレ Couche intermédiaire pour verre feuilleté
JPWO2015125690A1 (ja) * 2014-02-18 2017-03-30 株式会社クラレ 合わせガラス用中間膜
US10259198B2 (en) 2014-02-18 2019-04-16 Kuraray Co., Ltd. Interlayer film for laminated glass
CN112771100A (zh) * 2018-09-26 2021-05-07 株式会社可乐丽 聚乙烯醇缩醛树脂薄膜和包含其的层叠体
WO2020067184A1 (fr) * 2018-09-26 2020-04-02 株式会社クラレ Film de résine d'acétal polyvinylique et son rouleau de film, et produit en couches
WO2020067176A1 (fr) * 2018-09-26 2020-04-02 株式会社クラレ Film de résine d'acétal de polyvinyle et corps multicouche le contenant
US11623985B2 (en) 2018-09-26 2023-04-11 Kuraray Europe Gmbh Polyvinyl acetal resin film and film roll thereof, and laminate comprising same
JPWO2020067162A1 (ja) * 2018-09-26 2021-09-24 株式会社クラレ ポリビニルアセタール樹脂フィルムおよびそれを含む積層体
JPWO2020067184A1 (ja) * 2018-09-26 2021-09-24 株式会社クラレ ポリビニルアセタール樹脂フィルムおよびそのフィルムロール、並びに積層体
JPWO2020067176A1 (ja) * 2018-09-26 2021-09-24 株式会社クラレ ポリビニルアセタール樹脂フィルムおよびそれを含む積層体
WO2020067162A1 (fr) * 2018-09-26 2020-04-02 株式会社クラレ Film de résine d'acétal polyvinylique et stratifié comprenant celui-ci
EP3858896A4 (fr) * 2018-09-26 2022-06-22 Kuraray Europe GmbH Film de résine d'acétal de polyvinyle et corps multicouche le contenant
JP7466453B2 (ja) 2018-09-26 2024-04-12 クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリビニルアセタール樹脂フィルムおよびそれを含む積層体
JP7466454B2 (ja) 2018-09-26 2024-04-12 クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリビニルアセタール樹脂フィルムおよびそれを含む積層体
CN113527755A (zh) * 2021-07-08 2021-10-22 暨南大学 一种pva衍生物辐射制冷膜材料及其制备方法与应用
CN113527755B (zh) * 2021-07-08 2022-09-27 暨南大学 一种pva衍生物辐射制冷膜材料及其制备方法与应用
WO2023171710A1 (fr) * 2022-03-09 2023-09-14 株式会社クラレ Film d'alcool polyvinylique et procédé pour la production d'un film d'alcool polyvinylique
CN115266966A (zh) * 2022-07-07 2022-11-01 重庆光谱新材料科技有限公司 一种检测聚乙烯醇薄膜溶出物含量的方法
CN115266966B (zh) * 2022-07-07 2024-05-07 重庆光谱新材料科技有限公司 一种检测聚乙烯醇薄膜溶出物含量的方法
CN118085342A (zh) * 2024-04-23 2024-05-28 广东工业大学 一种自适应环境温度的水凝胶的制备方法

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